Separator for aluminum electrolytic capacitors, and aluminum electrolytic capacitor

Abstract

Provided is a separator for aluminum electrolytic capacitors, in which the separator has both good short circuit resistance and good impedance characteristics. A separator for aluminum electrolytic capacitors is formed, in which the separator is interposed between a positive electrode and a negative electrode of an aluminum electrolytic capacitor, and the separator includes at least one layer that is formed from plant fibers and has a dielectric breakdown strength of greater than or equal to 20 kV/mm.

Claims

1. A separator for aluminum electrolytic capacitors, the separator being interposed between a positive electrode and a negative electrode of an aluminum electrolytic capacitor, the separator comprising at least one layer that is formed from plant fibers and has a dielectric breakdown strength of greater than or equal to 21 kV/mm, an average fiber length in a range from 0.37 mm to 1.95 mm, a mode value of a fiber length distribution of every 0.05 mm being in a range from 0.20 mm to 0.40 mm, and a 0.15% freeness that is less than or equal to 300 ml.

2. An aluminum electrolytic capacitor comprising: a positive electrode and a negative electrode; and a separator interposed between the positive electrode and the negative electrode, wherein as the separator, a separator for aluminum electrolytic capacitors according to claim 1 is used.

Description

DESCRIPTION OF EMBODIMENTS

(1) Hereinafter, an embodiment example of the present invention will be described in detail.

(2) A separator for aluminum electrolytic capacitors of the present invention includes at least one layer that is formed from plant fibers and has a dielectric breakdown strength of greater than or equal to 20 kV/mm.

(3) In addition, an aluminum electrolytic capacitor of the present invention includes: a positive electrode and a negative electrode; and a separator interposed between the positive electrode and the negative electrode, in which, as the separator, a separator for aluminum electrolytic capacitors of the present invention is used.

(4) The plant fiber used in the present invention is not particularly limited, and any fiber can be used, and wood pulp or non-wood pulp are suitably used, for example.

(5) These pulps and fibers may be bleached, or may be ones purified such as dissolving pulp, or may be mercerized pulp.

(6) As wood pulps, it is possible to use conifers such as spruce, fir, pine, and hemlock, and broadleaved trees such as beech, oak, birch, and eucalyptus.

(7) As non-wood pulp, it is possible to use: vein fibers such as manila hemp, sisal hemp, banana, and pineapple; bast fibers such as paper mulberry, Edgeworthia papyrifera, Diplomorpha sikokiana, jute, kenaf, hemp, and flax; Gramineae plant fibers such as esparto, bamboo, bagasse, straw, and reed; seed hair fibers such as cotton, linters, and kapok; fruit fibers such as palm; and various other plants such as soft rush and sabai grass.

(8) In addition, these materials may be used in one type or in mixture of two or more types.

(9) The plant fibers used in the present invention need to be subjected to beating processing. For the beating processing, beating machines used for preparation of a papermaking raw material can be used without particular limitation, such as a disc refiner, a conical refiner, a high pressure homogenizer, and a beater.

(10) In these plant fibers containing cellulose, hydrogen bonds are formed in the fibers and between the fibers, and the fibers are bound together, whereby denseness of a sheet is improved. In the beaten plant fibers, the fibers are made finer, and this tendency is further enhanced, so that the fibers adhere to each other not by points but by lines or surfaces, and a denser sheet can be formed.

(11) When fibers other than plant fibers are used, such as synthetic fibers, the hydrogen bond of cellulose is inhibited, and the denseness of the sheet is reduced. In addition, even in the case of cellulose fibers, a chemical fiber such as rayon is hard compared to the above-described plant fibers, so that adhesion is weak between the fibers, and the short circuit resistance is reduced of the separator.

(12) For example, wet nonwoven fabric is formed using a papermaking method, whereby the separator of the present invention can be formed.

(13) The papermaking type of the separator is not particularly limited as long as the dielectric breakdown strength can be satisfied, and papermaking types can be used, such as Fourdrinier papermaking, tanmo papermaking, or cylinder papermaking. Among these papermaking types, Fourdrinier papermaking can further improve the denseness of the separator.

