CN102634823A - Preparation method of micro porous iron foil - Google Patents
Preparation method of micro porous iron foil Download PDFInfo
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- CN102634823A CN102634823A CN201210153067XA CN201210153067A CN102634823A CN 102634823 A CN102634823 A CN 102634823A CN 201210153067X A CN201210153067X A CN 201210153067XA CN 201210153067 A CN201210153067 A CN 201210153067A CN 102634823 A CN102634823 A CN 102634823A
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Abstract
The invention relates to a preparation method of a porous iron foil. The preparation method comprises the following steps: firstly acquiring an iron foil by an electrodeposition method, wherein a pure iron foil with certain thickness is obtained by controlling the electrodeposition conditions such as plating solution temperature, current density and electrodeposition time, and the iron content of the pure iron foil is greater than 99.9%; and then taking the obtained iron foil as an anode and a titanium sheet as a cathode, and acquiring the porous iron foil material with different apertures and hole densities by controlling the temperature of the solution, current density and anode corrosion time. The apertures of the material is 1-10 mu m, and the hole densities reach more than 10000 per square millimeter. The preparation method of the micro porous iron foil provided by the invention has the characteristics of simplicity in operation, low cast, and easiness for large-scale production; and the prepared micro porous iron foil material can be used in secondary battery (such as lithium iron phosphate type lithium ion battery), as a supporting body or current collector of the anode and cathode materials.
Description
Technical field
The present invention relates to micron preparation method of porous metal iron foil, be specifically related to first Means of Electrodeposition and prepare iron foil, corrode the preparation technology of pore-forming again through the anodic corrosion method.
Background technology
Porous metal have structure and function dual nature, therefore can be applicable to multiple field.As be applied in the secondary cell, can also can have both the collector performance as electrode materials, the internal space of conserve batteries effectively significantly improves the capacity of secondary cell.Porous metal still have broad application prospects in field of materials such as separation, catalysis and sound absorptions.
At present the preparation method of porous iron mainly contain powder metallurgic method, high-temperature sintering process and metal electrodeposition method (Liu Peisheng, Huang Linguo. Preparation methods for porous metal materials. functional materials, 2002,33 (01): 5-11).Powder metallurgic method prepares porous metal through carrying out the metal-powder of variable grain size being integrally formed behind the high pressure; Rely on the hole between the particle to form porous; Because the combination master between the particle is if it were not for leaning on metallic bond; Therefore the porous material that forms is generally all very crisp, and this has limited the application of this method.The metal electrodeposition method is realizing industriallization aspect the foam state nickel porous (being nickel foam), and theoretically, this method can prepare other porous metal, like porous iron.But since need be on the foam template electrodeposit metals, this just requires plating to have good covering power and covering power, especially in preparation micron porous metal.Chen Honghui etc. utilize UW optimize the structure of the foam iron that galvanic deposit obtains (plateau is opened graceful for Chen Honghui, Hao Shengce. UW is to the influence of foam iron construction. electroplate and environmental protection, 2009,29 (03): 15-17), but suitability for industrialized production has difficulties.The bubble hydrogen that Wang Ni etc. utilize negative electrode to generate prepares porous iron (Wang Ni for dynamic template; Hu Wencheng. the high-purity porous iron of electrochemical production is thin. Chinese invention patent; Publication number: CN102330119 A; 2012), pore size is by the control of the size of bubble hydrogen, bubble hydrogen size realize by the tensio-active agent that adds in the plating bath; Tensio-active agent can discharge in electrodeposition process at negative electrode, anode, and a part and metal codeposition have reduced the purity of metal, and another part forms baroque organism and influences the formation of bubble hydrogen; This has just caused industrialized difficulty.
Summary of the invention
For preparing in the process, a micron porous metal iron foil that exists in the solution background technology has the problem of difficulty owing to all technological difficulties cause industriallization; The present invention aims to provide the preparation method of a kind of micron porous iron foil material, adopts electro-deposition method to obtain iron foil earlier, at the deposition of the titanium matrix surface after polished finish iron foil; With the iron foil is anode; The titanium sheet is a negative electrode, and control anodic current density and etching time make the porous iron foil material in same electroplate liquid.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
It is the titanium sheet that micron porous iron foil material of the present invention adopts body material, in electrolytic solution, carries out the galvanic deposit iron foil, and the purity of the iron foil of acquisition is more than 99.9 %; Control current density, time are carried out anodic corrosion to iron foil in same electrolytic solution, thereby obtain a micron porous iron foil.
