CN113832511A - Preparation method of nickel with multi-stage cellular structure - Google Patents

Preparation method of nickel with multi-stage cellular structure Download PDF

Info

Publication number
CN113832511A
CN113832511A CN202111317401.6A CN202111317401A CN113832511A CN 113832511 A CN113832511 A CN 113832511A CN 202111317401 A CN202111317401 A CN 202111317401A CN 113832511 A CN113832511 A CN 113832511A
Authority
CN
China
Prior art keywords
nickel
preparing
copper
electrode
stage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111317401.6A
Other languages
Chinese (zh)
Inventor
窦艳丽
钱广广
管东波
姚卫国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202111317401.6A priority Critical patent/CN113832511A/en
Publication of CN113832511A publication Critical patent/CN113832511A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching

Abstract

The invention relates to the field of materials, and particularly discloses a preparation method of nickel with a multistage cellular structure. The electroplating solution selected by the invention contains nitro-tetrazolium blue chloride as an inhibitor, can generate a blocking effect on the copper deposition process, has strong electropositivity, can be adsorbed on the surface of a cathode to generate an inhibiting effect, and reduces the deposition amount of copper; and then the deposited composite plating layer is etched to remove the deposited copper to obtain the nickel electrode with a single-stage cellular structure, and the deposition and etching processes are repeated twice under the same condition to obtain the nickel electrode with a multi-stage cellular structure with a large surface area, more active sites can be provided, and the mechanical strength is good.