(14) However, as long as the dielectric breakdown strength of the present invention is satisfied, the method of forming the layers constituting the separator is not limited, and it is not limited to the papermaking method.

(15) In addition, the separator of the present invention may further include another layer if the layer has a dielectric breakdown strength of greater than or equal to 20 kV/mm. Regarding the other layer, there is no particular limitation on the constituent fibers and the dielectric breakdown strength as long as a function as the separator is not inhibited. In addition, in sheet formation of the separator of the present invention, additives may be added such as a dispersing agent, an antifoaming agent, and a paper strengthening agent as long as the impurity content does not affect the separator for capacitors.

(16) Further, the separator of the present invention may be subjected to post-processing such as paper strengthening processing, lyophilic processing, calendering, embossing after the sheet formation as long as the dielectric breakdown strength is satisfied.

(17) The separator of the present invention includes at least one layer having a dielectric breakdown strength of greater than or equal to 20 kV/mm. If the dielectric breakdown strength is greater than or equal to 20 kV/mm, a separator is made having excellent short circuit resistance, the separator being able to contribute to downsizing, coping with high voltage, coping with overvoltage, and the like of the aluminum electrolytic capacitor. Then, the separator having high short circuit resistance also enables thinning of the separator, and can also contribute to reduction of the impedance.

(18) From a viewpoint of short circuit resistance, the dielectric breakdown strength is preferably as high as possible, but practically it is considered that the upper limit is about 100 kV/mm. To make the dielectric breakdown strength greater than 100 kV/mm, it is necessary to significantly progress refinement of the plant fiber, but it may be difficult to form a separator with an excessively refined plant fiber.

(19) Note that, the dielectric breakdown strength is a value obtained by dividing a voltage (dielectric breakdown voltage) when a voltage is applied to electrodes sandwiching a separator and the separator is broken and short-circuited, by the thickness of the separator, and is used as an index for measuring short circuit resistance per unit thickness of the separator.

(20) When the dielectric breakdown strength is less than 20 kV/mm, it can be said that the dielectric breakdown voltage of the separator is too low compared to the thickness, or the thickness is too thick compared to the dielectric breakdown voltage of the separator. In other words, when the dielectric breakdown strength is less than 20 kV/mm, the separator cannot be made thinner than a certain level to satisfy the short circuit resistance of the separator, and it becomes difficult to reduce the impedance, or the separator cannot be made thicker than a certain level to satisfy a desired impedance, and it becomes difficult to improve the short circuit resistance of the separator.

(21) The thickness of the separator is preferably 10 to 80 m. By making a separator including a layer having a thickness of 10 to 80 m and a dielectric breakdown strength of greater than or equal to 20 kV/mm, the separator can be made to have both good short circuit resistance and good impedance characteristics.

(22) When the thickness is less than 10 m, it may be difficult to reduce the short circuit failure of the capacitor even with the separator of the present invention having good short circuit resistance. When the thickness exceeds 80 m, it may be difficult to lower the impedance of the capacitor even with the separator of the present invention having good impedance characteristics.

(23) The density of the separator generally used is about 0.60 to 1.00 g/cm.sup.3.

(24) In addition, in a multilayer separator, in some cases, a separator is used having a density of less than 0.60 g/cm.sup.3 as a whole by combining a layer of about 0.60 to 1.00 g/cm.sup.3 with a layer having a lower density; however, in the separator of the present invention, the density of the separator is not particularly limited as long as the dielectric breakdown strength is satisfied.

(25) For example, by making the freeness 0 to 300 ml measured in accordance with JIS P8121 [Pulps-Determination of drainability-Part 2: Canadian Standard freeness method] except that an 80 mesh wire mesh having an opening ratio of 31.3% is used and the sample concentration is 0.15 mass %, the separator of the present invention can be obtained having a dielectric breakdown strength of greater than or equal to 20 kV/mm.

