CN104818503A - Preparation method of porous copper full-impregnated film of three-dimensional network structure - Google Patents
Preparation method of porous copper full-impregnated film of three-dimensional network structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a porous copper full-impregnated film of a three-dimensional network structure. The method comprises the following steps that (1), a basic plating solution is prepared, wherein the basic plating solution comprises 1.0mol/L of H2SO4 and 0.2mol/L of CuSO4; (2), electrochemical deposition is carried out, wherein in a depositing cell, a graphite sheet serves as a positive electrode, aluminum foil serves as a negative electrode, the basic plating solution serves as electrolytes, and an electrochemistry working station is used for carrying out constant-current density electrolytic deposition to form the porous copper film on the aluminum foil; (3), vacuum annealing treatment is carried out on the porous copper film on the aluminum foil; (4), an aluminum substrate is removed, wherein aluminum foil obtained after vacuum annealing treatment is placed in alkali liquor to have a reaction, the aluminum foil is removed, and the porous copper full-impregnated film of the three-dimensional network structure is obtained. Compared with the prior art, the porous copper full-impregnated film of the three-dimensional network structure is even in bore diameter and stable in structure and has the good filtering separation function, and meanwhile due to the large specific area, and the good toughness, the film can be used as a good catalyst carrier.
Description
Technical field
The present invention relates to a kind of preparation method of Porous Cu, especially relate to a kind of preparation method of three-dimensional net structure Porous Cu full-trans-parent film.
Background technology
In recent decades, porous membrane material plays a part more and more important in purification of water quality, porous electrode and catalytic reaction etc., features such as especially porous metal film is because having excellent physicals, chemical property and mechanical property, as little in proportion, specific surface area is large, energy absorption is good and be widely used in the numerous areas such as petrochemical complex, energy environment protection, defence and military.And for porous noble metal film system, Porous Cu film has more wide application prospect undoubtedly.Porous Cu material preparation method traditional at present has a lot, as track etch method, powder metallurgic method, removal alloying method, melt solidifying method etc.But with regard to, uniform pore diameter good with regard to preparation compactness and constitutionally stable porous metal film, some drawbacks that the many existence of these methods cannot overcome, as track etch method limits its use range because of obtained pore diameter range narrower (<10 μm); Powder metallurgy fado is applicable to prepare porous metal bodies and the fluctuation of inner void magnitude range is larger; It is complicated and to problems such as equipment requirements are high to there is alloy material preparation difficulty, operating process in removal alloying rule.
In recent years, there is researchist to utilize in the process of acid copper, with the bubble hydrogen of side reaction generation for dynamic template is prepared into Porous Cu film.Shin etc. find CuSO in the electrolytic solution
4concentration range is at 0.1-0.4mol/L, H
2sO
4concentration range 0.5-1.5mol/L, cathode current density, when 0.8-4mol/L, can obtain the aperture Porous Cu film similar with pore structure by deposition different time, but its membrane structure aperture obtained is uneven and unstable.The Porous Cu electric conductivity that Liang Shuhua etc. (a kind of preparation method of enhanced nanoporous copper, Chinese invention patent, CN102329977A, 2012.01.25) adopt removal alloying method to obtain is higher, but porosity is low and easily rupture.Sun Yafeng etc. (Sun Yafeng, Niu Zhenjiang, ash fine jade, Li Zelin. electrochemistry .2006,12 (2): 177-182) prepare three-dimensional porous copper using bubble hydrogen as dynamic template.But the problem due to additive cause bonding strength between aperture lower so that cause metal film structures loosen.(a kind of micro-nano compound porous copper surface tissue and preparation method thereof and the device such as Tang Yong, Chinese invention patent, CNIO3046088A, 2013.04.17) three-dimensional porous copper is prepared using bubble hydrogen as dynamic template equally, but its product is matrix with copper thus causes separating the copper metal film of complete three-dimensional net structure, therefore its essence is just the surface tissue of matrix with copper, is not metallic membrane truly.
