WO2020129952A1 - Séparateur pour condensateur électrolytiques en aluminium et condensateur électrolytique en aluminium - Google Patents

Séparateur pour condensateur électrolytiques en aluminium et condensateur électrolytique en aluminium Download PDF

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WO2020129952A1
WO2020129952A1 PCT/JP2019/049317 JP2019049317W WO2020129952A1 WO 2020129952 A1 WO2020129952 A1 WO 2020129952A1 JP 2019049317 W JP2019049317 W JP 2019049317W WO 2020129952 A1 WO2020129952 A1 WO 2020129952A1
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Prior art keywords
separator
pva
aluminum electrolytic
electrolytic capacitor
density
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PCT/JP2019/049317
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English (en)
Japanese (ja)
Inventor
章祥 竹内
熊岡　弘倫
大 清水
愛 森川
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ニッポン高度紙工業株式会社
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Publication of WO2020129952A1 publication Critical patent/WO2020129952A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators

Definitions

  • the present invention relates to a separator for an aluminum electrolytic capacitor and an aluminum electrolytic capacitor using the separator.
  • ECUs electronic control units
  • the number of ECUs (electronic control units) installed in automobile-related equipment, which has been rapidly becoming electronic in recent years, is increasing. Since it is necessary for an automobile to mount a number of ECUs in a narrow space, miniaturization of the ECU is required. Therefore, the aluminum electrolytic capacitor mounted on the ECU is required to be downsized and have a large capacity.
  • the rated voltage of the aluminum electrolytic capacitor is 100V or less, low impedance property is required, so a net separator is used.
  • a long-mesh cylinder separator or a long-mesh separator is used in order to improve short-circuit resistance.
  • Aluminum capacitors of any rated voltage are required to be thin in order to enable higher impedance and lower capacitance in addition to higher short-circuit resistance.
  • aluminum electrolytic capacitors In medium- and high-voltage aluminum electrolytic capacitors with a rated voltage of 100 V or higher, especially at a rated voltage of 700 V or higher, aluminum electrolytic capacitors are inferior in withstand voltage, life and frequency characteristics to film capacitors, but capacity, space saving, The price is excellent.
  • low-voltage aluminum electrolytic capacitors with a rated voltage of 100 V or less are inferior in impedance, life, and space saving compared to monolithic ceramic capacitors, but are superior in capacity and price.
  • the aluminum electrolytic capacitor is required to have a smaller size and a lower impedance in addition to a larger capacity.
  • Patent Document 1 discloses a separator having at least one layer having an absolute value of zeta potential of 0 to 50.0 mV and a density of 0.700 to 1.400 g/cm 3. There is. By using the separator of Patent Document 1 which has good short-circuit resistance and impedance characteristics, it is possible to reduce the short-circuit defect rate and lower the impedance of the medium-high voltage aluminum electrolytic capacitor.
  • Patent Document 2 a high density layer 0.6 ⁇ 0.9g / cm 3, superimposed low density layer as a range of less than 0.6 cm 3, said deposited polyvinyl alcohol to the low-density layer (PVA)
  • PVA low-density layer
  • Patent Document 3 discloses an electrolytic capacitor characterized in that a separator made from solvent-spun rayon with highly developed microfibrils is impregnated and coated with a purified solution of a paper strength enhancer on electrolytic paper. .. By using this separator, it is possible to reduce the short circuit failure rate and the impedance of a low voltage aluminum electrolytic capacitor having a rated voltage of 100 V or less.
  • Patent Document 4 discloses a cross-linked PVA obtained by cross-linking a PVA-based resin with a glyoxylate composition, and a constitution of paper containing the cross-linked PVA.
  • the separator described in Patent Document 1 improves the performance of the separator by reducing the absolute value of the zeta potential, and the short-circuit resistance is the highest when the zeta potential is 0 mV. That is, only by controlling the zeta potential, it is impossible to further enhance the short circuit resistance as compared with the case where the zeta potential is 0 mV.
  • the separator described in Patent Document 3 is required to further reduce the short-circuit defect rate and lower impedance of the aluminum electrolytic capacitor, and to improve short-circuit resistance for lowering size, lower impedance, and thinning. It was
  • glyoxylic acid is a compound that corrodes aluminum
  • paper containing glyoxylic acid is used as a separator
  • corrosion of aluminum foil will occur.
  • the generated gas may cause the capacitor to burst.
  • the present invention has been made for the purpose of solving the above-mentioned problems and providing a separator in which short-circuit resistance of the separator is improved, thinning, and low impedance are provided in parallel.
  • the present invention is an invention made to provide an aluminum electrolytic capacitor having improved productivity, which enables miniaturization, large capacity, and low impedance by using the separator.
  • the present invention has, for example, the following configuration as means for solving the above-mentioned problems and achieving the above-mentioned object. That is, a separator for an aluminum electrolytic capacitor interposed between an anode and a cathode, which contains 0.1 to 10.0 g/m 2 of polyvinyl alcohol (PVA) having an ethylene glycol (EG) insolubilization rate of 90% or more.
