Background technology
Along with the development of electronic product, based on requirement, the medium-high voltage aluminum electrolytic capacitor of components and parts has the feature of heavy body and miniaturization, to meet the development need of electronic product.The anode electrode foil used in medium-high voltage aluminum electrolytic capacitor generally by the method for galvanic corrosion at a large amount of Tunnel-hole of anode high-purity aluminum foil Surface Creation to expand its surface-area, thus raising ratio capacitance, to realize heavy body and the miniaturization object of electrical condenser.In order to ensure that mesohigh anode electrode paper tinsel has required winding performance, the aluminium foil after corrosion also must have certain tensile strength and buckling performance, needs to keep the certain thickness aluminum layer be not corroded in the middle of corrosive aluminum foil for this reason.In addition in order to make the aluminium foil over-all properties optimization after corrosion, in corrosion process, need to improve the homogeneity of aluminium foil surface pit distribution, as far as possible avoid and the generation in hole and hair engaging aperture time reduce aluminium foil surface from corrosion phenomenon.
The technique of mesohigh anode high-purity aluminum foil corrosion mainly comprises: pre-treatment before corrosion, hair engaging aperture process, expanding treatment.During aluminium foil hair engaging aperture, the form in hole and distribution mode determine primarily of the condition of surface of aluminium foil, aluminium foil surface pre-treatment relates to the treating processes of various physics and chemistry, comprises thermal treatment, Roughness Surface on Control, oil removing cleaning, acid, alkaline purification, cathodic polarization process, anodic oxidation treatment, surface oxidation, deposition inert metal etc.At present, the performance improving mesohigh corrosive aluminum foil both at home and abroad is mainly realized by two kinds of approach.The first approach: add the trace elements such as Pb, Sn, In of ppm level in mesohigh aluminium foil, make Pb, Sn, In etc. in aluminium foil micro-in aluminium foil surface generation enrichment by annealing thermal treatment, Pb, Sn, In etc. of these surface enrichments are micro-in the electrolyte forms a large amount of corrosion microbatterys by with aluminum substrate.In anode etching process, these microbatterys that aluminium foil surface exists can improve the homogeneity of aluminium foil corrosion hair engaging aperture, although the homogeneity consequently generating Tunnel-hole improves, but the corrosion thinning of aluminium foil too increases simultaneously, the former makes the ratio capacitance of aluminium foil be improved, and the latter makes the mechanical property of corrosive aluminum foil decline.The second approach: the homogeneity being improved aluminium foil hair engaging aperture by pre-treatment further, even realizes the ordered arrangement of Tunnel-hole, and ratio capacitance is significantly improved, and suppresses the corrosion thinning of aluminium foil simultaneously.
Large quantifier elimination shows, at the sintered metal thin layer that aluminium foil surface sedimentation potential is more positive than aluminium, as Pb, In, Sn, Zn, Fe, Cu etc., make it be attached to aluminium foil surface uniformly, the microbattery that these loose metallic films of deposition and aluminum substrate are formed can improve the homogeneity of aluminium foil hair engaging aperture.But the corrosion certainly of aluminium foil surface can be accelerated simultaneously, cause the thinning (W.Lin of aluminium foil, G.C.Tu, C.F.Lin and Y.M.Peng, The effects of lead impurity on the DC-etching behavior of aluminum for electrolytic capacitor usage, Corrosion Science, Vol.38, No.6, (1996), pp.889-907.) (W.Lin, G.C.Tu, C.F.Lin and Y.M.Peng, The effects of indium impurity on the DC-etching behavior of aluminum for electrolytic capacitor usage, Corrosion Science, Vol.39, No.9, (1997), pp.1531-1543.) in these microbatterys, metallics in the loose metallic film of deposition is negative electrode, aluminum substrate is anode, thereby increase the active site that corrosion occurs aluminium foil surface, reduce the critical potential that pitting occurs, thus the homogeneity of Tunnel-hole hair engaging aperture is significantly improved.But because the area density of the metallics in these loose thin metal layers is very high, a large amount of corrosion microbatterys is defined at aluminium foil surface, its area density is considerably beyond the area density needing hair engaging aperture, thus aluminium foil surface is accelerated from corrosion, cause aluminium foil significantly thinning, both be unfavorable for increasing substantially of ratio capacitance, again reduce the mechanical property obtaining paper tinsel rate and etched foil of aluminium foil.Therefore, in capacitor aluminium foil industry, application is not obtained so far in the mesohigh anode technology of high-purity aluminum foil surface deposition Pb, In, Sn, Zn, Fe, Cu equi-potential calibration thin metal layer.
