CN101423964B - Method for manufacturing foil by composite oxidation film at low pressure - Google Patents
Method for manufacturing foil by composite oxidation film at low pressure Download PDFInfo
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- CN101423964B CN101423964B CN200810029792XA CN200810029792A CN101423964B CN 101423964 B CN101423964 B CN 101423964B CN 200810029792X A CN200810029792X A CN 200810029792XA CN 200810029792 A CN200810029792 A CN 200810029792A CN 101423964 B CN101423964 B CN 101423964B
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Abstract
The invention relates to the technical field of formed foils, in particular to a method for manufacturing a composite oxide film low-voltage formed foil. The method is as follows: firstly, a formed foil is treated by sodium silicate, and an aluminum silicate film is generated on the surface of the formed foil, is a good hydration resistant film and can improve the hydration resistance of the formed foil; and secondly, the formed foil is formed in a mixture of ATMP and ammonium adipate, and a hydrous aluminum phosphate film with good water resistance is generated. The aluminum silicate film and the hydrous aluminum phosphate film can effectively prevent reaction of an alumina film and water, improve the hydration resistance of the composite oxide film low-voltage formed foil, and prolong the service life of a capacitor.
Description
Technical field:
The present invention relates to change into the paper tinsel technical field, particularly a kind of manufacture method of foil by composite oxidation film at low pressure.
Background technology:
Electrolytic condenser is widely used in many relevant industries such as electronics.The progress and the industrial expansion of science and technology propose higher requirement to electrolytic condenser in power frequency, low resistance, long lifetime etc.Along with the development of electronic industry, more and more miniaturization of electronic product, portability.Therefore various electronic devices and components are tending towards the mini-direction and develop, and electrical condenser is no exception.The volume of aluminium electrolutic capacitor mainly is subjected to the restriction of the electrostatic capacity of anode foils (promptly changing into paper tinsel).The electrostatic capacity of anode foils is high more, and the volume of electrical condenser just can be done more for a short time.The electrostatic capacity of anode foils is directly proportional with the specific inductivity of anode oxide film, specific surface area; Be inversely proportional to the thickness of oxide film.The thickness of oxide film depends on the operating voltage of electrical condenser, decides according to the needs of complete machine.In order to improve the electrostatic capacity of anode foils, normally adopt to improve the method for the specific inductivity of the specific surface area of electrode foil and oxide film.At present, adopt the etching process technology to come increasing specific surface area.After the chemical synthesis technology technical finesse, generating main component on the electrode foil is the oxide film of aluminum oxide, and its specific inductivity of pellumina that this technology manufacturing is come out is 8～10, and the electrostatic capacity of paillon foil is little.
In order further to improve the electrostatic capacity of electrode foil, people have invented the specific inductivity that high dielectric process improves oxide film, thereby reach the purpose that improves specific volume.Complex oxide film changes into paper tinsel owing to mix other micro-metals and brought severe side effect, as the electrical property that changes into paper tinsel glides and be difficult to and promote, and high dielectric material stops up hole and causes specific surface area to reduce even specific volume reduction etc. when changing into.
Electrolytic condenser will reach higher electric property, in electrical condenser, need to adopt the electrolytic solution of high moisture content, but, at high temperature, aluminum foil oxidation film is meeting of anode foils oxide film and moisture generation hydration especially, thereby generate aluminium hydroxide on the anode foils surface, cause the decline of anode foils proof voltage, leakage current to increase, even can in electrical condenser, produce hydrogen, press liter in causing, shell drum shell and even quick-fried shell occur, have influence on electric property, the working life of electrolytic condenser and even whole electric system, even security incident takes place.
For addressing the above problem, industry has extensively taked the passivation measure to prevent aluminum foil oxidation film and moisture generation hydration at present.Generally speaking, different with inhibition, the degree of passivation of water reaction to aluminium according to negatively charged ion, general material can be divided into four classes promptly: unrestraint effect class, medium restraining effect class, strong restraining effect class and extremely strong restraining effect class.Wherein, extremely strong inhibition passivator aluminum orthophoshpate, it is water insoluble, the aluminum orthophoshpate structure on aluminum foil oxidation film surface is identical with the low quartz crystal formation, it is stable positive tetrahedron structure, the aluminum orthophoshpate film has suppressed the effect of water and aluminium, has improved the water-fast performance of closing that changes into paper tinsel, has prolonged the storage life that changes into paper tinsel and the working life of electrical condenser.
