CN108642547A - A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers - Google Patents
A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers Download PDFInfo
- Publication number
- CN108642547A CN108642547A CN201810521563.3A CN201810521563A CN108642547A CN 108642547 A CN108642547 A CN 108642547A CN 201810521563 A CN201810521563 A CN 201810521563A CN 108642547 A CN108642547 A CN 108642547A
- Authority
- CN
- China
- Prior art keywords
- electro
- graphene
- deposition
- electroplate liquid
- mesh
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of methods that electro-deposition prepares graphene Ni Fe Co composite deposites, including：By NiSO4·6H2O、FeSO4·7H2O、CoSO4·7H2O、NiCl·6H2O, graphene, NaCl, H3BO3, trisodium citrate (Na3C6H5O7·2H2O), saccharin sodium (C7H4NNaO3S·2H2O), ascorbic acid (C6H8O6) and lauryl sodium sulfate (C12H25NaO4S it) is add to deionized water and prepares electroplate liquid, it is in smooth mirror planar then to be polished matrix steel disc surface using abrasive paper for metallograph and be polished to no marking；After matrix steel disc surface is washed and is dried, you can carry out electro-deposition in electroplating bath and prepare the composite deposite.The present invention has devised a kind of method that completely new electro-deposition prepares graphene Ni Fe Co multi-elements alloying coatings on the basis of traditional Ni Fe base binary alloy plating preparation methods.The coating prepared by electro-plating method through the invention has the advantages that dense uniform, hardness is high, and wearability is good, corrosion resistance and good and good electrocatalytic hydrogen evolution performance.In addition, electro-plating method provided by the present invention also have many advantages, such as it is of low cost and easy to operate.
Description
Technical field
The present invention relates to Treatment of Metal Surface-plating alloy technical field, especially a kind of electro-deposition prepares graphene-
The method of Ni-Fe-Co alloy layers.
Background technology
With the development of science and technology, the application of new technology is more and more extensive, and electro-deposition techniques are also being constantly progressive innovation.
Nano material will be received because of its special structure and excellent performance, since the advent of the world just by extraneous greatly concern
Rice material is combined with traditional electro-deposition techniques also becomes an innovative point.Graphene as a kind of future revolutionary material,
Its specific surface area is very big and will not change with the variation of porosity, therefore graphene is very easy to reunite, usually
It is packed together the porous stereochemical structure of composition；In this stereochemical structure contain a large amount of hole, be very beneficial for graphene and
Ion diffusion is carried out between electrolyte, this can accelerate the absorption of ion and desorption, and therefore, graphene, which is one kind, to be applied to
Ideal material in electro-deposition techniques.
Ferro-nickel alloy plating is cathodic electrodeposition coating, and rustless property is suitable with nickel, and iron-holder is higher than 15% dilval
Coating also have preferable toughness and economic benefit, in recent years dilval technological development quickly because this alloy layer with
Cheap iron is instead of part of nickel, and the color and luster, Surface flat and hardness that are formed by alloy layer are all better than nickel coating；This
Outside, compared with bright nickel plating bath, there is the plating solution of dilval anti-foreign ion to interfere in stronger and electroplating process in short-term
Between power-off the advantages that not interfering with binding force.But the temperature use scope of dilval is relatively narrow, usually between 55~70 DEG C
It can get and be satisfied with coating, when temperature is too low, luminance difference, plating solution leveling ability is poor；And when the temperature is excessively high, stabilizer then easily decomposes.
In addition, dilval also requires pH value to be not higher than 3.8 in electroplating process.Therefore, in order to obtain the alloy layer of different purposes,
Other than achieving the goal in addition to its structure or change plating conditions can be regulated and controled, it can also be managed by adding other alloying components
Think coating；Such as：Cobalt can be added to and nickel surface is promoted to form fine and close passivating film in nickel, nickel is formed by can be improved
Cobalt alloy corrosion resistance；Nickel will produce solution strengthening effect when forming solid solution with cobalt, this makes nickel cobalt (alloy) possess and compares metallic nickel
Higher hardness also has white metal appearance containing 30% nickel cobalt (alloy) below of cobalt, and hardness is higher, good wearability and change
The advantages that learning stability.Therefore, a kind of tool can be developed by adding graphene, iron and cobalt into metallic nickel by the method for electro-deposition
There are the graphene-Ni-Fe-Co alloy layers of more dominance energy.
