CN1807673B - Production method of aluminium foil used in electrolytic capacitor high voltage anode - Google Patents

Production method of aluminium foil used in electrolytic capacitor high voltage anode Download PDF

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CN1807673B
CN1807673B CN 200510120932 CN200510120932A CN1807673B CN 1807673 B CN1807673 B CN 1807673B CN 200510120932 CN200510120932 CN 200510120932 CN 200510120932 A CN200510120932 A CN 200510120932A CN 1807673 B CN1807673 B CN 1807673B
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aluminium foil
annealing
manufacture method
rolling
electrolytic capacitor
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CN1807673A (en
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叶章良
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Ruyuan East Sunshine Ai Xijie fine foil Co., Ltd.
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DONGYANG GUANGJING FOIL Co Ltd RUYUAN
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Abstract

The invention discloses an aluminum foil producing method of electrolytic capacitor high-voltage anode, which comprises the following steps: (A) allocating auxiliary element in high-purity aluminium liquid; (B) ingotting homogenizing annealing and hot-rolled step; (C) cooling reducing step; (D) intermediating annealing step; annealing treatment before extreme end sub-rolling of cold reducing step.The producing cost is lower.

Description

A kind of manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor
Technical field
The present invention relates to a kind of aluminium foil for anode of electrical condenser, more particularly, the invention particularly relates to a kind of manufacture method of aluminium foil for high-voltage anode of electrolytic condenser.
Background technology
Along with the develop rapidly of electronic industry and information industry, electric equipment products and information technological equipment are constantly to high-performance, miniaturization, integrated development, and aluminium electrolutic capacitor is a requisite element in modern electric equipment products and the information technological equipment.To a great extent, the capacitance per unit volume amount of aluminium electrolutic capacitor depends on the ratio electric capacity of anode foils electrode wherein to a great extent.In order to adapt to the needs of electrolytic condenser miniaturization, improve the ratio electric capacity of anode foils electrode, be the important technique measure that adapts to electrolytic condenser and even whole electrical equipment miniaturization development.According to parallel plate capacitor capacitance equation C=ε S/d as can be known, condenser capacity C is directly proportional with the surface-area S and the DIELECTRIC CONSTANT of electrode, and is inversely proportional to the electroplax spacing.Therefore, under the situation that material is determined, DIELECTRIC CONSTANT is determined thereupon, and interelectrode distance d is unsuitable too small, otherwise can make capacitor breakdown.At this moment want to improve electrical capacity, enlarge electrode surface area and just become principal element.And the cubic texture of allocating suitable Chemical Composition and improving aluminum foil for electrolytic capacitor anode is the surface-area that enlarges electrode, and then improves the important channel of anode foils than electric capacity.
In this regard, it is the production technique that 01131402 Chinese patent file discloses a kind of aluminium foil for high-voltage anode of electrolytic capacitor that the patent No. is arranged, it consists essentially of (1) founding step, (2) ingot casting preheating, homogenizing and high temperature hot-rolled step, (3) cold rolling and paper tinsel rolls step, and (4) vacuum heat treatment step, so that aluminium foil surface is produced thin oxide film and make processing texture change cubic texture into, claim aluminium foil for high-voltage anode of electrolytic capacitor cubic texture occupation rate that this method makes more than 95%, changing into back electric capacity is 1.0~1.05 μ F/cm 2(375V f), cubic texture and be not very high than electric capacity.In addition, application number is to disclose a kind of aluminium foil and manufacture method that is used for electrolytic condenser in 00105387 the patent of invention, its manufacture method is by adding the part trace element, increase aluminium foil corrosion and send out hole density, utilize four annealing simultaneously, improve cubic texture, technology is comparatively complicated, it is higher to consume energy, and production cost is higher.Publication number is the manufacture method that the Japanese patent application file of 2002-173748 discloses a kind of high purity aluminium foil, needs through secondary process annealing in its cold-rolled process, and production cost is higher.