Normally in the aftertreatment of chemical synthesis technology process, and a certain amount of phosphoric acid class passivator of adding in the aftertreatment tank liquor, carry out the chemical after-treatment reason as phosphoric acid, promptly be to change into after paper tinsel arrives maximum and become voltage (being commonly called as the seal making alive), it is inserted soak certain hour in the phosphoric acid, in chemical after-treatment reason process, phosphoric acid has dissolved a part of pellumina, generates phosphatize phosphate coat.These materials can make alumite that the aquation sensitivity is reduced, thereby the passivation of playing has improved the anti-hydratability that changes into paper tinsel and capacitor product thereof.
But the chemical after-treatment reason is also brought very important defective when enhancing product performance.At first, when formation voltage reaches high value, because of the hole of low-pressure chemical synthesis foil is the spongy hole of non-straight hole, oxide film that its surface generates is thicker, thereby phosphate radical can't diffuse into hole inside and causes Passivation Treatment to be difficult to comprehensively and covering completely when chemical after-treatment manage; Secondly, because chemical after-treatment reason efficient is lower, and effect often improves concentration and temperature in order to reach preferably, can lose the electrostatic capacity of a part like this, and electrostatic capacity and anti-hydratability can not be got both.
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art, and provide a kind of manufacture method of foil by composite oxidation film at low pressure, present method to adopt water glass to handle earlier, generate the pure aluminium silicate film changing into the paper tinsel surface, adopt Amino Trimethylene Phosphonic Acid to handle again, generate the aluminum phosphate film.Two kinds of films can effectively stop the reaction of pellumina and water, improve the water-fast performance of closing of foil by composite oxidation film at low pressure, prolong life of capacitors.
For achieving the above object, the technical solution used in the present invention is:
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
A, place ammonium adipate solution to change into processing the low pressure etched foil;
B, will place the sodium silicate solution immersion treatment through the paper tinsel that changes into that step a changes into processing, pure water cleans then;
C, will place ammonium adipate solution to change into processing again through the paper tinsel that changes into of step b;
D, the paper tinsel that changes into after will changing into again through step c clean and heat-treat in air atmosphere;
E, will place the mixing solutions of ammonium adipate and Amino Trimethylene Phosphonic Acid to change into processing once more through the heat treated paper tinsel that changes into of steps d;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment under air atmosphere;
G, will be through step f change into paper tinsel immersion treatment in ammonium dihydrogen phosphate;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 100～150 ℃ through the paper tinsel that changes into of step g.
Described ammonium adipate solution concentration 0.1～1.2mol/L, 60～95 ℃ of temperature.
30～60 ℃ of the temperature of immersion treatment in the sodium silicate solution among the described step b, sodium silicate solution concentration is 0.01～0.02mol/L, 2～6 minutes treatment times.
The thermal treatment temp of described steps d and step f is 450～550 ℃, and the treatment time is 1.5～3.0 minutes.
Ammonium adipate among the described step e and Amino Trimethylene Phosphonic Acid mixing solutions, its proportioning is: Amino Trimethylene Phosphonic Acid: 1.0 * 10
-3～20 * 10
-3Mol/L, ammonium adipate: 0.1～1.2mol/L, mixing temperature are 60～95 ℃.
Primary ammonium phosphate immersion treatment in the described step g, biphosphate ammonium concentration are 0.05～0.25mol/L, and temperature is 30～90 ℃, 1～5 minute treatment time.
Changing among the described step a handled the step that changes into that chemical synthesizing method comprises one-level, secondary, three grades or level Four, and every step voltage allocation criterion is as follows,
The first step voltage that one-level changes into is to change into 100% of maximum voltage;
The first step voltage that secondary changes into is to change into 50% of maximum voltage, and second stage voltage is to change into 100% of maximum voltage;
Three grades of first step voltages that change into are to change into 40% of maximum voltage, and second stage voltage is to change into 80% of maximum voltage, and third stage voltage is to change into 100% of maximum voltage;
The first step voltage that level Four changes into is to change into 35% of maximum voltage, and second stage voltage is to change into 60% of maximum voltage, and third stage voltage is to change into 80% of maximum voltage, and fourth stage voltage is to change into 100% of maximum voltage.
