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Electrolytic Solution for Electrolytic Capacitor and Electrolytic Capacitor As Well As Method for Preparing an Organic Onium Tetrafluoroaluminate

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Electrolytic Solution for Electrolytic Capacitor and Electrolytic Capacitor As Well As Method for Preparing an Organic Onium Tetrafluoroaluminate (19) & (11) EP 2 323 145 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 18.05.2011 Bulletin 2011/20 H01G 9/035 (2006.01) H01G 9/04 (2006.01) H01G 9/02 (2006.01) (21) Application number: 11151369.3 (22) Date of filing: 31.10.2003 (84) Designated Contracting States: (72) Inventors: DE FR GB • Takeda, Masayuki Mie 510-8530 (JP) (30) Priority: 31.10.2002 JP 2002317860 • Miyauchi, Hiroo 06.11.2002 JP 2002322707 Mie 510-8530 (JP) 07.11.2002 JP 2002324179 • Ue, Makoto 08.11.2002 JP 2002325707 Ibaraki 300-0332 (JP) 04.03.2003 JP 2003056995 (74) Representative: HOFFMANN EITLE (62) Document number(s) of the earlier application(s) in Patent- und Rechtsanwälte accordance with Art. 76 EPC: Arabellastraße 4 03770097.8 / 1 564 768 81925 München (DE) (71) Applicant: MITSUBISHI CHEMICAL Remarks: CORPORATION This application was filed on 19-01-2011 as a Tokyo 108-0014 (JP) divisional application to the application mentioned under INID code 62. (54) Electrolytic solution for electrolytic capacitor and electrolytic capacitor as well as method for preparing an organic onium tetrafluoroaluminate (57) There are provided an electrolytic solution for electrolytic capacitor comprising a quaternary cyclic amidinium tetrafluoroaluminate and a solvent and con- taining specific impurity compounds in a total amount of 0.6% by weight or less; an electrolytic capacitor using the electrolytic solution; and a method for preparing an organic onium tetrafluoroaluminate which is advanta- geously used in an aluminum electrolytic capacitor. EP 2 323 145 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 323 145 A1 Description Field of the Invention 5 [0001] The present invention relates to an electrolytic capacitor and an electrolytic solution for electrolytic capacitor, and more particularly to an aluminum electrolytic capacitor and an electrolytic solution for aluminum electrolytic capacitor. [0002] Further, the present invention relates to a method for preparing an organic onium tetrafluoroaluminate. The organic onium tetrafluoroaluminate is a useful chemical substance used in a wide variety of fields, for example, as a surfactant; a phase transfer catalyst; a softener; an antistatic agent such as a detergent; a dispersant for asphalt or 10 cement; a germicide; a preservative; an antiblocking agent for fertilizer or granulated product; or an anticoagulant, and especially useful as an electrolyte for an electrochemical device such as a battery or an electrolytic capacitor. Background Art 15 [0003] An aluminum electrolytic capacitor has an advantageous feature such that it has a reduced size and a large electrostatic capacity, and is widely used in low frequency filter and by-pass. The aluminum electrolytic capacitor generally has a structure such that an anode foil and a cathode foil are spirally wound via a separator which prevents the occurrence of short-circuiting between the anode and the cathode, and placed and be sealed up in a casing (see Fig. 1 and Fig. 2). As the anode foil, aluminum having an insulating oxide film formed thereon as a dielectric layer is used, and as the 20 cathode foil, an aluminum foil treated by etching is generally used. The separator disposed between the anode and the cathode is impregnated with an electrolytic solution which functions as an actual cathode. [0004] Among the properties of the electrolytic solution, electric conductivity directly affects the electrolytic capacitor in respect of energy loss and impedance characteristics, and therefore an electrolytic solution having high electric conductivity is being vigorously developed. For example, electrolytic solutions comprising a quaternary ammonium salt 25 (e.g., Japanese Prov. Patent Publication Nos. 145715/1987 and 145713/1987) or a quaternary amidinium salt (e.g., WO95/15572 pamphlet and Japanese Prov. Patent Publication No. 283379/1997) of phthalic acid or maleic acid dissolved in an aprotic solvent such as γ-butyrolactone, have been proposed. However, these electrolytic solutions do not have satisfactory ionic mobility, and further they unsatisfactorily achieve anodization of the anode aluminum, and hence they can be generally used only in capacitors having a rated voltage of 35 V or less. 30 [0005] For removing the disadvantages, an electrolytic solution for electrolytic capacitor having high electric conduc- tivity and excellent heat stability as well as higher withstand voltage, and an electrolytic capacitor having lower impedance and excellent heat stability as well as higher withstand voltage are desired. [0006] The present inventors have previously found that an