Summary of the invention
The technical purpose that the present invention will reach be to provide that a kind of production cost is lower, the manufacture method of cubic texture and the aluminium foil for high-voltage anode of electrolytic capacitor higher than electric capacity.
For this reason, technical solution of the present invention is a kind of manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor, this manufacture method comprises the steps: (A) founding step: suitably allocate auxiliary element in rafifinal liquid, making aluminium liquid reach following weight forms, Fe:0.0005%~0.0018%, Si:0.0005%~0.003%, Cu:0.003%~0.007%, Mg:0.002%~0.003%, Al: 〉=99.98%, other single impurity element :≤0.001%, fast cooling shaping is an ingot casting then; (B) ingot homogenization annealing and hot-rolled step: the moulding ingot casting is carried out homogenizing annealing 580 ℃~620 ℃ temperature ranges handle 5 hours~30 hours metal heat preservation time; Carry out the hot rolling open rolling 480 ℃~560 ℃ temperature then, temperature of hot-rolled end is controlled at 270 ℃~360 ℃, and hot rolling pass is 13~21 roads, makes the coils of hot rolled that thickness is 5mm~14mm; (C) cold rolling step:, roll into hard attitude aluminium foil with coils of hot rolled cold rolling through 7~10 passages; (D) process annealing step: before the extreme trace of described cold rolling step is time rolling, carry out anneal one time; In the described steps A, described ingot casting is of a size of: wide 1020mm~1100mm, thick 500mm~600mm, long 2500mm~6000mm.
It is as follows further to optimize technological measure of the present invention: if Fe content was at 0.0009%~0.0018% o'clock in the aluminium liquid after the allotment, the weight percent content of preferred Si is higher by 0.00005%~0.0015% than the weight percent content of Fe; The ingot casting specification is preferably: wide 1020mm~1100mm, thick 280mm~600mm, long 2500mm~6000mm; The hot rolling start rolling temperature is preferably 510 ℃~550 ℃, and temperature of hot-rolled end is preferably 270 ℃~320 ℃; Coils of hot rolled thickness is preferably 5mm~7mm; Hot rolling pass is preferably 15~19 roads; The holding temperature of process annealing is preferably 210 ℃~270 ℃, and preferred 1 hour~4 hours of metal heat preservation time, annealing atmosphere is preferably air annealing, protection of inert gas annealing or vacuum annealing; The machining deformation rate was preferably 18%~35% when extreme trace was time rolling; Described manufacture method further comprises makes anneal to the hard attitude aluminium foil after cold rolling, and this hard attitude aluminium foil annealing is at vacuum or Ar or N 2Carry out in the gas, the annealing holding temperature is 480 ℃~550 ℃; Steps A comprises that aluminium liquid stirs, and preferably adopts electromagnetic agitation method to finish; Manufacture method of the present invention further comprises the cleaning step after the hard attitude aluminum foil finished product rolling pass, clean to adopt temperature more than or equal to 70 ℃ neutral cleaners water for example.
As is generally known, high-pressure aluminium foil belongs to the electric aluminum foil category, this is a kind of material that is corroded of working under polarity condition, the electric aluminum foil of different voltage ranges requires to have the different types that is corroded, wherein the high-voltage anode paper tinsel is generally post hole tunnel-like corrosion structure, because need high voltage bearing thicker oxide film relatively when under high pressure working, but this thick oxide film can not stop up the corrosion hole that produces when corrosion is produced again, otherwise can cause than electric capacity and descend.Should possess thicker oxide film and bigger these two conditions of ratio electric capacity for satisfying the high-voltage anode paper tinsel simultaneously, tunnel-like corrosion in post hole is best selection.Therefore, the aluminum foil material characteristics that should possess comprise: (1) corrosion core; (2) corrosion passage.The corrosion core is to guarantee the local micropore corrosive of material production prerequisite, be to enlarge aluminium foil surface to amass, and then improve the important measures of anode foils than electric capacity, and the corrosion core, i.e. it is main relevant with the existing way of Chemical Composition proportioning and each impurity element that hole density is sent out in corrosion.The corrosion passage then supplies corrosive medium to internal diffusion, and corrosion process is carried out smoothly.The high-voltage anode paper tinsel generally adopts the anodic etching method both at home and abroad, since 100} face<001〉and the orientation Young's modulus very little, intensity is minimum, so under galvanic effect corrosion just along 100} face<001〉the preferential corrosion expansion of orientation, form square pit, and square aperture useful area maximum helps enlarging the surface-area of aluminium foil, thereby improves the ratio electric capacity of anode foils.And the development degree of cube texture is influenced by technological factors such as aluminium foil purity, hot rolling parameter, cold rolling parameter, annealing mainly.
