CN1266311C - Aluminum foil enlarging erosion method using perforating graphite electrode - Google Patents
Aluminum foil enlarging erosion method using perforating graphite electrode Download PDFInfo
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- CN1266311C CN1266311C CN 03135390 CN03135390A CN1266311C CN 1266311 C CN1266311 C CN 1266311C CN 03135390 CN03135390 CN 03135390 CN 03135390 A CN03135390 A CN 03135390A CN 1266311 C CN1266311 C CN 1266311C
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Abstract
The present invention relates to graphite electrodes used for the face expansion corrosion of aluminum foil used for an aluminum electrolytic capacitor and a technology of the graphite electrodes, particularly to a corrosion method in which a through hole graphite combined electrode is used. Through holes arranged in the width direction and the length direction of the graphite combined electrode penetrate through the integral thickness of the graphite electrodes. Aluminum ions and hydrogen which are generated in an aluminum foil corrosion electrolytic tank are emitted out of the through holes on graphite, and solution circulation is promoted. Solutions on both sides of aluminum foil positioned between the graphite electrodes have uniform components. Simultaneously, the graphite combined electrode also effectively improves the current uniformity of the upper part, the lower part, the left side and the right side of the graphite electrodes. Consequently, the corrosion effect is improved; the aluminum foil of the capacitor can obtain higher specific capacitance; the capacitance deviation of the left side, the middle part and the right side of the corrosion aluminum foil is obviously reduced.
Description
Technical background of the present invention
The present invention relates to be used for the Graphite Electrodes and the technology thereof of aluminium electrolutic capacitor aluminium foil face-expanding erosion, particularly be mounted in pairs in the through hole combinatory graphite electrode and the erosion method that corrode in the aluminium foil electrolyzer.
The explanation of prior art
The electrode of aluminium electrolutic capacitor is an aluminium foil, and the electrical capacity of electrical condenser is directly proportional with the real surface of electrode for capacitors is long-pending.The electrical capacity (than electric capacity) of unit surface aluminium foil electrode materials is big more, the electrode materials that the electrical condenser of rated capacity uses is just few more, the volume of electrical condenser is just more little, thereby can dwindle the volume of aluminium electrolutic capacitor, adapts to the miniaturization and the microminiaturization of current electronics.Long-pending for the real surface that increases the electrode aluminium foil, usual method is to corrode aluminium foil to form a large amount of apertures, and expansion is long-pending as the real surface of the aluminium foil of electrode for capacitors, is referred to as face-expanding erosion.
General face-expanding erosion technology is the acid electrolyte that aluminium foil is immersed contain chlorion and additive, and aluminium foil is in two of electrolyzer and powers up between the graphite, applies electric current and aluminium foil is carried out electrochemical etching expand face on the graphite of electrolyzer.At this moment, cathodic reaction produces the pH value rising that hydrogen causes electrolytic solution; Be etched a large amount of aluminum ions of generation as the anodic aluminium foil, cause the aluminum ion accumulation.Owing to the spacing between two Graphite Electrodess that power up is all less, circulation of elecrolyte mass transfer difficulty, so the solution composition that aluminium foil is between the Graphite Electrodes changes a lot, concentration of electrolyte usually departs from the scope of technique initialization, have a strong impact on the ratio electric capacity and the homogeneity thereof that corrode aluminium foil, and cause the electrical capacity of aluminium foil left, center, right to have than large deviation.Simultaneously, because the resistance ratio of Graphite Electrodes is big and the ununiformity of graphite density, cause the distribution of current on the top of Graphite Electrodes and bottom, the left side and the right inhomogeneous, also have a strong impact on the ratio electric capacity and the homogeneity thereof that corrode aluminium foil, and cause the electrical capacity that corrodes the aluminium foil left, center, right to have than large deviation.
China utility model ZL00223665 discloses a kind of aluminium foil erosive combination Graphite Electrodes that is used for, and improves the electric current homogeneity of Graphite Electrodes upper and lower.
China utility model ZL01259960 discloses a kind of aluminium foil erosive Graphite Electrodes that is used for, and solves aluminium foil discontinuous current between two graphite in electrolyzer.
Above-mentioned utility model does not all relate to the circulation and the homogenizing problem of solution between the paired graphite that powers up in the electrolyzer.