Description

Preparation method of nickel with multi-stage cellular structure
Technical Field
The invention relates to the field of materials, in particular to a preparation method of nickel with a multistage cellular structure.
Background
The metal nickel is widely applied to machinery and production due to good corrosion resistance and good rigidity, and the nickel material with the microporous structure is widely applied to catalytic electrolysis of water, a super capacitor, catalytic cracking of organic matters and addition reaction due to high specific surface area and high catalytic activity. Utilize the in-process of copper-nickel codeposition system hole, copper-nickel deposit is inhomogeneous, copper is deposited more easily than nickel, because its resistance is compared nickel littleer after the copper deposit forms the crystal nucleus, make copper form dendrite, further accelerated the deposit of copper, finally only there is a small amount of nickel deposit, it is little to lead to nickel ion deposition volume, the pore-forming is poor and the active point is few, homogeneity when consequently improving electrode composite deposition, improve the pore-forming performance, it is the technical problem that needs to solve at present to increase the active site of electrode.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method capable of realizing uniform plating and effectively etching a hierarchical pore structure electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing nickel with a multi-stage cellular structure, wherein a working electrode is a cylindrical rotatable electrode, an auxiliary electrode is an arc sheet electrode, and nickel with the multi-stage cellular structure is prepared by utilizing electroplated copper-nickel alloy and electroetched copper alternately, comprises the following steps:
step 1: cleaning and pretreating the working electrode;
step 2: putting the rotary working electrode in an electroplating solution containing an inhibitor to electrodeposit copper-nickel alloy, and cleaning;
and step 3: placing the electrode obtained in the step 2 in electrolyte to electroetch copper;
and 4, step 4: repeating the step 2 and the step 3;
and 5: cleaning and drying the electrode obtained in the step 5 to obtain the multi-stage cellular structure nickel;
and 2, the inhibitor in the electroplating solution in the step 2 is an inhibitor containing nitrogen and halogen, and the inhibitor comprises nitro-tetrazolium blue chloride.
Preferably, the electroplating solution in the step 2 comprises the following components: sodium polydithio-dipropyl sulfonate, polyethylene glycol, nitrotetrazolium chloride, malic acid and mannitol.
Preferably, the electroplating solution in the step 2 comprises 0.01g/L-0.4g/L of sodium polydithio dipropyl sulfonate, 0.01g/L-0.2g/L of polyethylene glycol, 0.01g/L-0.6g/L of nitro blue tetrazolium chloride, 5g/L-10g/L of malic acid and 0.1g/L-5g/L of mannitol.
Preferably, the electrolyte in step 3 includes soluble salts capable of undergoing redox reactions.
Preferably, the working electrode in the step 1 is a cylindrical structure with the diameter of 4cm-6cm and the height of 5cm-8 cm.
Preferably, the rotating speed of the working electrode as the rotary working motor in the step 2 is 30RPM to 180 RPM.
Preferably, the electroplating temperature in the step 2 is 45-65 ℃, and the current for electroplating is 10-40 mA.
Preferably, the duration of the copper electroetching in the step 3 is 3600s to 7200s, and the current density is 0.2A/square meter to 1A/square meter.
Preferably, step 4 is repeated 2 times.
Preferably, the cleaning pretreatment in step 1 comprises the following steps: and sequentially putting the working electrode into a hydrogen chloride solution, an acetone solution and deionized water, and carrying out ultrasonic cleaning each time.
The invention has the beneficial effects that:
the selected electroplating solution contains nitro-tetrazolium blue chloride as an inhibitor, a Cu + -NBT-Cl-complex can be formed in the solution, the complex can be adsorbed on the surface of a cathode and has a blocking effect on the copper deposition process, a product dissolved in water is a nitrogen-containing organic monomer, and the nitrogen-containing organic monomer has strong electropositivity and can be adsorbed on the surface of the cathode to generate the inhibiting effect, so that more nickel ions can be deposited on the surface of an electrode in the electroplating process, and the deposition amount of copper is reduced; and then the deposited composite plating layer is etched to remove the deposited copper to obtain the nickel electrode with a single-stage cellular structure, and the deposition and etching processes are repeated twice under the same condition to obtain the nickel electrode with a multi-stage cellular structure with a large surface area, and can provide more active sites and better mechanical strength.
Drawings
FIG. 1 is a SEM and partially enlarged view of a multi-stage cell structure nickel prepared according to an example of the invention.
Detailed Description
The technical solution of the embodiment of the present invention will be clearly and completely described below, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, but not all embodiments, the working electrode of the present invention is a cylindrical rotatable electrode, the auxiliary electrode is a circular arc sheet electrode, and nickel with a multi-stage cell structure is prepared by using electroplated copper-nickel alloy and electroetched copper alternately.