And manufacture method principal feature of the present invention is: suitably allocate the Chemical Composition of aluminium liquid, ingot casting, homogenizing annealing and hot rolling, cold rolling then before the last cold rolling pass is rolling, carried out a process annealing, makes high-voltage anode with hard attitude aluminium foil.Its mechanism is: distinctive prescription and manufacturing process make and generate suitable corrosion core on the aluminium foil, simultaneously can increase { 100} face cubic texture content, make later corrosion process can produce suitable corrosion hole with vertical paper tinsel face { the 100} direction produces various corrusion tunnels, improve the surface-area of aluminium foil, and then improve anode foils and compare electric capacity; And in cold rolling, the present invention's control makes draught per pass unlikely too big, to prevent the regressive generation of tissue motion attitude, guarantees that rolling deformation is more even, more efficient, and rolling texture is evenly distributed, the homogeneity of cubic texture behind the enhancing finished products.Because in cold rolling step, under the big cold deformation condition, the cubic texture in the aluminium foil destroys to some extent, the process annealing step specially is set to regain more substantial cubic texture core again, and the cubic texture that forms when making the finished products recrystallize occupies absolute predominance.Experiment showed, the aluminium foil that the technological measures such as rolling step of characteristic of the present invention make, its cubic texture reaches more than 98%, and the ratio electric capacity after corrosion changes into reaches 1.05~1.3 μ F/cm 2(375V f).
In the steps A of the present invention, the mass percent of described deployed aluminium liquid is controlled to be: Fe:0.0005%~0.0018%, Si:0.0005%~0.003%, Cu:0.003%~0.007%, Mg:0.002%~0.003%, Al: 〉=99.98%, other single impurity element :≤0.001%, hinder the formation of cubic texture if Fe content is higher than this scope, and easily separate out thick compound, reduce the ratio electric capacity of anode foils and the leakage current of increase anode foils; Fe content is lower than this scope, cold rolling processing difficulties, and production cost height; Si content is higher than this scope then can be influenced the formation of cubic texture and change into the time, is lower than this scope and then is unfavorable for production control; Cu is the most effective corrosion core in the high blocking, if but its content is higher than this scope, can be interconnected to form big corrosion pit owing to the density of corrosion pit is too high, reduce electrical capacity, and high in addition Cu content also can increase the leakage current of anode foils; Cu content is lower than this scope, and the corrosion core of paper tinsel is few, and corrosive effect is poor, and is lower than electric capacity; Mg content is sometimes because the relation of raw material is inevitable sometimes, and being higher than this scope then influences intensity after aluminium foil corrosion changes into, is lower than this scope and then is not easy to production control; Other foreign matter content is higher than this scope, and then quality product is not easy to control as not higher than electric capacity etc.; When Fe content is 0.0009%~0.0018%, the weight percent content of preferred Si is higher by 0.00005%~0.00015% than the weight percent content of Fe, helps eliminating the disadvantageous effect of high ferro, improves cubic texture and compares electric capacity, reduce the aluminium foil purity requirement, reduce production costs.
