JPS58191414A - Solid electrolytic condenser - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a IIJlti electrolytic container.

Monolithic electrolytic content has a structure in which a monolithic electrolyte is attached to a film-forming material such as aluminum having a titanium oxide film. In this hinoki cypress condenser, which has been mass-produced in the past, the electrolyte that constitutes it is mostly manganese dioxide and alkali, which is the weak point of manganese dioxide. Organic semiconductors, mainly TC, are used as an integral electrolyte to improve the damage to the anode oxide film of cedar wood and the poor repairability of the monopolar oxide film caused by manganese dioxide.
It was proposed to use NQ salt. Here, TCNQ and t 7.7, 8.8 tetraanoquinodimethane are the rules.

However, TCNQ salt is usually in the form of powder crystals, and although the crystals themselves exhibit high electrical conductivity and good repairability of the above-mentioned film, they are difficult to process even though they are powder crystals.

lp, W1, and how to deposit the film-forming gold XKTCNQ salt crystals. In particular, skin-forming metals used in solid electrolytic capacitors are often porous, but it is extremely difficult to uniformly impregnate TCNQ salt onto porous metals. What is more important is that the TCNQ salt itself is always at risk of deterioration due to deterioration during the adhesion process.

Conventionally proposed methods for attaching TCNQ salt can be classified into the following three types.

(1) Solvent KT such as DMF (dimethylformamide)
A method of dissolving CNQ salt and applying the solution to Tokikin Arashi, then drying it to remove the solvent.

1! l T CN A method in which Q salt is made into fine crystals using a ball mill, etc., and the crystals are dissolved in alcohol 41, and then applied to Ekikin@ and dried.

+ml T CN Q salt above gold nil! Power swim to vacuum evaporate.

In the above (1) force swimming, even if the entire solvent is DMF, which has a high solubility for the TCNQ salt, and the desired solvent is heated to, for example, 100° C., its solubility is limited to 1ON. This means that the solid electrolyte must be adhered to the required thickness to the foil-shaped metal, or the solid electrolyte must be sufficiently impregnated to the porous metal several times. ! ! i cloth, meaning that repeated drying is required 0 For example, for porous metals rated IJIF, 5 to 10 applications,
The impregnation rate achieved by drying is 30 at most, assuming that the impregnation rate when manganese dioxide is used as a solid electrolyte KMI is 100X.
It is. At such a low impregnation rate, the capacitance value of the capacitor cannot be increased to a large extent even though the metal is porous. Further, the metal coated with the solvent T is left in a high temperature every time the 11L is dried, but at this time more or less alteration of the rcNQ@ occurs, leading to a change in the conductivity of the solid electrolyte to f. In addition,
The integrated electrolytic cage formed on the wire mesh in this way:
Since TcNQ salt consists of fine crystals, a coagulating resin such as polyvinylpyrrolidone is added to the coating solution to strengthen the adhesion strength of the fine crystals. Since is an electrical insulator, the conductivity of the solid electrolyte is lowered even further (80
0f1. degree (25°C)) Kft.

In the above (phantom method), there is a limit to the miniaturization of TCNQ salt, and the strength of the M attachment to Joki Kinho is particularly weak. and deterioration of characteristics, for example, T
An increase in ANS and a decrease in capacity can be seen. The above-mentioned bond strength can be improved to some extent by employing a coagulating resin as described above, but this leads to a decrease in the electrical strength of the same mK solid electrolyte. Because of the material used, the impregnation rate into the porous metal is poor, and even if the ultrasonic diffusion method is used, the impregnation rate is at most the same as the 7j method described in (1) above.

The above method (1) not only requires complicated vacuum deposition work, but is also completely unsuitable for adhesion to porous metals.

Zero origin #4Fi, a completely new solid electrolytic capacitor, Yosho Gutai #JK provides a solid electrolytic capacitor comprising a condenser element and a solid electrolyte consisting of a TCNQ@salt impregnated into said element in a liquefaction tunnel. It is something to do. When carrying out the present invention, it is necessary to liquefy the TCNQ salt, but liquefying the VcTcNQ salt in this way for forming a solid electrolyte has never been considered.