The method of the said porous iron foil material of the present invention's preparation may further comprise the steps: (1) is containing that chlorination is ferrous, in the electrolytic solution of boric acid, Lanthanum trichloride and calcium chloride, is being that negative electrode carries out the prepared by electrodeposition iron foil with the titanium sheet; (2) in same electroplate liquid, the iron foil that obtains is carried out anodic corrosion.
The technology of the present invention's galvanic deposit iron foil is that the electroplate liquid concentration of component is iron protochloride 300-700 g/L, boric acid 5-30 g/L, Lanthanum trichloride 1-40 g/L and calcium chloride 50-200 g/L; Electrodeposition technology is: current density 10-100 A/dm
2, preferred 40-60 A/dm
2Electrolyte temperature 80-105 ℃, preferred 95-100 ℃.
The technology of the present invention's anodic corrosion iron is in above-mentioned electrolytic solution, to carry out the anodic corrosion of iron foil, current density 15-100 A/dm
2, preferred 20-30 A/dm
2Electrolyte temperature 70-100 ℃, preferred 80-90 ℃; Etching time is 120-240 s.
Beneficial effect of the present invention is following:
1) the porous iron foil material of the present invention's preparation is made up of the hole of irregular micron below 10 microns, and the number density in micron hole can be individual more than 10000 up to every square millimeter.Micron porous iron foil has good toughness, even doubling is not ruptured yet.
2) pore size of porous iron foil material of the present invention, hole count density are sparse can realize through the temperature of adjustment anodic current density and etching time and electrolytic solution.
When 3) the present invention prepared the porous iron foil material, galvanic deposit obtained the different thickness iron foil in inorganic salt electrolytic solution earlier, carried out anodic corrosion again and on iron foil, formed the micron porous.Each step all has ready-made industrial manufacture process to use for reference, and can use for reference the production technique of electrolytic copper foil like the production of iron foil.Therefore this micron porous iron foil preparation method is easy to suitability for industrialized production.
4) the present invention adopts electro-deposition method to obtain iron foil earlier; At the deposition of the titanium matrix surface after polished finish iron foil; Control current density and electrodeposition time can obtain the iron foil of different thickness, because the electrolyte system of selecting all is inorganic salt, so it is very high to obtain iron foil purity; Utilize atomic analysis, its purity is all more than 99.9 %; Be anode again with the iron foil, the titanium sheet is a negative electrode, and control anodic current density and etching time make the porous iron foil material in same electroplate liquid, and hole is between 1-10 μ m.
Description of drawings
Fig. 1 is at 15 A/dm
2Etching time is 150 s.(a) 1000 times, (b) the Electronic Speculum figure of iron foil anodic corrosion under 10000 times of conditions.
Fig. 2. at 15 A/dm
2Etching time is 210 s.(a) 1000 times, (b) the Electronic Speculum figure of iron foil anodic corrosion under 10000 times of conditions.
Fig. 3. at 25 A/dm
2(a) 1000 times and (b) 10000 times Electronic Speculum figure after the iron foil anodic corrosion under the condition, its etching time is 150 s; (c) be the preceding Electronic Speculum figure of corrosion of iron foil; (d) be the spectrum of the XRD before and after the corrosion.
Fig. 4. the photo of the micron porous iron foil for preparing under instance 3 conditions.
Fig. 5. at (a) 35 A/dm
2(b) 100 A/dm
2Electronic Speculum figure under the condition after the iron foil anodic corrosion.
Specific embodiments
Below in conjunction with instance the present invention is described further.
Before carrying out the galvanic deposit iron foil, the titanium matrix is implemented mechanical polishing, skimming treatment.After electroplating, at once with washing (washing with distilling again with tap water earlier), dry, air-dry, be placed in the valve bag subsequent use.