Beneficial effect of the present invention is: the present invention adopts water glass to handle, changing into paper tinsel surface generation pure aluminium silicate film, the dilute solution of water glass slightly is alkalescence, with after having generated changing in sodium silicate solution of oxide film and having soaked, generate pure aluminium silicate on its surface, pure aluminium silicate is a clear crystal, and is water insoluble, be good anti-hydrated film, improved the water-fast performance of closing that changes into paper tinsel.
Adopt Amino Trimethylene Phosphonic Acid to handle again, amino trimethylene methyl tri methylene phosphonic acid claims again " Amino Trimethylene Phosphonic Acid " that be called for short ATMP, English name: Amino trimethylene phosphonicacid is a kind of organic multicomponent phosphonic acids.Chemical formula is: N (CH
2PO (OH)
2)
3, relative molecular mass: 299.05, pH value (1% aqueous solution): 1.5～2.5, structural formula is as follows:
To change into paper tinsel changes in ATMP and ammonium adipate mixing solutions, generate the good hypophosphite monohydrate aluminium film of water resistance, pure aluminium silicate film and two kinds of films of hypophosphite monohydrate aluminium film can effectively stop the reaction of pellumina and water, improve the water-fast performance of closing of foil by composite oxidation film at low pressure, prolong life of capacitors, hypophosphite monohydrate aluminium film also and have a Passivation Treatment efficient height, the covering of Passivation Treatment more comprehensively, thoroughly, the solvability of oxide film is lower, can obtain higher electrostatic capacity simultaneously.
Embodiment:
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
Becoming voltage according to method making maximum of the present invention is the paper tinsel that changes into of 20V, and concrete grammar is as follows:
A, with the low pressure etched foil under 70 ℃, in the ammonium adipate solution of 0.4mol/L, change into processing, be divided into level Four and carry out, voltage is respectively: the first step voltage that level Four changes into is: 20v * 35%=7v; The second stage voltage that level Four changes into is: 20 * 60%=12v; The third stage voltage that level Four changes into is: 20 * 80%=16v; The fourth stage voltage that level Four changes into is: 20 * 100%=20v is that maximum becomes voltage 20V;
B, will change into paper tinsel under 60 ℃ through what step a changed into processing, immersion treatment is 2 minutes in the sodium silicate solution of 0.01mol/L, and pure water cleans then;
C, will through step b change into paper tinsel under 70 ℃, place the ammonium adipate solution of 0.4mol/L to change into processing again, formation voltage is 20V;
D, will clean and heat-treat in air atmosphere through the paper tinsel that changes into that step c changes into processing again, thermal treatment temp is 500 ℃, and the treatment time is 2 minutes;
E, will through the heat treated paper tinsel that changes into of steps d under 70 ℃, in 0.4mol/L ammonium adipate and 0.02mol/L ATMP mixed solution, change into processing once more;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment 3 minutes under 480 ℃ of air atmosphere;
G, will be through step f change into paper tinsel under 60 ℃, immersion treatment in the 0.2mol/L ammonium dihydrogen phosphate, 3 minutes treatment times;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 100 ℃ through the paper tinsel that changes into of step g.
Comparative example 1
The sample identical with embodiment 1 handled according to the production technique of routine, and its maximum becomes voltage still to be 20V, and treating processes is as follows:
A, with the low pressure etched foil under 70 ℃, in the 0.4mol/L ammonium adipate solution, change into processing, be divided into level Four and carry out, wherein every grade voltage is as follows: the first step that level Four changes into: 20v * 35%=7v; The second stage that level Four changes into: 20 * 60%=12v; The third stage that level Four changes into: 20 * 80%=16v; The fourth stage that level Four changes into: 20 * 100%=20v is that maximum becomes voltage 20V;
B, will change into paper tinsel under 60 ℃, immersion treatment is 2 minutes in the phosphoric acid solution of 0.25mol/L, and pure water cleans then;
C, will change into paper tinsel under 70 ℃, and change into processing once more in the 0.4mol/L ammonium adipate solution, formation voltage is 20v;
D, the paper tinsel that changes into after will changing into again clean and heat-treat in air atmosphere, 500 ℃ of temperature, 2 minutes time;
F, will change into paper tinsel under 80 ℃, carry out immersion treatment 3 minutes in the ammonium dihydrogen phosphate of 0.2mol/L, and clean then, 120 ℃ of oven dry down make low-pressure chemical synthesis foil.