  • PVA polyvinyl alcohol
  • EG ethylene glycol
  • a polyvinyl alcohol layer having an EG insolubilization rate of 90% or more is laminated on a cellulose layer having a density of 0.7 to 1.0 g/cm 3 . Further, for example, it is characterized in that polyvinyl alcohol having an EG insolubilization rate of 90% or more is attached to the cellulose fiber entanglement point of the cellulose fiber layer having a density of 0.2 to 0.6 g/cm 3 .
  • the aluminum electrolytic capacitor is characterized by using the separator described above.
  • the present invention it is possible to provide a separator for an aluminum electrolytic capacitor having high impact resistance and high short-circuit resistance when an overvoltage is applied or aging, and an aluminum electrolytic capacitor using the separator.
  • a separator according to an embodiment for carrying out the present invention is a polyvinyl alcohol (hereinafter sometimes referred to as “PVA”) having an ethylene glycol (hereinafter sometimes referred to as “EG”) insolubilization rate of 90% or more. And a cellulose fiber.
  • PVA polyvinyl alcohol
  • EG ethylene glycol
  • Cellulose fiber used in the present invention wood pulp made of softwood and hardwood, hemp and herbs, non-wood pulp obtained from seed hair, and also dissolved pulp or mercerized pulp obtained by purifying these, after dissolving cellulose in a solvent.
  • Cellulose fibers such as regenerated cellulose fibers regenerated into a fibrous shape can be used without particular limitation.
  • the cellulose fibers may be beaten (mechanical shearing in water) before use.
  • PVA polyvinyl alcohol having an EG (ethylene glycol) insolubilization ratio of 90% or more
  • EG ethylene glycol
  • the EG insolubilization rate is preferably 95% or more, more preferably 99% or more.
  • the EG insolubilization rate can be increased to 90% or more.
  • the type of the cross-linking agent for cross-linking PVA is not particularly limited. The higher the impedance of the separator, the higher the impedance. Therefore, polymer crosslinking agents such as polyallylamine, polyethyleneimine, and polycarboxylic acid are preferable. Further, a known general cross-linking agent may be combined with the PVA having an EG insolubilization rate of 90% or more of the present invention, as long as it does not cause deterioration of impedance characteristics.
  • PVA having an EG insolubilization rate of 90% or more in the present embodiment means being immersed in EG heated to 85° C. for 30 minutes and then washed with ion-exchanged water to remove EG. It refers to PVA having an insolubilization rate of 90% or more calculated from the weight of PVA in an absolutely dry state afterwards.
  • the PVA having an EG insolubilization rate of 90% or more may be formed as a film on the surface of the cellulose fiber layer or may be formed so as to be attached to the fiber entanglement point in the cellulose fiber layer.
  • the rated voltage of the aluminum electrolytic capacitor is 100 V or less, a low-impedance is used, so a net separator is used.
  • a rated voltage higher than that, in order to improve short-circuit resistance in order to improve short-circuit resistance, Fourdrinier separator or Fourdrinier separator is used.
  • the rated voltage of the aluminum electrolytic capacitor is 100 V or lower, it is preferable to form PVA having an EG insolubilization rate of 90% or more so as to adhere to the fiber entanglement points of the gauze separator in order to obtain low impedance.
  • a rated voltage higher than that it is preferable to form a film on the Fourdrinier separator or the high-density cellulose fiber layer of the Fourdrinth separator in order to enhance the short-circuit resistance.
  • a mixed solution of PVA and the above crosslinking agent is applied to a high density cellulose fiber layer of 0.7 to 1.0 g/cm 3. It can be obtained. Further, in order to form so as to adhere to the fiber entanglement point, it can be obtained by applying a mixed solution of PVA and the above-mentioned cross-linking agent to a cellulose layer having a density of 0.2 to 0.6 g/cm 3. It is not limited.
  • the EG insolubilization rate can significantly improve the short-circuit resistance at the time of applying an overvoltage and aging of the separator by the PVA film having a rate of 90% or more, by using the separator, The short-circuit resistance of the electrolytic capacitor can be improved.
  • the entanglement and hydrogen bonds of the fibers constituting the separator are less likely to be loosened even when impregnated with the electrolytic solution, resistance to spark discharge of the separator Can be improved. Further, as compared with the case where it is formed in a film shape, it is less likely that the movement of the electrolyte inside the separator is hindered, and the impedance is not significantly increased.
  • PVA having an EG insolubilization rate of 90% or more has a content of 0.1 to 10.0 g/m 2 . This is because if the content is less than 0.1 g/m 2, it is difficult to obtain the effect of improving the short-circuit resistance, and if the content exceeds 10.0 g/m 2 , the impedance characteristics of the aluminum electrolytic capacitor rise sharply. Because it will be.