Summary of the invention
Object of the present invention is exactly provide a kind of preparation method of three-dimensional net structure Porous Cu full-trans-parent film to overcome defect that above-mentioned prior art exists, the method obtains three-dimensional network " funnel " the structural porous copper metal film with whole-permeable, the controlled and Stability Analysis of Structures of the uniform pore diameter of film.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for three-dimensional net structure Porous Cu full-trans-parent film, comprises the following steps:
(1) basic bath is prepared: described basic bath is containing 1.0mol/L H
2sO
4with 0.2mol/L CuSO
4, as preferably, also containing additive in described basic bath, described additive is the NH of 5-10mmol/L
4the polyoxyethylene glycol of Cl and 1-2g/L.In addition improve the glossiness of settled layer, make copper dendrite arm more level and smooth, in electroplate liquid, add appropriate soluble saccharin (C
7h
40
3nSNaH
20) as finishing agent.The boric acid that can add suitable concentration makes pH buffer reagent, stablizes with the pH maintaining electrodeposit liquid.
(2) electrochemical deposition: in galvanic deposition cell take graphite flake as anode, and the aluminium foil of purity 99.5% is negative electrode, and graphite flake surface requirements is smooth, and area is 4cm × 5cm, to ensure that between negative electrode and positive electrode, electric field distribution is even.Wherein aluminium foil to be positioned at bottom sedimentation tank and to make mask with plastic material, and make cathode area be fixed as 1cm × lcm, the graphite side of being located thereon is relatively in parallel, both distance 2-3cm.Take basic bath as electrolytic solution, use electrochemical workstation to carry out constant current density galvanic deposit, current density is 1-2.5A/cm
2, electrolyte temperature is room temperature, and depositing time 20s-60s forms porous copper film on aluminium foil, electrolytic solution will be kept to stablize, prevent from rocking stirring in deposition process.
(3) take out galvanic deposit sample priority deionized water and alcohol flushing 3-4 time, then dry up preservation with nitrogen.And because film that electrochemical deposition method is obtained is comparatively loose and internal bond strength is more weak, for the compactness and stability improving copper metal film needs to carry out vacuum annealing process.Vacuum annealing treatment process is: first controlling rate of heating is that temperature is increased to 300-500 DEG C by 5 DEG C/min, at 300-500 DEG C, is then incubated 30-120min to eliminate the internal stress produced in temperature-rise period, ensures the integrity of surface copper membrane structure.
(4) aluminum substrate is removed: repeatedly rinse well with deionized water after the aluminium foil after vacuum annealing process is soaked 20min in ethanol again, then the NaOH solution 30min putting into 30%wt makes matrix aluminium foil fully react, and reaction terminates carefully to pull porous copper film out afterwards.Porous Cu film now has whole-permeable and aperture, two sides changes step by step, forms three-dimensional network " funnel " structure, and then in purification of water quality, particle separation etc., has more wide application prospect.And in order to prevent or delay the oxidation of this porous copper film, by its isolated water and air, therefore can place it in alcohol and with preservative film and seal, sealing two layers preservative film better effects if.
Wherein, cathode aluminum foil needs to carry out pre-treatment before using, concrete grammar is that it is put into acetone, dehydrated alcohol successively, use ultrasonic washing instrument oscillation cleaning 5min respectively, aluminium foil deionized water after process of deoiling is rinsed well repeatedly, then the NaOH solution putting into 10%wt soaks 15min, removing aluminium foil surface zone of oxidation.Put afterwards and rinse 20min with clear water under a tap, finally clean with deionized water rinsing.Electrochemical method carries out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join, take graphite as negative electrode, aluminium foil is anode, polishing 15min under 20V voltage.Anode graphite need rinse repeatedly with deionized water.
The three-dimensional net structure porous metal copper film of prepared by the present invention have whole-permeable is mainly used in purification of water quality and filtering separation field; Also a kind of good catalyst support material is can be used as in catalytic reaction.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the three-dimensional net structure Porous Cu membrane pore size prepared of the present invention evenly, Stability Analysis of Structures, have good filtering separation function, large specific surface area and good toughness make it can be used as preferably support of the catalyst simultaneously.
