CN105040032A - Method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition - Google Patents
Method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition Download PDFInfo
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- CN105040032A CN105040032A CN201510162569.2A CN201510162569A CN105040032A CN 105040032 A CN105040032 A CN 105040032A CN 201510162569 A CN201510162569 A CN 201510162569A CN 105040032 A CN105040032 A CN 105040032A
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Abstract
A method of preparing transition metal and alloy thereof through low temperature molten salt electro-deposition is characterized by comprising the steps of (1) mixing anhydrous urea, acetamide and anhydrous LiX uniformly and heating and stirring the mixture to form a colorless uniform liquid molten salt; (2) dissolving a transition metal chloride TMCl2 in low temperature molten salt and stirring and mixing the mixture uniformly to form a low temperature molten salt electrolyte; (3) with a copper sheet or stainless steel as a cathode and graphite as an anode, performing electro-deposition in the low temperature molten salt electrolyte at the electrolyzing temperature of 70-90 DEG C in a manner of constant potential and constant current to control the potential or cathode current density; and (4) when the electrolysis is finished, taking the copper sheet or stainless steel out and cleaning and drying it to obtain the transition metal and alloy thereof deposited on the surface of the cathode. The molten salt is low in price and is low in eutectic temperature so that the method is low in cost, is low in electrolysis temperature, is energy-saving, is less in pollution and is slight in corrosion on equipment.
Description
Technical field
The present invention relates to a kind of method preparing Transition metal and their alloy, particularly relate to a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy, belong to technical field of inorganic.
Background technology
Transition metal and their alloy is widely used in the functional materialss such as anticorrosive, the magnetic of preparation, electrocatalysis and magnetic recording because of its special character.At present, Transition metal and their alloy galvanic deposit research is main concentrates in aqueous.Aqueous electrolysis has the advantages such as cheap, electrolysis temperature less energy-consumption is little, but due to the electrochemical window of water narrow, usually can with the generation of evolving hydrogen reaction in electrodeposition process, cause current efficiency to reduce and quality of coating is deteriorated.Therefore, find and a kind ofly do not have evolving hydrogen reaction pollution-free low temperature green solvent just aobvious particularly important.
With other solvent phase ratios, low-temperature molten salt has a lot of unique characteristics, as nontoxic, steam forces down, thermostability is high, specific conductivity is high, electrochemical window is wide.Low-temperature molten salt is a kind of desirable medium, has the advantage of high-temperature molten salt and organic solvent, and at room temperature can obtain in high-temperature molten salt could the metal that obtains of galvanic deposit and alloy thereof, but the severe corrosive not having again high-temperature molten salt such.The fusing point of urea is 132 DEG C, and it can form eutectic (28 ~ 116 DEG C) with some metal halides.The fusing point of such as urea-NaCl eutectic is 109.5 DEG C, and the fusing point of urea-NaBr-KBr eutectic is 51 DEG C.This kind of melt has surfusion.During higher than 100 DEG C, urea melt can remove wherein a small amount of water, and also some metal oxide of solubilized, makes metal surface activation.This urea low-temperature melt is large to the muriatic solubleness of magnesium-yttrium-transition metal simultaneously, has good conductivity.In addition, the very high and very easily dissolve inorganic salts of the specific inductivity of ethanamide.Thus in urea melt, add the specific conductivity that eutectic temperature that ethanamide can reduce fused salt further improves fused salt simultaneously.The eutectic temperature of such as ethanamide-urea-LiBr eutectic can be reduced to below room temperature.
Publication number is that the application for a patent for invention of CN102936738A gives " a kind of method utilizing ionic liquid low-temperature electro-deposition cobalt ", it is characterized in that, comprises the steps: with waterless cobaltous chloride CoCl
2for raw material, take ionic liquid as ionogen, first cobalt chloride is dissolved completely in ionic liquid, direct supply is adopted to carry out galvanic deposit again, during galvanic deposit the groove pressure of electrolyzer higher than cobalt chloride decomposition voltage lower than the electrochemical window of ionic liquid, thus cobalt is produced on negative electrode, anode releases chlorine.
Publication number is that the application for a patent for invention of CN102912391A gives " a kind of method utilizing ionic liquid low-temperature electro-deposition nickel ", comprises the steps: 1) by Dehydrated nickel chloride NiCl
2be dissolved in mixed ionic liquid, preparation electrolytic solution; 2) be anode with high-purity nickel, copper sheet is negative electrode, carries out DC electrodeposition; 3) negative electrode and positive electrode is vertically arranged in galvanic deposition cell; 4) control electrodeposition temperature, pole span, in bath voltage, the cathode current density constant-current electrolysis of setting, produce chlorine at anode, negative electrode separates out solid nickel.In electrodeposition process, bath voltage is higher than the decomposition voltage of nickelous chloride, and lower than the electrochemical window of ionic liquid, negative electrode is produced nickel, anode releases chlorine.
