JP7218423B2 - Hybrid capacitor and method of manufacturing capacitor - Google Patents

Description

[Cross reference to related applications]
This application is a continuation-in-part of pending U.S. patent application Ser. This is a continuation-in-part of pending US patent application Ser. No. 15/095,902, the contents of both of which are hereby incorporated by reference. This invention is also a continuation-in-part of pending U.S. patent application Ser. This application claims priority to expired US patent application Ser. No. 62/116,043, the contents of which are incorporated herein by reference.

The present invention relates to a capacitor comprising a conductive polymer solid electrolyte and optionally a liquid electrolyte. More particularly, the present invention relates to capacitors that include conductive separators and methods of forming such hybrid capacitors, wherein at least one of the conductive polymer layers, within that layer, has an adjacent surface, or The conductive polymer layer is crosslinked with the adjacent conductive polymer layer, and the coverage of the conductive polymer is improved in the gap portion of the wound structure.

Capacitors have historically been defined by two general types, one type utilizing a liquid electrolyte and the other type utilizing a solid electrolyte. A liquid electrolyte capacitor is generally a layered structure comprising an anode conductor immersed in a liquid electrolyte, a cathode conductor, and a separator disposed therebetween, all enclosed, preferably sealed, within a container. and typically includes a layered structure as a wound body. A solid electrolyte capacitor generally includes a conductive monolith or foil having a dielectric layer thereon over which a conductive polymer or a solid such as manganese dioxide is deposited. have a cathode. Both common capacitor types are in widespread commercial use, and each has advantages and disadvantages not shared by the other. For example, liquid electrolyte capacitors have a high capacitance but a poor equivalent series resistance (ESR), typically not exceeding about 0.015 S/cm, due to the poor conductivity of the liquid electrolyte. However, on the other hand, conductive polymers are highly conductive, up to 600 S/cm, so capacitors utilizing conductive polymer cathodes have much lower ESR.

Conducting polymer cathodes have become commercially widespread, at least in part due to their low equivalent series resistance (ESR) and non-destructive failure mode. For the purpose of achieving the high voltage normally possessed by liquid electrolyte capacitors while maintaining the low ESR normally possessed by conductive polymer solid electrolytes, a conductive polymer normally employed in solid electrolyte capacitors is used in a liquid electrolyte winding structure. There is a need to form hybrid capacitors for use in the body. Examples of hybrid capacitors are taught in US Pat.

Hybrid capacitors have typically been formed by forming an interleaved wound structure containing an anode, a cathode, and a separator, and then impregnating with a conductive polymer. Impregnation has been accomplished by polymerizing monomers in situ or by diffusing a pre-formed polymer slurry into the interstitial regions of the interleaved wound structure.

First generation hybrid capacitors were fabricated by in situ polymerization of monomers in the presence of an oxidizing agent. In situ polymerization is a complex process with many problems including contamination of the final product by monomers and oxidants, complex working environment conditions and poor process reliability. These problems have been alleviated by impregnating the interstitial regions of the capacitor windings with a pre-formed aqueous dispersion or slurry of conductive polymer.

By immersing the working element in a solution containing the conducting polymer or by adding this solution onto the working element, the conducting polymer is caused to migrate or diffuse into the interstitial regions, thereby winding the preformed conducting polymer. Impregnate the body. Manufacturing steps are complicated by limitations associated with diffusion rate and diffusion efficiency in the working element. The passage of polymer particles and counterions through the separator limits effective diffusion, thereby limiting the length of the working element. As a result, only small capacitors have been successfully achieved, while large capacitors have proven difficult to fabricate. As a matter of fact, the largest commercially available case size is about 10 mm in diameter and about 12.5 mm in length with a maximum capacitance of about 22 μF (at a rated voltage of 63 V), and the lowest ESR achieved is It is about 16 mΩ.

Hybrid capacitors have been primarily radial capacitors because manufacturing limitations make the manufacturing process unsuitable for small axial capacitors. In axial capacitors, the bottom tabs or leads are inevitably immersed in a polymer precursor or polymer slurry, which coats the tabs with polymer and interferes with subsequent processing. Furthermore, because the bottom tab is in solution, it is virtually impossible to apply a voltage to the capacitor to form polymer in situ and repair the damaged area.