  • the EG-insolubilized PVA content is preferably 2.0 to 9.0 g/in order to enhance the short-circuit resistance when formed into a film on the long-net cylinder separator or the high-density cellulose fiber layer of the long-net separator.
  • the fiber entanglement point of the cylinder separator When it is formed so as to adhere to the fiber entanglement point of the cylinder separator, it has a low impedance, so that it is preferably 0.1 to 3.0 g/m 2 , and more preferably 0.1 to 2.5 g. It is preferably in the range of /m 2 .
  • the thickness of the separator of this embodiment is preferably 10 to 65 ⁇ m. If the thickness of the separator exceeds 65 ⁇ m, it may be difficult to downsize the capacitor or the resistance of the separator may increase. If the thickness of the separator is less than 10 ⁇ m, the separator of the present invention having good short circuit resistance. Even in this case, the short circuit defect of the capacitor may not be suppressed in some cases.
  • the separator according to the present embodiment has high short-circuit resistance, so that the basis weight of the separator is large and it is not necessary to thicken the separator. Therefore, since the basis weight of the separator can be reduced and the thickness of the separator can be reduced, the impedance of the separator can be reduced.
  • Wo Basic weight of base material in an absolutely dry state (g/m 2 ).
  • Crosslinking agent ratio was calculated by the following formula by measuring the weight of the cross-linking agent in an absolutely dry state and the weight of EG insolubilized PVA in an absolutely dry state.
  • Crosslinking agent ratio (%) C/Co ⁇ 100
  • C Weight of crosslinking agent in an absolutely dry state
  • Co EG insolubilized PVA weight in absolute dry state
  • the electrolytic solution is removed by immersing it in ethylene glycol heated to 85° C. for 30 minutes and then washing with ion-exchanged water. Before impregnation with ethylene glycol and after impregnation washing, the PVA weight in an absolutely dry state was measured and calculated by the following formula.
  • the short-circuit rate using a capacitor element that can be wound without breakage failure, count the number of short-circuit failure during aging, divide the number of these short-circuit failure elements by the number of elements that can be wound without breakage failure, The percentage was taken as the aging short-circuit rate.
  • the impedance of the produced aluminum electrolytic capacitor was measured at a frequency of 120 Hz at 20° C. using an LCR meter.
  • the method for producing the cellulose layer and the method for containing PVA are not particularly limited.
  • a capacitor element was made using this separator, impregnated with ethylene glycol-based electrolytic solution, inserted into the case, and sealed to obtain an aluminum electrolytic capacitor of each rated voltage.
  • Example 1 Cellulose fiber softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier paper using a raw material with a CSF value of 500 ml which turned to an increase and beaten cotton pulp and sisal pulp to 400 ml Using the above raw materials, the layers formed by cylinder papermaking were combined to obtain a separator base material.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 5.7% by weight of polyethyleneimine as a cross-linking agent on this base material, and dried to give a thickness of 59.0 ⁇ m and a density of 0.787 g/cm 3. 3 , a separator having an EG insolubilized PVA content of 5.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 99.3%.
  • Example 2 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier using a raw material having a CSF value of 500 ml which turned to an increase, and a raw material beaten to 400 ml of cotton pulp and sisal pulp were used. The layers made from cylinder paper were combined to obtain a separator base material.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 5.7% by weight of polyethyleneimine as a cross-linking agent on this base material, and dried to obtain a thickness of 61.2 ⁇ m and a density of 0.819 g/ A separator having a cm 3 and an EG insolubilized PVA content of 5.6 g/m 2 was obtained. The EG insolubilization rate of this EG insolubilized PVA was 99.3%.
  • Example 3 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier using a raw material having a CSF value of 500 ml which turned to an increase, and a raw material beaten to 400 ml of cotton pulp and sisal pulp were used. The layers made from cylinder paper were combined to obtain a separator base material.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 5.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol, and dried to give a thickness of 58.9 ⁇ m and a density of 0.811 g/ A separator having a cm 3 and an EG insolubilized PVA content of 5.6 g/m 2 was obtained. The EG insolubilization rate of this EG insolubilized PVA was 99.3%.
  • Example 4 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier using a raw material having a CSF value of 500 ml which turned to an increase, and a raw material beaten to 400 ml of cotton pulp and sisal pulp were used. The layers made from cylinder paper were combined to obtain a separator base material.
  • a coating liquid prepared by mixing PVA with 11.7% by weight of polyethyleneimine as a cross-linking agent is applied to this high-density cellulose fiber layer and dried to give a thickness of 60.4 ⁇ m and a density of 0.768 g/cm 3. 3 , a separator having an EG insolubilized PVA content of 5.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 5.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol, and dried to give a thickness of 61.8 ⁇ m and a density of 0.729 g/
  • a separator having a cm 3 and an EG insolubilized PVA content of 5.4 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 99.3%.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 5.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol, and dried to give a thickness of 57.4 ⁇ m and a density of 0.922 g/
  • a separator having a cm 3 and an EG insolubilized PVA content of 5.9 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 99.3%.