Publication number is that the application for a patent for invention of CN103046082A gives " a kind of method utilizing ionic liquid low-temperature electro-deposition iron ", comprise the steps: to take Anhydrous Ferric Chloride as raw material, ionic liquid is ionogen, first iron(ic) chloride is dissolved completely in wherein, direct supply is adopted to carry out galvanic deposit again, during galvanic deposit, bath voltage is higher than iron(ic) chloride decomposition voltage lower than the electrochemical window of ionic liquid, thus produces on negative electrode and taps a blast furnace, and anode releases chlorine.
Technique scheme using ionic liquid as ionogen, anhydrous CoCl
2, NiCl
2and FeCl
3for cobalt, nickel and iron ion source, copper sheet is as negative electrode, and using cobalt plate, nickel plate and tungsten as anode, galvanostatic deposition prepares cobalt metal, nickel and iron.The imidazoles that this application patent adopts, pyridine and pyrrolidinium ion liquid price general charged are costly, and limited to the solubleness of metal chloride.
Summary of the invention
Object of the present invention is just the problems referred to above solving prior art existence, for existing aqueous solution electrodeposition magnesium-yttrium-transition metal Problems existing and deficiency, the problem such as the electrolytic coating as low and hydrogen embrittlement causes with evolving hydrogen reaction, current efficiency in electrodeposition process is second-rate, proposes a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy.
The present invention is achieved through the following technical solutions.
Utilize low-temperature molten salt galvanic deposit to prepare a method for Transition metal and their alloy, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiX are mixed, and heated and stirred forms colourless uniform liquid fused salt.
2) by magnesium-yttrium-transition metal muriate TMCl
2in the cryogenic liquid fused salt prepared in above-mentioned steps of a kind of, two or three compound dissolution in, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and magnesium-yttrium-transition metal muriate TMCl
2mass ratio be: 100:(1 ~ 3).
3) using treated copper sheet or stainless steel as negative electrode, graphite is as anode, be 70 ~ 90 DEG C at electrolysis temperature, adopt constant potential and continuous current mode, controlling potential is-0.7 ~-0.9V (vs.Ag) or cathode current density is 0.05 ~ 0.15A/cm
2under condition and in step 2) galvanic deposit 1 ~ 3h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet or stainless steel first uses ethanol purge, then with water cleaning, then dries, obtain the Transition metal and their alloy being deposited on cathode surface.
X in aforesaid method in LiX is the negatively charged ion of lithium compound, as Br
-, Cl
-.
In aforesaid method, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
In aforesaid method, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
TMCl in aforesaid method
2in TM be the muriatic positively charged ion of magnesium-yttrium-transition metal, as Fe
2+, Co
2+, Ni
2+.
Anhydrous urea purity>=99% used in aforesaid method, anhydrous ethanamide purity>=98.5%, anhydrous LiBr purity>=96%, anhydrous LiCl purity>=96%, anhydrous CoCl
2purity>=99%, anhydrous NiCl
2purity>=99%, anhydrous FeCl
2purity>=99%, ethanamide is vacuum-drying 24h at 75 DEG C, all the other all compounds all more than vacuum-drying 24h at 120 DEG C before using.
Negative electrode copper sheet purity >=99.99% is used in aforesaid method.
Use anode for graphite or carbon material in aforesaid method.
In aforesaid method, copper sheet and stainless steel process concrete steps are: adopt different model sand paper to copper sheet and stainless steel surface polishing, make copper sheet and stainless steel surface smooth, then clean with EtOH Sonicate ripple, then use washed with de-ionized water, final drying is for subsequent use.
In aforesaid method, electrolytic solution configuration step is as follows: a) take in proportion respective compound mix and heated and stirred form colourless uniform liquid fused salt, b) appropriate Anhydrous transition race metal chloride is taken, then joined in liquid fused salt, c) electrolytic solution of configuration is adopted magnetic stirrer, Anhydrous transition race metal chloride is fully dissolved, is configured to corresponding electrolytic solution.
The ZNCL-BS type that the intelligent digital magnetic force hot-plate used in aforesaid method is produced for Beijing Century China Tech laboratory apparatus company limited.
Electrolyzer in aforesaid method is the glass cylinder of a 10mL.
The AUTOLABPGSTAT30 that the potentiostat used in aforesaid method is produced for Wan Tong company of Switzerland.
In aforesaid method, the pattern of the Transition metal and their alloy that galvanic deposit obtains and composition analysis are the SSX-550 type scanning electronic microscope (SEM) that Japanese Shimadzu Corporation produces, and product Analysis of components is the MPDDY2094 type X-ray diffractometer (XRD) that Dutch PANalytical company produces.
