CN104711663B - It is a kind of to use seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions - Google Patents

It is a kind of to use seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions Download PDF

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CN104711663B
CN104711663B CN201310727798.5A CN201310727798A CN104711663B CN 104711663 B CN104711663 B CN 104711663B CN 201310727798 A CN201310727798 A CN 201310727798A CN 104711663 B CN104711663 B CN 104711663B
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陈建军
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Jiangsu Rong Sheng Electronics Co Ltd
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Abstract

It is a kind of using seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions, mainly comprise the following steps pre-treatment and once wash the secondary washing Chemical cleanings four times of the washing paper tinsel surface expanding treatment three times washing pure water of the direct current hair engaging aperture treatment paper tinsel surface second direct current hair engaging aperture treatment paper tinsel surface three times in the paper tinsel surface direct current hair engaging aperture treatment paper tinsel surface five times of direct current hair engaging aperture treatment paper tinsel surface four times direct current hair engaging aperture treatment paper tinsel surface six direct current hair engaging aperture treatment paper tinsel surfaces, seven direct current hair engaging aperture treatment and be cleaned and dried.Patent of the present invention by changing the concentration of reaming corrosive liquid and the height of temperature, can effective controlling paper tinsel hole generation and production, the increase of accurate control hole area reaches production Technology requirement, obtains high-quality middle-high voltage electrode foil, improves production efficiency.

