CN101191238A - Method for preparing nickel-neodymium-phosphorus hydrogen-precipitating electrode with high catalytic activity - Google Patents
Method for preparing nickel-neodymium-phosphorus hydrogen-precipitating electrode with high catalytic activity Download PDFInfo
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- CN101191238A CN101191238A CNA2006101367865A CN200610136786A CN101191238A CN 101191238 A CN101191238 A CN 101191238A CN A2006101367865 A CNA2006101367865 A CN A2006101367865A CN 200610136786 A CN200610136786 A CN 200610136786A CN 101191238 A CN101191238 A CN 101191238A
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Abstract
The invention provides a preparation method for nickel neodymium phosphor hydrogen evolution electrode with high catalytic activity, wherein, 10 to 50g of NiCl2.H2O, 10 to 15g of the NH4Cl, 1 to 5g of NdCl3.7H2O, 8 to 15 g of C6H8O7.H2O, 10 to 20g of H3PO3 and 45 to 75g of H3BO3 are added in each liter of the water solution bath; the pH value and the temperature of the bath are 1.8 to 2.5 and 45 to 70 DEG C respectively; the anode and the cathode are made of the platinum sheet and the copper sheet respectively, the distance between the electrodes is 2 to 10 mm; the average current density of the impulse current is 30 to 40 mA/cm2, the impulse frequency is 950 to 1100Hz, the duty ratio is 1:3.8 to 4.2; the electroplating time is 3 to 10 minutes. The invention has the advantages of acquiring rare earth hydrogen evolution membrane electrode with good corrosion resisting property, obviously improving the quality of the plating coat and being realized in an electroplating factory with relatively large industrial scale.
Description
Technical field
The present invention relates to the preparation method of the high electrocatalysis material of a kind of liberation of hydrogen efficient.
Background technology
Along with the development of society, fossil oil is day by day exhausted, and the NO of combustion of fossil fuel generation
X, CO
X, SO etc. causes severe contamination to environment.Hydrogen Energy is gradually well known as a kind of cleaning, efficient and abundant new forms of energy.Over nearly 20 years, the development and utilization of Hydrogen Energy is developed rapidly, has particularly entered since the nineties in 20th century, and the development and use of Hydrogen Energy have caused global attention more, and water electrolysis hydrogen production is the important means that realizes industrialization, cheap preparation hydrogen.Utilizing sun power to carry out photodissociation water or light helps brine electrolysis, will be the ideal scheme of a kind of " sunlight economy ".Realize electric energy electrolysis or sun power photodissociation water, the high catalytic activity electrode of evolving hydrogen reaction is vital.Obtained bigger progress in developed countries such as Japan, the U.S. at present, and domestic in this respect research is also at the startup.
Electrode is as the place of electrochemical reaction, its structure Design, selection of catalysts and optimization of preparation are the keys of brine electrolysis technology always, it plays important role to utilization ratio, the minimizing electrolysis energy consumption that reduces electrode cost, raising catalyzer, simultaneously influence its practicality again, promptly can heavy industrialization.
The Ni-P alloy layer obtains extensive studies, exploitation and application because of it has good wear-resisting, corrosion resisting property and can substitute the environmental protection effect that hard chromium brought.Adopt to electroplate (containing brush plating and the compound plating of electric current), electroless plating (containing Ni-P) obtains in the Ni-P alloy process, the adding of a small amount of rare earth compound can make plating bath and coating performance obtain in various degree improvement.In alloy plating, rare earth element not only only plays the effect of catalyzer, be limited to and improve plating bath and coating performance, if rare earth element enters and forms Ni-P base rare earth alloy film in the Ni-P coating, such coating had both kept the good corrosion resisting property of Ni-P alloy film, have rare earth element again owing to the special specific function that electron structure brought, this will greatly widen the Application Areas of Ni-P alloy functional membrane.Aqueous solution galvanic deposit is the effective way that obtains the rare earth function film.The liberation of hydrogen electrocatalysis behavior of the nickel-base alloy that contains rare earth has been studied in the study of the Chinese classic flat [Chinese rare-earth journal, 2001,19 (3): 243-245] etc., finds that its liberation of hydrogen ability has improved several times than Ni-P binary alloy film.
