CN101707141A

CN101707141A - Method for manufacturing anodic foil of aluminum electrolytic capacitor

Info

Publication number: CN101707141A
Application number: CN200910114537A
Authority: CN
Inventors: 宋洪洲; 陆宝琳; 杨林桑
Original assignee: Guangxi Hezhou Guidong Electronic Technology Co Ltd
Current assignee: Guangxi Hezhou Guidong Electronic Technology Co Ltd
Priority date: 2009-11-09
Filing date: 2009-11-09
Publication date: 2010-05-12

Abstract

The invention discloses a method for manufacturing an anodic foil of an aluminum electrolytic capacitor, which comprises the following steps of boiling treatment, three polarization, heat treatment, formation, phosphate treatment, formation, heat treatment, and reformation. Different from the prior art, the phosphate treatment is carried out before the second heat treatment, and an after-treatment is removed. The phosphate treatment is dipping treatment performed under the conditions of the concentration of a phosphate treating agent of between 1 and 5 v/v%, and the temperature of between 20 and 80 DEG C for 1 to 10 minutes. The method can ensure that after three months of storage, the anodic foil of the aluminum electrolytic capacitor has short boosting time, short hydration resistance boosting time, stable pressure resistance and good bending performance.

Description

A kind of manufacture method of aluminum electrolysis capacitor anode foil

Technical field

The invention belongs to electronic material manufacturing technology field, be specifically related to a kind of manufacture method of aluminum electrolysis capacitor anode foil.

Background technology

At present, the manufacture method of aluminium electrolytic capacitor high-voltage anode paper tinsel, comprise boil processing, then carry out three grades change into, heat treatment, change into, phosphoric acid is handled, change into, heat treatment, change into and postprocessing working procedures again.Product bending intensity difference, water-fast long, storage fast, poach rear oxidation film withstand voltage decline of rise pressure rising time after 3 months pressure rising time, the unstable product quality of closing of using this kind chemical synthesizing method to be produced.

Summary of the invention

The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and can improve aluminum electrolysis capacitor anode foil bending intensity, water-fast manufacture method of closing the aluminum electrolysis capacitor anode foil that pressure rising time is short, storage rise pressure rising time is slow, poach rear oxidation film withstand voltage is stable.

The present invention achieves the above object by the following technical programs: a kind of manufacture method of aluminum electrolysis capacitor anode foil, comprise boil that processing, three is polarized to, heat treatment, change into, phosphoric acid is handled, change into, heat treatment, formation process again, before second heat treatment step, carry out phosphatization and handle, remove postprocessing working procedures simultaneously; It is to be 1～5v/v% in phosphate inorganic agent concentration that described phosphatization is handled, and temperature is impregnation process 1～10min under 20～80 ℃ the condition.

The phosphorous acidic group inorganic agent that described phosphatization processing is adopted is one or more in phosphoric acid, ammonium dihydrogen phosphate, phosphorous acid, the ammonium hypophosphite.

Method step and controlled condition that the present invention is concrete are:

Employing purity is that the middle and high pressure etched foil more than 99.99% boils processing 5～15min in the pure water more than 95 ℃, then carrying out the one-level constant voltage in the liquid changing into of citric acid and its esters changes into 10～20min, then carrying out the secondary constant voltage in the liquid changing into of citric acid and its esters changes into 10～20min, and then carry out three grades of constant voltages in the liquid changing into of azelaic acid and its esters and change into 20～40min, under 400～550 ℃ of conditions, heat-treat 1～5min; Change into constant voltage 10～20min again; In phosphoric acid liquid concentration is that 1.0～10v/v%, temperature are to carry out phosphoric acid under 60～80 ℃ the condition to handle 5～15min; Be 1～5v/v% in phosphate inorganic agent concentration then, temperature is to carry out impregnation process 1～10min, 80～400 ℃ of heat treatments, time 1～5min under 20～80 ℃ the condition.