Example 1
Pretreatment of a working electrode: putting the cylindrical working electrode into 0.1M sodium chloride, acetone and deionized water at one time, and carrying out ultrasonic cleaning for 30min each time;
the components for preparing the electroplating solution are as follows: 0.2g/L of sodium polydithio-dipropyl sulfonate, 0.2g/L of polyethylene glycol, 0.2g/L of nitro-tetrazole blue chloride, 5g/L of malic acid, 0.1g/L of mannitol and 100mg/L of sodium laureth sulfate;
depositing for 100s at 25 deg.C and 50 deg.C at 40mA respectively by using cylindrical working electrode and profiling auxiliary electrode; the cathode was held at 30RPM and the mass of copper deposit on the working electrode was 2.76mg at 25 c and 2.87mg at 50 c, with a 3.98% weight gain as shown by a high precision electronic balance.
Example 2
Pretreatment of a working electrode: putting the working electrode into 0.1M hydrogen chloride, acetone and deionized water once, and carrying out ultrasonic cleaning for 30min each time;
the components for preparing the electroplating solution are as follows: 0.2g/L of sodium polydithio-dipropyl sulfonate, 0.2g/L of polyethylene glycol (PEG), 0.2g/L of nitro-tetrazole blue chloride, 5g/L of malic acid, 0.1g/L of mannitol and 100mg/L of sodium lauryl polyether sulfate;
depositing for 100s at 25 deg.C and 50 deg.C at 40mA respectively by using cylindrical working electrode and profiling auxiliary electrode; the cathode was held at 30RPM and the mass of the nickel deposited was found by comparison to be 1.51mg at 25 ℃ and 2.7mg at 50 ℃ with an 98.67% weight gain.
Example 3
Pretreatment of a working electrode: putting the working electrode into 0.1M hydrogen chloride, acetone and deionized water once, and carrying out ultrasonic cleaning for 30min each time;
263g of NiSO were then charged4·6H2O、25g CuSO4·5H2Adding O, 0.5g of nitro-tetrazolium chloride, 0.2g of polyethylene glycol, 5g of malic acid and 100mg of sodium laureth sulfate into a beaker to prepare 1L of solution, and stirring for 30min at 50 ℃ to fully dissolve;
the working electrode was clamped to the cathode and held at 30RPM with a current density set at 40mA and a deposition time of 100 s; after deposition is finished and cleaning is carried out, the working electrode is placed into a potassium sulfate solution for etching, the voltage is 0.5, and the etching time is 7200 s; depositing and etching again after finishing; the weight of the multi-stage cell nickel is increased by 8.12mg through a high-precision electronic balance, and the micro-morphology is shown in figure 1.
Example 4
Sequentially putting a working electrode with the diameter of 4cm and the height of 5cm into a hydrogen chloride solution, an acetone solution and deionized water, and carrying out ultrasonic cleaning for 30min each time;
preparing electroplating solution according to the dosage of 0.01g/L sodium polydithio-dipropyl sulfonate, 0.01g/L polyethylene glycol, 0.01g/L nitrotetrazolium chloride, 5g/L malic acid and 0.1g/L mannitol;
putting the rotary working electrode into electroplating solution, rotating at the rotating speed of 30RPM, and electrodepositing the copper-nickel alloy in the environment with the temperature of 45 ℃ and the current of 10 mA; then putting the electrode subjected to electrodeposition into a potassium sulfate solution with the current density of 0.2A/square meter, and carrying out copper electroetching for 3600 s; and (3) repeatedly electroplating and electrolyzing the electrode for 2 times, and cleaning and drying the electrode to obtain the multi-stage cell structure nickel.
Example 5
Sequentially putting a working electrode with the diameter of 6cm and the height of 8cm into a hydrogen chloride solution, an acetone solution and deionized water, and carrying out ultrasonic cleaning for 30min each time;
preparing electroplating solution according to the dosage of 0.4g/L of sodium polydithio-dipropyl sulfonate, 0.2g/L of polyethylene glycol, 0.6g/L of nitrotetrazolium chloride, 10g/L of malic acid and 5g/L of mannitol;
putting the rotary working electrode into electroplating solution, rotating at the rotating speed of 180RPM, and electrodepositing the copper-nickel alloy in the environment of 65 ℃ and 40mA current; then putting the electrode subjected to electrodeposition into a potassium sulfate solution with the current density of 1A/square meter, and carrying out electroetching on copper for 7200 s; and (3) repeatedly electroplating and electrolyzing the electrode for 2 times, and cleaning and drying the electrode to obtain the multi-stage cell structure nickel.
Example 6
Sequentially putting a working electrode with the diameter of 5cm and the height of 7cm into a hydrogen chloride solution, an acetone solution and deionized water, and carrying out ultrasonic cleaning for 30min each time;
preparing electroplating solution according to the dosage of 0.2g/L sodium polydithio-dipropyl sulfonate, 0.1g/L polyethylene glycol, 0.3g/L nitro-tetrazole blue chloride, 7g/L malic acid and 3g/L mannitol;
putting the rotary working electrode into electroplating solution, rotating at the rotating speed of 100RPM, and electrodepositing the copper-nickel alloy in the environment with the temperature of 55 ℃ and the current of 25 mA; then putting the electrode subjected to electrodeposition into a potassium sulfate solution with the current density of 0.6A/square meter, and carrying out 5400s copper electroetching; and (3) repeatedly electroplating and electrolyzing the electrode for 2 times, and cleaning and drying the electrode to obtain the multi-stage cell structure nickel.
