CN103590078A - Method for making Mg-Ni-Al alloy film through electrodeposition - Google Patents
Method for making Mg-Ni-Al alloy film through electrodeposition Download PDFInfo
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- CN103590078A CN103590078A CN201310611791.7A CN201310611791A CN103590078A CN 103590078 A CN103590078 A CN 103590078A CN 201310611791 A CN201310611791 A CN 201310611791A CN 103590078 A CN103590078 A CN 103590078A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 59
- 239000000956 alloy Substances 0.000 title claims abstract description 59
- 229910003310 Ni-Al Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004070 electrodeposition Methods 0.000 title abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 120
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 45
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910010082 LiAlH Inorganic materials 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 239000006259 organic additive Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- 229910015463 Mo3S4 Inorganic materials 0.000 abstract 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- HSLXOARVFIWOQF-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSLXOARVFIWOQF-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 56
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910003023 Mg-Al Inorganic materials 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- -1 lithium aluminum hydride Chemical compound 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910002070 thin film alloy Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for making an Mg-Ni-Al alloy film through electrodeposition, and belongs to the technical field of materials. The method comprises the following steps: 1, heating N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide to 60-100DEG C as a molten salt; adding a solute to the molten salt under stirring, and stirring for 5-10h, wherein the solute comprises Mg[(CF3SO2)2N] 2, AlCl3 and NiCl2; and 2, electrolyzing at a cathode current density of 0.02-0.2A/cm<2> for 0.5-2h through electrifying with a Pt electrode as an inert anode or an Mg electrode as a soluble anode, an Mo3S4 electrode as a cathode and an Al wire as a reference electrode to obtain the Mg-Ni-Al alloy film on the surface of the cathode. The Mg-Ni-Al alloy film is made by controlling proper technological conditions like optimizing technological parameters, adopting a pulse electrodeposition technology and adding organic additives; and compared with preparation technologies comprising a melting method and a ball milling method, the method disclosed in the invention has the advantages of simple apparatus, short making time, less energy consumption and the like.
Description
Technical field
The invention belongs to material technology field, particularly the method for Mg-Ni-Al alloy firm is prepared in a kind of galvanic deposit.
Background technology
Hydrogen Energy is pollution-free and aboundresources, and being described as is optimal clean energy of 21 century, but effective utilization of Hydrogen Energy is restricted by hydrogen storage material exploitation; Compare other hydrogen storage materials, magnesium is large with its hydrogen storage capacity, density is little, aboundresources and low price, to the avirulent advantage of environment, become an important research direction of solid-state hydrogen storage material.In recent years, because Al density is little, good thermal conduction, can reduce MgH
2thermostability and good antioxidant property, make Mg-Ni-Al base hydrogenous alloy become one of focus of hydrogen storage material research field; Mg-Ni-Al hydrogen storage alloy is put low than pure Mg of the apparent activation energy of hydrogen process, and antioxidant property and resistance to chalking can all be greatly improved.
Oxygen-storaged alloy film development rapidly, is compared with the block hydrogen storage alloy of routine and is had the advantages such as activation is fast, Pulverization ratio is low; Hull cell also for micromodule equipment and machine provide electric power energy and realize microminiaturization provide may, be a kind of trend of development.
The standard deposition potential of aluminium is-1.68V that the standard deposition potential of magnesium is-2.36V that the standard deposition potential of these two kinds of metals is also more negative than the deposition potential of hydrogen, so the galvanic deposit of magnalium is generally carried out in non-aqueous solution electrolysis plastome; Non-aqueous solution system is divided into 3 kinds of high temperature inorganic fused salt, organic solvent and room temperature fused salts (also claiming ionic liquid).
In inorganic fused salt system, prepare Mg-Al alloy, mainly take liquid aluminium as negative electrode, on negative electrode, be reduced into MAGNESIUM METAL and form aluminum magnesium alloy; Inorganic fused salt system galvanic deposit Mg-Al alloy also exists electrolysis temperature higher, and energy consumption is large, to shortcomings such as equipment requirements height; In organic solvent system, during galvanic deposit Mg-Al, add magnalium chloride salt and lithium aluminum hydride galvanic deposit Mg-Al alloy in the system of organic metal salt, ether or tetrahydrofuran (THF)-benzene, the method Mg content is low, and the highest only have 13%; And room temperature fused salt have fusing point low, non-volatile, the advantage such as do not fire, being widely used of the various metals of room temperature fused salt galvanic deposit and alloy.