(26) As an index of the degree of beating of fibers, a Canadian standard freeness is generally used that is measured in accordance with JIS P 812 1-2 Pulps-Determination of drainability-Part 2: Canadian Standard freeness method. The Canadian standard freeness is a volume of drainage collected from a side orifice of a Canadian standard freeness tester, expressed in ml. Specifically, the amount of drainage is measured that passes through a fiber mat formed on a sieve plate including 97 holes having a diameter of 0.5 mm per 1 cm.sup.2, and is drained from the side orifice in the measuring funnel.

(27) The fibers are refined by beating. Since drainability is reduced in the refined fiber, the value of the Canadian standard freeness decreases as the beating progresses, and reaches 0 ml. When the beating is further progressed, fine fibers passing through the sieve plate holes increase, and the value of the freeness turns to rise.

(28) In other words, the Canadian standard freeness is not appropriate as an index for evaluating drainability of highly beaten fibers. To measure an accurate freeness, it is necessary to use a fine mesh to capture the refined fiber. Further, since drainability is further degraded when the fine mesh is used, it is necessary to set the sample concentration low to obtain an adequate drainage rate.

(29) Thus, in the embodiment example of the present invention, to measure the accurate freeness, a 0.15% freeness is used measured in accordance with JIS P8121-2 except that the 80 mesh wire mesh having the opening ratio of 31.3% is used and the sample concentration is 0.15 mass %.

(30) When the value of the 0.15% freeness is greater than 300 ml, the degree of refinement of the fiber is low, so that a dense paper layer cannot be formed and the dielectric breakdown strength may be less than 20 kV/mm. In addition, even in the case of the 0.15% freeness, when the beating is highly progressed, the number of fine fibers passing through the sieve plate holes may increase, and the value of the freeness may turn to rise. In fibers that are highly beaten and whose value of the 0.15% freeness is turned to rise and become greater than 300 ml, problems occur such as a decrease in a yield on the wire of the raw material at the time of papermaking, and a significant reduction in productivity due to a decrease in drainage rate, so that the fibers are not suitable for the separator of the present invention.

(31) As described above, in the embodiment example of the present invention, the freeness is used as an index of the refinement of the fiber; however, the implementation means is not particularly limited as long as the dielectric breakdown strength of the present invention can be satisfied, and it is not limited to the above-described freeness. In addition, the concentration of the sample for measuring the freeness, and the mesh of the wire for measuring the freeness are not particularly limited.

(32) It has been found that the configuration of the above separator can provide an aluminum electrolytic capacitor excellent in short circuit resistance.

EXAMPLES

(33) Hereinafter, various specific examples and comparative examples will be described in detail of the separator for aluminum electrolytic capacitors according to the present invention and the aluminum electrolytic capacitor including the separator for aluminum electrolytic capacitors.

Method of Measuring Characteristics of Separator and Aluminum Electrolytic Capacitor

(34) The specific measurement of characteristics of the separator and the aluminum electrolytic capacitor of the present embodiment was performed on the following conditions and methods.

Thickness

(35) The thickness of the separator was measured by using a micrometer of 5.1.1 Measuring instrument and measuring method a) The case of using outside micrometer defined in JIS C 2300-2 Cellulosic papers for electrical purposes-Part 2: Methods of test 5.1 Thickness, by a method of folding on 10 sheets of 5.1.3 The case measuring thickness by folding paper.

Density

(36) The density of the separator in the bone dry condition was measured by a method defined in Method B of JIS C 2300-2 Cellulosic papers for electrical purposes-Part 2: Methods of test 7.0A Density.

Average Fiber Length

(37) The average fiber length is a value of the length weighted average fiber length measured by using a fiber length measurement apparatus (Kajaani FiberLab V4 (made by Metso Automation)) in accordance with JIS P 8226-2 Pulps-Determination of fibre length by automated optical analysis-Part 2: Unpolarized light method (ISO 16065-2 Pulps-Determination of Fibre length by automated optical analysis-Part 2: Unpolarized light method).

Mode Value in Fiber Length Distribution of Every 0.05 mm

(38) The mode value in the fiber length distribution of every 0.05 mm is a value having the highest frequency in the fiber length distribution of every 0.05 mm obtained in the average fiber length measurement.