Improvements have been made in hybrid capacitors to form a polymer coating prior to winding. This has advanced the technology of hybrid capacitors that utilize conductive polymers and liquid electrolytes, but unfortunately have been formed by coating a layer of conductive polymer onto the anode, separator, or cathode prior to winding. Hybrid capacitors have failed to achieve the expected benefits due to delamination or delamination of the conductive polymer layers and the formation of electron blocking layers between adjacent conductive polymer layers. It is now known that

The present invention provides an improved hybrid capacitor by cross-linking the conductive polymer layer. This cross-linking can occur within a conductive polymer layer, between adjacent conductive polymer layers, or between a conductive polymer layer and a component such as an anode, separator, or cathode.

U.S. Pat. No. 8,462,484 U.S. Pat. No. 8,767,377

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved method of forming a hybrid capacitor and an improved capacitor formed by that method.

A particular feature of the present invention is the ability to provide a hybrid capacitor without limiting the size, structure, and shape of the capacitor.

These and other benefits that may be realized are provided in capacitors having active elements. The working element includes a first dielectric and an anodic conductive polymer layer on the first dielectric. The working element also includes a cathode and a separator between the anode conductive polymer layer and the cathode. The separator includes a separator conductive polymer layer, and at least one of the anode conductive polymer layer or the separator conductive polymer layer is crosslinked. The working element also includes a liquid electrolyte.

Yet another embodiment is provided in a method of forming a capacitor. The method includes forming a working element, wherein forming the working element comprises:
forming an anode comprising a first dielectric and an anode conductive polymer layer on the first dielectric;
forming a cathode;
forming a separator comprising a separator conductive polymer layer;
forming a layered structure comprising the anode, the cathode and the separator, the separator being between the anode and the cathode;
Forming a wound body of the layered structure;
Impregnating the wound body with a liquid electrolyte;
to crosslink at least one of the anode conductive polymer layer or the separator conductive polymer layer.

FIG. 4 is a perspective view schematically showing a partially unwound state in the embodiment of the present invention; FIG. 2 is a cross-sectional view taken along line 2-2 of FIG. 1; 1 is a schematic diagram of an embodiment of the present invention; FIG. 1 is a schematic diagram of an embodiment of the present invention; FIG. 1 is a schematic diagram illustrating the advantages of the present invention; FIG. 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically embodiment of this invention. FIG. 4 is a perspective view schematically showing a partially unwound state in the embodiment of the present invention; 13 is a cross-sectional view taken along line 13-13 of FIG. 12; FIG. Fig. 2 schematically shows two sides of an asymmetric anode of the present invention; Fig. 2 schematically shows two sides of an asymmetric anode of the present invention; 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; 4 is a graph showing electrical performance; 1 is an electrical wiring diagram of an embodiment of the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically embodiment of this invention. It is a figure showing an embodiment of the present invention typically. 4 is a graph illustrating advantages of embodiments of the present invention;

The present invention is a capacitor comprising a conductive polymer solid electrolyte and optionally, but preferably, a liquid electrolyte interspersed in a capacitor winding comprising alternating anodes, cathodes, and separators. is specialized in More particularly, the present invention relates to capacitors and methods of making capacitors of unlimited size, improved quality, and suitable for the manufacture of axial capacitors. More particularly, the present invention is not limited to case size, is not limited to virtually any design, such as axial, radial, planar, etc., and provides improved performance, specifically low ESR and high static. It enables the production of capacitors with capacitance. More particularly, the present invention provides hybrid capacitors in which the conductive polymer layers are crosslinked. This cross-linking may occur within a conductive polymer layer, between adjacent layers, or between a conductive polymer layer and a component such as an anode, separator, or cathode.

The principle of the present invention is to utilize anodes, cathodes, and separators pretreated with a conductive polymer, the pretreatment may be with a coating or, particularly in the case of separators, with a conductive polymer. may be impregnated. A pretreatment with a conductive polymer is performed prior to forming the working element, which can improve the polymer layer compared to the prior art. Since the method is not limited to polymer diffusion into the windings, the present invention eliminates capacitor size constraints and significantly increases volumetric efficiency, defined as capacitance as a function of capacitor size. In a particularly preferred embodiment, the conductive polymer layer is crosslinked before winding, after winding, or some combination before and after winding, preferably by introducing a crosslinking agent prior to winding.