Respectively two kinds of finished products of embodiment 1 and comparative example 1 are tested, testing method is undertaken by SJ/T 11140 standards, and test result is listed in the table 1.
Embodiment 2
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
Becoming voltage according to method making maximum of the present invention is the paper tinsel that changes into of 100V, and concrete grammar is as follows:
A, with the low pressure etched foil under 85 ℃, in the ammonium adipate solution of 0.6mol/L, change into processing, be divided into level Four and carry out, voltage is respectively: the first step voltage that level Four changes into is: 100v * 35%=35v; The second stage voltage that level Four changes into is: 100 * 60%=60v; The third stage voltage that level Four changes into is: 100 * 80%=80v; The fourth stage voltage that level Four changes into is: 100 * 100%=100v is that maximum becomes voltage 100V;
B, will change into paper tinsel under 60 ℃ through what step a changed into processing, immersion treatment is 6 minutes in the sodium silicate solution of 0.01mol/L, and pure water cleans then;
C, will through step b change into paper tinsel under 85 ℃, place the ammonium adipate solution of 0.6mol/L to change into processing again, formation voltage is 100V;
D, will clean and heat-treat in air atmosphere through the paper tinsel that changes into that step c changes into processing again, thermal treatment temp is 510 ℃, and the treatment time is 2 minutes;
E, will through the heat treated paper tinsel that changes into of steps d under 70 ℃, in 0.6mol/L ammonium adipate and 0.02mol/L ATMP mixed solution, change into processing once more;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment 3 minutes under 510 ℃ of air atmosphere;
G, will be through step f change into paper tinsel under 80 ℃, immersion treatment in the 0.25mol/L ammonium dihydrogen phosphate, 5 minutes treatment times;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 120 ℃ through the paper tinsel that changes into of step g.
Comparative example 2
The sample identical with embodiment 2 handled according to the production technique of routine, and its maximum becomes voltage still to be 100V, and treating processes is as follows:
A, with the low pressure etched foil under 85 ℃, in the 0.6mol/L ammonium adipate solution, change into processing, be divided into level Four and carry out, wherein every grade voltage is as follows: the first step that level Four changes into: 100v * 35%=35v; The second stage that level Four changes into: 100 * 60%=60v; The third stage that level Four changes into: 100 * 80%=80v; The fourth stage that level Four changes into: 100 * 100%=100v is that maximum becomes voltage 100V;
B, will change into paper tinsel under 70 ℃, immersion treatment is 2 minutes in the phosphoric acid solution of 0.25mol/L, and pure water cleans then;
C, will change into paper tinsel under 85 ℃, and change into processing once more in the 0.6mol/L ammonium adipate solution, formation voltage is 100v;
D, the paper tinsel that changes into after will changing into again clean and heat-treat in air atmosphere, 520 ℃ of temperature, 2.5 minutes time;
F, will change into paper tinsel under 80 ℃, carry out immersion treatment 3 minutes in the ammonium dihydrogen phosphate of 0.35mol/L, and clean then, 120 ℃ of oven dry down make low-pressure chemical synthesis foil.
Respectively two kinds of finished products of embodiment 2 and comparative example 2 are tested, testing method is undertaken by SJ/T 11140 standards, and test result is listed in the table 1.
Embodiment 3
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
Becoming voltage according to method making maximum of the present invention is the paper tinsel that changes into of 50V, and concrete grammar is as follows:
A, with the low pressure etched foil under 80 ℃, in the ammonium adipate solution of 0.9mol/L, change into processing, be divided into three grades and carry out, voltage is respectively: three grades of first step voltages that change into are: 50v * 40%=20v; Three grades of second stage voltages that change into are: 50 * 80%=40v; Three grades of third stage voltages that change into are: 50 * 100%=50v; Be that maximum becomes voltage 50V;
B, will change into paper tinsel under 60 ℃ through what step a changed into processing, immersion treatment is 6 minutes in the sodium silicate solution of 0.01mol/L, and pure water cleans then;
C, will through step b change into paper tinsel under 80 ℃, place the ammonium adipate solution of 0.9mol/L to change into processing again, formation voltage is 50V;
D, will clean and heat-treat in air atmosphere through the paper tinsel that changes into that step c changes into processing again, thermal treatment temp is 500 ℃, and the treatment time is 3 minutes;
E, will through the heat treated paper tinsel that changes into of steps d under 70 ℃, in 0.4mol/L ammonium adipate and 0.02mol/L ATMP mixed solution, change into processing once more;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment 3 minutes under 500 ℃ of air atmosphere;
G, will be through step f change into paper tinsel under 60 ℃, immersion treatment in the 0.20mol/L ammonium dihydrogen phosphate, 4 minutes treatment times;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 120 ℃ through the paper tinsel that changes into of step g.