For the bonding apparatus particular case realizes efficient suitability for industrialized production, reduce production costs to greatest extent, the present invention is in described steps A, and described ingot casting specification is preferably: wide 1020mm~1100mm, thick 500mm~600mm, long 2500mm~6000mm; Described aluminium liquid preferably adopts induction stirring, helps making aluminium liquid more even, makes produced aluminium foil horizontal and vertical more even than electric capacity after corroding, and is better with a collection of aluminium foil consistence.
Among the step B of the present invention, the homogenizing holding temperature is selected 580 ℃~620 ℃ in the described homogenizing operation, the metal heat preservation time selects 5 hours~and 30 hours, help guaranteeing the abundant solid solution of iron, eliminate the segregation of iron, composition is even everywhere to make ingot casting, homogenization temperature is higher than this scope, and the ingot casting surface can produce high temperature oxidation, influences quality product, homogenization temperature is lower than this scope or the too short effect that does not then reach homogenization of composition of soaking time, soaking time surpasses this scope, and then production efficiency is low, and energy consumption is big, production cost is higher, and is uneconomical.Described hot rolling start rolling temperature control is selected 480 ℃~560 ℃, temperature of hot-rolled end selects 270 ℃~350 ℃, help forming high cubic texture, general start rolling temperature height, finishing temperature is also high, and start rolling temperature is not less than 480 ℃, helping finishing temperature reaches easily and is not less than 270 ℃, and help separating out the compound of the Fe that size is big, quantity is few, recrystallize core when the compound of this size helps becoming annealing promotes the formation of aluminium foil cubic texture; Finishing temperature is not less than 270 ℃, the preceding hot rolled coil of expecting to cool down is had than adequate time carry out recrystallize, increase cubic texture content, the contained cubic texture of hot rolled coil is many more, and the cold rolling cubic texture that remains is also many, forms high cubic texture when helping finished products, and if finishing temperature is lower than 270 ℃, then hot rolling speed of cooling is too fast, is unfavorable for separating out of compounds such as Fe, is unfavorable for the formation of cubic texture; The hot rolling start rolling temperature preferably is controlled at 510 ℃~550 ℃, and temperature of hot-rolled end preferably is controlled at 270 ℃~320 ℃, and is favourable to the raising of aluminium foil cubic texture, can reduce simultaneously the generation of situations such as sticking aluminium or crystal grain is thick.Coils of hot rolled thickness selects 5mm~14mm, and coils of hot rolled then is not easy control during hot rolling if thickness is lower than 5mm, to the equipment requirements height, coils of hot rolled thickness is higher than 14mm, and rolling pass increases when then cold rolling, and production cost is raise, preferred 5mm~the 7mm of coils of hot rolled thickness, the coils of hot rolled thin thickness can reduce the rolling pass when cold rolling, and production efficiency is improved, production cost is lower, improves cubic texture.Hot rolling pass selects 13~21 roads, and hot rolling pass then is unfavorable for the control of finishing temperature not in this scope, and to the equipment requirements height, production control is convenient in preferred 15~19 roads of hot rolling pass.
Among the described step C, described cold rolling passage is selected 7~10 passages, and then production efficiency is low more than this scope for cold rolling pass, and then reduction in pass is too big to be lower than this scope, easily makes rolling deformation inhomogeneous.
Among the described step D, described process annealing step is carried out preferred 210 ℃~240 ℃ of holding temperature, preferred 1 hour~4 hours of metal heat preservation time before cold rolling extreme trace is time rolling.The process annealing temperature is lower than this scope and is difficult for recrystallize takes place, and does not reach the purpose that increases cubic texture; Annealing temperature be higher than this scope then recrystallize finish substantially, unfavorable to the recrystallization annealing of finished product; Annealing time is higher than this scope, and then efficient is not high, and aluminium foil is too soft, be difficult for follow-up rolling, be lower than this scope then cubic texture decrease; Process annealing atmosphere can adopt air annealing, protection of inert gas annealing or vacuum annealing, and the vacuum tightness general requirement of vacuum annealing is less than or equal to 0.05Pa; The rolling machining deformation rate of described the last passage is preferred 18%~35%, and the machining deformation rate can not make cubic texture decrease in this scope, is lower than this scope, is difficult for rolling.