The Ni-P alloy layer mainly is to obtain by electroless plating or electro-plating method, because the rare earth element reduction potential is very low, its reduction is short of power, and is difficult to contain with the chemical plating method acquisition Ni-P alloy layer of rare earth, and electroless plating rare earth Ni-P alloy rarely has report.We once adopted the direct current electrode position method to prepare Ni-P base rare earth alloy film.Find that there is following shortcoming in dc electrodeposition Ni-P base rare earth alloy: because power line is inhomogeneous, its covering power is short of (1); (2) rare earth element will produce physics and chemical specific adsorption at the plating initial stage, and it is very fast that cathode surface rare earth ion concentration is reduced, and the diffusion layer that direct current electrode position forms is thicker, has limited the speed of the additional and galvanic deposit of metal ion; (3) the rare earth element reduction potential is very low, and the alloy deposition current potential is usually less than the hydrogen evolution current potential, and in the dc electrodeposition process, alloy layer is acutely separated out and entered in a large number to hydrogen, and this has had a strong impact on current efficiency and quality of coating.Therefore, direct current electrode position uses than high current density not only can not improve plating speed, makes the hydrogen amount of separating out increase on the negative electrode on the contrary, and current efficiency reduces, quality of coating degenerates, and makes coating hydrogen embrittlement occur, pin hole, pit is burnt and is bubbled, even produces coarse or dendritic coating.
Summary of the invention
The objective of the invention is, a kind of preparation method of nickel-neodymium-phosphorus hydrogen-precipitating electrode of high catalytic activity is provided, utilize this method can obtain to have good corrosion resistance can rare earth liberation of hydrogen membrane electrode, to overcome the defective of prior art.
Technical scheme of the present invention is:
(1) prescription of aqueous solution plating bath (every liter of plating bath ingredient):
NiCl
2H
2O 10 grams-50 grams;
NH
4Cl 10 grams-15 grams;
NdCl
37H
2O 1 gram-5 grams;
C
6H
8O
7H
2O 8 grams-15 grams;
H
3PO
310 grams-20 grams;
H
3BO
345 grams-75 grams;
(2) the pH value of plating bath is 1.8-2.5,45 ℃-70 ℃ of temperature;
(3) do anode with platinized platinum, copper sheet is done negative electrode, and distance between electrodes is 2mm-10mm.
(4) pulsed current: average current density 30mA/cm
2-40mA/cm
2, pulse-repetition 950Hz-1100Hz, dutycycle 1: 3.8-4.2;
(5) electroplating time is 3-10 minute;
Adopt above-mentioned pulse electrodeposition method in aqueous medium, can make the Ni-Nd-P hydrogen-precipitating electrode.Pulse plating can overcome the shortcoming of direct current electrode position, improves quality of coating.Test piece (electrode) is average current density 35mA/cm at electrical parameter
2, pulse-repetition 1000Hz, 1: 4 o'clock coating of dutycycle liberation of hydrogen performance the best.
Utilize JEOL JSM-5600LV type scanning electronic microscope that the rare earth hydrogen-precipitating electrode that the present invention obtained is carried out surface tissue and morphology observation as shown in Figure 2, its vesicular structure has increased the surface-area of electrode, and the catalytic activity for hydrogen evolution that improves electrode is had valuable help.Utilize composition such as Fig. 3 of the EDS energy spectrum analysis test rare earth hydrogen-precipitating electrode microcell that the present invention obtained.Fig. 2 and Fig. 3 show that employing prescription of the present invention and processing method can obtain high-quality rare earth hydrogen-precipitating electrode.
As known from the above, the present invention is a kind of preparation method of nickel-neodymium-phosphorus hydrogen-precipitating electrode of high catalytic activity, utilize this method can obtain to have the rare earth liberation of hydrogen membrane electrode of good corrosion resistance energy, its coating tradition plating institute no longer occurs and hydrogen embrittlement occurs, pin hole, pit is burnt and is bubbled, even produce coarse or phenomenon such as dendritic coating, significantly improved quality of coating.
Description of drawings
Fig. 1 is the preparation facilities synoptic diagram of an embodiment of the present invention;
Fig. 2 is the typical shape appearance figure of Ni-Nd-P hydrogen-precipitating electrode;
Fig. 3 is that the typical case of Ni-Nd-P hydrogen-precipitating electrode can spectrogram.
Wherein:
The saturated KCl solution of 1-; The 2-thermostatic bath; The 3-plating tank;
The 4-digital voltmeter (DVM); The 5-numerical control pulse power; The 6-oscilloscope.
Embodiment
The preparation facilities of nickel-neodymium-phosphorus hydrogen-precipitating electrode of the present invention as shown in Figure 1.