Embodiment 1:
Galvanic deposit iron foil in the electrolytic solution of iron protochloride 600 g/L, boric acid 14 g/L, Lanthanum trichloride 35 g/L and calcium chloride 105 g/L, electrolysis temperature is 100 ℃, cathode current density is 50 A/dm
2, galvanic deposit 300 s; Regulating the temperature to 85 ℃ of electrolytic solution then, is 15 A/dm in anodic current density
2Carry out anodic corrosion under the condition, etching time is 150 s.The micron porous iron foil thickness that forms is 13 μ m, and as shown in Figure 1, the aperture is in the 2-15 mu m range, and the surface has very coarse microstructure, and useful area helps the discharge of electrode activity much larger than geometric area, improves the capacity of secondary cell.
Embodiment 2:
On the basis of instance 1; Increase anodic corrosion time to 210 s, the hole count density of the micron porous iron foil of acquisition increases, and pore size is also in the 2-15 mu m range; This moment, the thickness of micron porous iron foil was reduced to 7 μ m, and Surface Microstructure is similar to Fig. 1 (seeing Fig. 2).
Embodiment 3:
On the basis of instance 1, the current density that changes anodic corrosion is 25 A/dm
2, the time is 150 s, and the micron porous iron foil of acquisition is shown in Fig. 3 a and b, and the number density in hole is about 15000/cm
2, wherein the hole of aperture about 2 μ m is about 5000/cm
2, iron foil thickness is 10 μ m, the microscopic appearance after the corrosion is still very coarse.Relatively the SEM picture (Fig. 3 a and c) before and after the corrosion can think that the corrosion speed ratio crystal at crystal boundary place itself wants fast, to such an extent as to form porous.Yet relatively the XRD spectrum (Fig. 3 d) before and after the anodic corrosion can find that change has also taken place iron crystalline preferred orientation, shows that the corrosion speed of different crystal faces is also different, also possibly be to form the porous reason.The photomacrograph of gained micron porous iron foil is as shown in Figure 4, can see following literal through micron porous iron foil.
Embodiment 4:
On the basis of instance 1 and 3, the current density that improves anodic corrosion again is 35 A/dm
2, the time is 150s, and the micron porous iron foil of acquisition is shown in Fig. 5 a, and the number density in hole significantly tails off, but the thickness of porous iron foil increases, and is 15 μ m, and it is comparatively smooth that microstructure becomes.If improve the anodic corrosion current density to 100 A/dm again
2, it is more smooth that microstructure becomes, hole also very sparse (seeing Fig. 5 b).Be illustrated under the high anodic current condition, can open certain leveling effect, be similar to anodic polishing, the corrosion speed in high district along with etching time prolongs, shows high district by floating phenomenon greater than low district.
Embodiment 5:
On the basis of instance 1, the current density when improving the galvanic deposit iron foil is to 60-100 A/dm
2, iron foil has tension stress and the phenomenon that takes place to curl, and does not therefore carry out anodic corrosion.If be reduced to 10-30 A/dm
2, the crystal grain of the iron foil of gained is thick, and the hole after the anodic corrosion is also bigger, considers that again under the low current density, sedimentation velocity is lower, and production efficiency is just low, so we think that the current density of galvanic deposit iron foil is 40-60 A/dm
2Be advisable.
Embodiment 6:
On the basis of instance 3, when carrying out anodic corrosion, improve the temperature to 100 ℃ of electrolytic solution, the porous iron foil is extremely thin, can not form complete porous-film.Show that iron foil corrosive speed has increased, wayward.Therefore the temperature that should control electrolytic solution is again between 80-90 ℃.
Claims (7)
1. the preparation method of a micron porous iron foil is characterized in that: galvanic deposit obtains iron foil in chloride electrolyte earlier; Iron foil with gained is an anode again, in this electrolytic solution, carries out anodic corrosion, control anodic corrosion electric current and the time, can obtain a micron porous iron foil, and its aperture is in 1-10 mu m range, and hole count density is every square millimeter more than 10000.
2. according to the preparation method of said micron porous iron foil of claim 1, it is characterized in that said chloride electrolyte is made up of compounds such as iron protochloride, boric acid, Lanthanum trichloride and calcium chloride; Its concentration is: iron protochloride 300-700 g/L, boric acid 5-30 g/L, Lanthanum trichloride 1-40 g/L and calcium chloride 50-200 g/L.