Description

It is a kind of to use seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions
Technical field
It is particularly a kind of using seven grades of mesohigh electrodes of different hair engaging aperture conditions the present invention relates to the manufacture method of electrode foil Foil making method.
Background technology
Since reform and opening-up, national economy rapid growth, " scientific and technical innovation, autonomous innovation " has turned into current domestic industry hair The main flow of exhibition, China's electronic industry is developed rapidly, especially the urgency in the machine product such as communication products, computer, household electrical appliances market Play expands, and the development to aluminum electric pole foil industry has play a part of to add fuel to the flames.Simultaneously because the miniaturization of aluminium electrolutic capacitor, height Performance-based, chip type requirement it is more and more urgent, the manufacturing industry to electrode foil it is also proposed technology and quality requirement higher.Electricity Pole paper tinsel is the key raw material of aluminium electrolutic capacitor manufacture, and the quality of electrode foil will directly influence aluminium electrolutic capacitor Functionality, quality and appealing design is poor.The conventional corrosion technology flow of currently manufactured electrode foil is pre-treatment-washing-Chemical cleaning-washing-pure water Cleaning-dry, is main corrosive liquid with hydrochloric acid sulfuric acid or nitric acid, using direct current hair engaging aperture for several times, each corrosive liquid and electricity Stream, temperature all same.Such as existing five-stage manufacturing method:Aluminium foil that first learn from else's experience excessive erosion, that purity is 99.99%, 90~ Impregnated 5~10 minutes in 100 DEG C of pure water, the water-soluble of 0.1~8% citric acid and 0.1~5% citrate is placed in after taking-up It is then that one-level is melted into 8~15 points under conditions of 20mA/ (cm) 2, voltage is 140V in 70~95 DEG C, current density in liquid Clock;Aluminium foil after one-level is melted into again is rinsed after taking out with water, then is placed in 0.1~5% azelaic acid and 0.1~5% nonyl two It is two grades of changes under conditions of 20rriA/ (CIII) 2, voltage is 280V in 70~95 DEG C, current density in the aqueous solution of hydrochlorate Into 8~15 minutes;Aluminium foil after two grades are melted into is placed in the water of 0.1~5% azelaic acid and 0.1~50/ azelate again It is that three-level is melted into 8~15 minutes under conditions of 20mA/ (cm) 2, voltage is 450V in 70~95 DEG C, current density in solution; Aluminium foil after the chemical conversion of special three-level is placed in the aqueous solution of 0.1~5% azelaic acid and 0.1~5% azelate again, 70~ 95 DEG C, current density be 20mA/ (cm) 2, voltage be 580V under conditions of, level Four be melted into 8~15 minutes;After level Four is melted into Aluminium foil is placed in the aqueous solution of 0.1~3% azelaic acid and 0.1~3% azelate again, in 70~95 DEG C, current density Be 20mA/ (cm) 2, voltage be 620V under conditions of, Pyatyi be melted into 8~15 minutes;Aluminium foil after Pyatyi is melted into is from electrolyte Taken out in groove, carry out 500 DEG C of high-temperature heat treatment 3~4 minutes;0.1~3% azelaic acid and 0.1~3% nonyl two are placed in again It is under conditions of 20mA/ (cm) 2, voltage is 620V, to be melted into 8~15 points in 70~95 DEG C, current density in the aqueous solution of hydrochlorate Clock;Then processed with temperature as 50~80 DEG C in 1~8% phosphoric acid solution;Be placed in again 0.1~3% azelaic acid and It is then that 20mA/ (cm) 2, voltage is 620V's in 70~95 DEG C, current density in the aqueous solution of 0.1~3% azelate Under the conditions of, it is melted into 8~15 minutes;Finally take out, dry.The manufacturing process of electrode foil for aluminum electrolytic capacitors is also aluminium foil surface The process that hole produces and grows, in generation and production process, the length change in aperture and hole can be because of the structure shape in hole itself in hole State and it is different, and in existing manufacturing technology, hair engaging aperture condition is single, it is impossible to fully meet hole different phase pair in growth course Required in the difference of etching condition, cause pore size distribution uneven or the problem that hole merges and reduces effective hole number occurs.In order to This problem is solved, R&D institution and the technical staff of enterprise are explored constantly, research, it is desirable to find out a kind of more advanced Method manufacture meets the electrode foil of market demands, although makes some progress, but is remained still in practice The technical barrier not overcome.
The content of the invention
It is an object of the invention to overcome the above not enough, there is provided a kind of using seven grades of mesohigh electrodes of different hair engaging aperture conditions Foil making method.By changing the concentration of reaming corrosive liquid and the height of temperature, can effective controlling paper tinsel hole generation and production, it is accurate The really increase of control hole area, reaches production Technology requirement, obtains high-quality middle-high voltage electrode foil, improves production efficiency.
The present invention solves the technical step that is used of its technical problem:Washing-paper tinsel the surface of pre-treatment-once is once straight Stream hair engaging aperture treatment-paper tinsel surface second direct current hair engaging aperture treatment-paper tinsel surface three times direct current hair engaging aperture treatment-paper tinsel surface four times direct current hair At the direct current hair engaging aperture treatment-paper tinsel surface seven times direct current hair engaging aperture of the direct current hair engaging aperture treatment-paper tinsel surface six times of hole treatment-paper tinsel surface five times Reason-secondary washing-paper tinsel surface expanding treatment-tri- time washing-Chemical cleaning-tetra- time washing-pure water is cleaned-dried.
A kind of detailed process using seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions is as follows:
1st step:Pre-treatment:Pre-treatment mixes the solution of 1%~10% hydrochloric acid using 8%~40% sulfuric acid solution, At 30~70 DEG C, process 1~5 minute;
Second step:The direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2
Third step:The treatment of paper tinsel surface second direct current hair engaging aperture:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is the 98% of step 2 sulfuric acid content in rapid, and remaining condition is identical with previous step;
4th step:The three direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is 98% of sulfuric acid content in step 3 in rapid, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
5th step:The four direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is 96% of sulfuric acid content in step 3 in rapid, and remaining condition is identical with step 3;
6th step:The five direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is 96% of sulfuric acid content in step 3 in rapid, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
7th step:The six direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is 94% of sulfuric acid content in step 3 in rapid, and remaining condition is identical with step 3;
8th step:The seven direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% mixed in hydrochloric acid Liquid, temperature is 50~90 DEG C, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, this step Sulfuric acid content is 94% of sulfuric acid content in step 3 in rapid, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
9th step:Paper tinsel surface expanding treatment:Corrosive liquid is 1~10% nitric acid, and temperature is 50~90 DEG C, process time At 60 seconds~360 seconds, using direct current, electricity was 30~80C/cm for control2
10th step:Chemical cleaning:Cleaning fluid is 1~10% nitric acid, and temperature is 30~70 DEG C, 1~5 point of scavenging period Clock;
11st step:Under above-mentioned washing is normal temperature condition, clean 1~3 minute;
12nd step:Pure water is cleaned:Under normal temperature condition, clean 2~6 minutes;
13rd step:Dry:Under the conditions of 150~350 DEG C, dry 1~5 minute.
Beneficial effects of the present invention:By changing the concentration of reaming corrosive liquid and the height of temperature, can effective controlling paper tinsel hole Generation and production, the increase of accurate control hole area reaches production Technology requirement, obtains high-quality middle-high voltage electrode foil, Improve production efficiency.
The technology of the present invention and the electrode foil performance comparison table made by prior art
Comparative example Embodiment
Bending (returning) 60 65
Specific volume (μ F/cm2) 0.57(640vf) 0.59(640vf)
Embodiment
(1) pre-treatment:Pre-treatment mixes the solution of 1%~10% hydrochloric acid, 30 using 8%~40% sulfuric acid solution At~70 DEG C, process 1~5 minute;
(2) wash:Under normal temperature condition, clean 1~3 minute;
(3) the direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2
(4) paper tinsel surface second direct current hair engaging aperture treatment:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is the 98% of step 3 sulfuric acid content, and remaining condition is identical with previous step;
(5) the three direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 98% of sulfuric acid content in step 3, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
(6) the four direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 96% of sulfuric acid content in step 3, and remaining condition is identical with step 3;
(7) the five direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 96% of sulfuric acid content in step 3, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
(8) the six direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 94% of sulfuric acid content in step 3, and remaining condition is identical with step 3;
(9) the seven direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 94% of sulfuric acid content in step 3, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
(10) wash:Under normal temperature condition, clean 1~3 minute;
(11) paper tinsel surface expanding treatment:Corrosive liquid is 1~10% nitric acid, and temperature is 50~90 DEG C, process time control At 60 seconds~360 seconds, using direct current, electricity was 30~80C/cm2
(12) wash:Under normal temperature condition, clean 1~3 minute;
(13) Chemical cleaning:Cleaning fluid is 1~10% nitric acid, and temperature is 30~70 DEG C, scavenging period 1~5 minute;
(14) wash:Under normal temperature condition, clean 1~3 minute;
(15) pure water cleaning:Under normal temperature condition, clean 2~6 minutes;
(16) dry:Under the conditions of 150~350 DEG C, dry 1~5 minute;
Comparative example
(1) pre-treatment:Pre-treatment mixes the solution of 1%~10% hydrochloric acid, 30 using 8%~40% sulfuric acid solution At~70 DEG C, process 1~5 minute;
(2) wash:Under normal temperature condition, clean 1~3 minute;
(3) the direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2
(4) paper tinsel surface second direct current hair engaging aperture treatment:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is the 98% of step 3 sulfuric acid content, and remaining condition is identical with previous step;
(5) the three direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 98% of sulfuric acid content in step 3, and temperature increases by 0.3 DEG C compared with step 3, and remaining condition is identical with step 3;
(6) the four direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It is 50~90 DEG C to spend, and process time is controlled at 30 seconds~120 seconds, and using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is 96% of sulfuric acid content in step 3, and remaining condition is identical with step 3;
(7) wash:Under normal temperature condition, clean 1~3 minute;
(8) paper tinsel surface expanding treatment:Corrosive liquid is 1~10% nitric acid, and temperature is 50~90 DEG C, and process time control exists 60 seconds~360 seconds, using direct current, electricity was 30~80C/cm2
(9) wash:Under normal temperature condition, clean 1~3 minute;
(10) Chemical cleaning:Cleaning fluid is 1~10% nitric acid, and temperature is 30~70 DEG C, scavenging period 1~5 minute;
(11) wash:Under normal temperature condition, clean 1~3 minute;
(12) pure water cleaning:Under normal temperature condition, clean 2~6 minutes;
(13) dry:Under the conditions of 150~350 DEG C, dry 1~5 minute;
As shown by data that embodiments of the invention and comparative example draw, by the concentration and temperature that change reaming corrosive liquid Just, specific volume increases to 0.59 (640vf), and bending (returning) is 65, can effective controlling paper tinsel hole generation and production, accurate control hole The increase of area, reaches production Technology requirement, obtains high-quality middle-high voltage electrode foil, improves production efficiency.