  • aqueous PVA solution was applied to this base material on the low-density cellulose fiber layer and dried to obtain a separator having a thickness of 71.2 ⁇ m, a density of 0.624 g/cm 3 , and a PVA content of 5.0 g/m 2 . ..
  • Polyethyleneimine resin was applied to this substrate at a solid content of 1.0% by weight with respect to the mass of the high-density layer, and the coating was dried to give a thickness of 60.8 ⁇ m, a density of 0.580 g/cm 3 , and a zeta potential of ⁇ 47.
  • a separator of 0.0 mV was obtained.
  • Example 5 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier paper using a raw material having a CSF value of 300 ml which turned to an increase, and a raw material obtained by beatening softwood dissolved pulp and jute pulp to 400 ml were used. The layers made from cylinder paper were combined to obtain a separator base material.
  • a coating liquid prepared by mixing 1.2% by weight of polyallylamine as a cross-linking agent with polyvinyl alcohol is applied to this base material to form a high-density cellulose fiber layer and dried to give a thickness of 30.9 ⁇ m and a density of 0.766 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 7.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 90.7%.
  • Example 6 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and a layer made of Fourdrinier paper using a raw material having a CSF value of 300 ml which turned to an increase, and a raw material obtained by beatening softwood dissolved pulp and jute pulp to 400 ml were used. The layers made from cylinder paper were combined to obtain a separator base material.
  • a coating liquid prepared by mixing 2.8% by weight of polyallylamine as a cross-linking agent with polyvinyl alcohol is applied to the base material on the high-density cellulose fiber layer and dried to give a thickness of 31.4 ⁇ m and a density of 0.754 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 7.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 95.1%.
  • Example 7 The softwood kraft pulp was further beaten even after the CSF value showed 0 ml, and fourdrinier papermaking was performed using a raw material having a CSF value of 300 ml, which had turned upward, to obtain a separator substrate.
  • a coating liquid prepared by mixing 2.8% by weight of polyallylamine as a cross-linking agent with polyvinyl alcohol is applied to this base material and dried to give a thickness of 30.2 ⁇ m, a density of 0.801 g/cm 3 , and an EG insolubilized PVA.
  • a separator having a content of 2.9 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 95.1%.
  • a high-density cellulose fiber layer was coated with a coating liquid prepared by mixing 2.8% by weight of sodium glyoxylate as a cross-linking agent with polyvinyl alcohol, and dried to give a thickness of 31.9 ⁇ m and a density of 0.742 g. /Cm 3 , EG insolubilized PVA content of 7.8 g/m 2 of a separator was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 98.0%.
  • a coating liquid prepared by mixing polyvinyl alcohol with 0.2% by weight of polyallylamine as a cross-linking agent is applied to this high-density cellulose fiber layer and dried to give a thickness of 31.0 ⁇ m and a density of 0.764 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 7.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 87.4%.
  • Example 8 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material on the high-density cellulose fiber layer and dried to give a thickness of 50.5 ⁇ m and a density of 0.708 g/ A cm 3 separator having a EG insolubilized PVA content of 0.2 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 9 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a coating liquid prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material to form a high density cellulose fiber layer and dried to give a thickness of 51.0 ⁇ m and a density of 0.740 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 2.2 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 10 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material on the high-density cellulose fiber layer and dried to give a thickness of 51.1 ⁇ m and a density of 0.756 g/ A cm 3 separator having an EG insolubilized PVA content of 3.1 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 11 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material to form a high density cellulose fiber layer and dried to give a thickness of 51.3 ⁇ m and a density of 0.845 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 7.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 12 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material on the high-density cellulose fiber layer and dried to give a thickness of 51.5 ⁇ m and a density of 0.863 g/
  • a separator having a cm 3 content of EG insolubilized PVA of 8.9 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 13 Softwood kraft pulp was further beaten even after the CSF value showed 0 ml, a layer made of fourdrinier paper using a raw material having a CSF value of 200 ml that turned to an increase, and a cylinder net papermaking using the raw material beaten to 400 ml of the same raw material. The layers were combined together to obtain a separator base material.
  • a high-density cellulose fiber layer was coated with a coating liquid obtained by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol, and dried to give 51.7 ⁇ m in thickness and 0.877 g/in density.
  • a separator having a cm 3 and an EG insolubilized PVA content of 9.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material to form a high-density cellulose fiber layer and dried to give a thickness of 50.3 ⁇ m and a density of 0.708 g/
  • a separator having a cm 3 and an EG insolubilized PVA content of 0.07 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • a high-density cellulose fiber layer was coated with a coating solution prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol, and dried to give a thickness of 51.8 ⁇ m and a density of 0.893 g/
  • a separator having a cm 3 and an EG insolubilized PVA content of 10.7 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 14 Using a raw material obtained by beating 400 ml of Manila hemp pulp, sisal pulp and esparto pulp, two layers of cylinder papermaking were combined to obtain a separator base material. A coating liquid prepared by mixing 4.6% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol was applied to this base material and dried to obtain a thickness of 30.2 ⁇ m, a density of 0.586 g/cm 3 , and an EG-insolubilized PVA. A separator having a content of 0.5 g/m 2 was obtained. The EG insolubilization rate of this EG insolubilized PVA was 99.1%.