Japanese patent laid-open 9-176900 discloses a kind of aluminium foil erosive Graphite Electrodes, metal sheet or wire netting is positioned between two graphite cakes as interlayer constitute electrode, improves the electric current homogeneity of Graphite Electrodes upper and lower.The Japanese Patent spy opens 2002-266100 (openly speciallyying permit communique), discloses a kind of aluminium foil erosive Graphite Electrodes, and metal sheet is positioned over the graphite cake both sides, improves the electric current homogeneity of Graphite Electrodes, and communicating pores is arranged on graphite cake.But the porousness of graphite (when especially on graphite cake communicating pores being arranged) is infiltrated hydrochloric acid in the electrolytic solution or sulfuric acid etc. easily, and the corroding metal plate causes poisonous metal element such as Cu in the electrolytic solution
2+Increase, seriously increased the corrosion certainly of aluminium foil, the ratio electric capacity of aluminium foil and intensity are reduced.In addition, the coefficient of expansion of metal and graphite has than big-difference and also can cause producing the gap between metal and the graphite in the intensification of electrolytic solution is used, and reduces electrical efficiency and reduces the electric current homogeneity, and the ratio electric capacity and the homogeneity of aluminium foil corroded in influence.
Summary of the invention
In order to address the above problem, the objective of the invention is to avoid the weak point of prior art, provide and to obtain more the through hole combinatory graphite electrode and the erosion method thereof of the electrochemical etching of high capacitance and good uniformity, can make in the electrolyzer between the Graphite Electrodes, the bath composition of aluminium foil both sides is evenly distributed, make the distribution of current of Graphite Electrodes even simultaneously, and do not increase the poisonous metal element in the electrolytic solution, effectively improve the electrical capacity that corrodes aluminium foil and reduce the capacitance tolerance that corrodes the aluminium foil left, center, right.
In order to achieve the above object, through hole combinatory graphite electrode of the present invention as shown in Figure 1, the upper parallel of Graphite Electrodes is cut open, insulate with insulating material in its gap, the bottom of Graphite Electrodes connects conducting; The top of Graphite Electrodes connects conducting with metal sheet and metal bolts, constitutes combinatory graphite electrode.Metal sheet and metal bolts are generally with copper or copper alloy made, and when using in the combinatory graphite electrode electrolyzer, metal sheet all is in metal bolts and is connected external power (as Fig. 2) on the electrolytic solution.Width and length direction at whole combinatory graphite electrode all have a plurality of through holes, and through hole runs through the whole thickness of combinatory graphite electrode, constitute the through hole combinatory graphite electrode.
As shown in Figure 2, the through hole combinatory graphite electrode is installed in parallel in the electrolyzer that is used for corroding aluminium foil in couples, and capacitor aluminium foil passes through between each is to the through hole combinatory graphite electrode.Each piece through hole combinatory graphite electrode towards the graphite of aluminium foil as working electrode, the graphite of another side is as the electrode of additional conductive, improved the electric current homogeneity on combinatory graphite electrode upper and lower, the left side and the right, made and corrode high ratio electric capacity and the homogeneity of aluminium foil acquisition.
The width of combinatory graphite electrode as shown in Figure 1 and length direction all have through hole, and through hole runs through the whole thickness of combinatory graphite electrode, and establishing through-hole diameter is d, and the thickness of graphite is D.Hydrogen that electrolyzer as shown in Figure 2 produces when the electrolytic attack aluminium foil and aluminum ion pass this through hole and from each the through hole combinatory graphite electrode are outwards overflowed, promoted between the graphite, the solution circulated of aluminium foil both sides, aluminum ions accumulation when having reduced electrolysis has guaranteed pH condition, chlorion and aluminium ion concentration that aluminium foil well corrodes to be needed.Corrode high ratio electric capacity and the homogeneity of aluminium foil acquisition thereby make.
The diameter d of through hole equals the 10%～100% better of graphite thickness D on the graphite, and promptly d=D * (10%～100%) is better.If through-hole diameter d is less than D * 10%, hydrogen that electrolytic attack produces and aluminum ion are difficult to pass through hole outwards overflows from graphite, stops solution circulated, reduces erosion effect; If through-hole diameter d greater than D * 100%, outwards overflows from graphite though hydrogen and aluminum ion pass through hole easily, it is inhomogeneous to cause the current density of graphite surface to present, and also can reduce erosion effect.
The axial area S1 that delegation's through hole number n on the graphite width and this hole of working are occupied on the Graphite Electrodes cross section is relevant with the ratio S1/S of Graphite Electrodes cross-sectional area S.As shown in Figure 1, the width of establishing Graphite Electrodes is that H, Graphite Electrodes cross-sectional area are S, and S=H * D is then arranged, again because the long-pending S1=n * d of the axial cross section that through hole occupies on the graphite cross section * D then has: S1/S=nd/H.
Obtain thus, the delegation's through hole number n on the graphite width=(S1/S) * (H/d) (round up and get positive integer), n through hole evenly arranged on the width of combinatory graphite electrode and is delegation.
At this moment, the uniform distance of center circle that is arranged as the through hole of delegation of graphite width is h, h=(H-nd)/(n+1).