Manufacture method of the present invention further comprises the annealing of hard attitude aluminium foil, and the hard attitude aluminium foil annealing after cold rolling is at vacuum or Ar 2Or N 2Carry out in the gas, the annealing holding temperature is 480 ℃~550 ℃, if temperature is higher than 550 ℃, can produce sticking paper tinsel, is lower than 480 ℃, and then cubic texture is not high.
Manufacture method of the present invention further comprises the cleaning step after the finished product aluminum foil rolling passage, clean to adopt temperature more than or equal to 70 ℃ water or other neutral cleaners, help washing the residual ROLLING OIL of aluminium foil surface, make the oxide film of aluminium foil surface more even, thereby make aluminium foil corrosion rear surface uniformity, aluminium foil is everywhere than electric capacity uniformity, and deviation is further dwindled.
Outside this, the present invention do not have explanation ingot mill surface, aluminium strip or aluminium foil incidental works such as rewinding, aluminium foil cutting all routinely, can suitably select.
Above-mentioned characteristic manufacture method of the present invention is produced the high blocking of high-quality that obtains, aluminium purity 〉=99.98%, and have following advantage:
1, testing method adopts the metallographic quantitative microscope to measure, and print adopts metallographic pit method to make, and { 100} face cubic texture reaches more than 98% to record aluminium foil;
2, testing method farad bridge method records corrosion and changes into back anode foils electrostatic capacity and reach 1.05~1.3 μ F/cm 2(375V f).
The invention will be further described below in conjunction with specific embodiment.
Embodiment
The embodiment of the invention specifically sees Table 1, table 2 and table 3
The control of embodiment Chemical Composition sees Table 1:
Composition control is learned in the liquefaction of table 1 aluminium
Figure G2005101209320D00051
In the normal process process, Chemical Composition does not change, and the Chemical Composition of ingot casting, aluminium sheet, aluminium strip, aluminium foil is identical with aluminium liquefaction composition.
The control of embodiment process parameters sees Table 2:
Table 2 manufacturing processed and parameter control
Figure G2005101209320D00061
The process numbering of not listing in the table 2: A 1When melting, adopt induction stirring, other same A; A 2After finish to gauge, adopt 80 ℃ water to clean other same A; A 3After finish to gauge, adopt neutral cleaners to clean other same A; A 4When melting, adopt induction stirring, and after finish to gauge, adopt 85 ℃ water to clean other same A.The engineerings such as ingot mill surface, aluminium foil cutting that do not have explanation in the table 2 can be selected all routinely as required.
The aluminium foil that above-mentioned technology is made carries out the measurement after the measurement of cubic texture and corrosion change into processing, the results are shown in Table 3.
Table 3 aluminium foil performance and the performance comparison after corrosion changes into
Figure G2005101209320D00062
Cubic texture in the table 3 adopts the method among the GB/T 3246.1 to measure, and the electrostatic capacity after corrosion changes into adopts the method among the SJ/T 11140 to test, and the electrostatic capacity deviation is calculated by the method among the SJ/T 11140.
By above-mentioned serial embodiment as seen, have the cubic texture height with the aluminium foil for high-voltage anode of electrolytic capacitor of the method for the invention manufacturing, corrosion changes into back electrostatic capacity height, characteristics that the electrostatic capacity deviation is little, and production efficiency is higher, and production cost is lower.