A problem with the distribution of the solid electrolyte across the electrode surface is the formation of a conductive porous layer prior to winding, which allows conventional liquid electrolytes to pass through the conductive porous layer to perform typical tasks such as self-healing. The solution is to provide a conductor between the anodic and cathodic conductive polymer coatings that can provide the desired functionality. After winding, the windings are impregnated with a liquid electrolyte to form a conductive polymer layer prior to winding. The liquid electrolyte becomes more fluid and can diffuse or move more easily into the interstitial regions. In some embodiments, the winding may be impregnated with a cross-linking agent after winding. This allows for design versatility as the liquid electrolyte is not prevented from moving to the most distant interstitial regions. Furthermore, the conventional problem of interrupted conduction, essentially an imperfect conduction path, between polymer-coated electrodes causes the typical non-conducting separator to have an anode conducting polymer coating and a cathode conducting polymer coating. is alleviated by replacing with a conductive porous layer between

Herein, the integrity of the membrane is enhanced, thereby forming intermolecular bonds between the reactive groups of the solid electrolyte and the reactive groups of the liquid electrolyte to enhance the interaction between the liquid electrolyte and the solid electrolyte. This further improves the durability of the hybrid capacitor. Intermolecular bonds can be formed by reacting reactive groups of a solid electrolyte with reactive groups of a liquid electrolyte in situ. The intermolecular bond may be an ionic bond or a covalent bond, but is preferably a covalent bond.

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

An embodiment of the present invention will be described with reference to FIG. FIG. 1 schematically shows a partially unwound working element before insertion into a container and before impregnation with a liquid electrolyte. A working element, generally designated 10 in FIG. . The conductive separator has a conductive polymer 18, either by coating the conductive polymer onto the separator or by impregnating the separator with the conductive polymer, preferably by saturating the separator with the conductive polymer. Conductive coated anode 12 and conductive coated cathode 14 each have a conductive polymer layer thereon and are described in further detail herein. Anode lead 20 and cathode lead 22 extend from the capacitor windings and these leads will ultimately form the electrical connection to the circuit. From this description it will be seen that the anode lead is in electrical contact with the anode, the cathode lead is in electrical contact with the cathode, and is electrically isolated from the anode or anode lead. As is known in the art, tabs 24 and 26 are commonly employed to electrically connect the anode lead to the anode and the cathode lead to the cathode. A wrap 28, such as an adhesive tape, prevents the working element from unraveling during handling and assembly and becomes part of the finished capacitor, but does not play much role thereafter.

FIG. 2 schematically shows a cross-sectional view taken along line 2-2 in FIG. In FIG. 2, the separator 16 is shown with a conductive polymer 18 on both sides thereof for illustrative purposes, and the inclusion of the conductive polymer does not appreciably change the dimensions of the separator. It is understood that the conductive polymer may be impregnated into the separator and preferably the separator is saturated with the conductive polymer. Conductive polymer layer 18 is preferably crosslinked, and in a particularly preferred embodiment, conductive polymer layer 18 is crosslinked with separator 16 . The conductive coated anode 12, illustrated as a symmetrical anode, includes an anode foil 112 with an anodic conductive layer 212 on each side thereof, the preferred conductive layer being a conductive polymer layer. Conductive polymer layer 212 is preferably crosslinked, and in a particularly preferred embodiment, conductive polymer layer 212 is crosslinked to adjacent conductive polymer layer 18 . Conductively coated cathode 14 includes a cathode foil 114 with a conductive layer 214 on at least one side thereof. The conductive layer 214 on the cathode is preferably a conductive polymer layer, preferably crosslinked, more preferably crosslinked to the adjacent conductive polymer layer 18 . Alternatively, the conductive layer 214 on the cathode is a carbon layer. The separator is preferably porous so that the liquid electrolyte can pass through the separator. Once the working element is formed and inserted into the housing, all gaps or voids between the anode conducting polymer layer 212 and the cathode conducting polymer layer 214 are filled with a liquid electrolyte.

Although the cathode is illustrated herein as having a conductive polymer coating, the invention is not so limited. The cathode layer may include a conductive carbon layer or a metal layer, and in some embodiments it is preferred that the cathode does not include a conductive polymer layer. In a preferred embodiment, the cathode and anode layers are the same for manufacturing convenience.

An embodiment of the present invention will be described with reference to FIG. In FIG. 3, a series of layers are provided, including anode layer 302 . Here, the anode foil 112 is treated to form a dielectric on the surface of the anode foil, and then preferably a conductive polymer application process 304 forms a conductive polymer on the dielectric on at least a portion of one side. Layer 212 is formed. The conductive polymer application process is applied to the dielectric on at least part of one side of the anode foil, and in the case of a symmetrical anode, on both sides of the anode foil by a simultaneous coating step or a sequential coating step. The conductive polymer layer 212 on the anode may be crosslinked during the application process or may contain a crosslinker that crosslinks the conductive polymer layer 212 or an adjacent layer after winding. If a cathode comprising a conductive polymer layer is employed, the conductive polymer application process 304 forms a cathode layer 306 with the conductive polymer layer 214 formed over the cathode 114 . This conductive polymer application process 304 can be the same process used for the anode conductive polymer layer or a different process. The conductive polymer layer 214 on the cathode may be crosslinked during the application process or may contain a crosslinker that crosslinks the conductive polymer layer 214 or an adjacent layer after winding. If a cathode layer that does not contain a conductive polymer is used, a suitable roll of material is provided and no polymer forming process is required for the cathode layer. Conductive polymer application process 304 forms separator layer 306 by forming impregnated regions of conductive polymer 18 . This conductive polymer application process 304 can be the same process as the anode layer formation and cathode layer formation, or it can be a different process. The conductive polymer layer 18 on the separator may be crosslinked during the application process or may contain a crosslinker that crosslinks the conductive polymer layer 18 or adjacent layers after winding. The layered structure 310 described in relation to FIG. 2 is formed by interleaving the layers described above. The layered structure is scored to electrically connect the anode tab 314 to the anode and the cathode tab 316 to the cathode, resulting in a tabbed working element 312 . The tabbed working element 312 preferably has a roll stop 28 that inhibits unraveling of the working element. A lead (not shown) is preferably attached to the tab, or the tab serves as a lead, or serves as a lead for a conductive, preferably metal can or a conductive, preferably metal lid, or the like. The tabs are electrically connected to the components of the housing that do so, thereby providing a leaded working element. For purposes of this description, an axial arrangement is shown, but is not intended to be limiting. The leaded working element is placed in housing 318, thereby forming an encased leaded working element. Optionally, the contained leaded working element is impregnated with a liquid electrolyte, which is preferably liquid at the temperature of use. In the technical field, liquid electrolytes are also referred to as impregnated electrolytes. A cross-linking agent is optionally impregnated into the contained leaded active element to cross-link the conductive polymer layers or to cross-link adjacent conductive polymer layers to each other. The housing is sealed and the capacitor is aged to obtain the finished capacitor 320 .

An embodiment of the present invention will be described with reference to FIGS. 12 and 13. FIG. FIG. 12 is a schematic diagram showing a state in which the working element is partially unwound, and FIG. 13 is a schematic cross-sectional diagram along line 13-13 of FIG. The working element, generally designated 1010, has an asymmetric anode layer 1012 comprising a first dielectric 1011 on a first side and a second dielectric 1011 on a second side. Includes body 1013 . In some embodiments, the first and second dielectrics are preferably the same for manufacturing convenience, but can be different to achieve different properties. The first dielectric is coated, at least partially coated, with a conductive polymer 212, optionally crosslinked, and optionally crosslinked with adjacent conductive polymer layers. there is The conductive cathode layer 14 and conductive separator can be as described with reference to FIG. A non-conductive separator 1017 is between the second dielectric and the adjacent cathode layer. A non-conductive separator may not include any conductive polymer on or in it. In some embodiments, a conductive separator, described elsewhere herein, may be utilized adjacent to the second dielectric. While this minimizes the number of components required in the manufacturing process, it is not the preferred embodiment from a cost consideration.

FIG. 14 schematically illustrates an embodiment of an asymmetric anode layer 1012. FIG. In FIG. 14, the entirety of the second dielectric, preferably on the same side of attachment of the anode lead 20, is exposed without having a conductive polymer layer thereon. In a preferred embodiment, the asymmetric anode layer forms on one side a capacitive couple comprising a conductive polymer between the dielectric of the anode and the cathode layer. On the other side, which contains a polymer-free second dielectric, a liquid electrolyte and a non-conductive separator between the second dielectric and the cathode, thereby providing a conventional static electrode using a liquid electrolyte. form an electrical bond. As a result, a capacitor with parallel functionality is formed.

For the purposes of the present invention, an asymmetric anode is defined as an anode in which the surface area covered by the conductive polymer on one side is small compared to the amount of surface area covered by the conductive polymer on the opposite side.

FIG. 20 schematically illustrates an embodiment of an asymmetric capacitor that includes an asymmetric anode. In FIG. 20, an anode 112 including a first dielectric 1011 and a second dielectric 1013 is shown schematically. The first dielectric is covered by a conductive polymer layer 212 . Adjacent the conductive polymer layer 212 is a conductive separator 16 comprising a conductive polymer 18 as described in detail herein. A cathode layer 114, optionally including a first conductive polymer layer 214, is adjacent to the conductive separator to form a ^first circuit S1 having a first resistance and a first capacitance. do. The second dielectric 1013 of the anode is separated from the cathode by a non-conductive insulator 1017, thereby forming a ^second circuit S2 having a second resistance and a second capacitance. The capacitor illustrated in FIG. 20 may have the electrical wiring diagram shown in FIG. In FIG. 19, it has a first resistance ^R1 and a ^first capacitance C1 as the resistance and capacitance of the ^first capacitive coupling indicated by S1 with a conductive polymer in between. A ^second capacitive coupling, denoted S2, with no conductive polymer in between, has a second resistance ^R2 and a ^second capacitance C2. In FIG. 20, at least one conductive polymer layer is crosslinked, preferably with adjacent conductive polymer layers. In the preferred embodiment of Figure 20, the conductive polymer 18 on the separator 16 is crosslinked with the separator.

Hybrid capacitors with symmetrical anodes have a single capacitance by virtue of each capacitive coupling having an anode and a cathode with a combination of a conductive polymer and a liquid dielectric between them. With an asymmetric anode as shown in FIG. 20, the total capacitance of the capacitor is represented by two parallel capacitive couplings. one is the same as the capacitive coupling of a symmetrical anode and the other is formed of an anode, a cathode and a non-conductive separator impregnated with a liquid electrolyte without a complete conductive polymer layer therebetween; Capacitive coupling without any conductive polymer layer is preferred. Each capacitive coupling of the asymmetric anode has two ESRs. One is the ESR of capacitive coupling with a conductive polymer between the anode and cathode, referred to herein as polymer capacitive coupling, and the other is between the anode and cathode. Electrostatic coupling is the ESR of capacitive coupling that does not have a complete conductive polymer layer or has no conductive polymer layer at all, and is called electrolyte capacitive coupling.

^FIG . 16 is a graph showing the impedance |Z| of ^an uncrosslinked polymer capacitive bond S2 versus an electrolyte capacitive bond S1 as a function of frequency (Hz). Here, a polymer capacitive bond has an ESR of about 5 mOhm and an electrolyte capacitive bond without any conductive polymer layer on the second dielectric has an ESR of 150 mOhm. Both have a total capacitance of about 1000 μF.

FIG. 17 shows the frequency dependence of the fully asymmetric capacitor shown in FIG. 20 with an uncrosslinked polymer capacitive ESR of about 5 mOhm and an electrolyte capacitive ESR of about 150 mOhm. Here the capacitors are made to have capacitances of 400 μF, 1000 μF and 2000 μF. A large capacitance causes an ESR shift at low frequencies. Applying a high frequency can increase the ripple current capability of the capacitor.

FIG. 15 is a schematic illustration of a partially asymmetric anode layer in which at least the peripheral portion of the anode lead is exposed without the conductive polymer layer in the second dielectric. Preferably, at least a portion of the second dielectric is not covered by the conductive polymer, and at least 25% to 99% or less of the area of the second dielectric is covered. The portion not coated with conductive polymer is preferably applied to the attachment area of the tab. In FIG. 21 both the first dielectric and the second dielectric are incompletely coated with a conductive polymer. At least 25% to no more than 99% of the area of each dielectric is covered. The portion not coated with conductive polymer is preferably applied to the tab attachment area, which is often degraded on both sides by tab attachment.

Cathode foils, separators, and anode foils are typically provided as wide rolls and cut to size. The anode foil is preferably etched to form a dielectric thereon. The dielectric may be formed prior to cutting, in which case it is desirable to form the dielectric on the cut ends in a subsequent step prior to application of the conductive polymer coating. Cathodes, separators, and anodes can also be treated with coupling agents to improve adhesion between the surfaces and the conductive polymer layer, or to impart other specific surface behaviors. The cathode, separator, and anode may be washed and dried before or after conductive polymer layer formation or impregnation, and the conductive polymer layer formation step or impregnation step may be repeated several times as necessary. The electrical leads or tabs are typically electrically connected to the anode and cathode, preferably before being cut to length, and the leads are treated with a masking material to protect them from further denaturation; In addition, it is also possible to prepare for welding to the capacitor terminals.

Conductive polymers can be applied to the cathode, anode, or separator by any suitable method, including dipping, coating, and spraying. Immersion involves passing the cathode, anode, or separator through a bath or vessel containing a conductive polymer dispersion, preferably containing at least about 1% by weight up to about 10% by weight of the conductive polymer. Immersion is preferred in the case of separators. Coating and spraying can be done by printing or spraying the conductive polymer dispersion onto the surface of the cathode foil, anode foil, or separator by any printing technique, including screen printing. Coating or spraying is preferred for the cathode and anode. A conductive polymer coating is preferably applied to the anode, cathode, or separator in an amount of at least 0.1 mg/cm ² . Below about 0.1 mg/cm ² , the coating weight may be insufficient for proper conditions and incomplete coating may result. It is preferred to apply the conductive polymer coating in an amount sufficient to achieve a coating weight of about 10 mg/cm ² or less. Above about 10 mg/cm ² , additional coating thickness does not appreciably increase conductivity.

Axial capacitors are a particularly preferred embodiment. An axial capacitor has an anode terminal on one side of the capacitor and a cathode terminal on the opposite side. Axial capacitor windings containing a conductive polymer electrolyte relate to polymer impregnation in which the lower tabs or leads are necessarily immersed in the conductive polymer or precursor, forming detrimental deposits of the conductive polymer. It has been considered unusable due to problems. A particular advantage of axial capacitors, as currently available with the present invention, is the ability to utilize multiple tabs and multiple leads, especially as the anode and cathode lengths increase. The longer the foil length, the higher the percentage of foil resistance that reaches a higher ESR. Multiple tabs or multiple leads minimize the resistive effect of the foil. With one lead, the current has to flow the longest distance in the foil to the tab and lead, which is detrimental to ESR. Preferably, multiple anode leads and multiple cathode leads are utilized, which reduces the conduction path length. Various capacitor configurations are described with reference to FIG. FIG. 4 is a partially shaded view schematically showing the capacitor, allowing the components to be visualized. In FIG. 4, a single tab axial capacitor is illustrated as A, a multiple tab axial capacitor is illustrated as B, and a radial capacitor is illustrated as C. FIG. Axial capacitors have anode lead 40 and cathode lead 42 extending from different sides of working element 44, while radial capacitors have anode and cathode leads extending from the same side. FIG. 4B shows multiple anode tabs 40 and multiple cathode tabs 42 extending from the working element, each tab making electrical contact with the anode at a different location. For example, although FIG. 4B shows three tabs, this is not a limitation. These tabs are preferably evenly spaced along the length of the anode, which minimizes the conduction path length. Similarly, FIG. 4B shows three cathode leads, preferably evenly spaced along the length of the cathode. While multiple leads can be used in radial capacitors, they have historically not been suitable for use in hybrid capacitors. Because of the small size limitation, using multiple leads on the same side is difficult to manufacture. A single lead is preferred in radial capacitors, even if they are large.