Ratio S1/S is better 25～60%.If S1/S is less than 25%, then the number of through hole diameter less or through hole is less, and it is less from the outside amount of overflowing of graphite that hydrogen that electrolysis produces and aluminum ion pass through hole, is difficult to satisfy the good circulation of solution, reduces erosion effect; If S1/S is greater than 60%, then the number of through hole diameter more or through hole is bigger, outwards overflows from graphite though hydrogen and aluminum ion pass through hole easily, and solution circulated is good, and the current density of graphite surface presents inhomogeneous, reduces erosion effect.
Through hole on the graphite length L direction, corresponding to uniform n the through hole that is arranged as delegation on the graphite width, evenly arranging on the whole length L direction of graphite according to above-mentioned through hole distance of center circle h is that n arranges.
Through hole axially can be parallel with the Graphite Electrodes thickness direction or certain angle arranged.
The present invention has significantly improved the electric current homogeneity of circulation, homogeneity and the Graphite Electrodes of electrolytic solution between the Graphite Electrodes, improves the ratio electric capacity of erosion aluminium foil and the homogeneity of capacitance profile.
Another object of the present invention is not introduce other metal in electrolyzer, and equipment is simple, does not pollute electrolytic solution simultaneously, does not increase the corrosion certainly of aluminium foil.
The electrochemistry face-expanding erosion of mesohigh aluminium foil, cathode aluminum foil and low-voltage aluminium foil that the suitable aluminium electrolutic capacitor of the present invention is used, the multiple erosion technology that is fit to alternating-current, direct current and AC-to-DC combination is fit to contain the erosion electrolytic solution that chlorion, hydrochloric acid and additive thereof such as sulfuric acid, phosphoric acid, oxalic acid, nitric acid, chromic acid are formed.
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Description of drawings
The synoptic diagram and the nomenclature thereof of Fig. 1 through hole combinatory graphite electrode.
Fig. 2 adopts the aluminium foil of through hole combinatory graphite electrode to corrode the synoptic diagram of electrolyzer.
Among the figure: 1, Graphite Electrodes, 2, through hole, 3, metal sheet, 4, metal bolts,
5, insulation layer, 6, aluminium foil, 7, conductive rollers, 8, electrolyzer,
Embodiment
Embodiment 1: the through hole combinatory graphite electrode that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.Through-hole diameter d=D * 10%=50 * 10%=5mm, ratio S1/S gets 25%, the through hole number n of width=(S1/S) * (H/d)=30.
Embodiment 2: the through hole combinatory graphite electrode that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.Through-hole diameter d=D * 100%=50 * 100%=50mm, ratio S1/S gets 25%, the through hole number n of width=(S1/S) * (H/d)=3.
Embodiment 3: the through hole combinatory graphite electrode that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.Through-hole diameter d=D * 100%=50 * 100%=50mm, ratio S1/S gets 60%, the through hole number n of width=(S1/S) * (H/d)=7.
Embodiment 4: the through hole combinatory graphite electrode that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.Through-hole diameter d=D * 10%=50 * 10%=5mm, ratio S1/S gets 60%, width through hole number n=(S1/S) * (H/d)=72.
Embodiment 5: the through hole combinatory graphite electrode that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.Through-hole diameter d=D * 50%=50 * 50%=25mm, ratio S1/S gets 40%, the through hole number n of width=(S1/S) * (H/d)=10.
Conventional graphite compares: the Graphite Electrodes that aluminium foil corrodes the electrolyzer employing is of a size of L * H * D (length x width x thickness), 1500 * 600 * 50 millimeters.
Apply dc etching: as shown in Figure 2, above-mentioned through hole combinatory graphite electrode is mounted in pairs in the electrolyzer, aluminium foil passes through between the through hole combinatory graphite electrode, eating condition is sodium chloride concentration 10% (wt) at electrolytic solution for the first time, sulfuric acid concentration 95% (wt), 70 ℃ of temperature, direct current current density 200mA/cm
2For the second time eating condition is at concentration of hydrochloric acid 8% (wt), concentration of oxalic acid 0.5% (wt), 65 ℃ of temperature, direct current current density 90mA/cm
2
After aforesaid method erosive aluminium foil cleaned up, under the 200V volts DS with organic acid anodic oxidation (changing into), measure electrical capacity then, calculate the velocity of variation and the capacitance deviation rate that corrodes the aluminium foil left, center, right that corrode the aluminium foil electrical capacity of preparation with conventional graphite, the results are shown in Table 1.
