CN103132111A - Preparation method of three-dimensional micrometer level porous copper thin film - Google Patents
Preparation method of three-dimensional micrometer level porous copper thin film Download PDFInfo
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- CN103132111A CN103132111A CN2013100303245A CN201310030324A CN103132111A CN 103132111 A CN103132111 A CN 103132111A CN 2013100303245 A CN2013100303245 A CN 2013100303245A CN 201310030324 A CN201310030324 A CN 201310030324A CN 103132111 A CN103132111 A CN 103132111A
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Abstract
A preparation method of a three-dimensional micrometer level porous copper thin film comprises: a metal substrate is offered and serves as a negative electrode and a red copper sheet is offered and serves as a positive electrode; electroplating liquid is prepared, the content of Cu2+ in the electroplating liquid is 0.08mol/L to 0.2mol/L, the content of H2SO4 is 1.50mol/L to 3.00mol/L, the total content of a surface active agent is 0.5 mmol/L to 4.0mmol/L and the content of Cl- is 1.5mmol/L to 3.0mmol/L; and the three-dimensional porous copper thin film is formed on the metal substrate by using the electroplating liquid, the negative electrode and the positive electrode and adoption of a hydrogen bubble dynamic formwork electrodeposition method. The three-dimensional micrometer level porous copper thin film manufactured through the preparation method is even and small in hole diameter and high in porosity.
Description
Technical field
The present invention relates in general to the preparation method of porous material, is specifically related to a kind of controlled three-dimensional porous copper thin film technology method of pattern.
Background technology
Porous metal material is the important component part of porous material, is comprised of metallic framework and hole, the good functional materials of comprehensive mechanical property such as be a kind of good conductivity, dimensionally stable, high temperature resistant, anti-impact force is strong.Porous metal both can be used as the functional materials of many occasions, also can be used as the structured material of some occasions, were a kind of multiplex engineering materialss of excellent performance.Porous Cu is widely used in the aspects, field such as aerospace, fuel cell, support of the catalyst, separating substances and photoelectric device with its excellent electricity and thermal property.
At present, the method for preparing Porous Cu mainly contains removal alloying method, powder metallurgic method and template etc.(a kind of preparation method of nano porous copper such as Zhang Zhonghua, Chinese invention patent, CN101590528A, 2009-06-19) and (a kind of preparation method of enhanced nanoporous copper, the Chinese invention patent such as Liang Shuhua, CN102329977A, 2012-01-25) all adopt the removal alloying method, the average ligament of the nano porous copper of preparation is of a size of 148～272nm, and electric conductivity is high, Stability Analysis of Structures, but exist pore size distribution inhomogeneous, be prone to the deficiencies such as ductile rupture, porosity be low.Zhou Rui etc. (Zhou Rui, Lu Longsheng. the material heat treatment technology, 2011,40 (4): 59-62) foam copper and copper powder are carried out complex sintered rear formation composite porous material, prepared Porous Cu shrinking percentage is little, but varying aperture is large and the material porosity is lower.(Wang Qingzhou, Li Nuo, the Wang Qian such as Wang Qingzhou, Wu Aizhong, Cui Chunxiang. mechanical engineering material .2011,35 (4): 53-56) take NaCl as pore-forming material, adopt sintering-precipitation legal system for the perforate Porous Cu, hole shape looks, size and NaCl Particle Phase are seemingly, porosity is 67.2%, and mean pore size is 0.75mm, compresses preferably energy absorption characteristics although the perforate Porous Cu of the method preparation is compared to have with fine and close copper, but the aperture is bigger than normal, is prone to ductile rupture.
