CN102634823B - Preparation method of micro porous iron foil - Google Patents
Preparation method of micro porous iron foil Download PDFInfo
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- CN102634823B CN102634823B CN201210153067.XA CN201210153067A CN102634823B CN 102634823 B CN102634823 B CN 102634823B CN 201210153067 A CN201210153067 A CN 201210153067A CN 102634823 B CN102634823 B CN 102634823B
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Abstract
The invention relates to a preparation method of a micron 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 a micron preparation method for porous metal iron foil, be specifically related to first Means of Electrodeposition and prepare iron foil, then by the preparation technology of anodic corrosion method corrosion pore-forming.
Background technology
Porous metal have structure and function dual nature, therefore can be applicable to multiple fields.As be applied in secondary cell, can, as electrode materials, also can have both collector performance, can effectively save the internal space of battery, significantly improve the capacity of secondary cell.Porous metal still have broad application prospects at Material Fields 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 is prepared porous metal by the metal-powder of variable grain size being carried out form after high pressure one, rely on the hole between particle to form porous, because the combination master between particle is if it were not for leaning on metallic bond, therefore the porous material forming is generally all very crisp, and this has limited the application of this method.Metal electrodeposition method is realizing industrialization aspect foam state nickel porous (being nickel foam), and theoretically, this method can be prepared other porous metal, as porous iron.But because needs are at foam formwork substrates metal, this just requires plating to have good covering power and covering power, especially in preparation micron porous metal.Chen Honghui etc. utilize ultrasonic wave to optimize structure (Chen Honghui, Hao Shengce, the plateau of the foam iron of galvanic deposit acquisition, Zhang Ting. the impact of ultrasonic wave on foam iron construction. electroplate and environmental protection, 2009,29 (03): 15-17), but suitability for industrialized production has difficulties.Wang Ni etc. utilize the bubble hydrogen that negative electrode generates to prepare porous iron (Wang Ni for dynamic template, Hu Wencheng. it is thin that electrochemical method is prepared high-purity porous iron. Chinese invention patent, publication number: CN102330119 A, 2012), pore size is controlled by the size of bubble hydrogen, bubble hydrogen size by adding the tensio-active agent in plating solution to realize; Tensio-active agent can discharge at negative electrode, anode in electrodeposition process, and a part and metal codeposition have reduced the purity of metal, and another part forms baroque organism and affects the formation of bubble hydrogen; This has just caused industrialized difficulty.
Summary of the invention
Because causing industrialization, all technological difficulties there is the problem of difficulty for solving in the micron porous metal iron foil preparation process existing in background technology, the present invention aims to provide the preparation method of a kind of micron of porous iron foil material, first adopt electro-deposition method to obtain iron foil, at the titanium matrix surface deposition iron foil after polished finish, taking iron foil as anode, titanium sheet is negative electrode, controls anodic current density and etching time in same electroplate liquid, makes porous iron foil material.
For achieving the above object, the present invention is by the following technical solutions:
It is titanium sheet that micron porous iron foil material of the present invention adopts body material, carries out galvanic deposit iron foil in electrolytic solution, and the purity of the iron foil of acquisition is more than 99.9 %; In same electrolytic solution, controlling current density, time carries out anodic corrosion to iron foil, thereby obtains a micron porous iron foil.
The method of the present invention's the described porous iron foil material of preparation comprises the following steps: (1), in the electrolytic solution of chloride containing ferrous iron, boric acid, Lanthanum trichloride and calcium chloride, is carried out galvanic deposit and prepared iron foil taking titanium sheet as negative electrode; (2) in same electroplate liquid, the iron foil obtaining is carried out to anodic corrosion.
The technique of the present invention's galvanic deposit iron foil is, 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, preferably 40-60 A/dm
2; Electrolyte temperature 80-105 DEG C, preferably 95-100 DEG C.
The technique 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, preferably 20-30 A/dm
2; Electrolyte temperature 70-100 DEG C, preferably 80-90 DEG C; Etching time is 120-240 s.
Beneficial effect of the present invention is as follows:
1) the porous iron foil material that prepared by the present invention, is made up of 10 microns of following irregular micron holes, 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, and even doubling is not also ruptured.
2) pore size of porous iron foil material of the present invention, hole count density are sparse can realize by the temperature of adjusting anodic current density and etching time and electrolytic solution.
3) when the present invention prepares porous iron foil material, first in inorganic salt electrolytic solution, galvanic deposit obtains different thickness iron foil, then carries out anodic corrosion and on iron foil, forms a micron porous.Each step has ready-made industrial manufacture process to use for reference, as the production of iron foil can be used for reference the production technique of electrolytic copper foil.Therefore this micron of porous iron foil preparation method is easy to suitability for industrialized production.