  • Example 15 Using a raw material obtained by beating 400 ml of Manila hemp pulp, sisal pulp and esparto pulp, two layers of cylinder paper were laminated to obtain a separator base material. A coating liquid prepared by mixing 2.9% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol is applied to this base material and dried to give a thickness of 31.4 ⁇ m, a density of 0.564 g/cm 3 , and an EG-insolubilized PVA. A separator having a content of 0.5 g/m 2 was obtained. The EG insolubilization rate of this EG insolubilized PVA was 90.7%.
  • Example 16 Using a raw material obtained by beating 400 ml of Manila hemp pulp, sisal pulp and esparto pulp, two layers of cylinder papermaking were combined to obtain a separator base material. A coating liquid prepared by mixing 11.7% by weight of polyethyleneimine as a cross-linking agent with polyvinyl alcohol was applied to this base material and dried to obtain a thickness of 30.8 ⁇ m, a density of 0.575 g/cm 3 , and an EG-insolubilized PVA. A separator having a content of 0.5 g/m 2 was obtained. The EG insolubilization rate of this EG insolubilized PVA was 96.8%.
  • Example 17 Manila hemp pulp, sisal hemp pulp and esparto pulp were beaten to 600 ml, and three layers of cylinder net-making paper were combined to obtain a separator substrate.
  • a coating solution of polyvinyl alcohol mixed with 3.0% by weight of polyallylamine as a cross-linking agent was applied and dried to obtain a thickness of 49.2 ⁇ m, a density of 0.292 g/cm 3 , and an EG-insolubilized PVA.
  • a separator having a content of 1.9 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.0%.
  • Example 18 Manila hemp pulp, sisal hemp pulp and esparto pulp were beaten to 600 ml, and three layers of cylinder net-making paper were combined to obtain a separator substrate.
  • a coating solution of polyvinyl alcohol mixed with 3.0% by weight of polyallylamine as a cross-linking agent was applied and dried to obtain a thickness of 49.9 ⁇ m, a density of 0.311 g/cm 3 , and an EG-insolubilized PVA.
  • a separator having a content of 2.8 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.0%.
  • Example 19 Manila hemp pulp, sisal hemp pulp and esparto pulp were beaten to 600 ml, and three layers of cylinder net-making paper were combined to obtain a separator substrate.
  • a coating solution of polyvinyl alcohol mixed with 3.0% by weight of polyallylamine as a cross-linking agent was applied and dried to obtain a thickness of 52.1 ⁇ m, a density of 0.430 g/cm 3 , and an EG-insolubilized PVA.
  • a separator having a content of 9.7 g/m 2 was obtained.
  • the EG insolubilization rate of this EG insolubilized PVA was 96.0%.
  • Table 1 shows the evaluation results of the separators of Examples 1 to 13, Comparative Examples 1 to 6, Conventional Examples 1 and 2, and the aluminum electrolytic capacitors.
  • the size of each aluminum electrolytic capacitor was 18.0 mm in diameter and 36.0 mm in height.
  • Table 2 shows the evaluation results of the separators of Examples 14 to 19, Comparative Examples 7 to 11, Conventional Examples 3 and 4, and the aluminum electrolytic capacitors.
  • the size of each aluminum electrolytic capacitor was 18.0 mm in diameter and 36.0 mm in height.
  • Examples 1 to 4 use separators in which a PVA aqueous solution containing a cross-linking agent is applied to the high density cellulose fiber layer of the long net cylinder two-layer separator. Is as low as 0.0 to 0.8%. It is considered that this is because the separator has high short-circuit resistance.
  • Comparative Example 1 the same PVA aqueous solution containing a crosslinking agent as in Examples 1 to 3 was applied, but the high density cellulose layer density was low at 0.688 g/cm 3, and the PVA aqueous solution penetrated the separator. Therefore, the thickness of the film layer becomes thin. Therefore, the aging short-circuit rate is as high as 11.8%, which shows that the short-circuit resistance of the separator is low.
  • Comparative Example 2 the same PVA aqueous solution containing a crosslinking agent as in Examples 1 to 3 was applied, but the high density cellulose layer density was as high as 1.002 g/cm 3 , so the impedance was 0.899 ⁇ . It is higher than in Examples 1 to 3, and it can be seen that the impedance performance is inferior. It is considered that this is because the density of the high-density cellulose layer was too high, so that the ESR of the separator increased.
  • Conventional Example 1 has a configuration of PVA of Patent Document 4, in which a separator coated with PVA is used as the low density cellulose fiber layer of the long net cylinder two-layer separator, and boric acid was added to the electrolytic solution for gelation.
  • PVA PVA having an EG insolubilization rate of 90% or more.