The most practical force swimming using liquid τ consisting only of TCNQ salt?
The first step was to liquefy the powdered TCNQ salt by heating and melting it. However, simply heating and melting the TCNQ salt thermally decomposes the TCNQ salt and turns it into almost an electrical insulator, completely eliminating the function of the solid electric conductor for the condenser.

The present invention shows that even if some TCNQ salts are preheated and catalyzed, it will take only a short time to thermally decompose, but still provide enough time for the deposition process, so that they can be cooled and solidified in the IAI when fresh. This is a completely surprising finding that it is possible to obtain an integrated electrolytic tank made of TCNQ salt that maintains high conductivity! I'm watching.

1゛CumQ and its various salts, as well as its manufacturing method itself, are as follows:
For example, J, Am, Chgm, l5oc +1VoL
, 84.5574-3387 (1962) K. As a TCNQ salt, M n +(TCNQ
) n and a simple salt represented by Mn + (TCNQ )
There is a complex salt represented by n(TCNQ)m. Furthermore, the above M
is the organic kanion, n is the cation value, and Peng is the wI of 1 mole.
It means a positive value corresponding to the number of moles of neutral TCNQ contained in the salt.

In the present invention, however, the use of complex salts is more preferred for condenser properties. And the complex salt's Tokisho is 0.5
~1.5 is preferred, more preferably ~1.

Examples of TCNQ salts produced in the present invention include TCNQ salts of quinoline and inquinoline substituted at the N-position. In addition, the substituent at the N position is Cs to C Gobata (vertical prime number 2 to
18) alkylethyl, furovyl, butyl, pentyl, octyl, decyl, octadecyl), 05-C8 cycloalkyl (e.g. cyclopentyl, cyclohexyl)
, C1-C1-alkyl (e.g. allyl), phenyl or phenyl ((l-(:ts))alkyl (e.g. fechyl).

A more preferred hook td of the TCNQ salt used in the present invention,
TCNQ salt of N-n-propylquinoline, TCNQ4 of N-1 tylisoquinoline, TCNQ salt of N-isopropylquinoline, TCNQ field of N-n-hexylquinoline,
These are the TCNQ salt of Nn-propylisoquinoline, the TCNQ salt of N-isopropylisoquinoline, and the TCNQ salt of Nn-butylisoquinoline.

P- below one point of various TCNQjl used in this Yoriaki
1 to P-9 Toji-C describes the salts of nine oaks.

P-1...N-n-propylquinoline + (TCN9
(TCNQ) P-2...N-isopropylquinoline + (TCNQ
) (TCNQ) P-6...1m - n-propylinquinoline + (
TCNQ-) (TCNQ) P-4-=N-inpropylisoquinoline (TCNQ
-) (TCNQ) P-5・-N-mgutylisoquinoline (TCNQ
)(TCNQ) P-6...N-ethylquinoline (TCNQ)(
TCNQ) P-7...N-ethylisoquinoline (TCNQ-
) (TCNQ) P-8...N-hexylquinoline (TCNQ
) (TCNQ) P-9-...N-n-hexylisoquinoline (T
CNQ ) (TCNQ) Melting point ℃ E Each salt is produced, for example, as follows. N-alkylquinoline (or isoquinoline) iodite obtained by reacting N-argylrod and quinoline (or isoquinoline) and TCNQ are mixed in an appropriate molar ratio (for example, 3 : 4) to produce TCNQ salt.Since this salt has many impurities, it can be used in a suitable solvent (e.g. acetonyl) at a temperature below 82°C or in a solvent used for high purity. The molar ratio of the quinoline (or inquinoline) moiety and the TCNQ moiety changes slightly depending on the type of quinoline (or inquinoline) moiety.For example, when the solvent used in the reaction and in the crystal purification work is acetonidonyl, If TCNQ hazy is normally used or methanol is used during pure reaction work, m will be less than 1. For example, a molten solidified salt mixed with TUNQ of TCNQ salt KIN with m of 'l has m of about 1.
It becomes 14. In this way, even if icm changes slightly from 1, it can be used.
i1 is possible.

TCNQ salts not included in the present invention include TCNQ salts of H-quinoline (or isoquinoline) and N-methylquinoline (
When heated, the T CN Q barrier of T CN Q (or isoquinoline) decomposes without melting, or decomposes simultaneously with the melting of Fi.

