CN104562090A - Method for preparing nano-porous copper through in-situ electrolysis of eutectic ionic liquid - Google Patents
Method for preparing nano-porous copper through in-situ electrolysis of eutectic ionic liquid Download PDFInfo
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- CN104562090A CN104562090A CN201410838522.9A CN201410838522A CN104562090A CN 104562090 A CN104562090 A CN 104562090A CN 201410838522 A CN201410838522 A CN 201410838522A CN 104562090 A CN104562090 A CN 104562090A
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- 239000010949 copper Substances 0.000 title claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 61
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000005496 eutectics Effects 0.000 title claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 78
- 239000000956 alloy Substances 0.000 claims abstract description 78
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005275 alloying Methods 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 230000006698 induction Effects 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 claims description 5
- 229960004266 acetylcholine chloride Drugs 0.000 claims description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 229910017518 Cu Zn Inorganic materials 0.000 description 6
- 229910017752 Cu-Zn Inorganic materials 0.000 description 6
- 229910017943 Cu—Zn Inorganic materials 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007783 nanoporous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Abstract
The invention relates to a method for preparing nano-porous copper through in-situ electrolysis of a eutectic ionic liquid, and belongs to the technical field of material preparation. The method comprises the following steps: quaternary ammonium salt and amide are mixed to prepare the eutectic ionic liquid in inert atmosphere; alloy induced salt is added to the eutectic ionic liquid, the mixture is uniformly mixed to obtain an ionic liquid-alloy salt composite electrolyte; a copper sheet is taken as a cathode, graphite or an inert anode is taken as an anode, a homogeneous-phase alloy precursor is obtained through galvanostatic deposition in the obtained ionic liquid-alloy salt composite electrolyte; a three-electrode system is established under the original electrolyte system and used for dealloying, the cathode sheet after dealloying is washed by absolute ethyl alcohol and distilled water and dried to obtain a copper sheet with the nano-porous structure. The method has the advantages of mild reaction conditions, controllability, low cost, pollution prevention, simple process, stable product quality and the like.
Description
Technical field
The present invention relates to a kind of method that eutectic type ionic liquid in-situ electrolysis prepares nano porous copper, belong to technical field of material.
Background technology
Nano porous metal refers to the porous material with nano-scale.There is because of the co-continuous nano-porous structure of its uniqueness the features such as specific surface area is large, intensity is high, conduct electricity very well, catalytic activity is strong.Have in fields such as sensing, filtration, separation, catalysis, Chu Qing, electrode materials and surface enhanced Raman scatterings and apply widely.Compare noble metal nano porous material, nano porous copper production cost be low, aboundresources, suitability for mass industrialized production.
The method preparing nano porous copper (NPM) at present mainly contains template and de-alloyage.Template is using nano-porous materials as template, is prepared the method for porous metal by the structure copying template.Common template comprises: anodic oxidation aluminium formwork method (AAO), superpolymer template and hydrogen template.The nano porous metal structure utilizing the method to obtain depends on the structure of template self, is difficult to realize regulating; Meanwhile, the lock out operation of template and product easily causes damage to the structure of resulting materials.Hydrogen template, owing to being difficult to the structure controlling metal deposition layer on the size of bubble and hole wall, makes the mechanical property of nano-porous materials poor.De-alloyage utilizes intermetallic potential difference, the method compared with active metal component in selective removal alloy in acid or alkaline environment.Although de-alloyage can prepare high porosity and the nano porous copper be evenly distributed, its key is first to obtain the homogeneous equal phase alloy presoma of structure and composition.The equal phase alloy of tradition preparation often needs raw metal to carry out melting in high frequency furnace, annealing and quench treatment under inert conditions, complex manufacturing process, and energy consumption is large, cost is high; Later stage removal alloying adopts severe corrosive acid or alkali, and required time is long, easily causes equipment corrosion and environmental pollution.
Apply for a patent (publication No. CN102329977A) disclose " a kind of preparation method of enhanced nanoporous copper " first utilize vacuum melting furnace to prepare alloy cast ingot is linear is cut into alloy sheet; Alloy sheet is put into NH
4in Cl-HCl mixed solution, reaction can obtain nano porous copper; To be enhanced type nano porous copper by subsequent operations again.Apply for a patent (publication No. CN101590528A) to disclose " a kind of preparation method of nano porous copper ", first pure Cu and pure Mg is heated to molten state, casting becomes ingot casting; Then ingot casting is melted up to molten state again, then utilizes rare gas element to be blown out to the copper roller of high speed rotating or in copper mold by aluminium alloy, prepare metal alloy band; Finally, in acidic liquid, carry out de-Alloying Treatment and can obtain nano porous copper.Apply for a patent (publication No. CN102628112A) to disclose one and " prepare the method for three-dimensional netted nano porous copper ", arc melting is adopted to prepare Cu-Mn alloy, with rare gas element molten alloy blown out fast again and prepare alloy thin band to the copper roller of high speed rotating, finally alloy thin band is put into acid or strong acid weak base salts solution removal alloying can obtain nano porous copper.The above method preparing nano porous copper all adopts melting to prepare alloy presoma+de-reasonable offer nano porous copper.This method shortcoming is that preparation process is complicated, and fusion process is high to equipment requirements, and the later stage adopts severe corrosive acid or alkali to cause equipment corrosion, the wasting of resources, adds preparation cost.