Preparation Mg-Ni-Al base alloy main method has two kinds at present; The one, smelting process, it is according to alloying constituent, takes a certain proportion of metal-powder and mixes, and under high-temperature vacuum or protection of inert gas, will after melting of metal, pour into a mould, and prepares alloy pig, then ball milling after ingot casting is pulverized, crystal grain thinning; Because although the fusing point of Al and Mg is more or less the same, but vapour pressure differs greatly, in melting casting cycle, magnesium inevitably produces vaporization losses, make a mole proportioning off-design, therefore, need alloy ingot casting to carry out chemical analysis, add appropriate MAGNESIUM METAL, ingot casting is melted again, obtain required composition; There is the shortcoming that secondary remelting energy consumption is large in this method; The 2nd, ball milled, it is directly to take a certain proportion of Mg powder, Ni powder and Al powder, by mechanical ball milling, obtains the Mg-Ni-Al alloy powder that crystal grain is tiny; This method preparation time is long, and in mechanical milling process, has easily introduced the impurity such as iron, and the reactive behavior of Mg is reduced, and may cause being difficult to produce expected result.
Summary of the invention
For the problems referred to above that exist in existing Mg-Ni-Al base alloy technology of preparing, the invention provides a kind of galvanic deposit and prepare the method for Mg-Ni-Al alloy firm, by controlling suitable processing condition, optimizing technology parameters, adopt electro-deposition method, be added with organic additive, under the condition of short period and less energy consumption, prepare alloy firm.
Galvanic deposit of the present invention is prepared the method for Mg-Ni-Al alloy firm and is carried out according to the following steps:
1, adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃; Then under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.05 ~ 0.1mol/L fused salt, AlCl
30.02 ~ 0.05mol/L fused salt, NiCl
20.02 ~ 0.05mol/L fused salt; Add or do not add LiAlH
4; When adding LiAlH
4time, LiAlH
4add-on be 0.001 ~ 0.005 mol/L fused salt; Then stir 5 ~ 10h;
2, take Pt electrode as inert anode or take Mg electrode as soluble anode, Mo
3s
4electrode is negative electrode, and Al silk is reference electrode, and electrolysis is carried out in energising, during electrolysis, in cathode current density, is 0.02 ~ 0.2A/cm
2, electrolysis time is 0.5 ~ 2h, at cathode surface, obtains Mg-Ni-Al alloy firm.
The atomic percentage conc that in the Mg-Ni-Al alloy firm that aforesaid method obtains, the atomic percentage conc of Mg is 13 ~ 44%, Ni is 30 ~ 48%, and all the other are Al.
The thickness of the Mg-Ni-Al alloy firm that aforesaid method obtains is 20 ~ 150 μ m.
The present invention prepares Mg-Al with regard to galvanic deposit and is associated gold in room temperature fused salt system, and the positively charged ion in fused salt is N-butyl-N-methylpyrrole ([nBuMePy]
+), negatively charged ion is two trifluoromethane sulfimide ([N (CF
3sO
2)
2]
-); Compare with system with an organic solvent, use room temperature fused salt system to there is conductive capability good, the advantage such as non-volatile, can overcome organic solvent system exists solvent volatile, the problem such as inflammable and explosive, has also avoided use high-temperature molten salt system simultaneously, and volatility is large and to shortcomings such as equipment corrosion are serious; The cationic room temperature fused salt positively charged ion deposition potential of quaternary amine type and pyrroles is also born than the deposition potential of Mg, is all the room temperature fused salt system of applicable galvanic deposit Mg-Al; But both compare, the cationic room temperature fused salt of pyrroles has higher electric conductivity.
The present invention is by controlling suitable processing condition, such as optimizing technology parameters, adopt pulse electrodeposition technique, be added with the modes such as organic additive and prepare Mg-Ni-Al thin film alloys; Method of the present invention is compared with ball milled technology of preparing with smelting process, has that equipment is simple, preparation time is short, less cost of power.
Accompanying drawing explanation
Fig. 1 is the Mg-Ni-Al alloy firm photo figure of the cathode surface in the embodiment of the present invention 1;
Fig. 2 is the Mg-Ni-Al alloy firm photo figure of the cathode surface in the embodiment of the present invention 2.
