CN104057099B - The preparation method of a kind of ultrathin nanometer porous copper foil - Google Patents
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Abstract
The present invention discloses the preparation method of a kind of ultrathin nanometer porous copper foil, utilizes hydrothermal method, will containing Cu2+Precursor liquid under certain temperature after stoichiometric number hour, just can obtain ultrathin nanometer porous copper foil at reactor inwall in sealed high pressure reactor. Process of the present invention is simple, safe and reliable, nontoxic pollution-free, and cost is lower; Producing the nanoporous Copper Foil obtained is that its thickness can be thinned to 1.0��3.0 ��m, and size can reach tens square centimeters, and has good mechanical property without what support; The nanoporous Copper Foil in different-grain diameter and aperture can be obtained so that it is meet the demand of multiple use by the adjustment each constituent concentration of precursor liquid, temperature of reaction and time etc.
Description
Technical field
The invention belongs to the preparing technical field of nano material, it is specifically related to the preparation method of a kind of ultrathin nanometer porous copper foil.
Background technology
Nano porous metal is a kind of special metallic substance with nano-scale hole, and therefore it not only has the unusual characteristic of nano material, also retains the outstanding physics of metallic substance and chemical property. In recent years, various porous metal research receive the extensive concern of investigators, it is shown that it has great application prospect in fields such as catalyzer, electrode materials, sensor, surface enhanced Raman scattering substrate, Chu Qing. As a kind of low cost and environmentally friendly metallic substance, porous copper has evoked, with the physics of its excellence and chemical property, the very big interest that it is studied by investigators.
Publication number be CN102943187A Chinese patent application disclosed in the preparation method of nano porous copper, obtain nano porous copper by Cu-Hf-Al alloy is carried out removal alloying in the hydrofluoric acid solution of lower concentration. Publication number be CN101956090A Chinese patent application disclosed in a kind of method adopting Cu-Zn reasonable offer nano porous copper, utilize Cu-Zn alloy that scorification is obtained by electrochemical erosion method through row galvanic corrosion, finally obtain nano porous copper. Publication number be CN101596598A Chinese patent application disclosed in the preparation method of a kind of whole continuous nano-porous copper, the corrosive fluid corrosion of lower concentration put into by Cu-Al alloy melting obtained, and can obtain nano porous copper. Publication number be CN103343253A Chinese patent application disclosed in a kind of method preparing nano porous copper, adopt vacuum arc melting method prepare Cu-Zr (-Al) alloy, further removal alloying just can obtain nano porous copper. Publication number is the method for the Chinese patent application three-dimensional netted nano porous copper of disclosed preparation of CN102628112A, arc melting method obtains Cu-Mn alloy and puts into acid or strong acid weak base solution removal alloying, can obtain nano porous copper. Publication number be CN103132111A Chinese patent application disclosed in the preparation method of three dimensional micron level porous copper film, and publication number is the disclosed a kind of micro-nano rice composite porous surface structure of Chinese patent application of CN103046088A and its preparation method and device, hydrogen gas bubbles dynamic template electrodip process is adopted to form three-dimensional porous Copper thin film on the metallic substrate. Publication number be CN103357876A Chinese patent application disclosed in the preparation method of a kind of nano multihole copper film, the organic ink containing copper powder prepared in advance is coated on substrate surface, nano multihole copper film can be obtained after its thermal treatment, and hcl corrosion carrier can be adopted and obtain without the nano multihole copper film supported.
Aforesaid method has respective advantage, but also there is very big deficiency. Utilizing the de-alloyage of multi-element metal alloy to prepare nano porous copper, the particle diameter of the porous copper obtained and aperture equal one and controlled, the physical strength of the block obtained is relatively better, meets the requirement of preparation of industrialization. But, the method process is complicated, and melting process is higher and easily cause the oxidation of copper to equipment requirements, and the corrosion process in later stage causes the waste of resource, adds preparation cost, is also difficult to all erode all elements that melts altogether, it is very difficult to obtain pure porous copper. Hydrogen gas bubbles dynamic template electrodip process preparation process is simple, and cost is lower, but the porous copper mechanical property obtained is poor, and is difficult to particle diameter and the aperture of control porous copper. Although organic ink coating method operation is quite simple, cost is lower, but the quality of the porous copper obtained is poor, and particle diameter and pore size and homogeneity are difficult to control. Therefore, explore the novel processing step preparing nano porous copper, reduction energy consumption, energy-saving and emission-reduction, raising rate of return on investment and raising production efficiency are had important actual meaning.