4) the present invention first adopts electro-deposition method to obtain iron foil, at the titanium matrix surface deposition iron foil after polished finish, control the iron foil that current density and electrodeposition time can obtain different thickness, because the electrolyte system of selecting is all inorganic salt, so it is very high to obtain iron foil purity, utilize atomic absorption spectrophotometer analysis, its purity is all more than 99.9 %; Taking iron foil as anode, titanium sheet is negative electrode, controls anodic current density and etching time in same electroplate liquid, makes porous iron foil material again, and hole is between 1-10 μ m.
Brief description of the 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) the Electronic Speculum figure of 10000 times after iron foil anodic corrosion under condition, its etching time is 150 s; (c) be the Electronic Speculum figure before the corrosion of iron foil; (d) be the XRD spectrum before and after corrosion.
Fig. 4. the photo of the micron porous iron foil of preparing under example 3 conditions.
Fig. 5. at (a) 35 A/dm
2(b) 100 A/dm
2electronic Speculum figure under condition after iron foil anodic corrosion.
Specific embodiments
Below in conjunction with example, the invention will be further described.
Before carrying out galvanic deposit iron foil, titanium matrix is implemented to mechanical polishing, skimming treatment.Electroplate after, wash with water at once (first with tap water again with distillation wash), dry, air-dry, be placed in valve bag for 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 DEG C, cathode current density is 50 A/dm
2, galvanic deposit 300 s; Then regulating the temperature to 85 DEG C of electrolytic solution, is 15 A/dm in anodic current density
2under condition, carry out anodic corrosion, etching time is 150 s.The micron porous iron foil thickness forming is 13 μ m, and as shown in Figure 1, aperture is within the scope of 2-15 μ m, and surface has very coarse microstructure, and useful area, much larger than geometric area, is conducive to the electric discharge of electrode activity, improves the capacity of secondary cell.
Embodiment 2:
On the basis of example 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 within the scope of 2-15 μ m, now thickness reduction to the 7 μ m of micron porous iron foil, Surface Microstructure is similar to Fig. 1 (seeing Fig. 2).
Embodiment 3:
On the basis of example 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 as shown in Fig. 3 a and b, and the number density in hole is about 15000/cm
2, its mesoporous is about 5000/cm in the hole of 2 μ m left and right
2, iron foil thickness is 10 μ m, the microscopic appearance after corrosion is still very coarse.Relatively (Fig. 3 a and c), can think that the corrosion speed ratio crystal of grain boundaries itself wants fast to the SEM picture before and after corrosion, to such an extent as to formation porous.But relatively (Fig. 3 d), can find that change has also occurred the preferred orientation of iron crystal to the XRD spectrum before and after anodic corrosion, shows that the corrosion speed of different crystal faces is also different, may be also the reason that forms porous.The photomacrograph of gained micron porous iron foil as shown in Figure 4, can be seen word below by micron porous iron foil.
Embodiment 4:
On the basis of example 1 and 3, then the current density that improves anodic corrosion is 35 A/dm
2, the time is 150s, and the micron porous iron foil of acquisition is as 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 again anodic corrosion current density to 100 A/dm
2, it is more smooth that microstructure becomes, and hole is also very sparse (sees Fig. 5 b).Show, under high anodic current condition, can open certain leveling effect, be similar to anodic polishing, the corrosion speed in high district is greater than low district, along with etching time extends, shows high district by floating phenomenon.
Embodiment 5:
On the basis of example 1, the current density while improving galvanic deposit iron foil is to 60-100 A/dm
2, iron foil has tension stress and curling phenomenon occurs, and does not therefore carry out anodic corrosion.If be reduced to 10-30 A/dm
2, the coarse grains of the iron foil of gained, the hole after anodic corrosion is also larger, considers that again, under 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 example 3, in the time carrying out anodic corrosion, improve the temperature to 100 DEG C of electrolytic solution, porous iron foil is very thin, can not form complete porous-film.The speed that shows iron foil corrosion has increased, wayward.Therefore should control the temperature of electrolytic solution again between 80-90 DEG C.
Claims (1)
1. a preparation method for micron porous iron foil, adopting body material is titanium sheet, carries out galvanic deposit iron foil in electrolytic solution, controls current density, time iron foil is carried out to anodic corrosion in same electrolytic solution, obtains a micron porous iron foil, it is characterized in that:
Described electrolyte component 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; Galvanic deposit control condition is: current density 40-60 A/dm
2, electrolyte temperature 80-105 DEG C;
Described anodic corrosion control condition of carrying out iron foil in electrolytic solution is: current density 15-100 A/dm
2, electrolyte temperature 80-90 DEG C, etching time 120-240 s.
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| 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 |
| CN113481548B (en) * | 2021-07-12 | 2022-05-10 | 湖南工程学院 | Self-control electrolytic iron foil solution |
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 |
-
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 |
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