Apply for a patent (publication No. CN102766893A) and disclose the preparation method of graphical nano porous copper " a kind of can ", sputter Cr-Cu Seed Layer first on the glass sheet, carry out according to this getting rid of positive photoresist, drying glue, exposure, development treatment; Electro-deposition techniques is utilized to obtain graphical precursor alloy firm; Finally precursor alloy firm is put into acid to carry out corrosion and carry out de-Alloying Treatment and obtain nano porous copper.Adopt and prepare complexity in this way, preparation cycle index is more, is not suitable for scale operation.Apply for a patent (publication No. CN103357876A) to disclose " a kind of preparation method of nano multihole copper film ", the organic ink containing copper powder prepared in advance is coated on substrate surface, after heat treatment can obtain nano multihole copper film, also can adopt hcl corrosion carrier and obtain unsupported nano multihole copper film.Although this method is simple, cost is also lower, and the Porous Cu obtained is second-rate, and pore size and homogeneity are difficult to control.
The eutectic mixture that eutectic solvent is normally combined by quaternary ammonium salt and the hydrogen-bond donor (as compounds such as acid amides, carboxylic acid and polyvalent alcohols) of certain stoichiometric ratio.Eutectic solvent has good solubility and electroconductibility, steam force down and the advantage such as good physical and chemical stability, synthesis material is cheap, making processes is simple, just can obtain the higher product of purity without the need to purifying, is a kind of novel green solvent.With traditional aqueous compared with organic solvent, eutectic type ionic liquid provides the chemical environment being different from conventional molecular solvent, not containing proton, polarity is strong, material nucleation rate is faster, and be easy to be formed with sequence structure under hydrogen bond action, chemical heat stability is high, during service temperature 100-150 DEG C, electrodepositable prepares equal phase alloy.Therefore, using eutectic type ionic liquid as solvent medium, prepare nano porous metal material by electro-deposited alloy-original position removal alloying, thus solve traditional preparation methods exist complex procedures, energy consumption is large, efficiency is low, equipment corrosion is serious, high in cost of production series of problems.
Summary of the invention
For above-mentioned existing nano porous copper preparation method Problems existing and deficiency, the invention provides in a kind of low melt type ionic liquid altogether with fine copper is matrix, and in-situ electrolysis prepares the method for nano porous copper.The advantages such as the present invention has reaction conditions gentleness, controlled, cheap, pollution-free, technique simple, constant product quality, the present invention is achieved through the following technical solutions.
Technological line provided by the invention is: using low melt type ionic liquid altogether as solvent, induced by alloy salt (zinc oxide or zinc chloride) to introduce wherein, make negative electrode with copper sheet etc., graphite or inert anode make anode, carry out electrolytic preparation under open system.
Eutectic type ionic liquid in-situ electrolysis prepares a method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, by quaternary ammonium salt and acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:(1 ~ 4) mix, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In low altogether melt type ionic liquid, add alloy induction salt mix and obtain ionic liquid-alloy salts composite electrolytic solution;
(2) make negative electrode with copper sheet, graphite or inert anode make anode, in ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 80 ~ 150 DEG C, without the need to stirring, cathode current density 0.20 ~ 2mAcm
-2galvanostatic deposition 0.50 ~ 2h under condition, obtains the alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.50 ~-0.20Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.
Quaternary ammonium salt in described step (1) is choline chloride 60, Acetylcholine Chloride or tetramethyl ammonium chloride.
Acid amides in described step (1) is urea, dimethyl formamide or ethanamide.
Described step (1) interalloy induction salt is zinc oxide or zinc chloride, and volume and the alloy of low melt type ionic liquid altogether induce the mass ratio of salt to be 100:(200 ~ 2500) mL/mg.
The invention has the beneficial effects as follows: (1) adopts the method can realize galvanic deposit to prepare alloy presoma and later stage removal alloying completes in same electrolysis system; (2) gained nano porous copper void size is prepared even, controlled; (3) do not relate to caustic acid or alkali, reaction conditions is gentle, and energy consumption of reaction is low; (4) cheap, pollution-free, technique is simple and capable of circulation, constant product quality.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 electrolytic preparation products therefrom when magnification is 10000 times;
Fig. 2 is the SEM figure of the embodiment of the present invention 1 electrolytic preparation products therefrom when magnification is 50000 times;
Fig. 3 is the SEM figure of the embodiment of the present invention 2 electrolytic preparation products therefrom when magnification is 50000 times;
Fig. 4 is the SEM figure of the embodiment of the present invention 3 electrolytic preparation products therefrom when magnification is 50000 times.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:2, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.150g alloy induction salt (alloy induction salt is zinc chloride, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:750mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is choline chloride 60, and acid amides is urea;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 120 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 1mAcm
-2galvanostatic deposition 1h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite is to electrode, filamentary silver is reference electrode, controlling potential-0.30Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.SEM figure when SEM figure when the nano porous copper magnification prepared is 10000 times is 50000 times with magnification as shown in Figure 1 as shown in Figure 2.