0.15% Freeness

(39) Measurement was performed in accordance with JIS P8121 [Pulps-Determination of drainability-Part 2: Canadian Standard freeness method] except that the 80 mesh wire mesh having the opening ratio of 31.3% is used and the sample concentration is 0.15 mass %.

Dielectric Breakdown Strength

(40) The dielectric breakdown strength of the separator was measured in accordance with a method specified in JIS C 2300-2 Cellulosic papers for electrical purposes-Part 2: Methods of test 24 Dielectric breakdown strength 24.2.2 The case of direct current Method B.

Production of Aluminum Electrolytic Capacitor Using Separator

(41) Hereinafter, a method will be described of producing the aluminum electrolytic capacitor using the separator of the present embodiment example.

(42) The separator of the present embodiment was interposed between a positive electrode foil and a negative electrode foil, and was wound, whereby an aluminum electrolytic capacitor element was obtained. The element was housed in a cylindrical aluminum case with a bottom, and an electrolyte was injected and vacuum impregnation was performed, and then sealing was performed with a sealing rubber, whereby an aluminum electrolytic capacitor was produced.

Short Circuit Failure Rate

(43) The short circuit failure rate was a percentage obtained by counting the number of short circuits of a wound element before electrolyte impregnation and the number of short circuit failures during aging of the winding element by using the produced capacitor element, and dividing the number of elements of these short circuit failures by the number of elements wound without breakage failure.

Impedance

(44) The impedance of the produced aluminum electrolytic capacitor was measured by using an LCR meter at a frequency of 1 kHz at 20 C.

Example 1

(45) A separator of Example 1 was obtained by using a raw material obtained by beating softwood unbleached kraft pulp with a disc refiner, and performing Fourdrinier papermaking.

(46) The separator had a thickness of 30 m, a density of 0.75 g/cm.sup.3, an average fiber length of 1.95 mm, a mode value of 0.40 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 280 ml, and a dielectric breakdown strength of 21 kV/mm.

(47) By using the separator, as an aluminum electrolytic capacitor of Example 1, an aluminum electrolytic capacitor was produced having a rated voltage of 250 V, a rated capacity of 47 F, a diameter of 12.5 mm, and a height of 20.0 mm. The short circuit failure rate of the aluminum electrolytic capacitor was 0.1%, and the impedance was 1.5.

Example 2

(48) A separator of Example 2 was obtained by using a raw material obtained by beating softwood TCF bleached kraft pulp with a disc refiner, and performing Fourdrinier papermaking.

(49) The separator had a thickness of 20 m, a density of 1.00 g/cm.sup.3, an average fiber length of 0.37 mm, a mode value of 0.20 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 270 ml (a value after the beating was further progressed from 0 ml and turned to rise), and a dielectric breakdown strength of 96 kV/mm.

(50) By using the separator, as an aluminum electrolytic capacitor of Example 2, an aluminum electrolytic capacitor was produced having a rated voltage of 250 V, a rated capacity of 47 F, a diameter of 12.0 mm, and a height of 20.0 mm. In the aluminum electrolytic capacitor, no short circuit failure occurred. In addition, the impedance was 1.4.

Comparative Example 1

(51) A separator of Comparative Example 1 was obtained by using a raw material obtained by beating softwood unbleached kraft pulp with a disc refiner, and performing Fourdrinier papermaking.

(52) The separator had a thickness of 40 m, a density of 0.90 g/cm.sup.3, an average fiber length of 2.08 mm, a mode value of 0.60 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 315 ml, and a dielectric breakdown strength of 17 kV/mm.

(53) By using the separator, as an aluminum electrolytic capacitor of Comparative Example 1, an aluminum electrolytic capacitor was produced having a rated voltage of 250 V, a rated capacity of 47 F, a diameter of 13.0 mm, and a height of 20.0 mm. The short circuit failure rate of the aluminum electrolytic capacitor was 3.3%, and the impedance was 2.0.

Comparative Example 2

(54) A separator of Comparative Example 2 was obtained by mixing softwood unbleached kraft pulp beaten with a disc refiner and solvent-spun cellulose fibers beaten with a disc refiner at a ratio of 2:1, and performing Fourdrinier papermaking.