In examples 1-2, a single metal is deposited at different temperatures according to the relationship of metal deposition rates at different temperatures, the deposition quality is measured, and then the deposition amount of nickel is tested, and as can be seen from the comparison of the deposition amounts of nickel at 25 ℃ and 50 ℃ in examples 4-5, the deposition amount of nickel at high temperature is larger, and the experiment is carried out at 50 ℃ in order to ensure that the nickel has larger deposition amount.
The rotary cylindrical working electrode and the arc-shaped flaky auxiliary electrode can ensure that power lines are distributed in parallel, and the electrodes are uniformly plated in all areas.
The electroplating solution selected by the invention contains nitro-tetrazolium blue chloride as an inhibitor, can form a Cu + -NBT-Cl-complex in the solution, the complex can be adsorbed on the surface of a cathode to generate a blocking effect on the copper deposition process, a dissolved product in water is a nitrogen-containing organic monomer, has strong electropositivity and can be adsorbed on the surface of the cathode to generate the inhibiting effect, more nickel ions can be deposited on the surface of an electrode in the electroplating process, and the deposition amount of copper is reduced; and then the deposited composite plating layer is etched to remove the deposited copper to obtain the nickel electrode with a single-stage cellular structure, and the deposition and etching processes are repeated twice under the same condition to obtain the nickel electrode with a multi-stage cellular structure with a large surface area, and can provide more active sites and better mechanical strength.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A preparation method of nickel with a multi-stage cellular structure is characterized in that a working electrode is a cylindrical rotatable electrode, an auxiliary electrode is an arc sheet electrode, and electroplating copper-nickel alloy and electroetching copper are alternately used for preparing the nickel with the multi-stage cellular structure, and comprises the following steps:
step 1: cleaning and pretreating the working electrode;
step 2: putting the rotary working electrode in an electroplating solution containing an inhibitor to electrodeposit copper-nickel alloy, and cleaning;
and step 3: placing the electrode obtained in the step 2 in electrolyte to electroetch copper;
and 4, step 4: repeating the step 2 and the step 3;
and 5: cleaning and drying the electrode obtained in the step 5 to obtain the multi-stage cellular structure nickel;
and 2, the inhibitor in the electroplating solution in the step 2 is an inhibitor containing nitrogen and halogen elements, and the inhibitor comprises nitro-tetrazolium blue chloride.
2. The method for preparing the multi-stage cell structure nickel according to claim 1, wherein the electroplating solution in the step 2 comprises the following components: sodium polydithio-dipropyl sulfonate, polyethylene glycol, nitrotetrazolium chloride, malic acid and mannitol.
3. The method for preparing the multi-stage cell structure nickel as claimed in claim 1, wherein the electroplating solution in step 2 comprises 0.01g/L-0.4g/L of sodium polydithio dipropyl sulfonate, 0.01g/L-0.2g/L of polyethylene glycol, 0.01g/L-0.6g/L of nitro-tetrazolium chloride, 5g/L-10g/L of malic acid and 0.1g/L-5g/L of mannitol.
4. The method for preparing the multi-stage cell structure nickel as claimed in claim 1, wherein the electrolyte in step 3 comprises soluble salt capable of oxidation reduction reaction.
5. The method for preparing the multistage cell structure nickel according to claim 1, wherein the working electrode in the step 1 is a cylindrical structure with a diameter of 4cm-6cm and a height of 5cm-8 cm.
6. The method for preparing the multi-stage cellular structure nickel according to claim 1, wherein the rotating speed of the working electrode serving as the rotary working motor in the step 2 is 30RPM to 180 RPM.
7. The method for preparing the multilevel cell structure nickel according to the claim 1, wherein the electroplating temperature in the step 2 is 45-65 ℃, and the current for electroplating is 10-40 mA.
8. The method for preparing the multistage cell structure nickel according to claim 1, wherein the duration of the electroetching of copper in the step 3 is 3600s to 7200s, and the current density is 0.2A per square meter-1A per square meter.
9. The method for preparing the multilevel cell structure nickel according to claim 1, wherein the step 4 is repeated 2 times.
10. The method for preparing the multi-stage cell structure nickel according to claim 1, wherein the cleaning pretreatment in the step 1 comprises the following steps: and sequentially putting the working electrode into a hydrogen chloride solution, an acetone solution and deionized water, and carrying out ultrasonic cleaning each time.
CN202111317401.6A 2021-11-09 2021-11-09 Preparation method of nickel with multi-stage cellular structure Pending CN113832511A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111317401.6A CN113832511A (en) 2021-11-09 2021-11-09 Preparation method of nickel with multi-stage cellular structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111317401.6A CN113832511A (en) 2021-11-09 2021-11-09 Preparation method of nickel with multi-stage cellular structure