Embodiment
The two trifluoromethane sulfimide salt of N-butyl-N-crassitude adopting in the embodiment of the present invention is purchased from Zhengzhou four seasons Chemicals company limited.
The Mg[(CF adopting in the embodiment of the present invention
3sO
2)
2n]
2, AlCl
3, NiCl
2and LiAlH
4for commercial analytical reagent.
The Al silk adopting in the embodiment of the present invention is commercial product, and weight purity is 99.999%.
While carrying out electrolysis in the embodiment of the present invention, the electrochemical workstation of employing is the comprehensive electrochemical analysis tester of Philip AutoLab-PGSTAT30.
Pt electrode as inert anode in the embodiment of the present invention is commercial product.
In the embodiment of the present invention as the Mo of negative electrode
3s
4electrode is commercial product.
Mg electrode as soluble anode in the embodiment of the present invention is commercial product.
In the embodiment of the present invention, working as cathode current density is 0.02 ~ 0.2A/cm
2time, voltage is-4 ~-10V.
The method that detects the employing of Mg-Ni-Al alloy firm composition in the embodiment of the present invention is that the energy spectrometer in scanning electronic microscope is measured, and the unit type of employing is SHIMADZU SSX-550.
The model that detects the scanning electron microscope of Mg-Ni-Al alloy firm thickness employing in the embodiment of the present invention is SHIMADZU SSX-550.
Embodiment 1
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.05mol/L fused salt, AlCl
30.02mol/L fused salt, NiCl
20.05mol/L fused salt; Then stir 5h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.02A/cm in cathode current density during electrolysis
2, electrolysis time is 0.5h, at cathode surface, obtains Mg-Ni-Al alloy firm; Photo as shown in Figure 1;
The thickness of Mg-Ni-Al alloy firm is 20 ~ 40 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 13%, Ni is 48%, and all the other are Al.
Embodiment 2
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.06mol/L fused salt, AlCl
30.03mol/L fused salt, NiCl
20.04mol/L fused salt; Then stir 6h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Mg electrode is soluble anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.04A/cm in cathode current density during electrolysis
2, electrolysis time is 0.5h, at cathode surface, obtains Mg-Ni-Al alloy firm; Photo as shown in Figure 2;
The thickness of Mg-Ni-Al alloy firm is 30 ~ 50 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 14%, Ni is 38%, and all the other are Al.
Embodiment 3
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.07mol/L fused salt, AlCl
30.04mol/L fused salt, NiCl
20.03mol/L fused salt; Then stir 7h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.06A/cm in cathode current density during electrolysis
2, electrolysis time is 1h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 40 ~ 60 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 19%, Ni is 48%, and all the other are Al.
Embodiment 4
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.08mol/L fused salt, AlCl
30.05mol/L fused salt, NiCl
20.02mol/L fused salt; Then stir 8h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Mg electrode is soluble anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.08A/cm in cathode current density during electrolysis
2, electrolysis time is 1h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 60 ~ 80 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 25%, Ni is 41%, and all the other are Al.
Embodiment 5
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.09mol/L fused salt, AlCl
30.02mol/L fused salt, NiCl
20.05mol/L fused salt; Then stir 9h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.1A/cm in cathode current density during electrolysis
2, electrolysis time is 1h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 70 ~ 90 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 28%, Ni is 42%, and all the other are Al.
Embodiment 6
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.1mol/L fused salt, AlCl
30.03mol/L fused salt, NiCl
20.04mol/L fused salt; Then stir 10h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Mg electrode is soluble anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.15A/cm in cathode current density during electrolysis
2, electrolysis time is 1.5h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 130 ~ 150 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 36%, Ni is 31%, and all the other are Al.
Embodiment 7
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.05mol/L fused salt, AlCl
30.04mol/L fused salt, NiCl
20.03mol/L fused salt; Add again LiAlH
4, add-on is 0.005 mol/L fused salt; Then stir 5h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.02A/cm in cathode current density during electrolysis
2, electrolysis time is 1h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 30 ~ 50 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 14%, Ni is 43%, and all the other are Al.
Embodiment 8
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.06mol/L fused salt, AlCl
30.05mol/L fused salt, NiCl
20.02mol/L fused salt; Add again LiAlH
4, add-on is 0.005 mol/L fused salt; Then stir 6h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.08A/cm in cathode current density during electrolysis
2, electrolysis time is 1.5h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 60 ~ 80 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 22%, Ni is 41%, and all the other are Al.