Compared with prior art, the invention has the beneficial effects as follows: fused salt low price used, eutectic temperature are low, thus have with low cost, electrolysis temperature is low, saving energy, pollution be little and to advantages such as equipment corrosion are lighter.
In addition, technical solution of the present invention is equally applicable to the Low-temperature electro-deposition of chromium (Cr), copper (Cu), zinc (Zn), silver (Ag), the plumbous metal such as (Pb), cadmium (Cd).
Accompanying drawing explanation
Fig. 1 is the SEM figure of the cobalt of preparation in the embodiment of the present invention 1.
Fig. 2 is the EDS figure of the cobalt of preparation in the embodiment of the present invention 1.
Fig. 3 is the XRD figure of the cobalt of preparation in the embodiment of the present invention 1.
Fig. 4 is the SEM figure of the nickel of preparation in the embodiment of the present invention 2.
Fig. 5 is the EDS figure of the nickel of preparation in the embodiment of the present invention 2.
Fig. 6 is the XRD figure of the nickel of preparation in the embodiment of the present invention 2.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1.
The method of cobalt metal is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by magnesium-yttrium-transition metal muriate CoCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CoCl
2mass ratio be: 100:1.
3) using treated copper sheet as negative electrode, graphite is as anode, be 70 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.7V (vs.Ag) condition and in step 2) galvanic deposit 1h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the cobalt metal being deposited on copper sheet surface, as shown in Figure 1,2 and 3.
Embodiment 2.
The method of metallic nickel is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by magnesium-yttrium-transition metal muriate NiCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and NiCl
2mass ratio be: 100:2.
3) using treated copper sheet as negative electrode, graphite is as anode, be 80 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.8V (vs.Ag) condition and in step 2) galvanic deposit 2h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the metallic nickel being deposited on copper sheet surface, as shown in Fig. 4,5 and 6.
Embodiment 3.
The method of metallic iron is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiCl are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
2) by magnesium-yttrium-transition metal muriate FeCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and FeCl
2mass ratio be: 100:3.
3) using treated copper sheet as negative electrode, graphite is as anode, be 90 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.9V (vs.Ag) condition and in step 2) galvanic deposit 3h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the metallic iron being deposited on copper sheet surface.
Embodiment 4.
The method of chromium metal is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by metal chloride CrCl
3be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CrCl
3mass ratio be: 100:1.
3) using treated copper sheet as negative electrode, graphite, as anode, is 70 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.05A/cm
2under condition and in step 2) galvanic deposit 1h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the chromium metal being deposited on copper sheet surface.
Embodiment 5.
The method of metallic copper is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiCl are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
2) by metal chloride CuCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CuCl
2mass ratio be: 100:1.
3) using treated stainless steel as negative electrode, graphite, as anode, is 70 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.05A/cm
2under condition and in step 2) galvanic deposit 1h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up stainless steel and first uses ethanol purge, then with water cleaning, then dries, obtain the metallic copper being deposited on stainless steel surface.
Embodiment 6.
The method of metallic zinc is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by metal chloride ZnCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and ZnCl
2mass ratio be: 100:2.
3) using treated copper sheet as negative electrode, graphite, as anode, is 80 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.1A/cm
2under condition and in step 2) galvanic deposit 2h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the metallic zinc being deposited on copper sheet surface.
Embodiment 7.
The method of argent is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiCl are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
2) metal chloride AgCl is dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and is uniformly mixed and forms low temperature molten salt electrolysis liquid; Wherein the mass ratio of fused salt and AgCl is: 100:2.
3) using treated copper sheet as negative electrode, graphite, as anode, is 80 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.1A/cm
2under condition and in step 2) galvanic deposit 2h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the argent being deposited on copper sheet surface.
Embodiment 8.
The method of metallic lead is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by metal chloride PbCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and PbCl
2mass ratio be: 100:3.
3) using treated copper sheet as negative electrode, graphite, as anode, is 90 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.15A/cm
2under condition and in step 2) galvanic deposit 3h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the metallic lead being deposited on copper sheet surface.
Embodiment 9.
The method of cadmium metal is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiCl are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
2) by metal chloride CdCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CdCl
2mass ratio be: 100:3.
3) using treated copper sheet as negative electrode, graphite, as anode, is 90 DEG C at electrolysis temperature, and adopt continuous current mode, control cathode current density is 0.15A/cm
2under condition and in step 2) galvanic deposit 3h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the cadmium metal being deposited on copper sheet surface.
Embodiment 10.
The method of cobalt-nickel alloy is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by magnesium-yttrium-transition metal muriate CoCl
2and NiCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CoCl
2and NiCl
2mass ratio be: 100:1:1.