  • the aging short-circuit rate of the capacitor of Conventional Example 1 is 17.2%, and the numerical values of Examples 1 to 4 are lower. From this, it is understood that the gelled PVA increases the withstand voltage of the electrolytic solution, but does not enhance the short-circuit resistance of the separator against aging short-circuit, and thus the short-circuit resistance at the rated voltage of 750 V is insufficient.
  • Conventional Example 2 has the structure of Patent Document 1, and uses a separator in which polyethyleneimine is applied to the high-density cellulose fiber layer of the long-net cylinder two-layer separator and the absolute value of the zeta potential is set to 0 to 50 mV.
  • This is an example and does not contain PVA having an EG insolubilization rate of 90% or more.
  • the aging short-circuit rate of the capacitor of Conventional Example 2 is 8.0%, and the numerical values of Examples 1 to 4 are lower. From this, it is understood that the separators of Examples 1 to 4 have high short-circuit resistance.
  • the aluminum electrolytic capacitors of Examples 5 to 7 and Comparative Examples 3 and 4 all have a rated voltage of 450V.
  • Examples 5 and 6 use a separator in which a PVA aqueous solution containing a cross-linking agent is applied to the high-density cellulose fiber layer of the long-net cylinder two-layer separator, and
  • Example 7 is a long-net separator and a cross-linking agent.
  • a separator coated with a PVA aqueous solution added with is used. As shown in Table 1, the aging short-circuit rate is as low as 0.2 to 0.5% in all cases.
  • Comparative Example 3 uses a separator in which the same high density cellulose fiber layer as in Examples 5 and 6 is coated with an aqueous PVA solution containing sodium glyoxylate as a crosslinking agent.
  • the EG insolubilized PVA content is the same as in Examples 5 and 6, but the impedance is 0.433 ⁇ , which is higher than those in Examples 5 and 6.
  • the aging short circuit defect rate was 39.4%, which is higher than those in Examples 5 and 6. This is probably because aluminum was corroded by glyoxylic acid.
  • Comparative Example 4 uses a separator in which a PVA aqueous solution containing a cross-linking agent is applied to the high density cellulose fiber layer of the same separator as in Examples 5 and 6.
  • the EG insolubilized PVA content was the same as in Examples 5 and 6, but the crosslinker ratio was 0.2%, which was lower than those in Examples 5 and 6, and the EG insolubilized ratio was low, 87.4%.
  • the aging short-circuit rate is 10.1%, which is higher than those in Examples 5 and 6. It is considered that this is because the EG insolubilization rate was as low as 87.4% and the short-circuit resistance of the separator was reduced.
  • Examples 8 to 13 and Comparative Examples 5 and 6 all have a rated voltage of 550V.
  • Examples 8 to 13 use a separator in which a PVA aqueous solution containing a cross-linking agent is applied to the high density cellulose fiber layer of the Fourdrinier net two-layer separator. Is as low as 0.0 to 0.9%.
  • Comparative Example 5 uses a separator in which the same high density cellulose fiber layer as in Examples 8 to 13 is coated with a PVA aqueous solution containing a crosslinking agent.
  • the cross-linking agent ratio is the same as in Examples 8 to 13, but the EG insolubilized PVA content is 0.07 g/m 2, which is smaller than that in Examples 8 to 13.
  • the aging short-circuit rate is 19.7%, which is higher than those of Examples 8 to 13. It is considered that this is because the EG insolubilized PVA content was as low as 0.07 g/m 2 and the short-circuit resistance of the separator was reduced.
  • Comparative Example 6 uses a separator in which the same high density cellulose fiber layer as in Examples 8 to 13 is coated with a PVA aqueous solution containing a crosslinking agent.
  • the cross-linking agent ratio is the same as in Examples 8 to 13, but the EG insolubilized PVA content is 10.7 g/m 2, which is higher than those in Examples 8 to 13.
  • the impedance is 0.641 ⁇ , which is a numerical value higher than that of Examples 8 to 13. It is considered that this is because the EG insolubilized PVA content was as large as 10.7 g/m 2, and therefore the impedance was deteriorated.
  • Examples 14 to 16 use separators in which a PVA aqueous solution containing a cross-linking agent is applied to the cylinder double-layer separator, and as shown in Table 2, the aging short-circuit rate is 0.6 to 0.9%. It is a low number. It is considered that this is because the separator has high short-circuit resistance.
  • Comparative Example 7 uses a separator having a density of 0.6 g/cm 3 or more and a PVA aqueous solution obtained by adding the same crosslinking agent as in Example 14 to the separator.
  • the EG insolubilized PVA content is the same as that in Example 14, but the impedance is 0.301 ⁇ , which is a higher value than that in Example 14. It is considered that this is because the density of the base material was as high as 0.612 g/cm 3, and thus the PVA having an EG insolubilization rate of 90% or more became a film and the impedance deteriorated.