Chinese patent application 201310302175.5 and 201410004941.2 discloses a kind of method adopting fast electrochemical to deposit deposits disperse tin, zinc nucleus at aluminium foil surface, guides the corrosion hair engaging aperture of aluminium foil, achieves good effect.But owing to also going out the process of nucleus along with at aluminium foil surface by chemical replacement all the time in the process of fast electrochemical deposition nucleus, cause nucleus in the density of aluminium foil surface and the bad control of distribution.And adopt simple rapid chemical deposition nucleus technology, at aluminium foil surface deposit tin, the zinc nucleus of the uniformity that pre-treatment obtains, likely make nucleus be distributed in aluminium foil surface more even, thus promote to obtain even hair engaging aperture during aluminium foil hair engaging aperture.
Due to the metal that aluminium is very active, its surface is very easy to the oxide film generating protectiveness.In order to obtain the Tunnel-hole perpendicular to aluminium foil surface growth, mesohigh anode high-purity aluminum foil must have height, and { 100} plane texture, in order to obtain, higher { 100} texture occupation rate, aluminium foil needs to carry out long-time recrystallization annealing process at 500-600 DEG C.But in this annealing process, the oxide film of aluminium foil surface becomes finer and close, becomes the obstacle of follow-up electrolytic corrosion hair engaging aperture.Therefore, when traditional mesohigh anode high-purity aluminum foil electrolytic corrosion hair engaging aperture, pre-treatment must be carried out by this layer of fine and close oxide film removing, form the formation that the new film containing a large amount of defect is beneficial to Tunnel-hole.When electroless plating tin, zinc nucleus, because the aluminium foil surface through 500-600 DEG C of long term annealing exists fine and close oxide film, therefore tin, zinc nucleus can not be gone out at its surperficial Direct precipitation.Prior art Problems existing is mainly: although the thin metal layer that deposition is loosened effectively can improve the homogeneity of aluminium foil hair engaging aperture, but strongly can accelerate the corrosion certainly of aluminium foil surface, cause the corrosion thinning of aluminium foil, not only bad for the ratio capacitance increasing substantially etched foil, and reduce the mechanical property obtaining paper tinsel rate and etched foil of aluminium foil.
Summary of the invention
The present invention is directed to aluminium foil Problems existing in anode etching of the sintered metal thin layer of surface deposition current potential calibration, a kind of mesohigh anode high-purity aluminum foil surface chemistry is provided to deposit the method for disperse tin, zinc nucleus, aluminium foil can remove the oxide film of the densification on its surface through pre-treatment, and forms new Homogeneous Aqueous film.In the solution when electroless plating tin, zinc nucleus, tin, zine ion by this layer containing moisture film, thus can deposit tin, the zinc nucleus of disperse at aluminium foil surface.
Technical scheme of the present invention is: a kind of mesohigh anode high-purity aluminum foil surface chemistry deposition disperse tin, the method of zinc nucleus, comprising the steps: will after finished product recrystallization annealing process, { 100} plane texture occupation rate is greater than 95% in formation, the Mn that not enrichment electropotential in surface is higher than aluminium, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb element, Al purity is the mesohigh anode high-purity aluminum foil of more than 99.99%, at high purity water, or sodium hydroxide alkaline solution, or in phosphoric acid solution, or carry out pre-treatment in salpeter solution, or electrochemical polishing treatment is carried out in phosphorus acid-sulfur acid solution, or carry out chemical rightenning pre-treatment in phosphorus acid-sulfur acid mixing solutions to remove the oxide film on surface, and form new aqueous film at aluminium foil surface, then in deposit tin, tin in the solution of zinc nucleus, the aqueous film on zine ion aluminium foil surface, the tin of disperse is deposited at aluminium foil surface, zinc nucleus.