Embodiment 2
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:3, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.200g alloy induction salt (alloy induction salt is zinc oxide, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:1000mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is Acetylcholine Chloride, and acid amides is dimethyl formamide;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 100 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 0.5mAcm
-2galvanostatic deposition 0.5h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.50Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.SEM figure when the nano porous copper magnification prepared is 50000 times as shown in Figure 3.
Embodiment 3
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:2, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.350g alloy induction salt (alloy induction salt is zinc chloride, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:1750mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is Acetylcholine Chloride, and acid amides is urea;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 150 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 1mAcm
-2galvanostatic deposition 0.5h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.40Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.SEM figure when the nano porous copper magnification prepared is 50000 times as shown in Figure 4.
Embodiment 4
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:2, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.100g alloy induction salt (alloy induction salt is zinc oxide, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:500mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is tetramethyl ammonium chloride, and acid amides is ethanamide;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 100 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 2mAcm
-2galvanostatic deposition 1h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.30Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.
Embodiment 5
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:1, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.500g alloy induction salt (alloy induction salt is zinc chloride, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:2500mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is tetramethyl ammonium chloride, and acid amides is ethanamide;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 80 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 0.2mAcm
-2galvanostatic deposition 2h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.20Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.
Embodiment 6
This eutectic type ionic liquid in-situ electrolysis prepares the method for nano porous copper, and its concrete steps are as follows:
(1) under an inert atmosphere, mixed by quaternary ammonium salt with acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:4, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In the low altogether melt type ionic liquid of 20mL, add 0.04g alloy induction salt (alloy induction salt is zinc oxide, and wherein the volume of low melt type ionic liquid altogether induces the mass ratio of salt to be 100:200mL/mg with alloy) mix and obtain ionic liquid-alloy salts composite electrolytic solution; Wherein quaternary ammonium salt is Acetylcholine Chloride, and acid amides is ethanamide;
(2) negative electrode is made with copper sheet (2.0cm × 1.5cm × 0.1cm), graphite makes anode, filamentary silver does reference electrode, in 20mL ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 80 DEG C, interpole gap be 1cm, without the need to stir, cathode current density 2mAcm
-2galvanostatic deposition 0.8h under condition, obtains the Cu-Zn alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.25Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (4)
1. eutectic type ionic liquid in-situ electrolysis prepares a method for nano porous copper, it is characterized in that concrete steps are as follows:
(1) under an inert atmosphere, by quaternary ammonium salt and acid amides after 80 DEG C of vacuum-drying according to mol ratio 1:(1 ~ 4) mix, under 80 DEG C of thermostatically heating conditions, reaction 1h can prepare low melt type ionic liquid altogether; In low altogether melt type ionic liquid, add alloy induction salt mix and obtain ionic liquid-alloy salts composite electrolytic solution;
(2) make negative electrode with copper sheet, graphite or inert anode make anode, in ionic liquid-alloy salts composite electrolytic solution that step (1) obtains and temperature be 80 ~ 150 DEG C, without the need to stirring, cathode current density 0.20 ~ 2mAcm
-2galvanostatic deposition 0.50 ~ 2h under condition, obtains the alloy presoma of homogeneous phase;
(3) under original electrolyte system, set up three-electrode system, with alloy presoma for working electrode, graphite or inert anode are to electrode, filamentary silver is reference electrode, controlling potential-0.50 ~-0.20Vvs.Ag removal alloying in the alloy presoma of the homogeneous phase obtained in step (2), by the cathode sheets of removal alloying through dehydrated alcohol, distilled water flushing, namely obtains the copper sheet with nano-porous structure after drying.
2. eutectic type ionic liquid in-situ electrolysis according to claim 1 prepares the method for nano porous copper, it is characterized in that: the quaternary ammonium salt in described step (1) is choline chloride 60, Acetylcholine Chloride or tetramethyl ammonium chloride.
3. eutectic type ionic liquid in-situ electrolysis according to claim 1 prepares the method for nano porous copper, it is characterized in that: the acid amides in described step (1) is urea, dimethyl formamide or ethanamide.
4. eutectic type ionic liquid in-situ electrolysis according to claim 1 prepares the method for nano porous copper, it is characterized in that: described step (1) interalloy induction salt is zinc oxide or zinc chloride, volume and the alloy of low melt type ionic liquid altogether induce the mass ratio of salt to be 100:(200 ~ 2500) mL/mg.
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| CN106757214A (en) * | 2016-11-23 | 2017-05-31 | 昆明理工大学 | The method that nanoporous noble metal film is prepared in eutectic type ionic liquid |
| CN113013404A (en) * | 2021-02-23 | 2021-06-22 | 昆明理工大学 | In-situ growth type lithium ion battery electrode Cu2Preparation method of Sb nano material |
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