  • Comparative Example 8 the same separator as in Examples 14 to 16 is applied with a PVA aqueous solution containing a crosslinking agent.
  • the EG insolubilized PVA content was the same as that in Examples 14 to 16, but the crosslinking agent ratio was 0.2%, which was lower than that in Examples 14 to 16, and the EG insolubilized ratio was low, 87.8%.
  • the aging short-circuit rate is 12.0%, which is higher than those of Examples 14 to 16. It is considered that this is because the EG insolubilization rate was as low as 87.8% and the short-circuit resistance of the separator was reduced.
  • Example 3 uses a cylinder double-layer separator made of the same raw material as in Examples 14 to 16.
  • the aging short-circuit rate is 24.9%, which is a lower value in Examples 14 to 16, indicating that the separators in Examples 14 to 16 have higher short-circuit resistance.
  • Example 4 has a configuration of PVA of Patent Document 4, in which a separator coated with PVA is used as a cylinder two-layer separator made of the same raw material as in Examples 14 to 16, and used as an electrolytic solution for gelation. This is an example in which boric acid is added, and PVA having an EG insolubilization rate of 90% or more is not contained.
  • the aging short-circuit rate of the capacitor of Conventional Example 4 is 18.1%, which is lower in Examples 14 to 16. From this, it is understood that the gelled PVA increases the withstand voltage of the electrolytic solution, but does not enhance the short-circuit resistance of the separator against aging short-circuit, and thus the short-circuit resistance at the rated voltage of 100 V is insufficient.
  • Examples 17 to 19 and Comparative Examples 9 to 11 all have a rated voltage of 50V.
  • Examples 17 to 19 use a separator in which a crosslinked PVA aqueous solution is applied to the cylinder three-layer separator, and as shown in Table 2, the aging short-circuit rate is as low as 0.0 to 0.4%. ing. It is considered that this is because the separator has high short-circuit resistance.
  • Comparative Example 9 the same separator as in Examples 17 to 19 is applied with a PVA aqueous solution containing a crosslinking agent.
  • the cross-linking agent ratio is the same as in Examples 17 to 19, but the EG insolubilized PVA content is 0.05 g/m 2, which is smaller than that in Examples 17 to 19.
  • the aging short-circuit rate is 29.0%, which is higher than those of Examples 17 to 19. It is considered that this is because the EG insolubilized PVA content was as small as 0.05 g/m 2 and the short-circuit resistance of the separator was reduced.
  • Comparative Example 10 the same separator as in Examples 17 to 19 is applied with a PVA aqueous solution containing a crosslinking agent.
  • the cross-linking agent ratio is the same as in Examples 17 to 19, but the EG insolubilized PVA content is 10.4 g/m 2, which is higher than those in Examples 17 to 19.
  • the impedance is 0.589 ⁇ , which is higher than those of Examples 17 to 19. Since the EG insolubilized PVA content is as high as 10.4 g/m 2 , the PVA having an EG insolubilization rate of 90% or more becomes a film and fills the voids of the base material, which is considered to deteriorate the impedance. ..
  • Comparative Example 11 uses a separator having a density of less than 0.2 g/cm 3 and a PVA aqueous solution obtained by adding the same crosslinking agent as in Examples 17 to 19 to the separator.
  • the EG insolubilized PVA content was the same as in Example 17, but an aluminum electrolytic capacitor could not be obtained due to aging short-circuiting of all elements. Since the density of the base material is as low as 0.195 g/cm 3 , there are few entanglement points between the cellulose fibers, and it is difficult to obtain the effect of adhering the entanglement points between the fibers with PVA having an EG insolubilization rate of 90% or more. It is considered that the short-circuit resistance of No. 1 has deteriorated.
  • the short-circuit resistance of the aluminum electrolytic capacitor is improved, and it is possible to reduce the size, increase the capacity, and improve the productivity.
  • An aluminum electrolytic capacitor can be provided.
  • the separator of this embodiment contains PVA having an EG insolubilization rate of 90% or more.
  • PVA having an EG insolubilization rate of 90% or more does not dissolve and maintains its shape even after being immersed in the electrolytic solution of the aluminum electrolytic capacitor.
  • the separator containing PVA having an EG insolubilization rate of 90% or more has higher viscoelasticity than a separator made of only cellulose fibers, and thus has high impact resistance and high short-circuit resistance during overvoltage application or aging. There was found.
  • the oxide film may be dielectrically broken down and spark discharge may occur, resulting in a short circuit between the electrodes. Further, in the aging process of the aluminum electrolytic capacitor, a direct current voltage is applied to repair a partial defect of the oxide film, but at this time, spark discharge may occur and an aging short circuit may occur. Against a short circuit which is a failure mode at the time of such an abnormality, the separator according to the present embodiment has a high short circuit resistance at the time of applying an overvoltage or at the time of aging, and can reduce the short circuit defective rate of the aluminum electrolytic capacitor. ..
  • PVA having an EG insolubilization ratio of 90% or more enhances resistance to impact due to spark discharge generated during overvoltage application or aging, so that the separator is less likely to pierce.