3) using treated copper sheet as negative electrode, graphite is as anode, be 70 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.7V (vs.Ag) condition and in step 2) galvanic deposit 1h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the cobalt-nickel alloy being deposited on copper sheet surface.
Embodiment 11.
The method of ferro-cobalt is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by magnesium-yttrium-transition metal muriate CoCl
2and FeCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CoCl
2and FeCl
2mass ratio be: 100:1:2.
3) using treated copper sheet as negative electrode, graphite is as anode, be 80 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.8V (vs.Ag) condition and in step 2) galvanic deposit 2h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the ferro-cobalt being deposited on copper sheet surface.
Embodiment 12.
The method of Rhometal is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiCl are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
2) by magnesium-yttrium-transition metal muriate NiCl
2and FeCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and NiCl
2and FeCl
2mass ratio be: 100:1:3.
3) using treated copper sheet as negative electrode, graphite is as anode, be 90 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.9V (vs.Ag) condition and in step 2) galvanic deposit 3h in the low temperature molten salt electrolysis liquid for preparing.
4) electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the Rhometal being deposited on copper sheet surface.
Embodiment 13.
The method of CoNiFe alloy is prepared in this low-temperature molten salt galvanic deposit, it is characterized in that comprising the following steps.
1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiBr are fully mixed, and heated and stirred forms colourless uniform liquid fused salt, the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
2) by magnesium-yttrium-transition metal muriate CoCl
2, NiCl
2and FeCl
2be dissolved in cryogenic liquid fused salt prepared by above-mentioned steps, and be uniformly mixed and form low temperature molten salt electrolysis liquid; Wherein fused salt and CoCl
2, NiCl
2and FeCl
2mass ratio be: 100:1:1:1.
3) using treated copper sheet as negative electrode, graphite is as anode, be 80 DEG C at electrolysis temperature, adopt constant potential mode, controlling potential is under-0.8V (vs.Ag) condition and in step 2) galvanic deposit 2h in the low temperature molten salt electrolysis liquid for preparing.
Electrolysis terminates rear taking-up copper sheet and first uses ethanol purge, then with water cleaning, then dries, obtain the CoNiFe alloy being deposited on copper sheet surface.
Claims (5)
1. utilize low-temperature molten salt galvanic deposit to prepare a method for Transition metal and their alloy, it is characterized in that comprising the following steps:
(1) the anhydrous urea crossed through vacuum drying treatment, ethanamide and anhydrous LiX are mixed, and heated and stirred forms colourless uniform liquid fused salt;
(2) by magnesium-yttrium-transition metal muriate TMCl
2in the cryogenic liquid fused salt prepared in step (1) of one or both or three kinds of compound dissolutions in, and be uniformly mixed and form low temperature molten salt electrolysis liquid, wherein fused salt and magnesium-yttrium-transition metal muriate TMCl
2mass ratio be: 100:(1 ~ 3);
(3) using treated copper sheet or stainless steel as negative electrode, graphite is as anode, be 70 ~ 90 DEG C at electrolysis temperature, adopt constant potential and continuous current mode, controlling potential is-0.7 ~-0.9V (vs.Ag) or cathode current density is 0.05 ~ 0.15A/cm
2galvanic deposit 1 ~ 3h in the low temperature molten salt electrolysis liquid prepared under condition and in step (2);
(4) electrolysis terminates rear taking-up copper sheet or stainless steel first uses ethanol purge, then with water cleaning, then dries, obtain the Transition metal and their alloy being deposited on cathode surface.
2. a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy according to claim 1, is characterized in that: the X in described LiX is the negatively charged ion of lithium compound, as Br
-, Cl
-.
3. a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy according to claim 1, is characterized in that: the mass ratio of urea and ethanamide and LiBr is: 35.2:50:14.8.
4. a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy according to claim 1, is characterized in that: the mass ratio of urea and ethanamide and LiCl is: 40.45:50:9.55.
5. a kind of method utilizing low-temperature molten salt galvanic deposit to prepare Transition metal and their alloy according to claim 1, is characterized in that: described TMCl
2in TM be the muriatic positively charged ion of magnesium-yttrium-transition metal, as Fe
2+, Co
2+, Ni
2+.
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| CN107190283A (en) * | 2017-05-19 | 2017-09-22 | 东北大学 | A kind of method that nearly room temperature is co-deposited magnesium neodymium foundry alloy |
| CN110129834A (en) * | 2019-06-26 | 2019-08-16 | 东北大学 | A kind of preparation method of high Li content lithium alloy |
| CN110863218A (en) * | 2019-11-27 | 2020-03-06 | 东北大学 | Method for extracting gold by adopting molten salt electrolysis enrichment |
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