Preparation process condition is:
(1) prescription of aqueous solution plating bath (every liter of plating bath ingredient): NiCl
2H
2O 30 grams, NH
4Cl10 gram, NdCl
37H
2O 5 grams, C
6H
8O
7H
2O 15 grams, H
3PO
315 grams, H
3BO
365 grams;
(2) the pH value of plating bath is 2,60 ℃ of temperature;
(3) do anode with platinized platinum, copper sheet is done negative electrode, and distance between electrodes is 2.5mm.
(4) pulsed current: average current density 35mA/cm
2, pulse-repetition 1000Hz, dutycycle 1: 4;
(5) electroplating time is 5 minutes;
Adopt above-mentioned pulse electrodeposition mode in aqueous medium, can make the Ni-Nd-P hydrogen-precipitating electrode.
The present invention utilizes the numerical control Double-pulse Plating Power Source.Pulsed electrical is coated with pulse width t
On, recurrent interval t
OffWith three main pulse parameters of pulsed current, because pulse width t
OnWith recurrent interval t
OffAlso available pulse-repetition and dutycycle t
On/ (t
On+ t
Off) expression, definite t that also means of pulse-repetition and pulse duty factor
OnAnd t
OffDetermine.In order to obtain high-quality hydrogen-precipitating electrode, select best pulse-repetition, pulse duty factor and pulsed current very important.It is average current density 35mA/cm that the present invention makes power consumption parameter
2, pulse-repetition 1000Hz, dutycycle 1: 4, aqueous solution galvanic deposit number minute obtains coating.Monitor groove pressure and electropotential with digital voltmeter (DVM), and calculate its average electrode current.What particularly point out is that distance between negative electrode and the anode must be in 2～10mm scope.Test piece (electrode) treatment process: test piece → polishing → organic deoiling → clean → etch → cleaning → chemical rightenning → clean → dry up → weigh → electroplate → wash → dry up → weigh.
Claims (4)
1. the preparation method of the nickel-neodymium-phosphorus hydrogen-precipitating electrode of a high catalytic activity is characterized in that, this method is:
(1) prescription of aqueous solution plating bath (every liter of plating bath ingredient):
NiCl
2H
2O 10 grams-50 grams;
NH
4Cl 10 grams-15 grams;
NdCl
37H
2O 1 gram-5 grams;
C
6H
8O
7H
2O 8 grams-15 grams;
H
3PO
310 grams-20 grams;
H
3BO
345 grams-75 grams;
(2) the pH value of plating bath is 1.8-2.5,45 ℃-70 ℃ of temperature;
(3) do anode with platinized platinum, copper sheet is done negative electrode, and distance between electrodes is 2mm-10mm;
(4) pulsed current: average current density 30mA/cm
2-40mA/cm
2, pulse-repetition 950Hz-1100Hz, dutycycle 1: 3.8-4.2;
(5) electroplating time is 3-10 minute;
Adopt above-mentioned pulse electrodeposition method in aqueous medium, can make the Ni-Nd-P hydrogen-precipitating electrode.
2. according to the preparation method of the nickel-neodymium-phosphorus hydrogen-precipitating electrode of the described high catalytic activity of claim 1, it is characterized in that described aqueous solution electroplate liquid formulation is that every liter of plating bath contains NiCl
2H
2O 30 grams, NH
4Cl 10 grams, NdCl
37H
2O 5 grams, C
6H
8O
7H
2O 15 grams, H
3PO
315 grams, H
3BO
365 grams.
3. according to the preparation method of the nickel-neodymium-phosphorus hydrogen-precipitating electrode of the described high catalytic activity of claim 1, it is characterized in that the pH value of described plating bath is 2, temperature is 60 ℃, and electroplating time is 5 minutes, and distance between electrodes is 2.5mm.
4. according to the preparation method of the nickel-neodymium-phosphorus hydrogen-precipitating electrode of the described high catalytic activity of claim 1, it is characterized in that the average current density 35mA/cm of described pulsed current
2, pulse-repetition 1000Hz, dutycycle 1: 4.
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|---|---|---|---|
| CNA2006101367865A CN101191238A (en) | 2006-11-30 | 2006-11-30 | Method for preparing nickel-neodymium-phosphorus hydrogen-precipitating electrode with high catalytic activity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605386A (en) * | 2012-02-29 | 2012-07-25 | 华侨大学 | Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution |
| CN102787329A (en) * | 2012-08-31 | 2012-11-21 | 重庆大学 | Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode |
-
2006
- 2006-11-30 CN CNA2006101367865A patent/CN101191238A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605386A (en) * | 2012-02-29 | 2012-07-25 | 华侨大学 | Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution |
| CN102787329A (en) * | 2012-08-31 | 2012-11-21 | 重庆大学 | Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode |
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Open date: 20080604 |