Summary of the invention
For defect of the prior art, it is an object of the invention to provide the preparation method of a kind of ultrathin nanometer porous copper foil. The method process is simple, safe and reliable, nontoxic pollution-free, and cost is lower; By the concentration of each composition in change presoma, temperature of reaction and time, the nanoporous Copper Foil in different grain size, aperture just can be obtained.
The preparation that the present invention is nanoporous Copper Foil provides a kind of new method. The ultimate principle of the method is the self-assembly formation porous copper of nanometer copper utilizing reaction to be formed on reactor wall, and utilizing thermal expansivity different between inner liner of reaction kettle from porous copper in reacted process of cooling, porous copper obtains from stripping without the ultrathin nanometer porous copper foil supported.
It is an object of the invention to be achieved through the following technical solutions:
The present invention relates to the preparation method of a kind of ultrathin nanometer porous copper foil, comprise following step:
(1) preparation is containing Cu2+Precursor liquid: by sodium hydroxide solution and Cu2+Solion mixes, and obtains nattier blue milk sap after stirring; Drip and add ethylene glycol and constantly stir, obtain the solution of royal blue; Drip and add deionized water or deionized water and ethanol and surely hold;
(2) will containing Cu2+Precursor liquid loads in autoclave, reacts 4��24h after sealing at 120 DEG C��250 DEG C temperature:
(3) the nanoporous Copper Foil being grown on reactor wall is taken out, after washing for several times, filter paper absorbent drying.
Preferably, described containing Cu2+In precursor liquid, the content of sodium hydroxide is 0.1��5.0mol/L, Cu2+Content be 0.05��0.5mol/L, the volume percent of ethylene glycol is 5%��50%, and the volume percent of ethanol is 0%��50%. The concentration of reactant plays a key effect preparing in large-area ultrathin nanoporous Copper Foil. When the amount of NaOH is lower than 0.1mol/L, product can contain the oxide compound of copper; During higher than 5.0mol/L, it is difficult to form porous copper on reactor wall. Cu2+Amount all can not form porous copper foil lower than 0.05mol/L or higher than 0.5mol/L. When the volume percent of ethylene glycol is lower than 5%, the product obtained contains the oxide compound of copper, and porous copper foil can not be grown at reactor inwall; During higher than 50%, the porous copper of growth can not automatically peel off the ultrathin nanometer porous copper foil forming self-supporting at temperature-fall period. When the volume percent of ethanol is higher than 50%, it is difficult to form the nanoporous Copper Foil of self-supporting.
Preferably, the volume percent of described ethanol is 0%��10%. This concentration range is conducive to the preparation without support ultrathin nanometer porous copper foil of big area, uniform pore diameter.
Preferably, the volume percent of described ethylene glycol is 5%��25%. This concentration range is conducive to copper nano particles to form porous copper in the self-assembly of reactor inwall, and can realize the adjustment in aperture.
Preferably, in step (2), described temperature of reaction is 140 DEG C��200 DEG C. The nanoporous Copper Foil size that this temperature range obtains is relatively big, and uniform pore diameter is better.
Preferably, in step (2), the described reaction times is 8��12h. This time range ensures not contain in porous copper foil the oxide compound of copper on the one hand, and the homogeneity in porous copper aperture is better on the other hand, and can realize the adjustment in aperture.
Preferably, described containing Cu2+Cu in precursor liquid2+One or more being selected from cupric sulfate pentahydrate, copper chloride dihydrate, nitrate trihydrate copper, a water acetic acid copper, copper sulfate, cupric chloride, cupric nitrate, neutralized verdigris.
Preferably, described Cu2+Cu in precursor liquid2+One or more being selected from cupric sulfate pentahydrate, a water acetic acid copper, copper sulfate, neutralized verdigris.
Compared with prior art, the present invention has following useful effect:
1, preparation process of the present invention is simple, nontoxic pollution-free and cost lower, the demand of scale operation can be met.
2, the present invention produces the nanoporous Copper Foil obtained is that its thickness can be thinned to 1.0��3.0 ��m, and size can reach tens square centimeters, and has good mechanical property without what support.
3, the present invention can obtain the nanoporous Copper Foil in different-grain diameter and aperture by the adjustment each constituent concentration of precursor liquid, temperature of reaction and time etc. so that it is meets the demand of multiple use.
Accompanying drawing explanation
By reading with reference to the detailed description that non-limiting example is done by the following drawings, the other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the XRD figure of ultrathin nanometer porous copper foil in the present invention;
Fig. 2 is the SEM figure of ultrathin nanometer porous copper foil in the present invention; Wherein, (a) vertical view, (b) side-view.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail. The technician contributing to this area is understood the present invention by following examples further, but does not limit the present invention in any form. It should be appreciated that to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some distortion and improvement. These all belong to protection scope of the present invention.