Claims (1)

1. a kind of using seven grades of middle-high voltage electrode foil manufacture methods of different hair engaging aperture conditions, it is characterised in that:The manufacture method bag Include following steps:
(1)Pre-treatment:Pre-treatment mixes the solution of 1%~10% hydrochloric acid, 30~70 using 8%~40% sulfuric acid solution At DEG C, process 1~5 minute;
(2)Washing:Under normal temperature condition, clean 1~3 minute;
(3)The direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2
(4)The treatment of paper tinsel surface second direct current hair engaging aperture:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is(3)The 98% of middle sulfuric acid content, remaining condition with(3)It is identical;
(5)The three direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is(3)The 98% of middle sulfuric acid content, temperature compared with(3)It is middle increase by 0.3 DEG C, remaining condition with(3)It is identical;
(6)The four direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is(3)The 96% of middle sulfuric acid content, remaining condition with(3)It is identical;
(7)The five direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is(3)The 96% of middle sulfuric acid content, temperature compared with(3)It is middle increase by 0.3 DEG C, remaining condition with(3)It is identical;
(8)The six direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content(3)The 94% of middle sulfuric acid content, remaining condition with(3)It is identical;
(9)The seven direct current hair engaging aperture treatment in paper tinsel surface:Corrosive liquid is 8~40% sulfuric acid and 1~10% hydrochloric acid mixed solution, temperature It it is 50~90 DEG C, process time is controlled at 30 seconds~120 seconds, using direct current, electricity is 5~15C/cm2, sulphur in this step Acid content is(3)The 94% of middle sulfuric acid content, temperature compared with(3)It is middle increase by 0.3 DEG C, remaining condition with(3)It is identical;
(10)Washing:Under normal temperature condition, clean 1~3 minute;
(11)Paper tinsel surface expanding treatment:Corrosive liquid is 1~10% nitric acid, and temperature is 50~90 DEG C, and process time is controlled 60 Second~360 seconds, using direct current, electricity is 30~80C/cm2
(12)Washing:Under normal temperature condition, clean 1~3 minute;
(13)Chemical cleaning:Cleaning fluid is 1~10% nitric acid, and temperature is 30~70 DEG C, scavenging period 1~5 minute;
(14)Washing:Under normal temperature condition, clean 1~3 minute;
(15)Pure water is cleaned:Under normal temperature condition, clean 2~6 minutes;
(16)Dry:Under the conditions of 150~350 DEG C, dry 1~5 minute.
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Denomination of invention: A manufacturing method of medium and high voltage electrode foil with seven levels of different pore conditions

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