Applying alternating-current corrodes: as shown in Figure 2, above-mentioned through hole combinatory graphite electrode is mounted in pairs in the electrolyzer, aluminium foil passes through between the through hole combinatory graphite electrode, eating condition is when concentration of hydrochloric acid 10% (wt) concentration of nitric acid 0.2% (wt) phosphoric acid concentration 1.0% (wt) for the first time, 35 ℃ of temperature, ac electric current density 120mA/cm
2Corrode at concentration of hydrochloric acid 15% (wt) sulfuric acid concentration 0.5% (wt), 35 ℃ of temperature, ac electric current density 200mA/cm for the second time
2
After aforesaid method erosive aluminium foil cleaned up, under the 20V volts DS,, measure electrical capacity then with organic acid anodic oxidation (changing into), calculate than conventional graphite corrode preparation the aluminium foil electrical capacity velocity of variation and corrode the capacitance deviation rate of aluminium foil left, center, right.The results are shown in Table 1.
Table 1
| Processing method | Dc etching, 200V changes into | Alternating-current corrodes, and 20V changes into | ||
| Rate of change of capacitance % | Capacitance tolerance rate % | Rate of change of capacitance % | Capacitance tolerance rate % | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 conventional graphite | 110 105 108 112 109 100 | 5 7 6 4 5 9 | 110 106 109 116 112 100 | 4 6 5 3 4 10 |
As seen from Table 1, the aluminium foil electrical capacity of prepared of the present invention is significantly increased, and the deviation of electrical capacity has obvious minimizing, and can be fit to dc etching and alternating-current erosion.
Claims (6)
1, a kind of aluminium foil face-expanding erosion method that uses the through hole combinatory graphite electrode is characterized in that:
(1) the Graphite Electrodes upper parallel is cut open, and fill with insulating polymeric material in its gap, the conducting that interconnects of the bottom of Graphite Electrodes; The top that Graphite Electrodes is positioned on the electrolytic solution connects conducting with metal sheet and metal bolts, constituting thickness is the combinatory graphite electrode of S for the D cross-sectional area, in the width H of whole combinatory graphite electrode and length L direction a plurality of distance of center circle being arranged all is the through hole of h, the diameter of through hole is the long-pending S1 of being of d, axial cross section, constitutes the through hole combinatory graphite electrode.
(2) the through hole combinatory graphite electrode is installed in parallel in the electrolyzer that is used for aluminium foil face-expanding erosion in couples, passes to alternating-current or direct current on Graphite Electrodes, aluminium foil between graphite by the time by the electrochemistry face-expanding erosion; Corrode compositions such as electrolytic solution employing chlorion, hydrochloric acid and various additive thereof such as sulfuric acid, phosphoric acid, oxalic acid, nitric acid, chromic acid.
2, the aluminium foil face-expanding erosion method of use through hole combinatory graphite electrode according to claim 1 is characterized in that through hole runs through the whole thickness of combinatory graphite electrode, and the diameter d of through hole equals 10%～100% of graphite thickness D.
3, the aluminium foil face-expanding erosion method of use through hole combinatory graphite electrode according to claim 1 is characterized in that the ratio S1/S of the cross-sectional area S of long-pending S1 of axial cross section that through hole occupies and Graphite Electrodes equals 25～60% on the Graphite Electrodes cross section.
4, the aluminium foil face-expanding erosion method of use through hole combinatory graphite electrode according to claim 1, it is characterized in that the delegation's through hole number n=(S1/S) * (H/d) on the Graphite Electrodes width H direction, n rounds up and gets positive integer, n through hole is in the uniform delegation that is arranged as of graphite width, and distance of center circle is h=(H-nd)/(n+1).
5, the aluminium foil face-expanding erosion method of use through hole combinatory graphite electrode according to claim 1, it is characterized in that the through hole on the graphite length L direction, corresponding to uniform n the through hole that is arranged as delegation on the graphite width, the through hole on the graphite length L direction is evenly arranged on the whole length L direction of graphite according to distance of center circle h and is n row.
6, the aluminium foil face-expanding erosion method of use through hole combinatory graphite electrode according to claim 1, it is characterized in that through hole axially can be parallel with the thickness direction of Graphite Electrodes or certain angle arranged.
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| CN 03135390 CN1266311C (en) | 2003-07-11 | 2003-07-11 | Aluminum foil enlarging erosion method using perforating graphite electrode |
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| CN 03135390 CN1266311C (en) | 2003-07-11 | 2003-07-11 | Aluminum foil enlarging erosion method using perforating graphite electrode |
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| CN1266311C true CN1266311C (en) | 2006-07-26 |
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| CN103714974B (en) * | 2013-12-24 | 2016-09-14 | 南通海星电子股份有限公司 | A kind of method preparing aluminum electrolytic capacitor anode material |
| CN103774205A (en) * | 2014-01-06 | 2014-05-07 | 广西贺州市桂东电子科技有限责任公司 | Secondary pure-chemical erosion reaming method for medium-high-voltage anode aluminum-foil |
| CN108251889B (en) * | 2017-12-29 | 2019-08-09 | 广西贺州市桂东电子科技有限责任公司 | A kind of aluminium foil electrolysis powered electrode device |
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