Invention content
The purpose of the present invention is to provide the methods that electro-deposition prepares graphene-Ni-Fe-Co alloy layers.
In order to achieve the above objectives, solution of the invention is：
A kind of method that electro-deposition prepares graphene-Ni-Fe-Co composite deposites, which is characterized in that specifically include following step
Suddenly：
1) electroplate liquid is prepared：By NiSO4·6H2O、FeSO4·7H2O、CoSO4·7H2O、NiCl·6H2O, graphene,
NaCl、H3BO3, trisodium citrate (Na3C6H5O7·2H2O), saccharin sodium (C7H4NNaO3S·2H2O), ascorbic acid (C6H8O6) and
Lauryl sodium sulfate (C12H25NaO4S it) is add to deionized water progress ultrasonic disperse after stirring evenly and can be prepared by the electricity
Plating solution；
2) substrate pretreatment：Successively with the abrasive paper for metallograph of 200 mesh, 400 mesh, 800 mesh, 1200 mesh and 1500 mesh to matrix steel
The surface of piece is polished, and is then polished on polishing machine, until its surface no marking is in smooth mirror planar；
3) pre-electroplating treatment：By the surface for matrix steel disc polish in step 2) successively with absolute ethyl alcohol, deionized water,
Hydrochloric acid and deionized water cleaning, it is then dry that matrix to be plated is made；
4) electro-deposition：It is cathode by matrix to be plated obtained in step 3), nickel sheet is anode, and cathode and anode are put into dress
In the electroplating bath for having the electroplate liquid prepared in step 1), the pH value of electroplate liquid is adjusted to 3.8, adjusts distance between cathode and anode
For 3~5cm, current density 60mA/cm2, bath temperature is 60 DEG C, magnetic agitation speed 120r/min；0.5h, which is electroplated, is
Graphene-Ni-Fe-Co the composite deposites can be made.
Preferably, the mass concentration of the electroplate liquid each component is as follows：
Preferably, dilute sulfuric acid or sodium hydroxide can be used in the pH value of the adjusting electroplate liquid.
Preferably, the condition of the ultrasonic disperse described in step 1) is：A length of 2h when dispersion, ultrasonic power 150W,
Working frequency is 40KHZ.
Preferably, the matrix steel disc is Q235 steel discs.
Relative to the existing method for preparing nickel alloy coating, the principle of the present invention and gain effect are as follows：
(1) graphene is combined by the present invention with traditional Ni-Fe-Co bath systems, is used in electrodeposition process
Magnetic agitation mode, this can accelerate the convection current of solution, and the metal ion that cathode nearby consumes is made to be replenished in time and reduce the moon
The concentration polarization of pole acts on.Therefore, it after using magnetic agitation, can be obtained under higher current density and current efficiency close
Careful coating.In addition, result of study shows that the coating surface tissue that electro-deposition obtains under the conditions of magnetic agitation is finer and close
Even, crystal grain is more tiny, and the real table area with bigger, is 3 times of obtained coating under the conditions of sonic oscillation, and then can increase
Into the electrocatalytic hydrogen evolution activity of composite deposite.
(2) the composite deposite surface microstructure prepared by the present invention is intensive uniformly, has hardness high, corrosion resistance is good, electro-catalysis
The features such as Hydrogen Evolution Performance is good greatly increases the quality and performance of coating.
(3) preparation method of the invention also has easy to operate, low in raw material price, and quality and the performance stabilization of coating can
By the advantages that.
Description of the drawings
Fig. 1 is the SEM figures of the graphene-Ni-Fe-Co composite deposites of the present invention.