Template is divided into again the gentle attitude template of solid-state template.Have the advantages such as size is adjustable, good uniformity cancellation due to bubble, be widely used in the preparation of porous material.Sun Yafeng etc. (Sun Yafeng, Niu Zhenjiang, ash fine jade, Li Zelin. electrochemistry .2006,12 (2): 177-182) equally with bubble hydrogen as dynamic template, at concentration of copper sulfate 0.2mol/L, H
2SO
4Content 1.5mol/L, current density 1.0～6A/cm
2, 20～70 ℃ of solution temperature scopes, supporting electrolyte concentration 0～1.5mol/L and PEG mass concentration 2mg/L bath system in, prepare three-dimensional porous copper film.This technique has the following disadvantages: (1) coating three-dimensional structure not obvious (2) adjustable zone, aperture is narrow, and maximum can only reach 100 μ m, and minimum can arrive 25 μ m.(3) coating is dendroid, loosens easily to come off.(4) with batch in the aperture homogeneity relatively poor, as at current density 3A/cm
2, the aperture of the preparation at 20 ℃ of temperature is 40 ± 25 μ m.(the Heon-Cheol Shin such as Heon-Cheol, Meilin Liu.Chem.Mater.2004,16,5460-5464) with bubble hydrogen as dynamic template, be 0.2～0.8mol/L, depositing time 10～60s, acetate concentration 0～0.2mol/L, Cl at concentration of copper sulfate
-Concentration 1～50mmol/L, current density 3A/cm
2System in to have obtained the aperture be the three-dimensional porous copper of 50 ± 20 μ m, prepared Porous Cu film exists that the aperture consistence is poor, variation range is large, coating easily comes off and lacks practicality.(the Ying Li such as Ying Li, Wen-Zhi Jia, Yan-Yan Song, Xing-Hua Xia.Chem.Mater.2007,19,5758-5764) on the basis of former studies, by adding the merging between bubble stabilizer cetyl trimethylammonium bromide inhibition bubble, being arranged aspect the uniformity coefficient of aperture, larger improvement, aperture minimum deviation only have 5 μ m.Binding force of cladding material is poor and the aperture adjustment scope is less than normal but exist equally, and the Porous Cu aperture of preparation is 150 μ m to the maximum, minimum is 10 μ m.
Summary of the invention
The purpose of this invention is to provide a kind of Porous Cu thin film technology method, it can overcome certain or some shortcoming of aforesaid method.
Porous Cu thin film technology method according to the present invention comprises:
Provide metal base as negative electrode and provide copper sheet as anode;
The preparation electroplate liquid, Cu in described electroplate liquid
2+Content is 0.08～0.2mol/L, H
2SO
4Content is that 1.50～3.00mol/L, tensio-active agent total content are 0.5～4.0mmol/L, Cl
-Content is 1.5～3.0mmol/L; And
Utilize described electroplate liquid, described negative electrode and described anode, adopt bubble hydrogen dynamic template electrodip process to form three-dimensional porous copper film on described metal base.
Metal base can be copper sheet, copper zinc alloy sheet, aluminium flake, titanium sheet or magnalium sheet.
Metal base before as negative electrode and/or described copper sheet preferred through corresponding pre-treatment before as anode.Described pre-treatment can comprise polishing, deionization washing, alkali cleaning, deionization washing, pickling and deionization washing successively.Described alkali cleaning condition optimization is: washing soln 0.5～1mol/L Na
2CO
3Soak time 5～10min; And 10～35 ℃ of solution temperature scopes; And described acid washing conditions is preferably: washing soln 0.5～1mol/L HCl; Soak time 5～10min; 10～35 ℃ of solution temperature scopes.
In electrodeposition process, preferably electroplate liquid is not taked any stirring measure.
Method of the present invention can also comprise carries out aftertreatment to three-dimensional porous copper film, namely with deionized water, it is cleaned 3～5 times, then dries up preservation with protective gas.Described protective gas can be nitrogen or argon gas.
Tensio-active agent is preferably the combination of any two kinds in sodium lauryl sulphate, sodium laurylsulfonate, butynediol.
Electrodeposition condition is preferably: time 20～120s; Current density 1.2～3A/cm
2And bath temperature is 25 ± 5 ℃.
Preparation method of the present invention compares with existing Porous Cu preparation technology, has the following advantages: the Porous Cu of (1) the method preparation is three-dimensional porous structure; (2) the method to raw material and equipment require lowly, preparation time is short, suitable for mass production; (3) the Porous Cu even aperture distribution of the method preparation, minimum deviation only has 2 μ m, and porosity can be up to 90% left and right; (4) the Porous Cu aperture adjustment scope of the method preparation is wide, and I reaches 6 μ m, maximum can reach 250 μ m and the fine and close difficult drop-off of coating; (5) conditions such as the consumption by changing additive, electrodeposition time, current density, can reach target adjustable to the Porous Cu microcosmic, that macroscopic view is controlled.
Embodiment
Embodiment one
Successively with the sand paper of 400#, 600#, 800#, 1000# to being of a size of 2 * 2cm
2The negative electrode copper sheet with deionized water, that surface washing is clean after polishing, at 0.75mol/LNa
2CO
3Soak in solution (20 ℃) after 7min with deionized water rinsing, subsequently in 0.75mol/L HCl solution (20 ℃) immersion 7min, with deionized water rinsing after the employing protective gas for example nitrogen or argon gas dry up.Negative electrode copper sheet after above-mentioned pre-treatment is complete is placed in plating solution, adopts bubble hydrogen dynamic template electrodip process well known in the art to deposit the Porous Cu film thereon.Plating solution consists of: CuSO
45H
2O content 0.08mol/L, H
2SO
4Content 3.00mol/L, sodium laurylsulfonate and sodium lauryl sulphate (mol ratio 1:4) total content 3.5mmol/L, CuCl
2Content 1.5mmol/L.Distance between negative electrode copper sheet and anode copper sheet (anode always uses copper sheet in the present invention) remains on 1.5cm, and current density is 3A/cm
2, electrodeposition time is 20s, bath temperature is 20 ℃, does not add stirring in electrodeposition process.At last, then gained Porous Cu film is carried out aftertreatment: namely clean in deionized water 3～5 times, then for example nitrogen or argon gas dry up preservation with protective gas.