  • a short circuit defect of the aluminum electrolytic capacitor using the separator of the present embodiment can be suppressed. Therefore, even if the thickness of the separator is reduced, the short-circuit resistance of the separator can be maintained. Further, by making the separator thin, it is possible to contribute to downsizing and low impedance of an aluminum electrolytic capacitor using this separator.
  • the separator according to the present embodiment is short-circuit resistant during overvoltage application and aging. Since it has high properties, an electrolytic solution having a small specific resistance can be used, and this also contributes to lowering the impedance of the aluminum electrolytic capacitor.
  • PVA having an EG insolubilization rate of 90% or more is used to increase the resistance to impact of the separator, thereby increasing the short-circuit resistance of the aluminum electrolytic capacitor. There is no need for pretreatment such as.
  • the separator made of cellulose fiber swells greatly in an electrolytic solution containing alcohol such as ethylene glycol as a main solvent. This is because the hydrogen bond between the celluloses penetrates into the hydrogen bond between the celluloses and the hydrogen bond between the celluloses is broken. Then, when the cellulose fibers swell, the voids between the cellulose fibers become small, so that the permeation of the electrolytic solution into the separator is delayed.
  • the separator of the present embodiment contains PVA having an EG insolubilization rate of 90% or more, it does not significantly swell in the ethylene glycol-based electrolytic solution, so that the fiber void does not become small, and Does not hinder the permeation of the electrolyte. Therefore, the productivity of the aluminum electrolytic capacitor does not decrease.
  • the present embodiment it is possible to provide a separator for an aluminum electrolytic capacitor, which has excellent short circuit resistance, is thinned, and has low impedance. Further, by using the separator, it is possible to provide an aluminum electrolytic capacitor in which the short-circuit resistance of the aluminum electrolytic capacitor is improved, the size and the capacity can be increased, and the productivity is improved.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Cell Separators (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'objectif de la présente invention est de proposer : un séparateur pour un condensateur électrolytique en aluminium, le séparateur ayant une haute résistance aux chocs et présentant une haute résistance aux courts-circuits durant une application à surtension ou un vieillissement ; et un condensateur électrolytique en aluminium qui utilise le séparateur. La présente invention est pourvue de la caractéristique suivante en tant que moyen pour atteindre un tel objectif. L'invention concerne un séparateur pour un condensateur électrolytique en aluminium, une électrode positive et une électrode négative se trouvent de part et d'autre du séparateur et ce dernier comprend une fibre de cellulose et de 0,1 à 10,0 g/m2 d'un alcool polyvinylique qui a un rapport d'insolubilisation d'éthylène glycol d'au moins 90 %. Dans ladite invention, par exemple, une couche d'alcool polyvinylique qui a un rapport d'insolubilisation d'éthylène glycol d'au moins 90 % est stratifiée sur une couche de fibres de cellulose qui a une densité de 0,7 à 1,0 g/cm3, ou l'alcool polyvinylique qui a un rapport d'insolubilisation d'éthylène glycol d'au moins 90 % adhère à des points d'enchevêtrement de fibres de cellulose d'une couche de fibres de cellulose qui a une densité de 0,2 à 0,6 g/cm3.
PCT/JP2019/049317 2018-12-19 2019-12-17 Séparateur pour condensateur électrolytiques en aluminium et condensateur électrolytique en aluminium WO2020129952A1 (fr)

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JP2018-237456 2018-12-19
JP2018237456A JP2020098894A (ja) 2018-12-19 2018-12-19 アルミニウム電解コンデンサ用セパレータ及びアルミニウム電解コンデンサ

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS462291B1 (fr) * 1968-07-02 1971-01-20
JPS4893936A (fr) * 1972-03-13 1973-12-04
JPS62252065A (ja) * 1986-04-23 1987-11-02 Nippon Sheet Glass Co Ltd 密閉型鉛蓄電池用セパレータ
JP2001189241A (ja) * 1999-12-28 2001-07-10 Nippon Chemicon Corp 電解コンデンサ
JP2005294596A (ja) * 2004-03-31 2005-10-20 Nippon Chemicon Corp 電解コンデンサ
JP2007335294A (ja) * 2006-06-16 2007-12-27 Nissan Motor Co Ltd 積層型電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS462291B1 (fr) * 1968-07-02 1971-01-20
JPS4893936A (fr) * 1972-03-13 1973-12-04
JPS62252065A (ja) * 1986-04-23 1987-11-02 Nippon Sheet Glass Co Ltd 密閉型鉛蓄電池用セパレータ
JP2001189241A (ja) * 1999-12-28 2001-07-10 Nippon Chemicon Corp 電解コンデンサ
JP2005294596A (ja) * 2004-03-31 2005-10-20 Nippon Chemicon Corp 電解コンデンサ
JP2007335294A (ja) * 2006-06-16 2007-12-27 Nissan Motor Co Ltd 積層型電池

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