Specific implementation mode
Further below in conjunction with the embodiments with attached drawing with the present invention will be described in detail.It will similarly be understood that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, it is specific quality in example, anti-
Between seasonable and temperature, technological parameter etc. are also only an examples in OK range, and those skilled in the art is according to the present invention
Some nonessential modifications and adaptations for making of the above all belong to the scope of protection of the present invention.
Embodiment：
Agents useful for same is not further purified as being commercial reagents without particularly pointing out using preceding.
Step 1 prepares electroplate liquid, and the ingredient and content of electroplate liquid are added by the amount of table 1：
Table 1
Solvent is deionized water.All components are add to deionized water by the amount listed in table 1 and are mixed evenly
It can be prepared by the electroplate liquid.Electroplate liquid using preceding needing to adjust its pH value using dilute sulfuric acid or sodium hydroxide, make its at 60 DEG C (most
Excellent temperature) when pH value be 3.8.Then prepared electroplate liquid is put into ultrasound 2h in ultrasonic cleaner, keeps electroplate liquid complete
It is complete evenly dispersed, it is spare；
Step 2 takes one piece of Q235 steel disc, respectively with 200 mesh, the abrasive paper for metallograph of 400 mesh, 800 mesh, 1200 mesh, 1500 mesh
It polishes its surface, is then polished on polishing machine, until surface no marking is in smooth mirror planar；
Step 3 with absolute ethyl alcohol, deionized water, hydrochloric acid and goes on the surface for the Q235 steel discs polished in step 2 successively
Ionized water cleans, then dry that matrix to be plated is made, and the cleaning in matrix deposition face to be plated must be kept before electro-deposition；
As cathode, nickel sheet is put into step as anode, by cathode and anode for step 4, the matrix to be plated for obtaining step 3
In electroplate liquid made from 1, it is 3~5cm to keep the distance of two interpolars, and it is 60 DEG C to keep the bath temperature perseverance of electroplating bath, and adjusting is stirred
It is magnetic agitation, stir speed (S.S.) 120r/min, current density 60mA/cm to mix mode2, electroplating time 0.5h obtains
Cathode plating piece is rinsed using deionized water, then dry in drying box, you can to obtain graphene-Ni-Fe-Co composite deposites.
As shown in Figure 1, characterizing the spatial distribution and pattern that can get coating sample by SEM.It is molten that sample is immersed in KOH
In liquid, its electrocatalytic hydrogen evolution performance in alkaline solution can be tested by electrochemical workstation.
The hardness of graphene-Ni-Fe-Co composite deposites prepared by embodiment is 663.2HV, friction coefficient 0.39.
AC impedance is carried out to coating using the electrochemical workstation of model PGSTAT 302N and polarization curve is tested, electrolyte is
6mol/L KOH solutions, experimental temperature are room temperature (25 DEG C).The initial potential of electrochemical impedance test is open circuit potential, frequency model
Enclose is 105~10-2Hz, disturbance current potential are 5mV；The sweep speed of polarization curve is 2mV/s.
According to Tafel equation, i.e. graphene-Ni-Fe-Co composite deposites can be calculated in 6mol/L in η=a+b logi
The exchange current density and overpotential of hydrogen evolution being electrolysed in KOH solution are respectively 147.6 μ A/cm2And 0.486V.
It is intensive uniformly that the composite deposite surface microstructure prepared by the present invention is further demonstrated by above-mentioned characterization, is had hard
The features such as degree is high, and corrosion resistance is good, and electrocatalytic hydrogen evolution performance is good, greatly increases the quality and performance of coating.