3. according to the preparation method of claim 1 or 2 said porous iron foil material, it is characterized in that the electro-deposition process parameter of said preparation iron foil is: current density 10-100 A/dm
2, preferred 40-60 A/dm
2Electrolyte temperature 90-105 ℃.
4. according to the preparation method of claim 1 or 2 said porous iron foil material, it is characterized in that the electrolyte temperature of electrodeposition technology is 95-100 ℃.
5. according to the preparation method of claim 1 or 2 said porous iron foil material, it is characterized in that the processing parameter of anodic corrosion iron foil is: current density 15-100 A/dm
2, electrolyte temperature 70-100 ℃, etching time is 120-240 s, iron foil anodic corrosion and when forming porous, and the two pole tensions phenomenon that can raise, the increment of control voltage can obtain a micron porous iron foil when the 0.1-0.2 V left and right sides.
6. according to the preparation method of the said porous iron foil material of claim 3, it is characterized in that the current density of said anodic corrosion iron foil is 20-30 A/dm
2, electrolyte temperature is 80-90 ℃.
7. according to the preparation method of the said porous iron foil material of claim 4, it is characterized in that the current density of said anodic corrosion iron foil is 20-30 A/dm
2, electrolyte temperature is 80-90 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN110600256A (en) * | 2019-09-12 | 2019-12-20 | 安吉县宏铭磁性器材有限公司 | Preparation method of nano complex phase rare earth permanent magnetic material |
| CN113481548A (en) * | 2021-07-12 | 2021-10-08 | 湖南工程学院 | Self-control electrolytic iron foil solution |
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|---|---|---|---|---|
| CN85102762A (en) * | 1985-04-01 | 1986-08-06 | 大连工学院 | Electrochemical method for producing thermal-conducting elements with porous surfaces |
| CN1066478A (en) * | 1991-05-08 | 1992-11-25 | 中国科学院化工冶金研究所 | Electrolytic formation prepares the method for pure iron foil |
| JP2000200559A (en) * | 1999-01-07 | 2000-07-18 | Sumitomo Metal Mining Co Ltd | Aperture grill |
| WO2011021299A1 (en) * | 2009-08-20 | 2011-02-24 | 日新製鋼株式会社 | Dye-sensitized solar cell and method for manufacturing the same |
| CN102330119A (en) * | 2011-10-12 | 2012-01-25 | 电子科技大学 | Method for preparing high-purity porous iron film by adopting electrochemical method |
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2012
- 2012-05-17 CN CN201210153067.XA patent/CN102634823B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102762A (en) * | 1985-04-01 | 1986-08-06 | 大连工学院 | Electrochemical method for producing thermal-conducting elements with porous surfaces |
| CN1066478A (en) * | 1991-05-08 | 1992-11-25 | 中国科学院化工冶金研究所 | Electrolytic formation prepares the method for pure iron foil |
| JP2000200559A (en) * | 1999-01-07 | 2000-07-18 | Sumitomo Metal Mining Co Ltd | Aperture grill |
| WO2011021299A1 (en) * | 2009-08-20 | 2011-02-24 | 日新製鋼株式会社 | Dye-sensitized solar cell and method for manufacturing the same |
| CN102330119A (en) * | 2011-10-12 | 2012-01-25 | 电子科技大学 | Method for preparing high-purity porous iron film by adopting electrochemical method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN103556169B (en) * | 2013-11-15 | 2016-01-20 | 哈尔滨工业大学 | A kind of taraxacum shape tertiary iron phosphate micron ball and method for preparing electrochemical anodic oxidation thereof |
| CN110600256A (en) * | 2019-09-12 | 2019-12-20 | 安吉县宏铭磁性器材有限公司 | Preparation method of nano complex phase rare earth permanent magnetic material |
| CN113481548A (en) * | 2021-07-12 | 2021-10-08 | 湖南工程学院 | Self-control electrolytic iron foil solution |
| CN113481548B (en) * | 2021-07-12 | 2022-05-10 | 湖南工程学院 | Self-control electrolytic iron foil solution |
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