Gained Porous Cu film thickness 110 ± 5 μ m, aperture 6 ± 2 μ m, porosity 85.3%.
Embodiment two
Cathode substrate is the titanium sheet, and alkaline wash concentration is that 0.5mol/L (25 ℃), pickle solution concentration are that 0.5mol/L (25 ℃), soak time are 10min.Plating solution consists of: CuSO
45H
2O content is 0.15mol/L, H
2SO
4Content 2.5mol/L, sodium lauryl sulphate and butynediol (mol ratio 1:1) total content 1.5mmol/L, CuCl
2Content 1.20mmol/L.Current density is 2.5A/cm
2, electrodeposition time is 60s, bath temperature is 25 ℃.All the other conditions and step and embodiment one are consistent.
Porous Cu film thickness 200 ± 8 μ m, aperture 15 ± 5 μ m, porosity 87.5%.
Embodiment three
Cathode substrate is the copper zinc alloy sheet, and alkaline wash concentration is that 1mol/L (35 ℃), pickle solution concentration are that 1mol/L (35 ℃), soak time are 6min.Plating solution consists of: CuSO
45H
2O content is 0.10mol/L, H
2SO
4Content 1.5mol/L, sodium lauryl sulphate and sodium laurylsulfonate (1:1) total content 2.5mmol/L, CuCl
2Content is 1.0mmol/L.Current density is 1.5A/cm
2, electrodeposition time is 100s, bath temperature is 30 ℃.All the other conditions and step and embodiment one are consistent.
Porous Cu film thickness 250 ± 10 μ m, aperture 100 ± 8 μ m, porosity 86.4%.
Embodiment four
Cathode substrate is the magnalium sheet, and alkaline wash concentration is that 0.6mol/L (35 ℃), pickle solution concentration are that 0.6mol/L (35 ℃), soak time are 5min.Plating solution consists of: CuSO
45H
2O content is 0.12mol/L, H
2SO
4Content 1.75mol/L, sodium laurylsulfonate and butynediol (mol ratio 2:1) total content 0.5mmol/L, CuCl
2Content is 0.8mmol/L.Current density is 2.0A/cm
2, electrodeposition time is 40s, bath temperature is 23 ℃.All the other conditions and step and embodiment one are consistent.
Porous Cu film thickness 180 ± 8 μ m, aperture 85 ± 6 μ m, porosity 90.3%.
Embodiment five
Cathode substrate is the fine aluminium sheet, and alkaline wash concentration is that 0.7mol/L (10 ℃), pickle solution concentration are that 0.7mol/L (10 ℃), soak time are 9min.Plating solution consists of: CuSO
45H
2O content is 0.2mol/L, H
2SO
4Content 2.0mol/L, sodium lauryl sulphate and butynediol (mol ratio 3:1) total content 3.0mmol/L, CuCl
2Content is 1.0mmol/L.Current density is 1.8A/cm
2, electrodeposition time is 50s, bath temperature is 28 ℃.All the other conditions and step and embodiment one are consistent.
Porous Cu film thickness 300 μ m ± 12 μ m, aperture 200 ± 10 μ m, porosity 84.2%.
Embodiment six
Cathode substrate is copper sheet, and alkaline wash concentration is that 0.9mol/L (15 ℃), pickle solution concentration are that 0.9mol/L (15 ℃), soak time are 8min.Plating solution consists of: CuSO
45H
2O content is 0.2mol/L, H
2SO
4Content 3.0mol/L, sodium lauryl sulphate and butynediol (mol ratio 1:2) total content 3.0mmol/L, CuCl
2Content is 1.4mmol/L.Current density is 3.0A/cm
2, electrodeposition time is 120s, bath temperature is 26 ℃.All the other conditions and step and embodiment one are consistent.
Porous Cu film thickness 380 ± 15 μ m, aperture 250 ± 15 μ m, porosity 81.4%.