On the other hand, the TCNQ salt that is the subject of the present invention as described above melts and enters a liquefied state when heated, but it takes a substantial amount of time to thermally decompose in that state. In this case, thermal decomposition occurs suddenly, and #i turns into an electrical insulator. However, heating is carried out in an aluminum case filled with crystal powder of ζTCNQ salt until it becomes insulating. This is done by welding it onto a metal plate.

Therefore, TCNQ salt in liquefied state must be cooled and solidified before its decomposition. Thereby, a one-body electrolyte with high conductivity is obtained6 For example, in the case of P-1 and P-2,
It is heated to a temperature above the melting point and below about 300° C., and cooling at room temperature or in a coolant such as water is initiated within about 1 minute, preferably within 20 seconds, after completion of liquefaction. P-5 and? -4 and P-5, the temperature is heated to about 320°C or less at 111 points or more and within about 4 minutes, preferably 1 minute after completion of liquefaction.
Cooling at room temperature or in a coolant such as water begins within minutes.

In this way, the I of TCNQ salt obtained by cooling and solidifying before decomposition
The It conductivity is as follows.

Electrical conductivity Ωtx (25° C.) The solid electrolyte obtained by the present invention is not a fine crystalline TCNQ salt as in the case of the conventional method 11) or (1), but is close to a polycrystalline block IIK. In addition, the solid electrolyte obtained by the present invention has the inherent properties of TCNQ salt, such as skin II.
I! It maintains an excellent ability to repair the oxidized film on the surface of the vase.

According to the invention, TCNQ salt is 100X'J11! Since this is the same as adhering TCNQ salt to a film-forming metal by kneading, the above-mentioned conventional method 41) is gold < 14, and only one adhesion work is required. , Even when the gold w4 is not only in foil form but also porous, it is possible to form a necessary amount of solid electrolyte, which not only improves mass productivity, but also improves mass productivity.
The disadvantages of the conventional method are overcome as the KTCNQ salt deteriorates upon drying. Furthermore, according to the present invention, since the solid electrolyte has a multi-connectivity close to 1/IAK, the adhesion force to the metal is sufficiently large, and therefore there is no need to use resin as in the past, and the solid electrolyte Undesirable reduction in conductivity can be avoided.

An embodiment of the Iji according to the present invention will be described below.

An aluminium-etched aluminum foil was used as an anode foil, an aluminum etched cage was used as a cathode foil, and these were wound together with a separator made of cocoon paper to prepare a nine-condenser element. This element was then placed in a constant temperature bath at 250° C. for 4 hours to perform the above-mentioned aspect ratio treatment of the separator. On the other hand, this treatment is to improve the degree of impregnation of the solid electrolyte into the device, and is quite interesting. After that, preheat the Kisakuko to 250,141 degrees.

First, fill the powdered TCNQ salt (used for P-1, P-1, and P-5 above in this example) prepared by the method described above in a bottomed cylindrical aluminum case. , heat this case and place it on the 9th plate.
Melt and liquefy the CNQ salt.

1 (inserted in 1 m of TCNQ salt, then immersed this case in water to rapidly cool it. From this, the condenser Takako's separator KTCNQ salt is immersed in the warehouse, and the KTCNQ salt is immersed in the tank, and the TCNQ salt is immersed in the tank.
CNQ salts form solid electrolytes that exhibit electrical conductivity.

After forging, the tips of the anode lead and cathode lead are exposed, the opening of the booth mentioned above is sealed with resin in the ninth gallery, and the target solid electrolytic capacitor is completed by aging. lk
Inside, Cap, tin is capacitance at 4120Hg, loss, equivalent series resistance at ESRFlooKHs, Δ
CapFi + capK rate of capacitance change at 25°C, Lc is 15 seconds after applying 25V IIL! D means a large amount of leakage current.