Claims (5)
1. a kind of method that electro-deposition prepares graphene-Ni-Fe-Co composite deposites, which is characterized in that specifically include following step
Suddenly：
1) electroplate liquid is prepared：By NiSO4·6H2O、FeSO4·7H2O、CoSO4·7H2O、NiCl·6H2O, graphene, NaCl,
H3BO3, trisodium citrate (Na3C6H5O7·2H2O), saccharin sodium (C7H4NNaO3S·2H2O), ascorbic acid (C6H8O6) and 12
Sodium alkyl sulfate (C12H25NaO4S it) is add to deionized water progress ultrasonic disperse after stirring evenly and can be prepared by the plating
Liquid；
2) substrate pretreatment：Successively with the abrasive paper for metallograph of 200 mesh, 400 mesh, 800 mesh, 1200 mesh and 1500 mesh to matrix steel disc
Surface is polished, and is then polished on polishing machine, until its surface no marking is in smooth mirror planar；
3) pre-electroplating treatment：Absolute ethyl alcohol, deionized water, hydrochloric acid are used into the surface for the matrix steel disc polished in step 2) successively
It is cleaned with deionized water, it is then dry that matrix to be plated is made；
4) electro-deposition：It is cathode by matrix to be plated obtained in step 3), nickel sheet is anode, and cathode and anode are put into equipped with step
In the electroplating bath of rapid 1) the middle electroplate liquid prepared, the pH value of electroplate liquid is adjusted to 3.8, it is 3 to adjust distance between cathode and anode
~5cm, current density 60mA/cm2, bath temperature is 60 DEG C, magnetic agitation speed 120r/min；Plating 0.5h can make
Obtain the graphene-Ni-Fe-Co composite deposites.
2. the method for electro-deposition graphene-Ni-Fe-Co composite deposites according to claim 1, it is characterised in that：It is described
The mass concentration of electroplate liquid each component is as follows：
3. the method for electro-deposition graphene-Ni-Fe-Co composite deposites according to claim 1, it is characterised in that：It is described
The pH value of adjusting electroplate liquid dilute sulfuric acid or sodium hydroxide can be used.
4. the method for electro-deposition graphene-Ni-Fe-Co composite deposites according to claim 1, it is characterised in that：Step
1) condition of the ultrasonic disperse described in is：A length of 2h when dispersion, ultrasonic power 150W, working frequency 40KHZ.
5. the method for electro-deposition graphene-Ni-Fe-Co composite deposites according to claim 1, it is characterised in that：It is described
Matrix steel disc be Q235 steel discs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810521563.3A CN108642547A (en) | 2018-05-28 | 2018-05-28 | A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810521563.3A CN108642547A (en) | 2018-05-28 | 2018-05-28 | A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108642547A true CN108642547A (en) | 2018-10-12 |
Family
ID=63758219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810521563.3A Pending CN108642547A (en) | 2018-05-28 | 2018-05-28 | A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108642547A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421026A (en) * | 2020-11-19 | 2021-02-26 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239752C (en) * | 2003-01-08 | 2006-02-01 | 鞍钢集团机械制造公司机电装备厂 | Method for electroforming nickel-cobalt alloy |
| CN101760767A (en) * | 2009-12-03 | 2010-06-30 | 四川长虹电器股份有限公司 | Method for electroplating steel strip with nickel |
| CN102747389A (en) * | 2012-07-03 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Electroplating solution for preparation of nanocrystalline nickel alloy plating and application thereof |
| CN104611741A (en) * | 2013-11-05 | 2015-05-13 | 无锡市雪江环境工程设备有限公司 | Ni-Fe alloy plating solution and electroplate method |
| CN104846418A (en) * | 2015-04-10 | 2015-08-19 | 南京理工大学 | Preparation technology for dual-pulse electrodeposition based graphene/nickel based composite coating |
| CN105040052A (en) * | 2015-09-15 | 2015-11-11 | 河海大学常州校区 | Electroplate liquid and technology for preparing nanocrystalline iron-cobalt-nickel-phosphorus quaternary alloy coating using same |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN106498460A (en) * | 2016-11-02 | 2017-03-15 | 河南工程学院 | A kind of dilval plating solution, preparation method and application |
-
2018