The present invention is by adding combined surfactant, changing that plating solution forms or current density etc., provides that a kind of binding force of cladding material is good, adjustable zone, aperture is large, the uniform Porous Cu membrane preparation method in aperture.The method is safe and reliable, and is low to equipment, material requirements, can be used for scale operation, and the quality of production significantly improves---and not only the aperture is even for prepared Porous Cu film, and the aperture is little and porosity is high.
Claims (9)
1. Porous Cu thin film technology method comprises:
Provide metal base as negative electrode and provide copper sheet as anode;
The preparation electroplate liquid, Cu in described electroplate liquid
2+Content is 0.08～0.2mol/L, H
2SO
4Content is that 1.50～3.00mol/L, tensio-active agent total content are that 0.5～4.0mmol/L, Cl-content are 1.5～3.0mmol/L; And
Utilize described electroplate liquid, described negative electrode and described anode, adopt bubble hydrogen dynamic template electrodip process to form three-dimensional porous copper film on described metal base.
2. the process of claim 1 wherein that described metal base is copper sheet, copper zinc alloy sheet, aluminium flake, titanium sheet or magnalium sheet.
3. the process of claim 1 wherein described metal base before as negative electrode and/or described copper sheet before as anode through corresponding pre-treatment.
4. the method for claim 3, wherein said pre-treatment comprise polishing, deionization washing, alkali cleaning, deionization washing, pickling and deionization washing successively.
5. the method for claim 4, wherein alkali cleaning condition is: washing soln 0.5～1mol/LNa
2CO
3Soak time 5～10min; And 10～35 ℃ of solution temperature scopes; And
Acid washing conditions is: washing soln 0.5～1mol/L HCl; Soak time 5～10min; 10～35 ℃ of solution temperature scopes.
6. the process of claim 1 wherein and electroplate liquid is not taked any stirring measure in electrodeposition process.
7. the method for claim 1, also comprise three-dimensional porous copper film carried out aftertreatment, namely with deionized water, it cleaned 3～5 times, then dries up preservation with protective gas.
8. the process of claim 1 wherein that described tensio-active agent is the combination of any two kinds in sodium lauryl sulphate, sodium laurylsulfonate, butynediol.
9. the process of claim 1 wherein that electrodeposition condition is: time 20～120s; Current density 1.2～3A/cm
2And bath temperature is 25 ± 5 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818503A (en) * | 2015-04-15 | 2015-08-05 | 同济大学 | Preparation method of porous copper full-impregnated film of three-dimensional network structure |
| CN104878417A (en) * | 2015-06-26 | 2015-09-02 | 厦门理工学院 | Electroplate liquid, three-dimensional porous structure zinc film material and manufacturing method of three-dimensional porous structure zinc film material |
| CN104975309A (en) * | 2015-06-12 | 2015-10-14 | 东南大学 | Method for adjusting and controlling hole diameter of open-cell foamy copper |
| CN105538596A (en) * | 2016-01-28 | 2016-05-04 | 深圳市纳明特科技有限公司 | Composite plastic material and preparing 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 |
| CN110629258A (en) * | 2019-10-16 | 2019-12-31 | 东莞领杰金属精密制造科技有限公司 | Preparation method of porous copper liquid absorption core |
| CN111710873A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
| CN112962121A (en) * | 2021-02-02 | 2021-06-15 | 重庆大学 | Preparation of ultra-thick three-dimensional micron porous copper film |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818503A (en) * | 2015-04-15 | 2015-08-05 | 同济大学 | Preparation method of porous copper full-impregnated film of three-dimensional network structure |
| CN104975309A (en) * | 2015-06-12 | 2015-10-14 | 东南大学 | Method for adjusting and controlling hole diameter of open-cell foamy copper |
| CN104975309B (en) * | 2015-06-12 | 2017-07-07 | 东南大学 | A kind of open celled foam copper aperture control method |
| CN104878417A (en) * | 2015-06-26 | 2015-09-02 | 厦门理工学院 | Electroplate liquid, three-dimensional porous structure zinc film material and manufacturing method of three-dimensional porous structure zinc film material |
| CN105538596A (en) * | 2016-01-28 | 2016-05-04 | 深圳市纳明特科技有限公司 | Composite plastic material and preparing 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 |
| CN110629258A (en) * | 2019-10-16 | 2019-12-31 | 东莞领杰金属精密制造科技有限公司 | Preparation method of porous copper liquid absorption core |
| CN111710873A (en) * | 2020-06-23 | 2020-09-25 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
| CN111710873B (en) * | 2020-06-23 | 2021-09-17 | 深圳市德立新材料科技有限公司 | Method for preparing ultrathin lithium battery copper foil through photocatalytic deposition |
| CN112962121A (en) * | 2021-02-02 | 2021-06-15 | 重庆大学 | Preparation of ultra-thick three-dimensional micron porous copper film |
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