(55) The separator had a thickness of 40 m, a density of 0.65 g/cm.sup.3, an average fiber length of 1.65 mm, a mode value of 0.30 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 50 ml, and a dielectric breakdown strength of 15 kV/mm.

(56) By using the separator, as aluminum electrolytic capacitor of Comparative Example 2, an aluminum electrolytic capacitor was produced having a rated voltage of 250 V, a rated capacity of 47 F, a diameter of 13.0 mm, and a height of 20.0 mm. The short circuit failure rate of the aluminum electrolytic capacitor was 14.5%, and the impedance was 1.8.

Conventional Example

(57) A commercially available porous film was used as a separator of Conventional Example. The separator had a thickness of 20 m, a density of 0.40 g/cm.sup.3, and a dielectric breakdown strength of 170 kV/mm.

(58) By using the separator, as an aluminum electrolytic capacitor of Conventional Example, an aluminum electrolytic capacitor was produced having a rated voltage of 250 V, a rated capacity of 47 F, a diameter of 12.0 mm, and a height of 20.0 mm. In the aluminum electrolytic capacitor, no short circuit failure occurred. In addition, the impedance was 4.2.

Example 3

(59) A separator of Example 3 was obtained by using a Fourdrinier cylinder combination paper machine, and performing papermaking with a raw material obtained by mixing Manila hemp pulp and hemp pulp in a ratio of 1:1 and beating the pulp with a disc refiner, in the Fourdrinier section, and performing papermaking with a raw material obtained by mixing Manila hemp pulp and hemp pulp at a ratio of 1:1 and lightly beating the pulp with a disc refiner, in the cylinder section, and combining the papermakings together.

(60) The separator was formed from two layers of a Fourdrinier layer and a cylinder layer, and had a thickness of 50 m and a density of 0.72 g/cm.sup.3 in the separator as a whole. The Fourdrinier layer had a thickness of 20 m, a density of 0.85 g/cm.sup.3, an average fiber length of 0.86 mm, a mode value of 0.30 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 10 ml, and a dielectric breakdown strength of 49 kV/mm. The cylinder layer had a thickness of 30 m, a density of 0.63 g/cm.sup.3, an average fiber length of 2.10 mm, a mode value of 2.42 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 730 ml, and a dielectric breakdown strength of 13 kV/mm.

(61) By using the separator, as an aluminum electrolytic capacitor of Example 3, an aluminum electrolytic capacitor was produced having a rated voltage of 450 V, a rated capacity of 3.3 F, a diameter of 12.5 mm, and a height of 20.0 mm. The short circuit failure rate of the aluminum electrolytic capacitor was 0.2%, and the impedance was 20.5.

Comparative Example 3

(62) A separator of Comparative Example 3 was obtained by using a Fourdrinier cylinder combination paper machine, and performing papermaking with a raw material obtained by beating softwood unbleached kraft pulp with a disc refiner, in the Fourdrinier section, and performing papermaking with a raw material obtained by lightly beating softwood unbleached kraft pulp with a disc refiner, in the cylinder section, and combining the papermakings together.

(63) The separator was formed from two layers of a Fourdrinier layer and a cylinder layer, and had a thickness of 60 m and a density of 0.53 g/cm.sup.3 in the separator as a whole. The Fourdrinier layer had a thickness of 30 m, a density of 0.70 g/cm.sup.3, an average fiber length of 2.11 mm, a mode value of 2.00 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 380 ml, and a dielectric breakdown strength of 17 kV/mm. The cylinder layer had a thickness of 30 m, a density of 0.36 g/cm.sup.3, an average fiber length of 2.60 mm, a mode value of 3.03 mm in the fiber length distribution of every 0.05 mm, a 0.15% freeness of 750 ml, and a dielectric breakdown strength of 10 kV/mm.

(64) By using the separator, as an aluminum electrolytic capacitor of Comparative Example 3, an aluminum electrolytic capacitor was produced having a rated voltage of 450 V, a rated capacity of 3.3 F, a diameter of 13.0 mm, and a height of 20.0 mm. The short circuit failure rate of the aluminum electrolytic capacitor was 5.2%, and the impedance was 46.6.