The present invention compared with prior art has following advantage:

Because carrying out phosphatization before second heat treatment step handles, anode foils water-fast closed pressure rising time Tr60 and shortened 10～20s, bending intensity has improved 15～50 times, store that variable quantity pressure rising time of anode foils oxide-film has shortened 5～85s after 3 months, the oxide-film withstand voltage does not descend before and after the aquation 1h, has effectively improved the product quality of aluminum electrolysis capacitor anode foil; Production procedure is simple.

Description of drawings

Fig. 1 is the chemical synthesis technology flow chart of the manufacture method of aluminum electrolysis capacitor anode foil of the present invention.

Embodiment

Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but embodiments of the present invention are not limited thereto.

Embodiment 1

Employing purity is that the middle pressure etched foil more than 99.99% boils processing 5min in 96 ℃ pure water, and then carrying out one-level constant voltage 130V in the liquid changing into of citric acid and its esters changes into 10min; Then carrying out secondary constant voltage 280V in the liquid changing into of citric acid and its esters changes into 10min; And then carry out three grades of constant voltage 315V in the liquid changing into of azelaic acid and its esters and change into 20min; Under 400 ℃ of conditions, heat-treat 1min; Change into constant voltage 315V again and change into 10min; In 1v/v%, temperature are 80 ℃ phosphoric acid liquid, carry out phosphoric acid and handle 5min; It is to be 5v/v% in phosphate inorganic agent concentration that phosphatization is handled, and temperature is impregnation process 1min under 80 ℃ the condition, and described phosphate inorganic agent is a phosphoric acid.Heat treatment temperature is 400 ℃ for the second time, time 1min.

Variation delta Tr (Tr pressure rising time of test storage anode foils oxide-film after 3 months _{(3 months)}-Tr _(initially)), the withstand voltage variation delta TV (TV of oxide-film before and after the aquation 1h _{(behind the 1h)}-TV _{(before the 1h)}), water-fast Tr60 pressure rising time, the bending intensity of closing, compare with existing chemical synthesis technology, the result is as shown in table 1:

Table 1

Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)
Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)	Existing technological process A	??30	??-2	??20	??120
Existing process flow B	??50	??-4	??20	??140	Existing technological process A	??30	??-2	??20	??120
Existing process flow B	??50	??-4	??20	??140	Embodiment 1	??5	??+1	??10	??160

Table 1 shows: middle pressure 315Vf product, to store after 3 months, and rise pressure rising time value has reduced by 25～45s; The oxide-film withstand voltage does not descend before and after the aquation 1h; The water-fast pressure rising time Tr60 of closing has shortened 10s; The existing technological process of the bending strength ratio of embodiment has improved 20～40 times.

Embodiment 2

Employing purity is that the high pressure etched foil more than 99.99% boils processing 10min in 96 ℃ pure water, and then carrying out one-level constant voltage 200V in the liquid changing into of citric acid and its esters changes into 15min; Then carrying out secondary constant voltage 400 in the liquid changing into of citric acid and its esters changes into 15min; And then carry out three grades of constant voltage 530V in the liquid and change into 30min containing changing into of azelaic acid and its esters; Under 500 ℃ of conditions, heat-treat 3min; Change into constant voltage 530V again and change into 15min; In 6v/v%, temperature are 70 ℃ phosphoric acid liquid, carry out phosphoric acid and handle 10min; It is to be 2v/v% in phosphate inorganic agent concentration that phosphatization is handled, and temperature is impregnation process 5min under 60 ℃ the condition, and described phosphate inorganic agent is a phosphorous acid.Ammonium dihydrogen solution and 85% phosphorous acid.Heat treatment temperature is 300 ℃ for the second time, time 3min.