Publications (1)

Publication Number Publication Date
CN113832511A true CN113832511A (en) 2021-12-24

Family

ID=78971334

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111317401.6A Pending CN113832511A (en) 2021-11-09 2021-11-09 Preparation method of nickel with multi-stage cellular structure

Country Status (1)

Country Link
CN (1) CN113832511A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108070863A (en) * 2017-12-13 2018-05-25 扬州大学 A kind of surface protectant for silvering
CN111424296A (en) * 2020-05-18 2020-07-17 深圳市创智成功科技有限公司 Electroplating copper solution for filling through holes of IC carrier plate and electroplating method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108070863A (en) * 2017-12-13 2018-05-25 扬州大学 A kind of surface protectant for silvering
CN111424296A (en) * 2020-05-18 2020-07-17 深圳市创智成功科技有限公司 Electroplating copper solution for filling through holes of IC carrier plate and electroplating method

Similar Documents

Publication Publication Date Title
US20200373586A1 (en) Highly corrosion-resistant porous metal body
CN101638790A (en) Plating method of magnesium and magnesium alloy
CN107081163A (en) A kind of NiWP electrocatalyst materials of three-dimensional structure are prepared and applied
US11542615B2 (en) Method of producing an electrocatalyst
CN103227057B (en) A kind of method preparing manganese dioxide electrode of super capacitor
CN114883560B (en) Three-dimensional current collector/Zn/Zn-E composite negative electrode, preparation thereof and application thereof in water-based zinc ion battery
CN102433575B (en) Method for electrodepositing metal lanthanum in ionic liquid
US9476136B2 (en) Electrodeposition process of nickel—cobalt coatings with dendritic structure
Ni et al. The influence of sodium citrate and potassium sodium tartrate compound additives on copper electrodeposition
CN113832511A (en) Preparation method of nickel with multi-stage cellular structure
CN109786800B (en) Thermal regeneration ammonia battery adopting foam nickel-based copper-plated electrode and preparation method
CN116143248A (en) Preparation method of lead dioxide electrode material for wastewater treatment
CN102586821A (en) Tin-zinc alloy plating solution
CN113130957B (en) Thermal regeneration ammonia battery adopting graded porous surface composite electrode and preparation method
JP5735265B2 (en) Method for producing porous metal body having high corrosion resistance
CN114622238B (en) Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode
US3935082A (en) Process for making lead electrode
CN101580954B (en) Composition used for plating rhenium and use method thereof
JP2008138282A (en) Anode for alkaline electrolysis
CN113430557B (en) Multifunctional power layer electrode material and preparation method thereof
CN109056011A (en) A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil
CN114086228B (en) Method for preparing DSA electrode without intermediate layer by direct electrodeposition
EP2644722B1 (en) Method for producing highly corrosion-resistant porous metal body
TWI383529B (en) And a method for producing an electrode having a platinum film
CN116062844A (en) Preparation method and application of micron-sized copper electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination