JP7273946B2 - Method for forming electrolytic capacitors with high capacitance recovery and low ESR - Google Patents

Description

[Cross reference to related applications]
This application is a continuation-in-part of pending U.S. patent application Ser. Priority is claimed to expired US patent application Ser. No. 62/267,707. U.S. patent application Ser. No. 15/379,729 is based on U.S. patent application Ser. , 941,055), which is also a continuation-in-part of U.S. Patent Application Serial No. 13/777,769, filed February 26, 2013 (now filed April 12, 2016). Granted U.S. Patent No. 9,312,074), which is also a continuation-in-part of U.S. Provisional Patent Application No. 61/603, filed February 26, 2012. , 635. All these applications are incorporated herein by reference. This application is also a continuation-in-part of pending U.S. patent application Ser. This application claims priority to U.S. Provisional Patent Application No. 62/338,778. Both of these applications are incorporated herein by reference.

The present invention relates to an improved method of forming solid electrolytic capacitors, and improved capacitors formed by the method. More particularly, the present invention relates to improved conductive polymer slurries and methods of using the improved conductive polymer slurries to improve the capacitance and equivalent series resistance (ESR) of solid electrolytic capacitors.

The structure and fabrication of solid electrolytic capacitors are well documented. In the construction of solid electrolytic capacitors, a metal, preferably a valve metal, serves as the anode. The anode body may be a porous pellet formed by pressing and sintering a high purity powder, or a foil etched to increase the anode surface area. A valve metal oxide is formed by electrolysis to coat the entire surface of the anode, which serves as the dielectric of the capacitor. Solid cathode electrolytes are typically selected from a very limited group of materials including manganese dioxide or conductive organic materials such as polyaniline, polypyrrole, polythiophene, and derivatives thereof. Solid electrolytic capacitors containing intrinsically conductive polymers as cathode materials have been widely used in the electronics industry due to their advantageous low equivalent series resistance (ESR) and "non-combustion/non-ignition" failure mode. . In the case of conducting polymer cathodes, conducting polymers are typically applied by either chemical oxidative polymerization techniques, electrochemical oxidative polymerization techniques, or spray techniques, although other less desirable techniques have also been reported. ing.

The anode body is typically a porous structure. This is because the porous material has a large surface area and a high capacitance for a given volume. Conductive cathode layers often include a conductive material, such as a conductive polymer, and carbon and silver layers for connection to terminals. It is very important that the porous anode surface is sufficiently covered and in intimate contact with the conductive cathode layer so that the conductive cathode layer is completely impregnated with the pores to achieve the desired performance. Achieving capacitance is particularly preferred. In a method of making a conductive polymer-based valve metal capacitor, a valve metal powder such as tantalum is mechanically pressed into an anode, which is subsequently sintered to form a porous body. The anode is anodized to a predetermined voltage in a liquid electrolyte to form a dielectric layer and a cathode layer of conducting polymer is formed thereon. The conductive polymer is then coated with graphite and metal layers and assembled and molded into a finished device.

A major drawback of conductive polymer capacitors is their relatively low working voltage compared to their MnO ₂ counterparts, regardless of the type of conductive polymer employed. When the rated voltage exceeds 25V, the reliability of polymer capacitors becomes problematic to varying degrees. This is believed to be due to relatively poor dielectric-polymer interfaces with low "self-healing" capabilities. The ability to withstand high voltages can best be characterized by the breakdown voltage (BDV) of the capacitor. The higher the BDV, the higher the reliability. For reasons not yet understood, the breakdown voltage of capacitors containing conductive polymers is limited to about 55V, which allows capacitors to be used only at ratings of about 25V. This limitation has hampered efforts to use conductive polymers more widely.

Tantalum capacitors with conducting polymer cathodes have been commercially successful due to their low ESR and self-healing properties. These capacitors consist of at least two polymer layers, an inner polymer layer that fills the internal pores of the anode body and an outer polymer layer that protects the outer dielectric from subsequently formed carbon and silver layers. often configured. The internal conductive polymer layer is in direct contact with most of the available dielectric surfaces and is the primary factor affecting capacitance. The internal conductive polymer layer may be formed by in situ polymerization or by applying a preformed polymer dispersion or solution. In situ polymerization methods often result in higher capacitance and lower ESR. However, performing chemical reactions on the dielectric is a complicated process and can damage the dielectric. Also, residual metal salts from in situ polymerization can cause undesirable performance losses such as high leakage and low breakdown voltage. In situ polymerization is often carried out in a plurality of cycles to fill the pores of the anode body. should be reduced and replaced with less harmful processes.

For capacitors used in high voltage applications, the preformed polymer approach is more preferred. Application of pre-formed polymer reduces leakage and improves breakdown voltage, but these are trade-offs. The most successful pre-formed polymers utilizing PEDOT and polystyrene sulfonic acid (PSSA) as counterions are dispersions containing particles. Depending on the size of the particles, it is often difficult to impregnate all the pores, especially if the pores of the anode body are small, and the capacitance is affected by incomplete impregnation. US Pat. No. 5,300,002 teaches conductive polymer dispersions having an average particle size of 1 nm to 100 nm. Many efforts have been made to prepare conductive polymer dispersions with smaller average particle sizes, or even fully soluble conductive polymer solutions, but do these dispersions/solutions suffer from longevity problems? or, once applied, are often not stable under thermal or chemical treatments. Existing soluble conductive polymers typically have very low electrical conductivity, which means that the ESR of the capacitor will be higher.

Pre-formed conductive polymers are often much less conductive than conductive polymers made by in situ methods. For example, US Pat. No. 6,200,000 teaches that the conductivity of the conductive polymer is only 483 S/cm even with the addition of DMSO. Even with such high dispersion conductivity, the final ESR is still higher than the comparative example with 3,4-polyethylenedioxythiophene (PEDOT) in situ. The conductivity of PEDOT in situ can be as high as thousands of Siemens/cm (S/cm). Since the ESR of polymer-based capacitors is believed to be directly related to the conductivity of the cathode layer, it is usually desirable for the conductive polymer dispersion to have a higher conductivity.

Despite intense research, there is a need for materials and methods that improve capacitance and ESR without adversely affecting other aspects such as leakage and BDV. Provided herein are advances in cathode layer formation in solid electrolytic capacitors.

U.S. Pat. No. 8,058,135 U.S. Patent No. 9,514,888

An object of the present invention is to provide an improved solid electrolytic capacitor.

It is another object of the present invention to provide an improved method for manufacturing solid electrolytic cathode capacitors with improved capacitance and ESR.

These and other advantages that are realized are, as will be appreciated, a method of forming an electrolytic capacitor comprising:
preparing an anode, wherein the anode has a dielectric thereon and comprises a sintered powder, the powder having a powder charge of at least 45000 μFV/g; and
forming a first conductive polymer layer encasing at least a portion of the dielectric by applying a first slurry, wherein the first slurry comprises polyanions and conductive wherein the weight ratio of said polyanion to said conductive polymer is greater than 3, said conductive polymer and said polyanion forming conductive particles having an average particle size of 20 nm or less;
A method is provided comprising:

Yet another embodiment is provided in an electrolytic capacitor. An electrolytic capacitor includes an anode with a dielectric thereon. The anode comprises a sintered powder having a powder charge of at least 45000 μFV/g. A first conductive polymer layer covers at least a portion of the dielectric, the first conductive polymer comprising a polyanion and a conductive polymer. The weight ratio of polyanion to conductive polymer is greater than 3, and the conductive polymer and polyanion result in conductive particles having an average particle size of 20 nm or less.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically embodiment of this invention. 1 is a flow diagram of an embodiment of the invention; FIG. 2 is a graph showing conductivity as a function of weight ratio of polyanion to conductive polymer. FIG. Fig. 2 is a graph showing capacitance (normalized) as a function of weight ratio of polyanion to conductive polymer. FIG. 4 is a graph showing ESR (normalized) as a function of weight ratio of polyanion to conductive polymer.

The present invention is directed to a method of making solid electrolytic capacitors, and solid electrolytic capacitors made by the method. More particularly, the present invention provides solid electrolytic capacitors with improved capacitance and ESR achieved by using a slurry having a polyanion to conductive polymer weight ratio of greater than 3 and a particle size of 20 nm or less. is specialized in This slurry is applied to anodes made from powders with a charge greater than 45000 μFV/g. Surprisingly, a high ratio of polyanion to conducting polymer reduces the conductivity of the slurry, which has been suggested in the art to be detrimental to electrical properties. The synergistic effect realized by high charge powders and small average particle size results in improved capacitance and ESR, contrary to expectations in the art.

Here, a tantalum anode comprising a sintered powder having a specific charge of at least 45000 μFV/g comprises a conductive polymer and a polyanion such that the weight ratio of polyanion to conductive polymer is greater than 3 and has an average of 20 nm or less. It has been found that better capacitance and ESR can be achieved by using a first slurry having a particle size. Higher polyanion ratios have been shown to be detrimental to electrical conductivity, so improvements in capacitor electrical properties, particularly ESR, have run counter to expectations in the art. The art teaches that a lower weight ratio is necessary to increase the conductivity of the slurry. US Patent Application Publication No. 2015/0279503 teaches that a polyanion to conductive polymer weight ratio of less than 2 is important to improve capacitance. Surprisingly, however, the high specific charge, small particle size, and high weight ratio of polyanion to conductive polymer, when utilized with anodes formed from highly charged powders, have resulted in Contrary to expectations, it turns out that a conductivity of less than 200 S/cm is preferred.

The invention will be described with reference to the various drawings, which form an integral and non-limiting component of the disclosure. Like elements are numbered the same throughout this disclosure.

FIG. 1 is a side cross-sectional view schematically showing an embodiment of the present invention. A capacitor, generally designated 10 in FIG. The anode lead wire is preferably in electrical contact with anode lead 16 . An optional precursor conductive layer 15, preferably formed in situ, is formed over the anodized anode, the precursor conductive layer preferably at least partially covering a portion of the dielectric of the anodized anode. Alternatively, the precursor conductive layer is formed by applying and curing a soluble conductive polymer solution. A first conductive polymer layer 18 and a subsequent conductive polymer layer(s) 20 as a cathode layer are sequentially formed on the precursor conductive layer, forming at least one of the first conductive layers. forming a wrap around at least a portion of the dielectric, at least partially covering the portion; As those skilled in the art will appreciate, in a finished capacitor, the cathode and anode are not in direct electrical contact. A cathode lead 22 is in electrical contact with the cathode layer. It is well understood that soldering lead frames or external terminals to polymer cathodes is difficult. Therefore, it is customary in the art to provide a conductive intermediate layer 23 that allows solder bonding. In many embodiments, it is preferred to encase the capacitor in a non-conductive resin 24 to expose at least a portion of the anode and cathode leads for attachment to a circuit board. This will be readily understood by those skilled in the art.

The optional precursor conductive layer preferably comprises a conductive polymer formed by in situ polymerization or by application and curing of a soluble conductive polymer. It is believed that the in situ formed conductive polymer enters the interstices of the porous anodized anode more effectively, thereby forming an improved capacitor. Subsequent layers are preferably formed by dipping into a slurry containing pre-polymerized conductive polymer and additional additives, as described in more detail herein. A soluble conductive polymer is a conductive polymer that dissolves completely in a solvent or solvent mixture without the presence of detectable particles less than about 1 nm, which is considered below the typical particle size detection limit. Solvents for soluble conductive polymers include water or organic solvents, or water and miscible solvents such as alcohols, and non-hydroxy polar solvents such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc). can be a mixture of Conducting polymer solutions potentially impregnate the anode pores as effectively as conducting polymers formed by in situ methods and better than conducting polymer dispersions with detectable particles. be able to. Neither the in situ conductive polymer nor the soluble conductive polymer contain polyanionic dopants such as polystyrene sulfonic acid. In many cases, soluble conductive polymers have self-doping functionality, and examples of soluble conductive polymers include conductive polymers of polyaniline, polypyrrole, and polythiophene, each of which may be substituted.

Particularly preferred conductive polymers include poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy) -1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly (4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3 -octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxy pyrrole), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecyl thiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3 -methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly( 3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4 -ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene) , poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline) sulfonate), poly(3-aniline sulfonate), and the like.

A first conductive polymer layer is formed by applying a first slurry, preferably by dipping. Here, the first slurry contains the polyanion and the conductive polymer such that the weight ratio of the polyanion to the conductive polymer is greater than 3 to preferably 10 or less. While not wishing to be bound by theory, it is believed that the polyanion-rich first slurry improves the coating and thus the ESR of the final capacitor. More preferably, the weight ratio is greater than 3 to greater than 6. The first conductive polymer layer may be applied by multiple applications of the same slurry. For purposes of this disclosure, a first conductive polymer layer is a layer formed from a first slurry; a subsequent conductive polymer layer is a layer formed from a second slurry; The layers may each have the same or different composition.

Subsequent conductive polymer layers are formed by applying a second slurry, preferably by dipping. Here, the second slurry contains a polyanion and a conductive polymer, but the weight ratio of the polyanion and the conductive polymer is not particularly limited. Subsequent conductive polymer layers preferably have a polyanion to conductive polymer weight ratio of less than three. Slurries with a polyanion to conductive polymer weight ratio of less than 3 have higher conductivity, which is preferred for all but the first conductive polymer layer.

FIG. 2 illustrates an embodiment of the present invention in flow chart form. FIG. 2 illustrates a method of forming the solid electrolytic capacitor of the present invention. At 32 in FIG. 2, an anodized anode is provided. An optional precursor conductive polymer layer is formed at 34 . Here, the precursor conductive polymer preferably contains a conductive polymer and does not contain a polyanion. This precursor conductive polymer is preferably formed by in situ polymerization or by applying and curing a soluble conductive polymer solution. The first conductive polymer layer can be formed by applying the first slurry in multiple stages. A first conductive polymer layer is formed at 36 on the precursor conductive layer, if present, preferably by dipping into the first slurry described above. After forming and preferably curing the first conductive polymer layer, subsequent conductive polymer layers are formed over the first conductive polymer layer. Here, the subsequent conductive polymer layer comprises polyanions and a conductive polymer from the second slurry as defined above. A subsequent conductive polymer layer optionally includes a cross-linking agent, especially an amine cross-linking agent. Additional subsequent polymer layers can be applied as needed. At least one carbon-containing layer and at least one metal-containing layer are preferably applied at 40 onto the final conductive carbon layer. Anode and cathode leads are then attached to the anode and cathode, respectively, and the capacitor is optionally, but preferably, covered at 42 and tested. In one embodiment, the polyanion is preferably polystyrene sulfonate.

In one embodiment, the polyanion is preferably a copolymer of polystyrene sulfonate and polystyrene.

In one embodiment the polyanion has the formula A:
A _x B _y C _z
Formula A
[In the formula,
A is polystyrene sulfonic acid or polystyrene sulfonate,
B and C are individually
- a carboxyl group,
-C(O)OR ⁶
(where ^R6 is
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate and anhydride ,as well as,
—(CHR ⁷ CH ₂ O) _b —R ⁸
is selected from the group consisting of
R ⁷ is selected from hydrogen or C 1 -C 7 alkyl, preferably hydrogen or methyl,
b is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group, and
R ⁸ is hydrogen, silane, phosphate, acrylate;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C(O)—NHR ⁹
(where ^R9 is
hydrogen, or
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride is),
_{-C6H4 -} ^R10
(where R ¹⁰ is
hydrogen, or
alkyl optionally substituted with functional groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride;
reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, and
—(O(CHR ¹¹ CH ₂ O) _d —R ¹²
is selected from
R ¹¹ is hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl,
d is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
R ¹² is hydrogen;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C ₆ H ₄ —OR ¹³
(where R ¹³ is
hydrogen, or
alkyl optionally substituted with reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates; and
—(CHR ¹⁴ CH ₂ O) _e —R ¹⁵
is selected from
R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl,
e is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the ^-CHR CH ₂ O- group; and
R ¹⁵ is hydrogen, and
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride selected from the group consisting of),
and x, y and z taken together are sufficient to form a polyanion having a molecular weight of at least 100 up to 500,000, and y/x is 0 more preferably x represents 50% to 99% of the sum of x+y+z and y is 1 of the sum of x+y+z % to 50%, and z represents 0% to 49% of the sum of x + y + z; even more preferably x represents 70% to 90% of the sum of x + y + z, and y represents represents 10% to 30%, and z represents 0% to 20% of the sum of x + y + z]
It is preferably a random copolymer comprising groups A, B and C represented by the ratio of

In one embodiment, the polyanion functions as a coating aid with insufficient polystyrene sulfonate groups and serves as an efficient counterion to the conductive polymer. In this case, in the polyanion represented by formula A, it is preferable that x represents 1% to 40%, y represents 60% to 99%, and z represents 0% to 39% of the sum of x + y + z. , x+y+z, x represents 5% to 40%, y represents 60% to 95%, and z represents 0% to 35%.

が挙げられ、式中、ｂ、ｘ、ｙ、及びｚは上で定義した通りである。 Particularly preferred polyanions include

wherein b, x, y, and z are as defined above.

Polyanionic copolymers are preferably synthesized by free radical polymerization methods. By way of non-limiting example, various proportions of styrene sulfonate to form component A of formula A and appropriate monomers to form component B and component C of formula A are combined with an inert Polymerize under ambient conditions at elevated temperatures, preferably in the range of 25°C to 150°C, in the presence of a free radical initiator.

The solvent in which the monomer(s) are dissolved is preferably water. Water-soluble solvents may be used, or mixtures of water and water-soluble solvents may be used. The water-soluble solvent is not particularly limited, but examples of this solvent include acetone, tetrahydrofuran, methanol, ethanol, isopropanol, and N-methyl-2-pyrrolidone.

The polymerization initiator is not particularly limited and can be, for example, a peroxide or an azo compound. Examples of peroxides include ammonium persulfate, potassium persulfate, hydrogen peroxide, cumene hydroperoxide, and di-t-butyl peroxide. Examples of azo compounds include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), and 2,2′-azo Bisisobutyronitrile may be mentioned. Polyanionic copolymers can be used directly for the preparation of conductive polymer dispersions without further purification. The polyanionic copolymer can then be purified, preferably by dialysis, precipitation, ultrafiltration, or ion exchange methods prior to preparation of the conductive polymer dispersion.

The conductive polymer dispersion is preferably prepared according to US Pat. No. 9,030,806, incorporated herein by reference. Preferred polymerization methods include those using a status screen. This results in a uniform droplet size and a preferred average polymer particle size of less than about 20 nm.

The conductive polymer dispersions of the present invention can be prepared by various techniques. Conventional impeller mixing, rotor/stator high shear mixing, ultrasonic mixing, acoustic mixing, and other mixing techniques can all be used with their own advantages. The conductive polymer dispersions of the present invention are further processed to reduce the average diameter, preferably below 20 nm. For example, the dispersion can be further homogenized by a variety of methods such as high pressure homogenizers, high shear homogenizers, ultrasonic devices, acoustic mixers, and the like. The dispersion can also be purified and separated, such as by dialysis and ultrafiltration, to remove uncomplexed/undoped polyanions and separate different average particle sizes and different fractions from the dispersion. These post-treatment steps can improve capacitance, power cycle capacitance stability, ESR, impedance, and other properties.

Conducting the polymerization using a mixed rotor/stator system with a perforated screen stator, preferably with a pore size of less than about 6 mm, results in controllable smaller average particles in the polymerization without additional processing steps. A conductive polymer dispersion having a size can be prepared. The dispersion may be further processed or homogenized to smaller particle sizes.

The conductive polymer dispersions of the present invention can also be formulated by mixing with various additives to improve performance. Additives such as silane coupling agents, cross-linking compounds, especially epoxy and carboxyl cross-linking compounds, sugars, alcohols, non-ionic polyols, or ionic liquids may be added to the conductive polymer dispersion. or as a separate layer after the conductive polymer dispersion. When added as additives to the conductive polymer dispersion, these non-conductive additive molecules can form complexes with the conductive polymer. The conductive polymer complex, or particle, may consist of an insulating layer of excess compound on the conductive polymer particle. Advantages that conductive polymer particles made from these insulating additives may have include better adhesion to adjacent layers, better repair of the underlying dielectric layer, and better repair of the cathode layer. It lowers the work function and helps with capacitance, ESR, leakage, breakdown voltage, and peculiar charge behavior. Additives may be added to the conductive polymer dispersion in all of the multiple dipping cycles or in some of the dipping cycles.

で重合されるように示され、式中、
Ｒ^１及びＲ^２は、独立して、直鎖状若しくは分岐状のＣ_１～Ｃ_１６アルキル若しくはＣ_２～Ｃ_１８アルコキシアルキルを表す、又はＲ^１及びＲ^２は、非置換若しくはＣ_１～Ｃ_６アルキル、Ｃ_１～Ｃ_６アルコキシ、ハロゲン若しくはＯＲ^３により置換されたＣ_３～Ｃ_８シクロアルキル、フェニル若しくはベンジルである、又はＲ^１とＲ^２とは一緒になって、非置換若しくはＣ_１～Ｃ_６アルキル、Ｃ_１～Ｃ_６アルコキシ、ハロゲン、Ｃ_３～Ｃ_８シクロアルキル、フェニル、ベンジル、Ｃ_１～Ｃ_４アルキルフェニル、Ｃ_１～Ｃ_４アルコキシフェニル、ハロフェニル、Ｃ_１～Ｃ_４アルキルベンジル、Ｃ_１～Ｃ_４アルコキシベンジル若しくはハロベンジルにより置換された直鎖状のＣ_１～Ｃ_６アルキレン、２個の酸素元素を含む５員、６員若しくは７員のヘテロ環式構造であり、Ｒ^３は、好ましくは、水素、直鎖状若しくは分岐状のＣ_１～Ｃ_１６アルキル若しくはＣ_２～Ｃ_１８アルコキシアルキルを表す、又はＲ^３は、非置換若しくはＣ_１～Ｃ_６アルキルにより置換されたＣ_３～Ｃ_８シクロアルキル、フェニル若しくはベンジルであり；
Ｘは、Ｓ、Ｎ又はＯであり、最も好ましくは、Ｘは、Ｓであり；
式ＢのＲ^１及びＲ^２は、好ましくは、環のβ位での重合を禁止するように選択され、というのも、α位の重合だけを進行させることが最も好ましいからであり；Ｒ^１及びＲ^２が水素ではないことがより好ましく、より好ましくは、Ｒ^１及びＲ^２はα配向体（directors）であり、その際、アルキル結合よりもエーテル結合の方が好ましく；Ｒ^１及びＲ^２が小さくて立体障害が避けられることが最も好ましい。 The present invention is particularly suitable, but not limited, for use in forming conductive polymers of polyaniline, polypyrrole, and polythiophene, each of which may be substituted. Preferred monomers for polymerization are those of Formula B:

is shown to polymerize at, where:
R ¹ and R ² independently represent linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl, or R ¹ and R ² are unsubstituted or C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy ^, C ₃ -C ₈ cycloalkyl substituted by halogen or OR 3, phenyl or benzyl, or R ¹ and R ² together are unsubstituted or C _{1 -C6} alkyl, _C1 - _C6 alkoxy, halogen, _C3 - _C8 cycloalkyl, phenyl _{, benzyl, C1 - C4} alkylphenyl, C1- _C4 alkoxyphenyl, halophenyl, _C1 - _C4 alkyl linear C ₁ -C ₆ alkylene substituted by benzyl, C ₁ -C ₄ alkoxybenzyl or halobenzyl, 5-, 6- or 7-membered heterocyclic structure containing two oxygen atoms; ³ preferably represents hydrogen, linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl, or R ³ is unsubstituted or substituted by C ₁ -C ₆ alkyl is C ₃ -C ₈ cycloalkyl, phenyl or benzyl;
X is S, N or O, most preferably X is S;
R ¹ and R ² of Formula B are preferably selected to inhibit polymerization at the β-position of the ring, since it is most preferred to allow polymerization only at the α-position; R ¹ and R ² are not hydrogen, more preferably R ¹ and R ² are α directors, wherein ether linkages are preferred over alkyl linkages; R ¹ and R ² is most preferably small to avoid steric hindrance.

In a particularly preferred embodiment, R ¹ and R ² of Formula B together represent —O—(CHR ⁴ ) _n —O—, wherein
n is an integer from 1 to 5, most preferably 2;
^R4 is independently hydrogen, carboxylic acid, hydroxyl, amine, substituted amine, alkene, acrylate, thiol, alkyne, azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane and phosphate; Linear or branched C ₁ -C ₁₈ alkyl groups, C ₅ -C ₁₂ cycloalkyl groups, C ₆ -C ₁₄ aryl groups, C ₇ -C ₁₈ aralkyl groups optionally substituted with selected functional groups or is selected from C ₁ -C ₄ hydroxyalkyl groups, hydroxyl groups, or R ⁴ is —(CHR ⁵ ) _a —R ¹⁶ , —O(CHR ⁵ ) _a R ¹⁶ , —CH ₂ O(CHR ⁵ ) _a R ¹⁶ , —CH ₂ O(CH ₂ CHR ⁵ O) _a R ¹⁶ , or
^R4 is hydroxyl, carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene, thiol, alkyne, azide, sulfonic acid, benzenesulfonic acid, sulfate, _SO3M , anhydride, silane, acrylate and a functional group selected from the group consisting of phosphate;
R ⁵ is H or an alkyl chain of 1 to 5 carbon atoms optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, acrylate and anhydride;
R ¹⁶ is H or SO ₃ M or carboxylic acids, hydroxyls, amines, substituted amines, alkenes, thiols, alkynes, azides, amides, imides, sulfates, SO ₃ M, amides, epoxies, anhydrides, silanes, acrylates and phosphates An alkyl chain having 1 to 5 carbon atoms optionally substituted with a functional group selected from
a is an integer from 0 to 10, and
M is H or a cation preferably selected from ammonia, sodium or potassium.

The conductive polymer is preferably selected from polypyrrole, polyaniline, polythiophene and polymers containing repeating units of formula B, especially in combination with organic sulfonates. A particularly preferred polymer is 3,4-polyethylenedioxythiophene (PEDOT).

Particularly preferred conductive polymers include poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy) -1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly (4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxyalcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3 -octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxy pyrrole), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecyl thiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3 -methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly( 3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4 -ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene) , poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline) sulfonate), poly(3-aniline sulfonate), and the like.

Particularly preferred polymers or copolymers are polypyrrole, polythiophene, poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid , salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), selected from the group consisting of poly(N-methylpyrrole), poly(3-methylthiophene), poly(3-methoxythiophene), and poly(3,4-ethylenedioxythiophene);

Polyanionic copolymers of Formula A can be used as counterions for polythiophenes containing repeating units of Formula B. It is preferred that the polyanion have a molecular weight of at least about 100 to no more than about 500,000. Molecular weights less than about 100 can affect film integrity. Molecular weights above about 500,000 can adversely affect conductivity and viscosity.

Preferably, the viscosity of each polymer dispersion after polymerization and before homogenization is at least 200 cP at 20 RPM to no more than 4000 cP at 20 RPM at ambient temperature and at least 600 cP at 20 RPM to no more than 2000 cP at 20 RPM at ambient temperature. is preferred. The dispersion preferably has a solids content of 1% to 5% by weight or less. More preferably, the polymer dispersion has a solids percentage of at least 2 wt% to 3.5 wt% or less. The viscosity of the polymer dispersion of the present invention after homogenization is preferably less than 100 cPs at 100 RPM, more preferably less than 50 cPs at 100 RPM.

Dispersion and polymerization are preferably carried out at a temperature of at least about 15°C to no more than about 35°C. At temperatures below about 15°C, the rate of polymerization is very slow, and above about 35°C, conductivity and viscosity can be adversely affected.

A first conductive polymer dispersion or a second conductive polymer dispersion comprising a conductive polymer and a polyanion can be further stabilized by a polymeric steric stabilizer during or after polymerization. The steric stabilization system makes it less sensitive to fluctuations and increases in electrolyte concentration, thus significantly reducing clotting or gel formation. Moreover, since the stabilizing effect of the steric stabilizer is high, a high solid dispersion can be produced by this method.

Criteria for polymeric steric stabilizers for conductive polymer dispersion polymerization are that they should be stable under low pH polymerization conditions, should be stable to oxidizing agents, and should not interfere with monomer polymerization. Things are mentioned. Examples of steric stabilizers include high molecular weight polyethylene oxides and copolymers thereof, which are preferred as steric stabilizers because they are stable under low pH reaction conditions. Also, other examples of steric stabilizers include polydimethylsiloxane-polyethylene oxide (PDMS-PEO) block copolymers. PDMS-PEO copolymers have the advantage that the PDMS block can provide not only steric stabilization but also moisture resistance.

Particularly preferred polymeric steric stabilizers contain linking groups that crosslink to provide a linking matrix during coating layer formation. The connecting matrix functions as a binder, thereby providing the coating layer with suitable structural integrity. Steric stabilizers with reactive functional groups can be employed for post-polymerization cross-linking with polyanions. Any reactive steric stabilizer can be used as long as it has a reactive functional group that is stable during the polymerization reaction. Examples of such reactive stabilizers include hydroxyl- and dihydroxy-terminated polybutadiene. Precursors of reactive steric stabilizers can also be employed for post-polymerization activation of steric stabilizer reactive groups. The steric stabilizer is preferably added during the polymerization reaction as a solution in water or other polar solvents such as dimethylsulfoxide, ethylene glycol, N-methylpyrrolidone and the like.

As used herein, the term "steric stabilizer" refers to a compound that adsorbs to the polymer particles of the dispersion and to the protective layer around each particle to prevent the particles from agglomerating.

Suitable steric stabilizers include, for example, protective colloids and nonionic surfactants with a hydrophilic-lipophilic balance (HLB) greater than about 10. Hydrophilic-lipophilic balance is a measure of the degree of hydrophilicity or lipophilicity of a material.

Suitable protective colloids include polyethylene oxide, fully hydrolyzed polyvinyl alcohol, partially hydrolyzed poly(vinyl alcohol), poly(vinylpyrrolidone), hydroxyethylcellulose, polyethylene oxide copolymers, and derivatives thereof, and mixtures thereof. . Polyethylene oxide is preferred.

A first conductive polymer layer or subsequent conductive polymer layers may independently include materials such as surface active agents, eg, ionic surfactants and/or nonionic surfactants. Suitable nonionic surfactants include ethoxylated alkylphenols, ethoxylated acetylenediols, polyethylene oxide-propylene oxide block copolymers, and mixtures thereof.

The first conductive polymer slurry or the second conductive polymer slurry may further contain a cross-linking agent. Crosslinking involves the use of materials containing at least two crosslinkable functional groups. Here, one crosslinkable functional group forms a first bond and a second crosslinkable functional group forms a second bond, thereby forming a crosslink molecular bridge between two parts of the polymer. do. The crosslinkable functional groups may form covalent bonds or ionic bonds. Crosslinking provides a molecule, oligomer, or polymer with crosslinkable functional groups within or between layers, providing a process that improves layer integrity and surface coverage, thereby improving ESR stability. . Upon exposure to curing conditions, typically heat curing, the crosslinkable molecules react to form an interpenetrating network of strongly bound covalent and ionic bonds. The reaction between the cross-linkable functional group and the cross-linking agent is carried out at an elevated temperature and is carried out in the normal processing steps of capacitor manufacture.

Preferably, the crosslinkable material comprises two components. Here, one component is preferably a compound, oligomer or polymer having a multifunctional reactive group or multiple reactive groups. The second component is preferably carboxylic, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleic Crosslinking functionalities selected from the group consisting of salts, maleimides, itaconates, allyl alcohol esters, dicyclopentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates or quaternary ammonium salts. A molecule having a group is preferred.

One embodiment includes a solid electrolytic capacitor that includes a crosslinkable material system. Here, oligomers or polymers are the group consisting of polyesters, polyurethanes, polyamides, polyamines, polyimides, silicone polyesters, hydroxyl-functional silicones, hydroxyethylcellulose, polyvinyl alcohol, phenols, epoxies, butyrals, copolymers or mixtures of these polyfunctional polymers. containing polyfunctional reactive groups selected from Copolymers or mixtures include epoxy/amines, epoxy/anhydrides, isocyanates/amines, isocyanates/alcohols, unsaturated polyesters, vinyl esters, blends of unsaturated polyesters and vinyl esters, unsaturated polyester/urethane hybrid resins, polyurethane- Urea, reactive dicyclopentadiene resins, or reactive polyamides may be mentioned. Oligomers or polymers with multifunctional reactive groups or multiple reactive groups preferably comprise at least one carboxylic acid group and at least one hydroxyl functional group. Oligomers or polymers with multifunctional reactive groups are particularly preferably polyesters containing carboxyl and hydroxyl functional groups. In addition to oligomers or polymers, particles with surface functional groups can also participate in cross-linking. Carboxylic, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, Particles with functional groups selected from dicyclopentadiene-based unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates or quaternary ammonium salts are preferred. The particles can be nanoparticles or microparticles. One example of functionalized nanoparticles includes organo-modified nanoclays.

In one embodiment, at least one conductive layer comprises organic or inorganic particles or fibers with reactive functional groups, or carbon particle-filled polymers, metal particle-filled polymers, and conductive particle-filled polymers, or reactive functional groups. Alternatively, it further contains particles of fibers having crosslinkable groups.

The first conductive polymer layer or subsequent conductive polymer layers independently contain additives that enhance conductivity, such as ether group-containing compounds such as tetrahydrofuran, lactone group-containing compounds such as γ-butyrolactone, γ-valerolactone, and the like. compounds, caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methyl-acetamide, N,N-dimethylformamide (DMF), N-methyl-formamide, N-methylformanilide, N-methylpyrrolidone (NMP ), amide group- or lactam group-containing compounds such as N-octylpyrrolidone and pyrrolidone, sulfones and sulfoxides such as sulfolane (tetramethylene sulfone) and dimethylsulfoxide (DMSO), sugars or sugar derivatives such as sucrose, glucose, fructose and lactose, Sugar alcohols such as sorbitol and mannitol, imides such as succinimide or maleimide, furan derivatives such as 2-furancarboxylic acid and 3-furancarboxylic acid, and/or dialcohols such as ethylene glycol, glycerol, or diethylene glycol or triethylene glycol. or may contain polyalcohols. Ethylene glycol, dimethyl sulfoxide, glycerol or sorbitol are preferably used as conductivity enhancing additives.

The first or second slurry preferably contains reactive monomers that can function as film-forming agents that can improve polymer film strength upon drying of the film. Reactive monomers or oligomers can be made soluble in water or organic solvents or dispersible in water through the use of ionic/nonionic surfactants. Reactive monomers may have an average functionality of at least 2 and preferably greater. The monomer curing process can be catalyzed by heat, radiation or chemical catalysis. Examples of monomers such as compounds having two or more epoxy groups include ethylene glycol diglycidyl ether (EGDGE), propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether (BDDGE), pentylene glycol. Diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol di glycidyl ether (sorbitol-DGE), sorbitol polyglycidyl ether, polyethylene glycol diglycidyl ether (PEGDGE), polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3 -butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether , maleimide-epoxy compounds, diglycidyl ether, glycidyl acrylate, glycidyl methacrylate, bisphenol A epoxy resin, epoxidized bisphenol A novolak-modified epoxy resin, urethane-modified bisphenol A epoxy resin, epoxidized o-cresol novolac resin, and other epoxy resins. Dispersion liquid etc. are mentioned.

Examples of other suitable monomers containing acidic groups include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid, maleic acid. , muconic acid, citric acid, trimesic acid, polyacrylic acid and the like. Particularly preferred organic acids are aromatic acids such as phthalic acid, especially orthophthalic acid.

Examples of suitable monomers containing alcohol/acrylate groups include diethylene glycol, pentaerythritol, triethylene glycol, oligo/polyethylene glycol, triethylene glycol monochlorohydrin, diethylene glycol monochlorohydrin, oligoethylene glycol monochlorohydrin, triethylene glycol. monobromohydrin, diethylene glycol monobromohydrin, oligoethylene glycol monobromohydrin, polyethylene glycol, polyether, polyethylene oxide, triethylene glycol-dimethyl ether, tetraethylene glycol-dimethyl ether, diethylene glycol-dimethyl ether, diethylene glycol-diethyl ether-diethylene glycol-dibutyl ether , dipropylene glycol, tripropylene glycol, polypropylene glycol, polypropylene dioxide, polyoxyethylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid amide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butoxy Ethyl methacrylate, n-butoxyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, n-butoxyethyl acrylate, n-butoxyethylene glycol acrylate, methoxytriethylene glycol acrylates, methoxypolyethylene glycol acrylate, etc.; bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, etc.; glycidyl ethers such as ethylene glycol diglycidyl ether, glycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycidyl ether, tripropylene glycidyl ether, polypropylene glycidyl ether, glycerin diglycidyl ether, etc.; be done.

The first conductive polymer layer or subsequent conductive polymer layers also independently contain polyanions containing reactive groups such as epoxies, alcohols, silanes, phosphates, amines, alkenes, thiols, alkynes, azidocarboxylic acids. It's okay.

A first conductive polymer layer or subsequent conductive polymer layers may also independently comprise linear hyperbranched polymers disclosed in US Pat. No. 9,378,898. The first conductive polymer layer or the subsequent conductive polymer layer has at least two reactive terminal functional groups selected from hydroxyl groups, amino groups, epoxies, acrylates, acids, etc. in the chain blocks, and is hyperbranched. Linear-hyperbranched block containing polyether-epoxy, polyester-epoxy, polyester-silanol, polyester-acid, polyether-alcohol, polyamide-acid, polyether-acrylate, polyether-silanol and polyester-amine pendant groups type polymer.

The first conductive polymer layer or subsequent conductive polymer layers may independently further comprise work function modifiers disclosed in US Patent Application Publication No. 20150348715. Examples of work function modifiers include di-alkoxyacyl titanates, tri-alkoxyacyl titanates, alkoxytriacyl titanates, alkoxy titanates, neoalkoxy titanates, titanium IV2,2 (bis 2- propenolatomethyl)butanolate, trisneodecanato-O; titanium IV 2,2 (bis-2-propenolatomethyl)butanolate, iris(dodecyl)benzenesulfonato-O; titanium IV 2,2 (bis-2-propenolate) methyl)butanolate, tris(dioctyl)phosphato-O; titanium IV 2,2 (bis-2-propenolatomethyl) tris(dioctyl)pyrophosphatobutanolate-O; titanium IV 2,2 (bis-2-propenolatomethyl) ) butanolate, tris(2-ethylenediamino)ethylate; and titanium IV 2,2(bis-2-propenolatomethyl)butanolate, tris(3-amino)phenylate, which are representative neoalkoxytitanates, and their Examples include organic titanate derivatives selected from the group consisting of derivatives. Furthermore, work function modifiers include alicyclic epoxy resins, ethylene glycol diglycidyl ether, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, novolac epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, ethylene Glycol diglycidyl ether (EGDGE), propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether (BDDGE), pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether , resorcinol glycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether (sorbitol-DGE), sorbitol polyglycidyl ether, polyethylene glycol diglycidyl ether (PEGDGE), polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2, Compounds consisting of 7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and derivatives thereof.

A first conductive polymer layer or subsequent conductive polymer layers may independently further comprise a nonionic polymer, such as a hydroxy-functional nonionic polymer. The term "hydroxy-functional" generally means that the compound has at least one hydroxyl functional group. The molecular weight of the hydroxy functional polymer is from about 100 g/mol to 10000 g/mol, in some embodiments from about 200 to 2000, in some embodiments from about 300 to about 1200, in some embodiments from about It can be from 400 to about 800.

Any of a variety of hydroxy-functional nonionic polymers can generally be used. In one embodiment, for example, the hydroxy-functional polymer is a polyalkylene ether. Polyalkylene ethers may include polyalkylene glycols (eg, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyepichlorohydrin, etc.), polyoxetanes, polyphenylene ethers, polyether ketones, and the like. Polyalkylene ethers are typically mostly linear, nonionic polymers with terminal hydroxy groups. Particularly preferred are polyethylene glycol, polypropylene glycol and polytetramethylene glycol (polytetrahydrofuran). The diol component is especially It may be selected from 6-diols, neopentyl glycol, bis-(hydroxymethyl)-cyclohexane, bisphenol A, dimer diols, hydrogenated dimer diols, or even mixtures of the aforementioned diols.

In addition to the above, other hydroxy-functional nonionic polymers may also be used. Some examples of such polymers include, for example, ethoxylated alkylphenols; ethoxylated or propoxylated _C6 - _C24 fatty alcohols; general formula _CH3- ( _CH2 ) _10-16- (O- _{C2H4 )} . Polyoxyethylene glycol alkyl ethers (eg octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether) having _1-25 —OH; general formula CH ₃ —(CH ₂ ) _10-16 —(O—C ₃ H ₆ ) polyoxypropylene glycol alkyl ether having _1-25 -OH; polyoxyethylene having the following general formula C ₈ -H ₁₇ -(C ₆ H ₄ )-(O-C ₂ H ₄ ) _1-25 -OH Glycol octylphenol ethers (such as Triton™ X-100); polyoxyethylene glycols having the general formula C ₉ —H ₁₉ —(C ₆ H ₄ )—(O—C ₂ H ₄ ) _1-25 —OH below. Alkylphenol ethers (eg nonoxynol-9); polyoxyethylene glycol esters of _C8 - _C24 fatty acids such as polyoxyethylene glycol sorbitan alkyl esters (eg polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) Sorbitan Monopalmitate, Polyoxyethylene (20) Sorbitan Monostearate, Polyoxyethylene (20) Sorbitan Monooleate, PEG-20 Methyl Glucose Distearate, PEG-20 Methyl Glucose Sesquistearate, PEG-80 Castor Oil , and PEG-20 castor oil, PEG-3 castor oil, PEG600 diolate, and PEG400 diolate) and polyoxyethylene glycerol alkyl esters (e.g., polyoxyethylene-23 glycerol laurate and polyoxyethylene-20 glycerol stearate); Polyoxyethylene glycol ethers of _C8 - _C24 fatty acids (e.g. polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene -20 oleyl ether, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecyl ether); block copolymers of polyethylene glycol;

The first slurry or the second slurry can comprise an ionic liquid, including poly(ionic liquid) (PIL). The ionic liquid can also be applied as a separate layer before or after the conductive polymer dispersion. Ionic liquids (ILs) are usually defined as organic/inorganic salts with a melting point below 100° C., good chemical and electrochemical stability, low flammability and negligible vapor pressure. and high ionic conductivity. With negligible vapor pressure in the liquid state, ionic liquids are usually considered environmentally friendly solvents for industrial production. Ionic liquids are organic salts that do not have much coordinated ions and that melt below 100° C. or even at room temperature. Ionic liquids have a wide electrochemical operation window and relatively high matrix fluidity at room temperature. Because ionic liquids are composed entirely of ions, they have a much higher charge density than ordinary salt solutions. In capacitor applications, the unique charge structure of ionic liquids allows them to form complexes with conducting polymers having charged cations and charged anions. This can affect the impregnation behavior of the conductive polymer particles. Ionic liquids can also affect the healing of dielectrics in an electric field and thus can have a positive effect on capacitor leakage and breakdown voltage. Ionic liquids are composed of a cationic component and an anionic component. Examples of cationic moieties include ammonium, imidazolinium, pyridinium, pyrrolidinium, pyrrolinium, pyrazinium, pyrimidinium, triazonium, triazinium, triazine, quinolinium, isoquinolinium, indolinium, quinoxalinium, piperazinium, oxazolinium, thiazolinium, morpholinium, piperazine, sulfonium, and derivatives thereof. The cations may be substituted with functional groups such as aliphatic, cycloaliphatic, or aromatic hydrocarbon, hydroxy, amino, carboxylic acid, ester, ether, acyl, and acrylic functionalities. Preferably, the cationic component is ammonium or imidazolium. Examples of anionic components include BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , CH ₂ CHBF ₃ ⁻ , nC ₃ H ₇ BF ₃ ⁻ , nC ₄ H ₉ BF ₃ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , CHF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OSO ₃ ⁻ , CHF ₂ CF ₂ CF ₂ CF ₂ CH ₂ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , (COCF ₃ )(SO ₂ CF ₃ )N ⁻ , and fluorine-containing anions such as B(CN) ₄ ⁻ , N(CN) ₂ ⁻ , C(CN) ₃ ⁻ , SCN ⁻ , SeCN ⁻ , AlCl ₄ ⁻ , OH ⁻ , CH ₃ SO ₃ ⁻ , CH ₃ OSO ₃ ⁻ , (CH ₃ CH ₂ )PO ₄ ⁻ , and derivatives thereof.

Poly(ionic liquids) (PILs) are defined in Progress in Polymer Science Volume 38, Issue 7, July 2013, Pages 1009-1036 as described in Progress in Polymer Science Volume 38, Issue 7, July 2013, Pages 1009-1036. Refers to a subclass of polyelectrolytes characterized by binding vias to form a macromolecular structure. Several unique properties of ionic liquids are incorporated into the polymer chain, creating a new class of polymeric materials. Polymeric ionic liquids extend the properties and applications of ionic liquids and conventional polyelectrolytes. Polymeric ionic liquids are permanent and powerful polyelectrolytes because the ionic liquid species are solvent-independent in their ionized state. The characteristic property of absorbing water is a common feature of ionic and polyionic liquids.

１－エチル－３－メチルイミダゾリウムテトラフルオロボレート、及びこれらの誘導体からなる群から選ばれる。 Examples of polyionic liquids are

It is selected from the group consisting of 1-ethyl-3-methylimidazolium tetrafluoroborate and derivatives thereof.

The first slurry or the second slurry may have a pH of 1-14, with a pH of 1-10 being preferred, and a pH of 1-8 being particularly preferred, as measured at 25°C. Bases or acids, for example, can be added to the solutions or dispersions to adjust the pH. The bases used are inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia, or organic bases such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine. , butylamine, dibutylamine, tributylamine, isobutylamine, diisobutylamine, triisobutylamine, 1-methylpropylamine, methylethylamine, bis(1-methyl)propylamine, 1,1-dimethylethylamine, pentylamine, dipentylamine, tripentylamine, 2-pentylamine, 3-pentylamine, 2-methyl-butylamine, 3-methylbutylamine, bis(3-methyl-butylamine), tris(3-methylbutylamine), hexylamine, octylamine, 2- ethylhexylamine, decylamine, N-methyl-butylamine, N-ethylbutylamine, N,N-dimethylethylamine, N,N-dimethylpropyl, N-ethyldiisopropylamine, allylamine, diallylamine, ethanolamine, diethanolamine, triethanolamine, methyl ethanolamine, methyl-diethanolamine, dimethylethanolamine, diethyl-ethanolamine, N-butylethanolamine, N-butyldiethanol-amine, dibutylethanolamine, cyclohexylethanolamine, cyclohexyldiethanolamine, N-ethylethanolamine, N-propylethanol It may be an amine, tert-butylethanolamine, tert-butyl-diethanolamine, propanolamine, dipropanolamine, tripropanolamine or benzylamine, a difunctional, trifunctional or tetrafunctional amine. The acid used may be an inorganic acid such as sulfuric acid, phosphoric acid or nitric acid, or an organic acid such as a carboxylic acid or a sulfonic acid.

The anode material is not limited herein. The anode is preferably a conductor selected from metals or conductive metal oxides. Particularly preferred anode materials are metals, particularly preferred metals are valve metals or conductive valve metal oxides. More preferably, the anode comprises mixtures, alloys or conductive oxides of valve metals, preferably selected from Al, W, Ta, Nb, Ti, Zr, and Hf. Particularly preferred anodes include, but are not limited to, niobium, aluminum, tantalum, and NbO. Anodes consisting essentially of Ta are most preferred.

A dielectric is a non-conductive layer, but is not specifically limited herein. The dielectric can be a metal oxide or ceramic material. It is particularly preferred that the dielectric be a non-conducting metal anodic oxide because of its simplicity of formation and ease of use. The dielectric is preferably formed by immersing the anode in an anodizing solution that accompanies electrochemical conversion. Alternatively, the dielectric precursor can be applied by spraying or printing and then sintered to form the layer. Immersion is the preferred method when the dielectric is an anode material oxide, while spraying or painting techniques are preferred when it is another material such as a ceramic.

The anode lead is chosen to have low resistivity and match the anode material. The anode lead may have the same composition as the anode material or may be a conductive oxide thereof. Particularly preferred anode leads include Ta, Nb, and NbO. The shape of the anode lead wire is not particularly limited. Preferred shapes include circular, oval, rectangular, and combinations thereof. The shape of the anode lead is chosen for optimum electrical properties in the final capacitor.

Throughout this specification, the terms "slurry" and "dispersion" are used interchangeably.

Throughout this specification, terms such as "alkyl", "aryl", "alkylaryl", "arylalkyl" refer to unsubstituted or substituted groups, including already substituted groups such as "alkylalcohol". Where indicated, it refers to groups that are unsubstituted or may be further substituted.

Test Capacitance Recovery (%) is the percent ratio of the capacitance of the sealing component before application of the cathode layer to the capacitance of the sealing component tested in the liquid electrolyte. ESR is the equivalent series resistance of the encapsulation capacitor. DCL is the leakage current of the encapsulation capacitor. BDV is the breakdown voltage of the sealed capacitor. Vf is the formation voltage applied to the anode to form the dielectric layer. A power cycle test was performed at ambient room temperature by turning the rated voltage on for 5 seconds and then off for 5 seconds. The voltage on/off cycle was repeated 60000 times. The capacitance of the part is tested before and after power cycling and the percent capacitance change is calculated.

Preparation example 1
A dispersion containing PSSA and PEDOT in a weight ratio of 2 was prepared. Into a 4 L plastic jar equipped with a cooling jacket, first, 71.76 g of polystyrene sulfonic acid (PSSA) 30% aqueous solution, 1669 g of deionized (DI) water, 27.27 g of 1% iron(III) sulfate, and 20. 57 g of sodium peroxodisulfate were charged. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 10.76 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 4200 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 259 S/cm and the D50 was 18.1 nm.

Preparation example 2
A PSSA/PEDOT slurry was prepared with a weight ratio of 3.3. In a 4 L plastic jar equipped with a cooling jacket, first, 125 g of polystyrene sulfonic acid (PSSA) 30% aqueous solution, 2531 g of DI water, 28.5 g of 1% iron(III) sulfate, and 21.5 g of sodium peroxodisulfate I put The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 11.25 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 8000 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 210 S/cm and the D50 was 15.0 nm.

Preparation example 3
A PSSA/PEDOT slurry was prepared with a weight ratio of 3.3. In a 4 L plastic jar equipped with a cooling jacket, first, 92.00 g of polystyrene sulfonic acid (PSSA) 30% aqueous solution (sonicated for 2 hours before mixing), 1863 g of DI water, 20.98 g of 1% iron sulfate (III), and 15.82 g of sodium peroxodisulfate were charged. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 8.28 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 4200 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 257 S/cm and the D50 was 13.8 nm.

Preparation example 4
A PSSA/PEDOT slurry was prepared with a weight ratio of 5.0. In a 4 L plastic jar equipped with a cooling jacket, first 54.82 g of polystyrene sulfonic acid (PSSA) 30% aqueous solution, 1028 g of DI water, 6.80 g of 1% iron(III) sulfate, and 6.29 g of peroxodisulfate. Added sodium sulfate. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 3.29 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 5000 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 162 S/cm and the D50 was 14.7 nm.

Preparation example 5
A ST/PEDOT slurry was prepared with a weight ratio of 1.5. In a 4 L plastic jar equipped with a cooling jacket, first, 55.81 g of polystyrene-sodium polystyrene sulfonate copolymer (ST) 20% aqueous solution, 1290 g of DI water, 2.98 g of concentrated sulfuric acid, 31.54 g of 1% iron sulfate (III), and 14.58 g of sodium peroxodisulfate. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 7.63 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 6000 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 151 S/cm and the D50 was 16.1 nm.

Preparation example 6
A ST/PEDOT slurry was prepared with a weight ratio of 2.6. In a 4 L plastic jar equipped with a cooling jacket, first, 87.86 g of polystyrene-sodium polystyrene sulfonate (ST) copolymer 20% aqueous solution, 1644 g of DI water, 4.70 g of concentrated sulfuric acid, 28.59 g of 1% iron sulfate (III), and 13.22 g of sodium peroxodisulfate were charged. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 6.92 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 6000 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 125 S/cm and the D50 was 13.3 nm.

Preparation example 7
A ST/PEDOT slurry was prepared with a weight ratio of 3.5. In a 4 L plastic jar equipped with a cooling jacket, first, 58.31 g of polystyrene-sodium polystyrene sulfonate copolymer (ST) 20% aqueous solution, 1025 g of DI water, 3.12 g of concentrated sulfuric acid, 7.12 g of 1% iron sulfate (III), and 6.59 g of sodium peroxodisulfate were added. The contents were mixed using a rotor/stator mixing system equipped with a perforated stator screen with a round hole diameter of 1.6 mm. Subsequently, 6.92 g of 3,4-ethylenedioxythiophene (EDOT) was added dropwise. The reaction mixture was continuously sheared in this rotor/stator mixing system at a shear rate of 6000 RPM for an additional 23 hours. This dispersion was treated with a cation exchange resin and an anion exchange resin and filtered to obtain a PEDOT-PSSA based slurry. The PEDOT-PSSA based slurry was further homogenized with an ultrasonic device. The conductivity of the dispersion tested with the DMSO additive was 94 S/cm and the D50 was 12.9 nm.

Preparation Example 8
A soluble conductive polymer (S1) was prepared. Commercially available hydroxymethyl 3,4-ethylenedioxythiophene (0.50 g) dissolved in tetrahydrofuran was added to sodium hydride (0.084 g) under a nitrogen atmosphere. The resulting mixture was refluxed for 1 hour, then 1,4-butanesultone (0.41 g) dissolved in tetrahydrofuran (8 ml) was slowly added. The mixture was stirred for an additional 2 hours and then cooled. Acetone (45 ml) was poured into the mixture with vigorous stirring. The suspension was filtered, washed with hot acetone and concentrated under vacuum to give a pale orange monomer powder.

A solution of 0.2 g of monomer in water (5 ml) was added to 0.9 g of iron(III) p-toluenesulfonate hexahydrate. The resulting mixture was polymerized under nitrogen at room temperature for 24 hours. The resulting S1 polymer was isolated by precipitation in acetone. The precipitate was collected by vacuum filtration. The collected precipitate was dissolved in DI water and treated with an ion exchange resin for 6 hours. The resulting dark blue solution of conductive polymer S1 was isolated by vacuum filtration. The conductivity of S1 was measured to be 5 S/cm.

Preparation Example 9
9 g of the soluble conductive polymer aqueous solution (S2) was added to 81 g of Preparation Example 4.

Preparation Example 10
To 100 g of Clevios Knano LV was added 0.4 g of 3-glycidoxypropyltrimethoxysilane and 1.2 g of polyethylene glycol diglycidyl ether. D50 was measured to be 16.4 nm.

Example 1 (I-1)
A series of 47 microfarad, 16 V tantalum anodes with a specific charge of 133000 μFV/g were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was immersed in Preparative Example 2 for 1 minute and dried in an oven to remove water. This process was repeated until sufficient thickness was obtained. A second conductive polymer dispersion containing an epoxy compound and a silane compound was applied to form subsequent polymer layers. After drying, alternating layers of diamine salt and a second conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance and ESR of package parts were measured.

Example 2 (I-2)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 4 was used as the first conductive polymer dispersion.

Comparative Example 1 (C-1)
A series of tantalum capacitors were prepared as described in Example 1, except that a Clevios Knano LV sample commercially available from Heraeus was used as the first conductive polymer dispersion. Knano LV is reported to have a polyanion/EDOT weight ratio of 2.5.

Comparative Example 2 (C-2)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 1 was used as the first conductive polymer dispersion.

Comparative Example 3 (C-3)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 3 was used as the first conductive polymer dispersion.

Example 3 (I-3)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 7 was used as the first conductive polymer dispersion.

Comparative Example 4 (C-4)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 5 was used as the first conductive polymer dispersion.

Comparative Example 5 (C-5)
A series of tantalum capacitors were fabricated as described in Example 1, except that Preparative Example 6 was used as the first conductive polymer dispersion.

Example 4 (I-4)
A series of tantalum anodes (33 microfarads, 16V, with a specific charge of 65000 μFV/g) were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was immersed in Preparative Example 4 for 1 minute and dried in an oven to remove water. This process was repeated until sufficient thickness was obtained. A second conductive polymer dispersion containing an epoxy compound and a silane compound was applied to form subsequent polymer layers. After drying, alternating layers of diamine salt and a second conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance and ESR of package parts were measured.

Comparative Example 6 (C-6)
A series of tantalum capacitors were prepared as described in Example 4, except that the Clevios Knano LV sample commercially available from Heraeus was used as the first conductive polymer dispersion.

Example 5 (I-5)
A series of 68 microfarad, 16 V tantalum anodes with a specific charge of 48000 μFV/g were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was immersed in Preparative Example 2 for 1 minute and dried in an oven to remove water. This process was repeated until sufficient thickness was obtained. A second conductive polymer dispersion containing an epoxy compound and a silane compound was applied to form an outer polymer layer. After drying, alternating layers of diamine salt and a second conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance and ESR of package parts were measured.

Example 6 (I-6)
A series of tantalum capacitors were fabricated as described in Example 5, except that Preparative Example 4 was used as the first conductive polymer dispersion.

Comparative Example 7 (C-7)
A series of tantalum capacitors were prepared as described in Example 5, except that the Clevios Knano LV sample commercially available from Heraeus was used as the first conductive polymer dispersion.

Example 7 (I-7)
A series of tantalum anodes (4.7 microfarads, 63 V, with a specific charge of 13000 μFV/g) were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was immersed in Preparative Example 4 for 1 minute and dried in an oven to remove water. This process was repeated until sufficient thickness was obtained. A second conductive polymer dispersion containing an epoxy compound and a silane compound was applied to form subsequent polymer layers. After drying, alternating layers of diamine salt and a second conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance and ESR of package parts were measured.

Comparative Example 8 (C-8)
A series of tantalum capacitors were prepared as described in Example 7, except that the Clevios Knano LV sample commercially available from Heraeus was used as the first conductive polymer dispersion.

Example 8 (I-8)
A series of 47 microfarad, 16 V tantalum anodes with a specific charge of 133000 μFV/g were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was immersed in S1 obtained in Preparation Example 8 for 1 minute and dried in an oven to remove water. Repeated this process one more time. The anode was then immersed in Preparative Example 2 for 1 minute and dried in an oven to remove water. This process was repeated until sufficient thickness was obtained. Conductive polymer dispersion KV2, available from Heraeus, was then applied to form subsequent polymer layers. After drying, alternating layers of diamine salt solution and commercial conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance and ESR of package parts were measured.

Example 9 (I-9)
A series of tantalum capacitors were fabricated as described in Example 8, except that Preparative Example 4 was used instead of Preparative Example 2.

Comparative Example 9 (C-9)
A series of tantalum capacitors were fabricated as described in Example 8, except that Clevios Knano LV samples commercially available from Heraeus were used in place of Preparation 2.

Comparative Example 10 (C-10)
A series of tantalum capacitors were fabricated as described in Example 8, except that the soluble PEDOT solution S1 of Preparative Example 8 was used instead of Preparative Example 2.

Example 10 (I-10)
A series of 47 microfarad, 16V tantalum anodes with a specific charge of 133000 μFV/g were fabricated as described in Example 1, except that Preparation 9 was used instead of Preparation 2.

Comparative Example 11 (C-11)
A series of 47 microfarad, 16 V tantalum anodes with a specific charge of 133000 μFV/g were fabricated as described in Example 1, except that an aqueous soluble conductive polymer solution (S2) was used in Preparation Example 2. bottom.

Example 11 (I-11)
A series of 33 microfarad, 35 V tantalum anodes with a specific charge of 22000 μFV/g were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The anodized anode thus formed was immersed in an iron(III) toluenesulfonate oxidant solution for 1 minute followed by immersion in ethyldioxythiophene monomer for 1 minute. After 60 minutes of polymerization was completed, the anode was washed to remove excess monomer and reaction by-products. This formed a thin layer of conductive polymer (PEDOT) on the dielectric of the anodized anode. The anode was immersed in a conductive polymer dispersion, Clevios Knano LV, available from Heraeus, for 1 minute and dried in an oven to remove water. This process was repeated three more times. The same immersion drying process was repeated three times with the conductive polymer dispersion of Preparative Example 10. Conductive polymer dispersion KV2, available from Heraeus, was then applied to form the outer polymer layer. After drying, alternating layers of diamine salt solution and commercial conductive polymer dispersion were applied and repeated 4-5 more times. A solid electrolytic capacitor was fabricated by washing and drying the anode with the conductive polymer layer and then sequentially coating the graphite layer and the silver layer. Assemble and package the parts. The capacitance, ESR, leakage, and BDV of package parts were measured.

Comparative Example 12 (C-12)
A series of tantalum capacitors were prepared as described in Example 13, except that the commercially available conductive polymer dispersion Clevios Knano LV was used in all seven cycles of the first conductive polymer dispersion.

In Table 1, ratio is the weight ratio of polyanion to conductive polymer and D50 is the average particle size. Example I-2, which utilized the higher charge (133,000 μFV/g) part type, had the lowest slurry conductivity but the highest capacitance recovery and lowest ESR among the PSSA samples. . The improved capacitance is not solely due to the smaller average particle size. This is because although Comparative Example C-3 has a smaller average particle size, the improvement in capacitance over Example I-1 is minimal. As shown in FIGS. 4 and 5, the correlation between polyanion/PEDOT weight ratio and capacitance and ESR is contrary to expectations in the art as shown in US Patent Application Publication No. 2015/0279503. Also, as shown in FIG. 3, the conductivity decreases as the weight ratio of PSSA/PEDOT increases. Better ESR achieved with lower conductivity conductive polymer dispersions contradicts common understanding of the relationship between ESR and conductivity.

A particular advantage in capacitance recovery, ie Cap recovery, for powder charges above 100,000 μFV/g is that Cap recovery of at least 65% can be achieved. At powder charges above 65000 μFV/a, Cap recovery of at least 70% can be achieved. For charges above 45000 μFV/a, Cap recovery rates above 75% can be achieved.

Based on the results shown in Table 4, in the cases of Tables 2 and 3, the application of in situ or soluble conductive polymer precursors such as S1 or S2 allowed for higher Cap recovery. .

The same trend is observed when conducting polymer dispersions formed from polystyrene-polystyrene sulfonic acid (ST) are used as dopants. Example I-3, which used the dispersion with the highest polyanion/PEDOT ratio, was observed to have the best capacitance and ESR, even though the conductivity was only about 94 S/cm. On the other hand, Example I-7, which used the lower charge (13000 μFV/g) powder, showed only a small improvement in capacitance and ESR over Comparative Example C-8. From the results shown in Table 1, a first conductive polymer layer having a polyanion to conductive polymer weight ratio of greater than 3 and an average particle size of less than 20 nm average diameter (D50) is applied to a high charge capacitor. , the electrical properties are improved.

Table 2 shows the advantage of the present invention in its ability to achieve breakdown voltage (BDV)/formation voltage (Vf) ratios greater than 1 when using another higher charge (65000 μFV/g) powder.

Table 3 shows the invention for a charge power of 48000 μFV/g. Even with a higher PSSA/PEDOT ratio, it showed only slightly better ESR and capacitance compared to C-7. Although the advantage in capacitance was not as great, the change in capacitance with power cycling indicated that higher PSSA/EDOT ratios were beneficial in maintaining initial capacitance. As can be seen from the data presented in Table 3, a Cap reduction of less than 10% after 60000 power cycles can be achieved, and more preferably less than 5%.

From the results shown in Table 4, in situ PEDOT (without polyanions) and other conductive polymers such as soluble PEDOT, or with polyanions, were used as the precursor conductive polymer prior to the first and second slurries. It turns out that other conductive polymers are applicable. In Table 4, two layers of self-doped PEDOT solution (S1) were applied before the first slurry. Following the self-doped conductive polymer (S1), the highest capacitance and lowest ESR were achieved with a dispersion having a polyanion to conductive polymer weight ratio of about 5. A synergistic effect is obtained when a conductive polymer dispersion having a polyanion/conductive polymer weight ratio of greater than 3 is used in combination with the soluble conductive polymer (S1). Mixing another conductive polymer solution (S2) with a conductive polymer dispersion having a high polyanion to conductive polymer weight ratio, as shown by Example I-10 and Comparative Example C-11, Similar advantages were obtained. It was also possible to reverse the order of application, dipping first in the conductive polymer dispersion and then applying the conductive polymer solution, to obtain a similar benefit to capacitance.

From the results shown in Table 5, it can be seen that adding a silane coupling agent and an epoxy compound to the first slurry can improve capacitance, leakage, and breakdown voltage (BDV). Alternatively, the additive may be applied as a separate solution from the first slurry and similar performance enhancements can be achieved. While not wishing to be bound by theory, it is believed that the conductive particle size increased due to the epoxy compound forming a complex with the conductive polymer dispersion, creating a thicker insulating layer around the conductive core. This was confirmed by an increase in particle size D50. Despite the increased particle size, the insulating additive had a positive effect on the impregnation and coating of the anode pores. The silane coupling agent may also enhance adhesion between the first conductive polymer and the dielectric.

Although the invention has been described with reference to preferred embodiments, it is not so limited. Those skilled in the art will appreciate further embodiments and improvements not specifically described herein but within the scope of the invention as more particularly set forth in the claims appended hereto. be.

Claims (61)

A method of forming an electrolytic capacitor, comprising:
preparing an anode, wherein the anode has a dielectric thereon and comprises a sintered powder, the powder having a powder charge of at least 45000 μFV/g;
forming a first conductive polymer layer overlying at least a portion of the dielectric by applying a first slurry, wherein the first slurry comprises a polyanion and a conductive polymer; the weight ratio of the polyanion to the conductive polymer is greater than 3, wherein the conductive polymer and the polyanion form conductive particles having an average particle size of 20 nm or less; and
further forming a subsequent conductive polymer layer on the first conductive polymer layer;
including
forming the subsequent conductive polymer layer comprises applying a second slurry comprising a second polyanion and a second conductive polymer;
the weight ratio of the second polyanion to the second conductive polymer is less than 3;
wherein the second slurry has a higher electrical conductivity than the first slurry;
Method. 2. The method of forming an electrolytic capacitor of claim 1, wherein said first slurry has a conductivity of 200 S/cm or less. 2. The method of forming an electrolytic capacitor of claim 1, wherein said weight ratio is 10 or less. 4. The method of forming an electrolytic capacitor of claim 3, wherein said weight ratio is 6 or less. 2. The method of forming an electrolytic capacitor of claim 1, wherein the electrolytic capacitor exhibits a breakdown voltage/formation voltage ratio of greater than one. 3. The method of forming an electrolytic capacitor of claim 1, wherein the first slurry is prepared by a rotor/stator mixing device followed by homogenization. 2. The method of forming an electrolytic capacitor of claim 1, wherein said anode comprises a valve metal selected from the group consisting of Al, W, Ta, Nb, Ti, Zr, and Hf. 8. The method of forming an electrolytic capacitor of claim 7, wherein said anode comprises a valve metal selected from the group consisting of niobium, aluminum, tantalum, and NbO. 9. The method of forming an electrolytic capacitor of claim 8, wherein said anode comprises tantalum. 2. The method of forming an electrolytic capacitor of claim 1, wherein said conductive particles further comprise an insulating compound. 11. The method of forming an electrolytic capacitor of claim 10 , wherein said insulating compound comprises at least one of a silane compound or an epoxy compound. 11. The method of forming an electrolytic capacitor of Claim 10 , wherein the insulating compound comprises at least one of a silane compound, an epoxy compound, or an ionic liquid. 2. The method of forming an electrolytic capacitor of claim 1, wherein said first slurry comprises at least one ionic liquid. 2. The method of forming an electrolytic capacitor of claim 1, wherein said conductive polymer comprises a conductive polymer selected from the group consisting of polyaniline, polypyrrole, polythiophene, and derivatives thereof. The conductive polymer is poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)- 1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt ), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly( 4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy alcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3- octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly( 3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole ), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene) ), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3- methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3 -decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4- ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), Poly(3-methyl-4-carboxyethylthiophene), Poly(3-methyl-4-carboxybutylthiophene), Polyaniline, Poly(2-methylaniline), Poly(3-isobutylaniline), Poly(2-aniline sulfonate) ), and poly( 3 -aniline sulfonate). 16. The method of forming an electrolytic capacitor of claim 15 , wherein said conductive polymer is poly(3,4-ethylenedioxythiophene). 2. The method of forming an electrolytic capacitor of claim 1, wherein the polyanion comprises at least one of styrene sulfonate groups or styrene sulfonate groups. The polyanion has the formula A:
A _x B _y C _z
Formula A
[In the formula,
A is polystyrene sulfonic acid or polystyrene sulfonate,
B and C are individually
- a carboxyl group,
-C(O)OR ⁶
(where ^R6 is
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate and anhydride ,as well as,
—(CHR ⁷ CH ₂ O) _b —R ⁸
is selected from the group consisting of
R ⁷ is selected from hydrogen or alkyl having 1 to 7 carbon atoms,
b is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group, and
R ⁸ is hydrogen, silane, phosphate, acrylate;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C(O)—NHR ⁹
(where ^R9 is
hydrogen, or
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride is),
_{-C6H4 -} ^R10
(where R ¹⁰ is
hydrogen, or
alkyl optionally substituted with functional groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride;
reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, and
—(O(CHR ¹¹ CH ₂ O) _d —R ¹²
is selected from
R ¹¹ is hydrogen or alkyl having 1 to 7 carbon atoms,
d is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
R ¹² is hydrogen;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C ₆ H ₄ —OR ¹³
(where R ¹³ is
hydrogen, or
alkyl optionally substituted with reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates; and
—(CHR ¹⁴ CH ₂ O) _e —R ¹⁵
is selected from
R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms,
e is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the ^-CHR CH ₂ O- group; and
R ¹⁵ is hydrogen, and
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride selected from the group consisting of),
represents a polymerized unit substituted with a group selected from;
x, y and z together are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000 or less, y/x is 0.01 to 100; z is 0 to 100 or less /x ratio; y represents 1% to 50% of the sum of x + y + z, and z represents 0% to 49% of the sum of x + y + z]
2. A method of forming an electrolytic capacitor of claim 1, defined by: 19. The method of forming an electrolytic capacitor of claim 18 , wherein ^R7 is selected from the group consisting of hydrogen and methyl. 19. The method of forming an electrolytic capacitor of claim 18 , wherein ^R11 is selected from the group consisting of hydrogen and methyl. 19. The method of forming an electrolytic capacitor of claim 18 , wherein ^R14 is selected from the group consisting of hydrogen and methyl. 19. The method of forming an electrolytic capacitor of claim 18 , wherein x represents 50% to 99%, y represents 10% to 30%, and z represents 0% to 20%. 23. The method of forming an electrolytic capacitor of claim 22 , wherein x represents 70% to 90%. 2. The method of forming an electrolytic capacitor of claim 1, further comprising forming a precursor conductive layer prior to forming said first conductive polymer layer. 25. The method of forming an electrolytic capacitor of claim 24 , wherein forming the precursor conductive layer comprises in situ polymerizing. 25. The method of forming an electrolytic capacitor of claim 24 , wherein forming the precursor conductive layer comprises applying a soluble conductive polymer solution. 27. The method of forming an electrolytic capacitor of claim 26 , wherein said precursor conductive layer does not contain polyanions. 27. The method of forming an electrolytic capacitor of Claim 26 , further comprising cross-linking said soluble conductive polymer. 2. The method of forming an electrolytic capacitor of claim 1, wherein said capacitor has a capacitance recovery rate of at least 65%. 30. The method of forming an electrolytic capacitor of claim 29 , wherein said capacitor has a capacitance recovery rate of at least 70%. 31. The method of forming an electrolytic capacitor of claim 30 , wherein said capacitor has a capacitance recovery rate of at least 75%. 2. The method of forming an electrolytic capacitor of claim 1, wherein the capacitance of the capacitor decreases less than 5% after 60,000 power cycles at rated voltage. 33. The method of forming an electrolytic capacitor of claim 32 , wherein the capacitance of the capacitor decreases less than 10% after 60000 power cycles at rated voltage. an electrolytic capacitor,
an anode with a dielectric thereon and comprising a sintered powder, the powder having a powder charge of at least 45000 μFV/g;
A first conductive polymer layer covering at least a portion of the dielectric, the first conductive polymer comprising a polyanion and a conductive polymer, wherein the weight ratio of the polyanion to the conductive polymer is a first conductive polymer layer greater than 3, wherein the conductive polymer and the polyanion result in conductive particles having an average particle size of 20 nm or less;
including
further comprising a subsequent conductive polymer layer on the first conductive polymer layer;
said subsequent conductive polymer layer comprising a second polyanion and a second conductive polymer;
wherein the weight ratio of said second polyanion to said second conductive polymer is less than 3;
Electrolytic capacitor. 35. The electrolytic capacitor of claim 34 , wherein said weight ratio is 10 or less. 36. The electrolytic capacitor of claim 35 , wherein said weight ratio is 6 or less. 35. The electrolytic capacitor of claim 34 , having a breakdown voltage/formation voltage ratio greater than one. 35. The electrolytic capacitor of claim 34 , wherein said anode comprises a valve metal selected from the group consisting of Al, W, Ta, Nb, Ti, Zr, and Hf. 39. The electrolytic capacitor of claim 38 , wherein said anode comprises a valve metal selected from the group consisting of niobium, aluminum, tantalum, and NbO. 40. The electrolytic capacitor of Claim 39 , wherein said anode comprises tantalum. 35. The electrolytic capacitor of claim 34 , wherein said conductive polymer particles comprise an insulating compound. 42. The electrolytic capacitor of claim 41 , wherein said insulating compound comprises a silane compound or an epoxy compound. 42. The electrolytic capacitor of claim 41 , wherein said insulating compound comprises at least one ionic liquid. 35. The electrolytic capacitor of claim 34 , wherein said conductive polymer comprises a conductive polymer selected from the group consisting of polyaniline, polypyrrole, polythiophene, and derivatives thereof. The conductive polymer is poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)- 1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt ), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly( 4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy alcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3- octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly( 3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole ), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene) ), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3- methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3 -decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4- ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), Poly(3-methyl-4-carboxyethylthiophene), Poly(3-methyl-4-carboxybutylthiophene), Polyaniline, Poly(2-methylaniline), Poly(3-isobutylaniline), Poly(2-aniline sulfonate) ), and poly(3 - aniline sulfonate). 46. The electrolytic capacitor of claim 45 , wherein said conductive polymer is poly(3,4-ethylenedioxythiophene). 46. The electrolytic capacitor of claim 45 , wherein the polyanion comprises at least one of styrene sulfonate groups or styrene sulfonate groups. The polyanion has the formula A:
A _x B _y C _z
Formula A
[In the formula,
A is polystyrene sulfonic acid or polystyrene sulfonate,
B and C are individually
- a carboxyl group,
-C(O)OR ⁶
(where ^R6 is
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate and anhydride ,as well as,
—(CHR ⁷ CH ₂ O) _b —R ⁸
is selected from the group consisting of
R ⁷ is selected from hydrogen or alkyl having 1 to 7 carbon atoms,
b is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group, and
R ⁸ is hydrogen, silane, phosphate, acrylate;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C(O)—NHR ⁹
(where ^R9 is
hydrogen, or
C1-C20 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride is),
_{-C6H4 -} ^R10
(where R ¹⁰ is
hydrogen, or
alkyl optionally substituted with functional groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride;
reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, and
—(O(CHR ¹¹ CH ₂ O) _d —R ¹²
is selected from
R ¹¹ is hydrogen or alkyl having 1 to 7 carbon atoms,
d is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
R ¹² is hydrogen;
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride selected from the group consisting of),
—C ₆ H ₄ —OR ¹³
(where R ¹³ is
hydrogen, or
alkyl optionally substituted with reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates; and
—(CHR ¹⁴ CH ₂ O) _e —R ¹⁵
is selected from
R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms,
e is an integer from 1 to a number sufficient to give a molecular weight of up to 200,000 for the ^-CHR CH ₂ O- group; and
R ¹⁵ is hydrogen, and
C1-C9 alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride selected from the group consisting of),
and x, y and z taken together are sufficient to form a polyanion having a molecular weight of at least 100 up to 500,000, and y/x is 0. 01 to 100; z is from 0 to a z/x ratio of 100 or less; y represents 1% to 50% of the sum of x + y + z, and z represents 0% to 49% of the sum of x + y + z show〕
35. The electrolytic capacitor of claim 34 , defined by: 49. The electrolytic capacitor of claim 48 , wherein ^R7 is selected from the group consisting of hydrogen and methyl. 49. The electrolytic capacitor of claim 48 , wherein ^R11 is selected from the group consisting of hydrogen and methyl. 49. The electrolytic capacitor of claim 48 , wherein ^R14 is selected from the group consisting of hydrogen and methyl. 49. The electrolytic capacitor of claim 48 , wherein x represents 50% to 99%, y represents 10% to 30%, and z represents 0% to 20%. 53. The electrolytic capacitor of claim 52 , wherein x represents 70%-90%. 35. The electrolytic capacitor of claim 34 , further comprising a precursor conductive layer between said first conductive polymer layer and said dielectric. 55. The electrolytic capacitor of claim 54 , wherein said precursor conductive layer does not contain polyanions. 55. The electrolytic capacitor of claim 54 , wherein said precursor conductive layer is crosslinked. 35. The electrolytic capacitor of claim 34 , wherein said capacitor has a capacitance recovery rate of at least 65%. 58. The electrolytic capacitor of claim 57 , wherein said capacitor has a capacitance recovery rate of at least 70%. 59. The electrolytic capacitor of claim 58 , wherein said capacitor has a capacitance recovery rate of at least 75%. 35. The electrolytic capacitor of claim 34 , wherein the capacitance of the capacitor decreases less than 5% after 60000 power cycles at rated voltage. 61. The electrolytic capacitor of claim 60 , wherein the capacitance of the capacitor decreases less than 10% after 60,000 power cycles at rated voltage.

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