Claims (9)

1. the manufacture method of an aluminium foil for high-voltage anode of electrolytic capacitor, this manufacture method comprises the steps: (A) founding step: allocate auxiliary element in rafifinal liquid, making it reach following weight forms, Fe:0.0005%~0.0018%, Si:0.0005%~0.003%, Cu:0.003%~0.007%, Mg:0.002%~0.003%, Al: 〉=99.98%, other single impurity element :≤0.001%, fast cooling shaping is an ingot casting then; (B) ingot homogenization annealing and hot-rolled step: the moulding ingot casting is carried out homogenizing annealing 580 ℃~620 ℃ temperature ranges handle 5 hours~30 hours metal heat preservation time; Carry out the hot rolling open rolling 480 ℃~560 ℃ temperature ranges then, temperature of hot-rolled end is controlled at 270 ℃~350 ℃, and hot rolling pass is 13~21 roads, makes the coils of hot rolled that thickness is 5mm~14mm; (C) cold rolling step:, roll into hard attitude aluminium foil with coils of hot rolled cold rolling through 7~10 passages; (D) process annealing step: before the extreme trace of described cold rolling step is time rolling, carry out anneal one time; In the described steps A, described ingot casting is of a size of: wide 1020mm~1100mm, thick 500mm~600mm, long 2500mm~6000mm.
2. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1, it is characterized in that: in the described steps A, Fe content is 0.0009%~0.0018% in the aluminium liquid, and the weight percent content of Si is higher by 0.00005%~0.0015% than the weight percent content of Fe.
3. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1 or 2, it is characterized in that: among the described step B, described coils of hot rolled thickness is 5mm~7mm, and hot rolling pass is 15~19 roads.
4. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1 or 2, it is characterized in that: among the described step B, described hot rolling start rolling temperature is 510 ℃~550 ℃, and temperature of hot-rolled end is 270 ℃~320 ℃.
5. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1 or 2; it is characterized in that: among the described step D; the holding temperature of described process annealing is 210~270 ℃; 1 hour~4 hours metal heat preservation time, annealing atmosphere is air annealing, protection of inert gas annealing or vacuum annealing.
6. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1 or 2 is characterized in that: among the described step D, described extreme trace time rolling machining deformation rate is 18%~35%.
7. as the manufacture method of the aluminium foil for high-voltage anode of electrolytic capacitor of claim 1 or 2, it is characterized in that: described manufacture method further comprises makes anneal to the hard attitude aluminium foil after cold rolling, this hard attitude aluminium foil annealing is carried out in vacuum or Ar or N2 gas, and the annealing holding temperature is 480~550 ℃.
8. as the manufacture method of the aluminium foil for high-voltage anode of electrolytic capacitor of claim 1 or 2, it is characterized in that: described steps A comprises that also adopting electromagnetic agitation method to implement aluminium liquid stirs.
9. the manufacture method of aluminium foil for high-voltage anode of electrolytic capacitor as claimed in claim 1 or 2, it is characterized in that: described manufacture method further comprises the cleaning step to hard attitude aluminum foil finished product, cleans and adopts temperature more than or equal to 70 ℃ neutral cleaners.
CN 200510120932 2005-12-17 2005-12-17 Production method of aluminium foil used in electrolytic capacitor high voltage anode Expired - Fee Related CN1807673B (en)

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CN104451481A (en) * 2014-12-19 2015-03-25 内蒙古新长江矿业投资有限公司 Finished product annealing method of high voltage anode aluminum foil for electrolytic capacitor
CN107849671B (en) * 2015-07-30 2019-08-09 昭和电工株式会社 Manufacturing method, the manufacturing method of aluminium electrolutic capacitor electrode material and the manufacturing method of aluminium electrolutic capacitor of ALuminum material for electrode of electrolytic capacitor
CN105908021B (en) * 2016-05-18 2017-08-25 登电集团铝加工有限公司 A kind of capacitor fine aluminium Cathode Foil and its manufacture method
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CN110923528B (en) * 2019-11-27 2022-05-17 新疆众和股份有限公司 Method for manufacturing anode aluminum foil
CN111014295B (en) * 2019-11-27 2020-12-01 新疆众和股份有限公司 Hot rolling production process of aluminum foil for electrolytic capacitor
CN112030017B (en) * 2020-07-22 2022-03-11 乳源瑶族自治县东阳光高纯新材料有限公司 Production method of cast ingot for high-voltage anode aluminum foil
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Address after: Guangdong city of Shaoguan province Ruyuan 512721 Dragon Bay County

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