- 2018-05-28 CN CN201810521563.3A patent/CN108642547A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239752C (en) * | 2003-01-08 | 2006-02-01 | 鞍钢集团机械制造公司机电装备厂 | Method for electroforming nickel-cobalt alloy |
| CN101760767A (en) * | 2009-12-03 | 2010-06-30 | 四川长虹电器股份有限公司 | Method for electroplating steel strip with nickel |
| CN102747389A (en) * | 2012-07-03 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Electroplating solution for preparation of nanocrystalline nickel alloy plating and application thereof |
| CN104611741A (en) * | 2013-11-05 | 2015-05-13 | 无锡市雪江环境工程设备有限公司 | Ni-Fe alloy plating solution and electroplate method |
| CN104846418A (en) * | 2015-04-10 | 2015-08-19 | 南京理工大学 | Preparation technology for dual-pulse electrodeposition based graphene/nickel based composite coating |
| CN105040052A (en) * | 2015-09-15 | 2015-11-11 | 河海大学常州校区 | Electroplate liquid and technology for preparing nanocrystalline iron-cobalt-nickel-phosphorus quaternary alloy coating using same |
| CN105562636A (en) * | 2015-12-31 | 2016-05-11 | 张颖 | Preparation method for crystallizer copper plate coated with nickel-cobalt-iron alloy layer |
| CN106498460A (en) * | 2016-11-02 | 2017-03-15 | 河南工程学院 | A kind of dilval plating solution, preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421026A (en) * | 2020-11-19 | 2021-02-26 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
| CN112421026B (en) * | 2020-11-19 | 2022-04-19 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101298200B (en) | Magnesium alloy composite material and preparation thereof | |
| CN102260891B (en) | Method for electrodepositing nanocrystalline nickel-cobalt alloy by double-pulse | |
| CN105714360B (en) | Alkaline graphene nickel plating solution, its preparation method and application | |
| JP5366076B2 (en) | Electroplating bath for porous plating film containing additive for forming porous plating film | |
| CN109161941A (en) | A kind of Sintered NdFeB magnet copper composite graphite alkene coating bottoming is to improve corrosion proof method and product | |
| CN110724992A (en) | Method for preparing corrosion-resistant super-hydrophobic film on surface of aluminum alloy | |
| CN113089036B (en) | Preparation method of variable-frequency power ultrasonic electrodeposition nano metal ceramic composite layer | |
| Wu et al. | Effects of 2-butyne-1, 4-diol on structures and morphologies of electroplating Ni–W alloy | |
| CN102605393A (en) | Ni-W-Fe-Co alloy electroplating liquid and electroplating process thereof | |
| CN106283139A (en) | Nickel tungsten Graphene composite plating bath, coating and preparation method thereof | |
| CN101392400A (en) | Method for preparing peak-shaped convex appearance composite plating coating on surface of metal substrate | |
| CN113061945A (en) | Pulse electrodeposition Ni-B/B4Preparation method of C nano composite coating | |
| CN105543912A (en) | Method for preparing compound surfactant/La-Ni-Mo-W codeposited coating on copper matrix | |
| CN108642547A (en) | A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers | |
| CN103540975B (en) | A kind of method at copper electroplating surface metal manganese | |
| CN105420775A (en) | Method for preparing La-Ni-Mo-W/GO composite deposit layer on carbon steel substrate | |
| CN111286767B (en) | Imitation gold electroplating solution electroplating method and imitation gold electroplating solution | |
| CN116065208A (en) | Preparation method of variable-frequency power ultrasonic electro-deposition nano nickel-based composite layer on magnesium alloy surface | |
| CN104611741A (en) | Ni-Fe alloy plating solution and electroplate method | |
| CN103572339A (en) | Method for plating Ni-Mn alloy on surface of low-carbon steel | |
| Gao et al. | Effects of saccharin and pyridine derivatives on the electrocrystallization of nickel | |
| CN104630846A (en) | Electroplating solution for EDTA salt cyanide-free copper plating and electroplating method | |
| CN108411343A (en) | A kind of plating cobalt tungsten manganese high-strength steel and its preparation method and application | |
| CN108559915B (en) | A kind of dilval and preparation method thereof | |
| Thangaraj | Electrodeposition and corrosion behaviour of some Zn–Fe group metal alloys by pulsed current |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181012 |