Concrete operation step is: the mesohigh anode high-purity aluminum foil after finished product recrystallization annealing process is placed in the high purity water poach 5 ~ 50 seconds that temperature is 60 ~ 100 DEG C; Or to be 15 ~ 70 DEG C of concentration be processes 5 ~ 30 seconds in the sodium hydroxide alkaline solution of 0.5 ~ 1.5 mol/L in temperature; Or 40 ~ 60 DEG C of concentration be in the phosphoric acid solution of 0.1 ~ 1 mol/L process 30 ~ 60 seconds; Or to be 30 ~ 70 DEG C of concentration be processes 10 ~ 40 seconds in the salpeter solution of 0.5 ~ 2 mol/L in temperature; Or temperature be 40 ~ 70 DEG C containing carrying out electropolishing process in 5 ~ 14mol/L phosphoric acid+5 ~ 10 mol/L sulfuric acid+0.1 ~ 1 mol/L glycerol mixing solutions, polishing current density is 30 ~ 120 mA/cm2, and polishing time is 10 ~ 60 seconds; Or temperature be 40 ~ 90 DEG C containing carrying out chemical rightenning process in 10 ~ 20 mol/L phosphoric acid+1 ~ 10mol/L sulfuric acid mixed solutions, polishing time is the oxide film on 10 ~ 120 seconds removing surfaces and is formed new for moisture film.Afterwards, rapid chemical deposit tin, zinc nucleus technology is adopted in the solution of deposit tin, zinc nucleus, tin, the zinc nucleus of disperse is deposited, consisting of of its electroless plating disperse tin nucleus solution: 0.01 ~ 0.5 mol/L sodium stannate+0.02 ~ 0.2 mol/L sodium hydroxide+0.001 ~ 0.01 mol/L Seignette salt at aluminium foil surface; Consisting of of its electroless plating disperse zinc nucleus electrolytic solution: 0.01 ~ 0.3 mol/L zinc oxide+0.1 ~ 0.5 mol/L sodium hydroxide; Electroless plating temperature is 30 ~ 60 DEG C, and the electroless plating time is 5 ~ 30 seconds.
One of gordian technique of the present invention is just through the oxide film of the densification of pre-treatment removing aluminium foil surface, then forms new aqueous film.Afterwards in the process of electroless plating tin, zinc, tin ion or zine ion can pass through this layer of aqueous film, thus aluminium foil surface respectively fast deposition go out tin, zinc nucleus.Its principle and technical superiority as follows:
1. disperse tin, form microbattery between zinc nucleus and aluminium foil, in anode electrolysis process, these microbatterys become the preferential activity site producing Tunnel-hole, the density of hair engaging aperture can be controlled, improve the homogeneity of hair engaging aperture, reduce and the generation in hole, thus can significantly improve the ratio capacitance of corrosive aluminum foil.
2. because disperse tin, the number ratio that forms microbattery between zinc nucleus and aluminium foil deposit the significantly decline of loose thin metal layer, cause except hair engaging aperture position, the microbattery on other surface of aluminium foil is little, therefore except hair engaging aperture position, declining from corrosion thinning amount of other surface of aluminium foil, can significantly improve utilization ratio and the mechanical property of corrosive aluminum foil.
3. when the aluminium foil of employing deposition disperse tin of the present invention, zinc nucleus carries out anode etching, because aluminium foil overwhelming majority surface is rafifinal, thus insensitive to the impurity of etchant solution, can allow in etchant solution containing higher foreign matter content, significant aluminium foil can not be caused from corrosion thinning, reduce the difficulty of aluminium foil corrosion solution Industry Control, the quality of foil industry corrosion products can be improved.
4. the method for deposition disperse tin of the present invention, zinc nucleus as the last treatment technology manufacturing mesohigh anode high-purity aluminum foil, can manufacture novel mesohigh anode high-purity aluminum foil; Also as the pretreatment technology manufacturing mesohigh anode corrosive aluminum foil, high-quality mesohigh anode etched foil can be manufactured.
Embodiment
By the following examples technical scheme of the present invention is further described.
In employing the present invention, surface deposition goes out the tin of disperse, the aluminium foil of zinc nucleus carries out hair engaging aperture corrosion, hair engaging aperture solution is the aluminum ions mixing solutions of 0.8 mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out reaming corrosion again, reaming solution is the salpeter solution of 0.07 mol/L, and temperature is 70 DEG C, aftertreatment is salpeter solution, cleaning, dries, finally carries out 520 V according to industry standard and change into.
Comparative example
Al purity is 99.99%, thickness is 120 μm, { 100} plane texture occupation rate is greater than the high-purity aluminum foil of the surface enrichment micro lead element of 95%, adopt traditional mixing acid pretreatment technology, pretreatment fluid used is 1 mol/L hydrochloric acid+3 mol/L sulfuric acid, temperature is 80 DEG C, is directly soaked 120 seconds by aluminium foil, then carry out above-mentioned hair engaging aperture burn into reaming burn into aftertreatment and 520 V change into process in pretreatment fluid.