(2) adopt the aluminium foil after electrochemical etching as negative electrode at its surface deposition Porous Cu, can acid solution or base extraction be carried out to aluminium foil thus realize the separation of porous surface steel structure; And then obtain the three-dimensional net structure porous copper film with whole-permeable.
(3) on annealing process route, first control rate of heating is that temperature is increased to 300-500 DEG C by 5 DEG C/min, at 300-500 DEG C, is then incubated 30-120min to eliminate the internal stress produced in temperature-rise period, ensures the integrity of surface copper membrane structure.
Accompanying drawing explanation
Fig. 1 is the heat treatment cycle curve to electrochemical deposition gained Porous Cu.
Fig. 2 is at room temperature current density 1A/cm
2, 5mmol/LNH
4the additive of Cl, 0g/L polyoxyethylene glycol, the SEM image of 300 DEG C of vacuum heat treatment 2h gained porous copper films.
Fig. 3 is at room temperature current density 2A/cm
2, 10mmol/LNH
4the additive of Cl, 1g/L polyoxyethylene glycol, the SEM image of 400 DEG C of vacuum heat treatment 1h gained porous copper films.
Fig. 4 is at room temperature current density 2.5A/cm
2, 10mmol/LNH
4the additive of Cl, 2g/L polyoxyethylene glycol, the SEM image of porous copper film before vacuum heat treatment.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Carry out stirring with magnetic stirring apparatus to electrolytic solution after being mixed with additive by basic bath and make its Homogeneous phase mixing, additive is 5mmol/LNH
4cl, 0g/L polyoxyethylene glycol, appropriate soluble saccharin (C
7h
40
3nSNaH
20) and buffer reagent boric acid.Cathode aluminum foil is put into acetone successively, dehydrated alcohol carries out ultrasonic cleaning, complete process of deoiling.The NaOH solution putting into 10%wt afterwards soaks 15min, and removing aluminium foil surface zone of oxidation, finally utilizes electrochemical method to carry out polishing, electrolytic solution select dehydrated alcohol and perchloric acid by volume 4:1 join, take graphite as negative electrode, aluminium foil is anode, polishing 15min under 20V voltage.After previous work is ready, anode and cathode is put into electrolyzer, ensure aluminium foil at lower graphite upper and the two is relatively parallel, distance is 2-3cm.Utilize the current density in electrochemical workstation control loop to be 1A/cm2, depositing time 40s. takes out aluminium foil after depositing, and with deionized water and alcohol flushing 3-4 time, then dries up the follow-up anneal of preparation with nitrogen.Because the Porous Cu binding force of membrane grown on aluminium foil is weak and more unstable, therefore need to control rate of heating to prevent from being produced stress rupture membrane structure by the temperature difference in annealing process.Temperature controls rate of heating before being increased to 300 DEG C is for this reason 5 DEG C/min, and then at 300 DEG C, be incubated 120min, to remove the stress of copper film inside and stable crystal grain, its heat treatment cycle curve as shown in ① in Figure 1.Finally annealing specimen is immersed in 30min in the NaOH solution of 30%wt, to remove matrix aluminium foil, to ensure to obtain the Porous Cu full-trans-parent film with three-dimensional net structure.Fig. 2 is the SEM image of gained porous copper film under this condition.Can find out in figure that annealing causes the alligatoring of copper skeleton, add the stability of three-dimensional structure, porosity can decline to some extent compared with before annealing simultaneously.Now the aperture of full impregnated copper film is 50 ± 5 μm, and the average crystal particle scale of copper skeleton is 60.54nm.