(65) Table 1 indicates evaluation results of the separator alone and the capacitor of a rated voltage of 250 V of each of Examples 1 to 2, Comparative Examples 1 to 2, and Conventional Example. In addition, Table 2 indicates evaluation results of the separator alone and the capacitor of a rated voltage of 450 V of each of Example 3 and Comparative Example 3.

(66) TABLE-US-00001 TABLE 1 Dielectric Average Fiber iength 0.15% breakdown Rated Short circuit Thickness Density fiber length mode value freeness strength voltage failure rate Impedance m g/cm.sup.3 mm mm ml kV/mm V % Example 1 30 0.75 1.95 0.40 280 21 250 0.1 1.5 Example 2 20 1.00 0.37 0.20 270 96 250 0 1.4 Comparative Example 1 40 0.90 2.08 0.60 315 17 250 3.3 2.0 Comparative Example 2 40 0.65 1.65 0.30 50 15 250 14.5 1.8 Conventional Example 20 0.40 170 250 0.0 4.2

(67) TABLE-US-00002 TABLE 2 Fiber Short Average length Dielectric circuit fiber mode 0.15% breakdown Rated failure Thickness Density length value freeness strength voltage rate Impedance m g/cm.sup.3 mm mm ml kV/mm V % Example 3 Fourdrinier cylinder 50 0.72 28 450 0.2 20.5 two layers Fourdrinier layer 20 0.85 0.86 0.30 10 49 Cylinder layer 30 0.63 2.10 2.42 730 13 Comparative Fourdrinier cylinder 60 0.53 15 450 5.2 46.6 Example 3 two layers Fourdrinier layer 30 0.70 2.11 2.00 380 17 Cylinder layer 30 0.36 2.60 3.03 750 10

(68) The separator of Comparative Example 1 has the thickness and density of the high density layer described in Patent Literature 1, but the short circuit failure rate is high as compared with Examples 1 and 2. From a comparison of Example 1 and Example 2 with Comparative Example 1, it can be seen that the dielectric breakdown strength is required to be greater than or equal to 20 kV/mm.

(69) The separator of Comparative Example 2 contains solvent-spun cellulose fibers in addition to plant fibers. For this reason, it is considered that the dielectric breakdown strength is weakened and the short circuit failure rate of the capacitor became higher. From this, it can be seen that the separator only formed from plant fibers can have a higher dielectric breakdown strength than that of a separator also containing other fibers other than plant fibers.

(70) The separator of Conventional Example is a separator having very high dielectric breakdown strength, but the impedance of the capacitor is high as compared with Examples 1 and 2. This is considered to be the reason that the retaining ability of the electrolyte is small because the separator contains a polyolefin-based resin having low lyophilic property compared to cellulose.

(71) The separator of Comparative Example 3 does not include a layer having a dielectric breakdown strength of greater than or equal to 20 kV/mm. For this reason, the short circuit failure rate is high despite being thicker than the separator of Example 3. From this, it can be seen that by setting the dielectric breakdown strength to greater than or equal to 20 kV/mm, thinning of the separator is enabled, and eventually, the separator can contribute to downsizing of the capacitor.

(72) As described above, according to the present embodiment, the separator for aluminum electrolytic capacitors excellent in short circuit resistance can be provided by including at least one layer that is formed from plant fibers and has a dielectric breakdown strength of greater than or equal to 20 kV/mm.

(73) By using the above-described separator, the aluminum electrolytic capacitor can be provided that can be downsized, or enables coping with high voltage, coping with overvoltage, and the like.

(74) In the above, the example has been described in which the separator of the present embodiment is used for the aluminum electrolytic capacitor.

(75) Although descriptions are omitted of details of other configurations of the aluminum electrolytic capacitor and manufacturing methods, in the aluminum electrolytic capacitor of the present invention, the electrode material and the electrolyte material do not need to be particularly limited, and various materials can be used. In addition, as long as the element outer diameter allows, it is also possible to use a plurality of the separators of the present invention layered, or a plurality of separators layered using one or a plurality of the separators of the present invention.