Comparative example 3
The sample identical with embodiment 3 handled according to the production technique of routine, and its maximum becomes voltage still to be 50V, and treating processes is as follows:
A, with the low pressure etched foil under 80 ℃, in the 0.9mol/L ammonium adipate solution, change into processing, be divided into three grades and carry out, wherein every grade voltage is as follows: three grades of first step voltages that change into are: 50v * 40%=20v; Three grades of second stage voltages that change into are: 50 * 80%=40v; Three grades of third stage voltages that change into are: 50 * 100%=50v; Be that maximum becomes voltage 50V;
B, will change into paper tinsel under 60 ℃, immersion treatment is 2.5 minutes in the phosphoric acid solution of 0.28mol/L, and pure water cleans then;
C, will change into paper tinsel under 80 ℃, and change into processing once more in the 0.9mol/L ammonium adipate solution, formation voltage is 50v;
D, the paper tinsel that changes into after will changing into again clean and heat-treat in air atmosphere, 490 ℃ of temperature, 3 minutes time;
F, will change into paper tinsel under 80 ℃, carry out immersion treatment 3 minutes in the ammonium dihydrogen phosphate of 0.25mol/L, and clean then, 120 ℃ of oven dry down make low-pressure chemical synthesis foil.
Respectively two kinds of finished products of embodiment 3 and comparative example 3 are tested, testing method is undertaken by SJ/T 11140 standards, and test result is listed in the table 1.
Embodiment 4
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
Becoming voltage according to method making maximum of the present invention is the paper tinsel that changes into of 12V, and concrete grammar is as follows:
A, with the low pressure etched foil under 80 ℃, in the ammonium adipate solution of 1.0mol/L, change into processing, be divided into secondary and carry out, voltage is respectively: the first step voltage that secondary changes into is: 12v * 50%=6v; The second stage voltage that secondary changes into is: 12 * 100%=12v; Be that maximum becomes voltage 12V;
B, will change into paper tinsel under 30 ℃ through what step a changed into processing, immersion treatment is 2 minutes in the sodium silicate solution of 0.01mol/L, and pure water cleans then;
C, will through step b change into paper tinsel under 80 ℃, place the ammonium adipate solution of 1.0mol/L to change into processing again, formation voltage is 12V;
D, will clean and heat-treat in air atmosphere through the paper tinsel that changes into that step c changes into processing again, thermal treatment temp is 480 ℃, and the treatment time is 2 minutes;
E, will through the heat treated paper tinsel that changes into of steps d under 70 ℃, in 0.4mol/L ammonium adipate and 0.02mol/L ATMP mixed solution, change into processing once more;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment 2 minutes under 480 ℃ of air atmosphere;
G, will be through step f change into paper tinsel under 40 ℃, immersion treatment in the 0.08mol/L ammonium dihydrogen phosphate, 2 minutes treatment times;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 100 ℃ through the paper tinsel that changes into of step g.
Comparative example 4
The sample identical with embodiment 4 handled according to the production technique of routine, and its maximum becomes voltage still to be 50V, and treating processes is as follows:
A, with the low pressure etched foil under 80 ℃, in the 1.0mol/L ammonium adipate solution, change into processing, be divided into level Four and carry out, wherein every grade voltage is as follows:
Be divided into secondary and carry out, voltage is respectively: the first step voltage that secondary changes into is: 12v * 50%=6v; The second stage voltage that secondary changes into is: 12 * 100%=12v; Be that maximum becomes voltage 12V;
B, will change into paper tinsel under 50 ℃, immersion treatment is 1.5 minutes in the phosphoric acid solution of 0.15mol/L, and pure water cleans then;
C, will change into paper tinsel under 80 ℃, and change into processing once more in the 1.0mol/L ammonium adipate solution, formation voltage is 12v;
D, the paper tinsel that changes into after will changing into again clean and heat-treat in air atmosphere, 500 ℃ of temperature, 3 minutes time;
F, will change into paper tinsel under 80 ℃, carry out immersion treatment 3 minutes in the ammonium dihydrogen phosphate of 0.20mol/L, and clean then, 120 ℃ of oven dry down make low-pressure chemical synthesis foil.