Embodiment 2
Carry out stirring with magnetic stirring apparatus to electrolytic solution after being mixed with additive by basic bath and make its Homogeneous phase mixing, additive is 10mmol/LNH
4the additive of Cl, 1g/L polyoxyethylene glycol, appropriate soluble saccharin (C
7h
40
3nSNaH
20) and buffer reagent boric acid.By carrying out pre-treatment to electrode in embodiment 1 and completing the preparation work before electrochemical deposition.The current density in electrochemical workstation control loop is utilized to be 2A/cm
2, depositing time 30s. takes out aluminium foil after depositing, and with deionized water and alcohol flushing 3-4 time, then dries up the follow-up anneal of preparation with nitrogen.First controlling rate of heating is that temperature is increased to 300 DEG C by 5 DEG C/min, at 300 DEG C, is then incubated 30min to eliminate the internal stress produced in temperature-rise period.Continue afterwards to be warming up to 400 DEG C of insulation 60min furnace cooling again, its heat treatment cycle curve as shown in ② in Figure 1.Finally annealing specimen is immersed in temperature be in the NaOH solution of 40 DEG C of 30%wt 20min to remove matrix aluminium foil.Fig. 3 is the SEM image of gained porous copper film under this condition. now the aperture of copper film is 80 ± 10 μm, and the average crystal particle scale of copper skeleton is 52.41nm.
Embodiment 3
Carry out stirring with magnetic stirring apparatus to electrolytic solution after being mixed with additive by basic bath and make its Homogeneous phase mixing, additive is 10mmol/LNH
4the additive of Cl, 2g/L polyoxyethylene glycol, appropriate soluble saccharin (C
7h
40
3nSNaH
20) and buffer reagent boric acid.By carrying out pre-treatment to electrode in embodiment 1 and completing the preparation work before electrochemical deposition.The current density in electrochemical workstation control loop is utilized to be 2.5A/cm2, depositing time 40s. takes out aluminium foil after depositing, with deionized water and alcohol flushing 3-4 time, then dry up with nitrogen and prepare follow-up anneal. first controlling rate of heating is that temperature is increased to 300 DEG C by 5 DEG C/min, at 300 DEG C, is then incubated 30min to eliminate the internal stress produced in temperature-rise period.Continue afterwards to be warming up to 500 DEG C of insulation 60min furnace cooling again, its heat treatment cycle curve as shown in ③ in Figure 1.Finally annealing specimen to be immersed in the dilute hydrochloric acid solution of 1.5mol/L 20min to remove matrix aluminium foil.Fig. 4 be annealing before the deposition morphology of porous copper film of gained.Now the aperture of copper film is 60 ± 5 μm, and the average crystal particle scale of copper skeleton is 43.56nm.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. a preparation method for three-dimensional net structure Porous Cu full-trans-parent film, is characterized in that, comprises the following steps:
(1) basic bath is prepared: described basic bath is containing 1.0mol/L H
2sO
4with 0.2mol/L CuSO
4;
(2) electrochemical deposition: in galvanic deposition cell, take graphite flake as anode, aluminium foil is negative electrode, take basic bath as electrolytic solution, uses electrochemical workstation to carry out constant current density galvanic deposit, aluminium foil is formed porous copper film;
(3) vacuum annealing process is carried out to the porous copper film on aluminium foil;
(4) remove aluminum substrate: be placed in alkali lye by the aluminium foil after vacuum annealing process and react, remove aluminium foil, obtain three-dimensional net structure Porous Cu full-trans-parent film.
2. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, is characterized in that, also containing additive in described basic bath, described additive is the NH of 5-10mmol/L
4the polyoxyethylene glycol of Cl and 1-2g/L.
3. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, is characterized in that, also containing finishing agent in described basic bath, described finishing agent selects soluble saccharin.
4. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, is characterized in that, also containing pH buffer reagent in described basic bath.
5. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, is characterized in that, after the ultrasonic cleaning before use of described aluminium foil, removes surface oxide layer, and adopts electrochemical method to carry out polished finish.
6. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 5, is characterized in that, when carrying out polished finish, dehydrated alcohol used for electrolyte and perchloric acid by volume 4:1 are joined, take graphite as negative electrode, aluminium foil is anode, polishing 15min under 20V voltage.
7. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, it is characterized in that, the processing condition of the electrochemical deposition described in step (2) are: current density is 1-2.5A/cm
2, electrolyte temperature is room temperature, depositing time 20s-60s.
8. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, it is characterized in that, vacuum annealing treatment process described in step (3) is: first controlling rate of heating is that temperature is increased to 300-500 DEG C by 5 DEG C/min, then at 300-500 DEG C, is incubated 30-120min.
9. the preparation method of a kind of three-dimensional net structure Porous Cu full-trans-parent film according to claim 1, it is characterized in that, the alkali lye described in step (4) is the NaOH solution of 30wt%.
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| CN106847550A (en) * | 2017-02-15 | 2017-06-13 | 哈尔滨工业大学深圳研究生院 | A kind of laser boring template electroplates porous metal film and its method and application |
| CN107937943A (en) * | 2017-11-16 | 2018-04-20 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN108598451A (en) * | 2017-12-12 | 2018-09-28 | 湖北工业大学 | Sodium-ion battery red phosphorus cathode pole piece and preparation method thereof |
| CN109680309A (en) * | 2019-03-06 | 2019-04-26 | 重庆大学 | Super hydrophobic porous Al/CuO nanometers of aluminothermy composite material containing energy |
| CN109772330A (en) * | 2019-02-14 | 2019-05-21 | 安庆北化大科技园有限公司 | A kind of boron doping cobalt hydroxide is carried on the multilevel structure material and preparation method thereof of Porous Cu substrate |
| US20200392634A1 (en) * | 2017-06-19 | 2020-12-17 | Kyung Mo Yang | Method for Production of Metal Article of Manufacture and Uses Thereof |
| CN112176366A (en) * | 2020-09-07 | 2021-01-05 | 浙江大学 | Electrolyte of high-ductility electrolytic copper foil and application |
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| CN106847550A (en) * | 2017-02-15 | 2017-06-13 | 哈尔滨工业大学深圳研究生院 | A kind of laser boring template electroplates porous metal film and its method and application |
| CN106847550B (en) * | 2017-02-15 | 2018-10-09 | 哈尔滨工业大学深圳研究生院 | A kind of laser boring template plating porous metal film and its method and application |
| US20200392634A1 (en) * | 2017-06-19 | 2020-12-17 | Kyung Mo Yang | Method for Production of Metal Article of Manufacture and Uses Thereof |
| US11608562B2 (en) * | 2017-06-19 | 2023-03-21 | Kyung Mo Yang | Method for production of metal article of manufacture and uses thereof |
| CN107937943A (en) * | 2017-11-16 | 2018-04-20 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN107937943B (en) * | 2017-11-16 | 2019-04-26 | 中达电子(江苏)有限公司 | Porous wick structure and preparation method thereof |
| CN108598451A (en) * | 2017-12-12 | 2018-09-28 | 湖北工业大学 | Sodium-ion battery red phosphorus cathode pole piece and preparation method thereof |
| CN108598451B (en) * | 2017-12-12 | 2020-11-06 | 湖北工业大学 | Sodium ion battery red phosphorus negative pole piece and preparation method thereof |
| CN109772330A (en) * | 2019-02-14 | 2019-05-21 | 安庆北化大科技园有限公司 | A kind of boron doping cobalt hydroxide is carried on the multilevel structure material and preparation method thereof of Porous Cu substrate |
| CN109772330B (en) * | 2019-02-14 | 2021-11-05 | 安庆北化大科技园有限公司 | Multilevel structure material with boron-doped cobalt hydroxide loaded on porous copper substrate and preparation method thereof |
| CN109680309A (en) * | 2019-03-06 | 2019-04-26 | 重庆大学 | Super hydrophobic porous Al/CuO nanometers of aluminothermy composite material containing energy |
| CN112176366A (en) * | 2020-09-07 | 2021-01-05 | 浙江大学 | Electrolyte of high-ductility electrolytic copper foil and application |
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Application publication date: 20150805 |