Embodiment 1
A preparation method for ultrathin nanometer porous copper foil, comprises following steps:
(1) preparation is containing Cu precursor liquid: first, join in a certain amount of deionized water by 0.8g mono-water acetic acid copper; Secondly, the aqueous solution containing 1.6g sodium hydroxide is joined above-mentioned Cu2+In solion, obtain light blue milk sap; Again, in above-mentioned solution, 5mL ethylene glycol is added; Finally, adding a certain amount of deionized water makes cumulative volume be 40mL. Whole process needs continuous stirring, last stir about 1h.
(2) above-mentioned precursor liquid is loaded in autoclave and seal, then reactor is put into and be set as that the stove of 140 DEG C goes in advance, take out reactor after reaction 12h so that it is naturally cooling.
(3) opening reactor, reactor wall upper attaching plate shape thing is ultrathin nanometer porous copper foil, after taking off washing for several times, and filter paper absorbent drying.
The ultrathin nanometer porous copper foil that the present embodiment obtains, Fig. 1 is the XRD figure of this ultrathin nanometer porous copper foil; As shown in Figure 1, the peak of all corresponding copper in all peaks, illustrates the impurity phase of the oxide compound not containing copper in porous copper foil, and sharp-pointed XRD diffraction peak also shows that the crystallinity of Copper Foil is better.
Fig. 2 is the SEM figure of this ultrathin nanometer porous copper foil; By Fig. 2 (a) it will be seen that its size reaches 10cm2, a nanometer copper ligament diameter is about 400nm, and aperture is about 150nm; By Fig. 2 (b) it will be seen that its thickness is about 1.5 ��m.
Embodiment 2
A preparation method for ultrathin nanometer porous copper foil, comprises following steps:
(1) preparation is containing Cu precursor liquid: first, joined by 0.5g cupric sulfate pentahydrate in a certain amount of deionized water; Secondly, the aqueous solution containing 8g sodium hydroxide is joined above-mentioned Cu2+In solion, obtain light blue milk sap; Again, in above-mentioned solution, 2mL ethylene glycol is added; Finally, the ethanol and a certain amount of deionized water that add 5mL make cumulative volume be 40mL. Whole process needs continuous stirring, finally stirs 30min.
(2) above-mentioned precursor liquid is loaded in autoclave and seal, then reactor is put into and be set as that the stove of 250 DEG C goes in advance, take out reactor after reaction 14h so that it is naturally cooling.
(3) opening reactor, reactor wall upper attaching plate shape thing is ultrathin nanometer porous copper foil, after taking off washing for several times, and filter paper absorbent drying.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 450nm, and aperture is about 50nm.
Embodiment 3
A kind of ultrathin nanometer porous copper foil is obtained by following step:
(1) preparation is containing Cu precursor liquid: first, join in a certain amount of deionized water by 1.6g mono-water acetic acid copper; Secondly, the aqueous solution containing 0.16g sodium hydroxide is joined above-mentioned Cu2+In solion, obtain light blue milk sap; Again, in above-mentioned solution, 15mL ethylene glycol is added; Finally, adding a certain amount of deionized water makes cumulative volume be 40mL. Whole process needs continuous stirring, finally stirs 1h.
(2) above-mentioned precursor liquid is loaded in autoclave and seal, then reactor is put into and be set as that the stove of 200 DEG C goes in advance, take out reactor after reaction 16h so that it is naturally cooling.
(3) opening reactor, reactor wall upper attaching plate shape thing is ultrathin nanometer porous copper foil, after taking off washing for several times, and filter paper absorbent drying.
The ultrathin nanometer porous copper foil chi that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 350nm, and aperture is about 150nm.
Embodiment 4
A kind of ultrathin nanometer porous copper foil is obtained by following step:
(1) preparation is containing Cu precursor liquid: first, join in a certain amount of deionized water by 0.8g mono-water acetic acid copper; Secondly, the aqueous solution containing 1.6g sodium hydroxide is joined above-mentioned Cu2+In solion, obtain light blue milk sap; Again, in above-mentioned solution, 5mL ethylene glycol is added; Finally, adding a certain amount of deionized water makes cumulative volume be 40mL. Whole process needs continuous stirring, last stir about 1h.
(2) above-mentioned precursor liquid is loaded in autoclave and seal, then reactor is put into and be set as that the stove of 200 DEG C goes in advance, take out reactor after reaction 12h so that it is naturally cooling.
(3) opening reactor, reactor wall upper attaching plate shape thing is ultrathin nanometer porous copper foil, after taking off washing for several times, and filter paper absorbent drying.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 450nm, and aperture is about 250nm.