Embodiment 1
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in 95 DEG C of boiling water poach 30 seconds, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 2
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in 95 DEG C of boiling water poach 30 seconds, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2 mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 3
Be 99.99% by Al purity, thickness is 110 μm, { the sodium hydroxide alkaline solution process of the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in temperature to be 60 DEG C of concentration be 1 mol/L 15 seconds is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 4
Be 99.99% by Al purity, thickness is 110 μm, { the sodium hydroxide alkaline solution process of the mesohigh high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in temperature to be 60 DEG C of concentration be 1 mol/L 15 seconds is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 5
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in the phosphoric acid solution process 50 seconds that 60 DEG C of concentration are 0.5 mol/L, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 6
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in the phosphoric acid solution process 50 seconds that 60 DEG C of concentration are 0.5 mol/L, formed new for moisture film at aluminium foil surface, above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2 mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 7
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in the oxide film that 60 DEG C of concentration are salpeter solution process 30 seconds removing surfaces of 1 mol/L, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 8
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in the oxide film that 60 DEG C of concentration are salpeter solution process 30 seconds removing surfaces of 1 mol/L, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2 mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 9
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in polishing fluid and carries out electrochemical polishing treatment, and the composition of polishing fluid is: 12 mol/L phosphoric acid+7.6 mol/L sulfuric acid+0.2 mol/L glycerol mixing solutionss; When carrying out polishing, polishing current density is 60mA/cm
2, polishing time is 30 seconds, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 10
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in polishing fluid and carries out electrochemical polishing treatment, and the composition of polishing fluid is: 12 mol/L phosphoric acid+7.6 mol/L sulfuric acid+0.2 mol/L glycerol mixing solutionss; When carrying out polishing, polishing current density is 60mA/cm
2, polishing time is 30 seconds, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2 mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 11
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in polishing fluid and carries out chemical rightenning process, and the composition of polishing fluid is: 15 mol/L phosphoric acid+5 mol/L sulfuric acid mixed solutions; When carrying out polishing, polishing time is 60 seconds, and polish temperature is 60 DEG C, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating tin nucleus, the composition of solution is: 0.2 mol/L sodium stannate+0.1 mol/L sodium hydroxide+0.005 mol/L Seignette salt; Electroless plating temperature is 50 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse tin nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Embodiment 12
Be 99.99% by Al purity, thickness is 110 μm, { the mesohigh anode high-purity aluminum foil higher than aluminium through these electropotentials of finished product recrystallization annealing rear surface not enrichment Mn, Fe, Co, Ni, Cu, Zn, Cd, Ga, Ge, In, Sn, Pb that 100} plane texture occupation rate is greater than 95% is placed in polishing fluid and carries out chemical rightenning process, and the composition of polishing fluid is: 15 mol/L phosphoric acid+5 mol/L sulfuric acid mixed solutions; When carrying out polishing, polishing time is 60 seconds, and polish temperature is 60 DEG C, is formed new for moisture film at aluminium foil surface.Above-mentioned aluminium foil is placed in solution and carries out the process of electroless plating zinc nucleus, the composition of solution is: 0.2 mol/L zinc oxide+0.3 mol/L sodium hydroxide; Electroless plating temperature is 40 DEG C, and the electroless plating time is 20 seconds.
The above-mentioned aluminium foil having obtained disperse zinc nucleus on surface by electroless plating is carried out hair engaging aperture corrosion, hair engaging aperture solution is the mixing solutions of 0.8mol/L hydrochloric acid+3.6 mol/L sulfuric acid+0.8 mol/L, temperature is 75 DEG C, carry out the reaming corrosion identical with comparative example again, aftertreatment and 520 V change into process.
Table 1 be adopt in comparative example and embodiment surface deposition of the present invention go out disperse tin, zinc nucleus aluminium foil at anode etching with after changing into, the corrosion thinning amount of aluminium foil, ratio capacitance and bending times, surface deposition of the present invention is adopted to go out the tin of disperse, the aluminium foil of zinc nucleus as can be seen from Table 1, corrosion thinning reduces 1-3mm, ratio capacitance improves about 5%, and bending times improves about 15%.
The aluminium foil corrosion Reducing thickness of table 1 comparative example and embodiment, ratio capacitance and bending times
Sample |
Corrosion thinning amount |
Ratio capacitance (μ F/cm
2)
|
Bending times |
Comparative example |
5μm |
0.736 |
17 |
Embodiment 1 |
3μm |
0.758 |
21 |
Embodiment 2 |
3μm |
0.760 |
20 |
Embodiment 3 |
4μm |
0.765 |
20 |
Embodiment 4 |
4μm |
0.760 |
21 |
Embodiment 5 |
3μm |
0.763 |
20 |
Embodiment 6 |
3μm |
0.757 |
23 |
Embodiment 7 |
3μm |
0.768 |
23 |
Embodiment 8 |
3μm |
0.753 |
23 |
Embodiment 9 |
2μm |
0.775 |
22 |
Embodiment 10 |
2μm |
0.778 |
21 |
Embodiment 11 |
2μm |
0.796 |
24 |
Embodiment 12 |
2μm |
0.786 |
23 |