Respectively two kinds of finished products of embodiment 4 and comparative example 4 are tested, testing method is undertaken by the SJ/T11140 standard, and test result is listed in the table 1.
Embodiment 5
A kind of manufacture method of foil by composite oxidation film at low pressure may further comprise the steps:
Becoming voltage according to method making maximum of the present invention is the paper tinsel that changes into of 8V, and concrete grammar is as follows:
A, with the low pressure etched foil under 80 ℃, in the ammonium adipate solution of 1.0mol/L, carry out one-level and change into processing, formation voltage is 8V;
B, will change into paper tinsel under 30 ℃ through what step a changed into processing, immersion treatment is 2 minutes in the sodium silicate solution of 0.01mol/L, and pure water cleans then;
C, will through step b change into paper tinsel under 80 ℃, place the ammonium adipate solution of 1.0mol/L to change into processing again, formation voltage is 8V;
D, will clean and heat-treat in air atmosphere through the paper tinsel that changes into that step c changes into processing again, thermal treatment temp is 460 ℃, and the treatment time is 2 minutes;
E, will through the heat treated paper tinsel that changes into of steps d under 70 ℃, in 0.4mol/L ammonium adipate and 0.02mol/L ATMP mixed solution, change into processing once more;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment 2 minutes under 480 ℃ of air atmosphere;
G, will be through step f change into paper tinsel under 30 ℃, immersion treatment in the 0.06mol/L ammonium dihydrogen phosphate, 1 minute treatment time;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 100 ℃ through the paper tinsel that changes into of step g.
Comparative example 5
The sample identical with embodiment 5 handled according to the production technique of routine, and its maximum becomes voltage still to be 8V, and treating processes is as follows:
A, with the low pressure etched foil under 80 ℃, in the 1.0mol/L ammonium adipate solution, carry out one-level and change into processing, formation voltage 8V;
B, will change into paper tinsel under 40 ℃, immersion treatment is 1 minute in the phosphoric acid solution of 0.10mol/L, and pure water cleans then;
C, will change into paper tinsel under 80 ℃, and change into processing once more in the 1.0mol/L ammonium adipate solution, formation voltage is 8v;
D, the paper tinsel that changes into after will changing into again clean and heat-treat in air atmosphere, 480 ℃ of temperature, 2 minutes time;
F, will change into paper tinsel under 80 ℃, carry out immersion treatment 3 minutes in the ammonium dihydrogen phosphate of 0.20mol/L, and clean then, 120 ℃ of oven dry down make low-pressure chemical synthesis foil.
Respectively two kinds of finished products of embodiment 5 and comparative example 5 are tested, testing method is undertaken by SJ/T 11140 standards, and test result is listed in the table 1.
Table 1
| Technology | Electrostatic capacity (μ F/cm 2) | Pressure rising time (S) | Boil the boost in voltage time (S) after the survey | Directly boil the boost in voltage time (S) | |
| Embodiment 1 | The present invention | 78.2 | 32 | 12 | 44 |
| Comparative example 1 | Conventional | 76.5 | 78 | 39 | 81 |
| Embodiment 2 | The present invention | 7.55 | 71 | 20 | 79 |
| Comparative example 2 | Conventional | 6.75 | 139 | 64 | 155 |
| Embodiment 3 | The present invention | 26.8 | 51 | 21 | 59 |
| Comparative example 3 | Conventional | 27.0 | 110 | 55 | 123 |
| Embodiment 4 | The present invention | 98.4 | 36 | 11 | 38 |
| Comparative example 4 | Conventional | 93.9 | 60 | 40 | 67 |
[0132]
| Embodiment 5 | The present invention | 102.8 | 29 | 10 | 32 |
| Comparative example 5 | Conventional | 100.2 | 45 | 34 | 53 |
As seen from Table 1 the pressure rising time of technology of the present invention, boil the boost in voltage time after surveying, directly boil of the obvious reduction of boost in voltage time than common process, illustrate that the water-fast performance of closing of foil by composite oxidation film at low pressure of technology manufacturing of the present invention is good.