Embodiment 9
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.07mol/L fused salt, AlCl
30.02mol/L fused salt, NiCl
20.05mol/L fused salt; Add again LiAlH
4, add-on is 0.004 mol/L fused salt; Then stir 7h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Mg electrode is soluble anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.1A/cm in cathode current density during electrolysis
2, electrolysis time is 0.5h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 50 ~ 70 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 27%, Ni is 38%, and all the other are Al.
Embodiment 10
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.08mol/L fused salt, AlCl
30.03mol/L fused salt, NiCl
20.04mol/L fused salt; Add again LiAlH
4, add-on is 0.003 mol/L fused salt; Then stir 8h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.14A/cm in cathode current density during electrolysis
2, electrolysis time is 1h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 70 ~ 90 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 44%, Ni is 35%, and all the other are Al.
Embodiment 11
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.09mol/L fused salt, AlCl
30.04mol/L fused salt, NiCl
20.03mol/L fused salt; Add again LiAlH
4, add-on is 0.002 mol/L fused salt; Then stir 9h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Mg electrode is soluble anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.18A/cm in cathode current density during electrolysis
2, electrolysis time is 1.5h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 90 ~ 100 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 40%, Ni is 30%, and all the other are Al.
Embodiment 12
Adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃;
Under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.1mol/L fused salt, AlCl
30.05mol/L fused salt, NiCl
20.02mol/L fused salt; Add again LiAlH
4, add-on is 0.001mol/L fused salt; Then stir 10h;
Adopt Mo
3s
4electrode is as negative electrode, adopting Pt electrode is inert anode, adopting Al silk is reference electrode, one end of each electrode is connected with electrochemical workstation, the other end is inserted in the fused salt that has added solute, opening electrochemical workstation electrifying electrodes is carried out to electrolysis, is 0.2A/cm in cathode current density during electrolysis
2, electrolysis time is 2 h, at cathode surface, obtains Mg-Ni-Al alloy firm;
The thickness of Mg-Ni-Al alloy firm is 130 ~ 150 μ m, and the atomic percentage conc that the atomic percentage conc of Mg is 36%, Ni is 34%, and all the other are Al.
Claims (3)
1. a method for Mg-Ni-Al alloy firm is prepared in galvanic deposit, it is characterized in that carrying out according to the following steps:
(1) adopt the two trifluoromethane sulfimide salt of N-butyl-N-crassitude as fused salt, fused salt is heated to 60 ~ 100 ℃; Then under agitation condition, solute is joined in fused salt; Described solute is Mg[(CF
3sO
2)
2n]
2, AlCl
3and NiCl
2, add-on is respectively Mg[(CF
3sO
2)
2n]
20.05 ~ 0.1mol/L fused salt, AlCl
30.02 ~ 0.05mol/L fused salt, NiCl
20.02 ~ 0.05mol/L fused salt; Add or do not add LiAlH
4; When adding LiAlH
4time, LiAlH
4add-on be 0.001 ~ 0.005 mol/L fused salt; Then stir 5 ~ 10h;
(2) take Pt electrode as inert anode or take Mg electrode as soluble anode, Mo
3s
4electrode is negative electrode, and Al silk is reference electrode, and electrolysis is carried out in energising, during electrolysis, in cathode current density, is 0.02 ~ 0.2A/cm
2, electrolysis time is 0.5 ~ 2h, at cathode surface, obtains Mg-Ni-Al alloy firm.
2. the method for Mg-Ni-Al alloy firm is prepared in a kind of galvanic deposit according to claim 1, and the atomic percentage conc that the atomic percentage conc that it is characterized in that Mg in described Mg-Ni-Al alloy firm is 13 ~ 44%, Ni is 30 ~ 48%, and all the other are Al.
3. the method for Mg-Ni-Al alloy firm is prepared in a kind of galvanic deposit according to claim 1, it is characterized in that the thickness of described Mg-Ni-Al alloy firm is 20 ~ 150 μ m.
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| CN114196992A (en) * | 2021-11-29 | 2022-03-18 | 哈尔滨工业大学 | Ni-Al alloy component and electrodeposition incremental forming method thereof |
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