Temperature characteristics Life characteristics (In the Kisou example, the simple material constituting the capacitor element is aluminum, but other film-forming metals such as tantalum and niobium can also be used, as is clear from the explanation from #j-0 to According to the present invention, in a solid electrolytic condenser using a solid electrolyte made of a conductor having 1,000 vA, impregnating and adhering the film of a solid electrolytic tank to important metals can be carried out in an efficient work, and when the work is refused. Kid body electrolyte decomposition is also small, and K11
Since the single-body electrolyte has excellent electrical conductivity, its temperature characteristics,
It is sufficiently practical as it provides excellent and large wave-to-wave characteristics, especially ESR at high #s #L.

Handbook Continuation Supplementary Book (1st Edition) Dear Commissioner of the Japan Patent Office 1. Display of incident 1981 Patent Application No. 74956 2. Name of the invention solid electrolytic capacitor 6. Person who makes corrections patent applicant Address: Moriguchi Kata Keihan Hondori 2nd Lower 18 Name (188) Sanyo Electric Co., Ltd. Representative Kaoru Iue 4. Agent Address: 2-18 Keihan Hondori, Moriguchi City 6. Subject of correction +1) Claims column (21 Detailed explanation column of invention 6. Contents of correction (The scope of the 11th patent claim has been amended as shown in the attached sheet.

+21 In the specification.

On page 2 @ line 13, ``r thermal decomposition'' is corrected to ``thermal decomposition from manganese nitrate'' T6゜o w6 page 1
Line 84 d*kN1:, rfl:A61711゜"Quality layer"
and corrected it.

On page 6 @ line 15, the word ``touch'' is corrected to ``fusion''.

0 11s10 page 11!6 line 1: Oite, rQle)l:
The text ``humidity below 82℃'' has been corrected to ``1 degree below 82℃ in rills''.

0 On page 110, line s7, the word ``melt'' was corrected to ``melt.'' 6°O @ In the first row of page 10, the word ``liquefied state'' was deleted.

0 On page 1110 @ line 16, it says "fine"
Correct it to "pulverize" O@Page 15, line 184, it says "," V[.

J and amendment T6゜0 @ page 15, line 189, replace ``l, oJ'' with ``LCJ and amendment T6゜``Claims'' l) A capacitor element and a primary element impregnated in a liquefied state. ? Contains a solid electrolyte consisting of a CIIQ complex salt, and the above! CN QQ is a solid electrolytic capacitor that takes a substantial amount of time to thermally decompose in a liquefied state.

12+ In claim 181, ? CNQ
complex of n-hexylquinoline, N-ethylisoquinoline or N-n-butylisoquinoline/phosphorus! A solid electrolytic capacitor characterized by being a GHQ complex.

(In Section 31 Claim 1j!1, the above IC)
A solid electrolytic capacitor characterized in that lQ#iJI is a quinoline or isoquinoline substituted with a dihydrogen group at the N position.

(A solid electrolytic capacitor according to claim 5, characterized in that the hydrocarbon group is an alkyl group having 2 to 18 carbon atoms.

151 In claim 184, neutral IC
A solid electrolytic capacitor characterized in that the molar ratio of IQ to inquinoline whose shoulder is substituted with an alkyl group having 2 to 18 carbon atoms is approximately 1:1.

Claims (1)

[Scope of Claims] (1) Contains a condenser element and an integral electrolyte made of nine TCNQ complex salts impregnated with a liquefied substance, and before being thermally decomposed in the TCNQ complex salt #''i liquefied form. 1iE
Solid electrolytic condenser is characterized by being time-consuming. tit In claim 111, TCNQ
A solid electrolytic capacitor characterized in that the complex salt is a TCNQ complex salt of N-n-hexylquinoline, N-techfAI4soquinoline, or N-n-1 tylisoquinoline. (3) In paragraph 1 of the scope of the patent lit family, Okuki TCN
A picture electrolytic capacitor characterized in that the Q complex salt is a TCNQ complex salt of quinoline or inquinodan in which the N-position is substituted with a hydrogen group. (4) A solid electrolytic capacitor, characterized in that the E1 hydrogen group is an alkyl group in 2 to 181 of the patent 111I family category, item 5. lit special t + ask rice range 4th spear 2, TCNQ
And vertical cable J! A solid electrolytic capacitor characterized in that the molar ratio of 1 to 1 and isoquinoline substituted at the 2- to 18-position alkyl groups is approximately 1:1.