Embodiment 5
In the preparation of ultrathin nanometer porous copper foil, the amount of added sodium hydroxide is a 0.4g, and temperature of reaction is 180 DEG C, and other conditions are with embodiment 4.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 420nm, and aperture is about 170nm.
Embodiment 6
In the preparation of ultrathin nanometer porous copper foil, the amount of an added water acetic acid copper is a 2.4g, and the reaction times is 18h, and other conditions are with embodiment 4.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 500nm, and aperture is about 200nm.
Embodiment 7
In the preparation of ultrathin nanometer porous copper foil, the reaction times is a 6h, and other conditions are with embodiment 4.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 550nm, and aperture is about 150nm.
Embodiment 8
In the preparation of ultrathin nanometer porous copper foil, the amount of an added water acetic acid copper is a 4g, and other conditions are with embodiment 4.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 350nm, and aperture is about 130nm.
Embodiment 9
In the preparation of ultrathin nanometer porous copper foil, the amount of added ethylene glycol and ethanol is respectively a 20mL and 10mL, and other conditions are with embodiment 1.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 440nm, and aperture is about 110nm.
Embodiment 10
In the preparation of ultrathin nanometer porous copper foil, the amount of added ethanol is respectively a 20mL, and temperature of reaction is 120 DEG C, and other conditions are with embodiment 1.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 550nm, and aperture is about 90nm.
Embodiment 11
In the preparation of ultrathin nanometer porous copper foil, the amount of added ethanol is respectively a 4mL, and temperature of reaction is 160 DEG C, and other conditions are with embodiment 1.
The ultrathin nanometer porous copper foil that the present embodiment obtains, the oxide compound and the crystallinity that do not contain copper are better, and size reaches 10cm2, a nanometer copper ligament diameter is about 410nm, and aperture is about 150nm.
Above specific embodiments of the invention are described. It is understood that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect the flesh and blood of the present invention.
Claims (7)
1. the preparation method of a ultrathin nanometer porous copper foil, it is characterised in that, comprise following step:
(1) preparation is containing Cu2+Precursor liquid: by sodium hydroxide solution and Cu2+Solion mixes, and obtains nattier blue milk sap after stirring; Drip and add ethylene glycol and constantly stir, obtain the solution of royal blue; Drip and add deionized water or deionized water and ethanol and surely hold;
(2) will containing Cu2+Precursor liquid loads in autoclave, reacts 4��24h after sealing at 120 DEG C��250 DEG C;
(3) the nanoporous Copper Foil being grown on reactor wall is taken out, after washing for several times, filter paper absorbent drying;
Described contains Cu2+In precursor liquid, the content of sodium hydroxide is 0.1��5.0mol/L, Cu2+Content be 0.05��0.5mol/L, the volume percent of ethylene glycol is 5%��50%, and the volume percent of ethanol is 0%��50%.
2. preparation method according to claim 1, it is characterised in that, the volume percent of described ethanol is 0%��10%.
3. preparation method according to claim 2, it is characterised in that, the volume percent of described ethylene glycol is 5%��25%.
4. preparation method according to claim 1, it is characterised in that, in step (2), described temperature of reaction is 140 DEG C��200 DEG C.
5. preparation method according to claim 1, it is characterised in that, in step (2), the described reaction times is 8��12h.
6. preparation method according to claim 1, it is characterised in that, described contains Cu2+Cu in precursor liquid2+One or more being selected from cupric sulfate pentahydrate, copper chloride dihydrate, nitrate trihydrate copper, a water acetic acid copper, copper sulfate, cupric chloride, cupric nitrate, neutralized verdigris.
7. preparation method according to claim 6, it is characterised in that, described Cu2+Cu in precursor liquid2+One or more being selected from cupric sulfate pentahydrate, a water acetic acid copper, copper sulfate, neutralized verdigris.
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| CN105177696B (en) * | 2015-08-26 | 2017-10-17 | 湖北工程学院 | A kind of preparation method of the copper nano structural material of morphology controllable |
| CN108385069B (en) * | 2018-03-30 | 2020-07-28 | 西安理工大学 | Preparation method of hyperfine nano porous copper film |
| CN108436100B (en) * | 2018-04-09 | 2021-06-04 | 哈尔滨工业大学（深圳） | Preparation method of ultrathin porous nano nickel foil |
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| CN101332514B (en) * | 2008-07-30 | 2011-02-02 | 中南大学 | Preparation method of porous copper powder |
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101596598B (en) * | 2009-07-01 | 2011-06-22 | 济南大学 | Preparation method of whole continuous nano-porous copper |
| CN102363217B (en) * | 2011-10-26 | 2013-04-17 | 济南大学 | Method for preparing nanometer porous copper powder |
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