electrolytic solution for electrolytic capacitor containing tetrafluoroaluminate ions satisfies the requirements (Japanese Patent Application No. 2002-135387). However, the 35 electrolytic capacitor using this electrolytic solution has a problem in that it hardly maintains the initial properties including high electric conductivity, excellent heat stability and high withstand voltage for a long term. In addition, the electrolytic capacitor using the electrolytic solution has a problem in that a current which frequently flows after a direct voltage is applied to the electrolytic capacitor for a certain time, i.e., a leakage current is large. [0007] In this connection, the present inventors have made studies on the moisture in the electrolytic solution. The 40 moisture in the electrolytic solution is not considered to cause a problem in a conventional aluminum electrolytic capacitor using an electrolytic solution comprising an electrolyte such as a quaternary ammonium salt or a quaternary amidinium salt of phthalic acid or maleic acid dissolved in a polar aprotic solvent such as γ-butyrolactone, and for example, when the electrolytic solution has a moisture content of about 3% by weight, there is no problem in the practical use. [0008] However, from the studies made by the present inventors, it has been found that, in the aluminum electrolytic 45 capacitor using an onium salt of fluorine-containing anion as an electrolyte, the moisture in the electrolytic solution considerably affects the performance of the capacitor. The reason for this is presumed that the moisture in the electrolytic solution remarkably affects the state of surface of the aluminum electrode. They have found that, by restricting the moisture content of the electrolytic solution, there can be provided an electrolytic capacitor which solves the above problems, particularly which is improved in the leakage current properties and life properties of the capacitor and can 50 be used stably for a long term, and thus the present invention has been completed. [0009] Further, with respect to the two types of aluminum electrolytic capacitors each using an electrolytic solution containing tetrafluoroaluminate wherein one markedly deteriorates in performance and another does not deteriorate in performance during the use of them for a long term, the present inventors have made close studies on the surface of the respective electrodes. As a result, they have found that, in the electrolytic capacitor which markedly deteriorates in 55 performance, aluminum in the cathode is fluorinated. [0010] In the conventional aluminum electrolytic capacitor using an electrolytic solution comprising an electrolyte such as a quaternary ammonium salt or a quaternary amidinium salt of phthalic acid or maleic acid dissolved in a polar aprotic solvent such as γ-butyrolactone, the cathode surface is not fluorinated, and therefore the fluorination of the cathode 2 EP 2 323 145 A1 surface is found to be a cause of the deterioration of performance. It has been found that an aluminum electrolytic capacitor using a cathode having an A12p spectrum in the range of 74.0 to 75.8 eV as measured by a method in which the surface of the cathode subjected to a specific accelerated test is analyzed by X-ray photoelectron spectroscopy, is unlikely to suffer fluorination of the cathode and solves the above problems, particularly is improved in the life properties 5 so that it can be used stably for a long term, and thus the present invention has been completed. [0011] In addition, from the studies made by the present inventors, it has been found that, with respect to the electrolytic capacitor using an electrolytic solution which comprises a tetrafluoroaluminate and a solvent, when the total amount of specific compounds contained as impurities in the electrolytic solution is a certain concentration or more, the leakage current of the electrolytic capacitor increases. The reason for this is presumed that these compounds are poor in elec- 10 trochemical stability and hence a current flows due to the electrochemical reaction of the compounds. Thus, it has been found that, by using an electrolytic solution having a predetermined concentration or less of these compounds, an electrolytic capacitor having improved leakage current properties can be provided, and thus the present invention has been completed. [0012] On the other hand, as methods for preparing an organic onium tetrafluoroaluminate which is useful as an 15 electrolyte for electrochemical device as mentioned above, there are known a method in which an organoaluminum compound and a pyridine-hydrogen fluoride complex are reacted with each other (see, for example, Journal of the American Chemical Society, 1993, vol. 115, p. 3,028); a method in which an organic onium tetrafluoroaluminate and an amine compound are reacted with each other (see, for example, Journal of the American Chemical Society, 1993, vol. 115,
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