Variation delta Tr (Tr pressure rising time of test storage anode foils oxide-film after 3 months _{(3 months)}-Tr _(initially)), the withstand voltage variation delta TV (TV of oxide-film before and after the aquation 1h _{(behind the 1h)}-TV _{(before the 1h)}), water-fast Tr60 pressure rising time, the bending intensity of closing, compare with existing chemical synthesis technology, the result is as shown in table 2:

Table 2

Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)
Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)	Existing technological process A	??20	??-2	??28	??100
Existing process flow B	??60	??-5	??25	??120	Existing technological process A	??20	??-2	??28	??100
Existing process flow B	??60	??-5	??25	??120	Embodiment 2	??10	??+1	??12	??140

Table 2 is the result show: to high pressure 530Vf product, store after 3 months, rise pressure rising time value has reduced by 10～50s; The oxide-film withstand voltage does not descend before and after the aquation 1h; The water-fast pressure rising time Tr60 of closing has shortened 13～16s; The existing technological process of the bending strength ratio of embodiment has improved 20～40 times.

Embodiment 3

Employing purity is that the high pressure etched foil more than 99.99% boils processing 15min in 96 ℃ pure water, and then carrying out one-level constant voltage 250V in the liquid changing into of citric acid and its esters changes into 20min; Then carrying out secondary constant voltage 480 in the liquid changing into of citric acid and its esters changes into 20min; And then carry out three grades of constant voltage 590V in the liquid changing into of azelaic acid and its esters and change into 40min; Under 550 ℃ of conditions, heat-treat 5min; Change into constant voltage 590V again and change into 20min; In 10v/v%, temperature are 60 ℃ phosphoric acid liquid, carry out phosphoric acid and handle 15min; It is to be 1v/v% in phosphate inorganic agent concentration that phosphatization is handled, and temperature is impregnation process 10min under 20 ℃ the condition, and described phosphate inorganic agent is 50wt% ammonium dihydrogen phosphate and 50wt% ortho phosphorous acid ammonium salt solution.Heat treatment temperature is 80 ℃ for the second time, time 5min.

Variation delta Tr (Tr pressure rising time of test storage anode foils oxide-film after 3 months _{(3 months)}-Tr _(initially)), the withstand voltage variation delta TV (TV of oxide-film before and after the aquation 1h _{(behind the 1h)}-TV _{(before the 1h)}), water-fast Tr60 pressure rising time, the bending intensity of closing, compare with existing chemical synthesis technology, the result is as shown in table 3:

Table 3

Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)
Technology	??ΔTr(s)	??ΔTV(v)	??Tr60	Bending intensity (returning)	Existing technological process A	??20	??-2	??35	??80
Existing process flow B	??100	??-6	??25	??115	Existing technological process A	??20	??-2	??35	??80
Existing process flow B	??100	??-6	??25	??115	Embodiment 3	??15	??+2	??15	??130

The result finds out from table 3: high pressure 590Vf product, to store after 3 months, and rise pressure rising time value has reduced by 5～85s; The oxide-film withstand voltage does not descend before and after the aquation 1h; The water-fast pressure rising time Tr60 of closing has shortened 10～20s; The existing technological process of the bending strength ratio of embodiment has improved 15～50 times.

From table 1,2,3 as can be seen, with existing boric acid system or azelaic acid is that treatment process is compared, after oxide-film of the present invention is handled through phosphatization, the bending intensity of anode foils has improved 15～50 times, store that variable quantity pressure rising time of anode foils oxide-film has shortened 5～85s after 3 months, the oxide-film withstand voltage does not descend before and after the aquation 1h, the water-fast pressure rising time Tr60 of closing has shortened 10～20s, shows that the anode foils performance that the manufacture method of aluminum electrolysis capacitor anode foil of the present invention is produced effectively improves.

Claims

1. the manufacture method of an aluminum electrolysis capacitor anode foil, comprise boil that processing, three is polarized to, heat treatment, change into, phosphoric acid is handled, change into, heat treatment, formation process again, it is characterized in that, carrying out phosphatization before second heat treatment step handles, it is to be 1～5v/v% in phosphate inorganic agent concentration that described phosphatization is handled, and temperature is impregnation process 1～10min under 20～80 ℃ the condition.

2. the manufacture method of aluminum electrolysis capacitor anode foil according to claim 1 is characterized in that, the phosphorous acidic group inorganic agent that described phosphatization processing is adopted is one or more in phosphoric acid, phosphorous acid, ammonium dihydrogen phosphate, the ammonium hypophosphite.