Claims (7)
1. the manufacture method of a foil by composite oxidation film at low pressure is characterized in that: may further comprise the steps:
A, place ammonium adipate solution to change into processing the low pressure etched foil;
B, will place the sodium silicate solution immersion treatment through the paper tinsel that changes into that step a changes into processing, pure water cleans then;
C, will place ammonium adipate solution to change into processing again through the paper tinsel that changes into of step b;
D, will clean and in air atmosphere, heat-treat through the paper tinsel that changes into that step c changes into again;
E, will place the mixing solutions of ammonium adipate and Amino Trimethylene Phosphonic Acid to change into processing once more through the heat treated paper tinsel that changes into of steps d;
F, will be through step e change into that paper tinsel cleans once more and thermal treatment under air atmosphere;
G, will be through step f change into paper tinsel immersion treatment in ammonium dihydrogen phosphate;
H, will clean loft drier oven dry the becoming foil by composite oxidation film at low pressure put into 100～150 ℃ through the paper tinsel that changes into of step g.
2. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1 is characterized in that: described ammonium adipate solution concentration 0.1～1.2mol/L, 60～95 ℃ of temperature.
3. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1, it is characterized in that: 30～60 ℃ of the temperature of immersion treatment in the sodium silicate solution among the described step b, sodium silicate solution concentration is 0.01～0.02mol/L, 2～6 minutes treatment times.
4. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1, it is characterized in that: the thermal treatment temp of described steps d and step f is 450～550 ℃, the treatment time is 1.5～3.0 minutes.
5. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1, it is characterized in that: ammonium adipate among the described step e and Amino Trimethylene Phosphonic Acid mixing solutions, its proportioning is: Amino Trimethylene Phosphonic Acid: 1.0 * 10
-3～20 * 10
-3Mol/L, ammonium adipate: 0.1～1.2mol/L, mixing temperature are 60～95 ℃.
6. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1, it is characterized in that: the primary ammonium phosphate immersion treatment in the described step g, the biphosphate ammonium concentration is 0.05～0.25mol/L, and temperature is 30～90 ℃, 1～5 minute treatment time.
7. the manufacture method of a kind of foil by composite oxidation film at low pressure according to claim 1 is characterized in that: changing among the described step a handled the step that changes into that chemical synthesizing method comprises one-level, secondary, three grades or level Four, and every step voltage allocation criterion is as follows,
The first step voltage that one-level changes into is to change into 100% of maximum voltage;
The first step voltage that secondary changes into is to change into 50% of maximum voltage, and second stage voltage is to change into 100% of maximum voltage;
Three grades of first step voltages that change into are to change into 40% of maximum voltage, and second stage voltage is to change into 80% of maximum voltage, and third stage voltage is to change into 100% of maximum voltage;
The first step voltage that level Four changes into is to change into 35% of maximum voltage, and second stage voltage is to change into 60% of maximum voltage, and third stage voltage is to change into 80% of maximum voltage, and fourth stage voltage is to change into 100% of maximum voltage.
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| CN114411219B (en) * | 2021-12-30 | 2023-10-27 | 立敦电子科技（惠州）有限公司 | High acid-resistant low-pressure formed foil, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1366095A (en) * | 2001-01-19 | 2002-08-28 | 江苏中联科技集团有限公司 | Three-stage process for preparing electrode foil used for low-voltage aluminium-electrolytic capacitor |
| CN1873865A (en) * | 2006-04-05 | 2006-12-06 | 江苏中联科技集团有限公司 | Manufacturing method for raising specific volume of electrode foil in use for aluminium electrolytic capacitor |
| CN101221855A (en) * | 2007-12-14 | 2008-07-16 | 横店集团东磁有限公司 | Method for manufacturing formed foil used for medium-high pressure aluminum electrolytic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1366095A (en) * | 2001-01-19 | 2002-08-28 | 江苏中联科技集团有限公司 | Three-stage process for preparing electrode foil used for low-voltage aluminium-electrolytic capacitor |
| CN1873865A (en) * | 2006-04-05 | 2006-12-06 | 江苏中联科技集团有限公司 | Manufacturing method for raising specific volume of electrode foil in use for aluminium electrolytic capacitor |
| CN101221855A (en) * | 2007-12-14 | 2008-07-16 | 横店集团东磁有限公司 | Method for manufacturing formed foil used for medium-high pressure aluminum electrolytic capacitor |
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| JP平8-64481A 1996.03.08 |
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