FIG. 11 is a cross-sectional view schematically showing an axial capacitor. Capacitor, generally designated 400 in FIG. The housing, which may be referred to in the art as a can, is preferably electrically conductive and may serve as a lead or make electrical contact with the lower lead 405, which is preferably the cathode lead. A lower tab 406, preferably a cathode tab, is in electrical contact with the housing or lower lead. An upper tab 408, preferably an anode tab, is in electrical contact with an upper lead 410, preferably an anode lead, or the upper tab is in electrical contact with a conductive lid 412, which is electrically conductive. 412 is in electrical contact with the upper lead. A sealant 414, such as a gasket, seals the enclosure and inhibits atmospheric exchange between the interior of the enclosure and the surrounding atmosphere. In one embodiment, the sealant and lid create a seal. The encapsulant may be a resin material, in particular an epoxy resin, or a rubber material such as ethylene propylene diene terpolymer (EPT) or butyl rubber (IIR).

The anode is preferably a conductive metal in foil form. Preferably, the conductive metal is a valve metal or a conductive oxide of a valve metal. Particularly preferred anodes include valve metals such as tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, or conductive oxides thereof, such as NbO. A particularly preferred anode material is aluminum.

An oxide film is preferably formed as a dielectric on the anode. The dielectric can be formed using any suitable electrolyte, referred to as a forming electrolyte, such as phosphoric acid or phosphoric acid-containing solutions. Formation voltages of about 9V to about 450V are typically applied. Formation voltages are typically in the range of 2.0 to 3.5 times the rated voltage of the capacitor.

The conductive polymer application process is typically selected from in situ polymer formation and application from a slurry of pre-formed polymer, such as a coating process. In the in situ process, an impregnation solution is applied to the surface, preferably containing monomers, oxidants, dopants, and other auxiliary agents known to those skilled in the art. Choosing a suitable solvent for this solution is well within the level of skill in the art. Examples of suitable solvents include ketones and alcohols such as acetone, pyridine, tetrahydrofuran, methanol, ethanol, 2-propanol, and 1-butanol. To practice the present invention, the monomer concentration can be from about 1.5% to about 20% by weight, more preferably from about 5% to about 15% by weight. Suitable monomers for preparing conductive polymers include, but are not limited to, aniline, pyrrole, thiophene, and derivatives thereof. A preferred monomer is 3,4-ethylenedioxythiophene. To practice the present invention, the concentration of oxidizing agent can be from about 6% to about 45% by weight, more preferably from about 16% to about 42% by weight. Oxidizing agents for preparing the conductive polymer include organic and inorganic acid salts of iron (III), alkali metal persulfates, ammonium persulfate, and the like. A preferred oxidizing agent for the practice of this invention is iron(III) tosylate. The dopant concentration can be from about 5% to about 30% by weight, more preferably from about 12% to about 25% by weight. Any suitable dopant can be used, such as dodecylbenzenesulfonic acid, p-tosylate, or chloride. A preferred dopant is p-tosylate. The pellets are cured at a temperature of 65° C. to about 160° C., more preferably at a temperature of about 80° C. to about 120° C., thereby polymerizing the monomer. After curing, the polymer layer is preferably washed with deionized water or other solvent.

Application from a slurry of preformed polymer is a preferred method. The polymer can be prepared as a slurry or obtained commercially as a slurry and applied to a surface without any particular technical limitation, preferably followed by drying. Examples for the practice of the invention include solvent slurries of polymerized 3,4-ethylenedioxythiophene having particle sizes of at least 0.5 nm to 200 nm or less, more preferably at least 20 nm to 200 nm or less. When applied to a separator, it is preferable to sufficiently impregnate the separator with the slurry before drying. To maximize the conductive surface area, it is preferred to apply a continuous coating of conductive polymer. In particularly preferred embodiments, at least 80% of the surface area of the anode and at least 80% of the surface area of the cathode are coated with a conductive polymer. More preferably, at least 90% of the surface area of the anode and at least 90% of the surface area of the cathode are coated with the conductive polymer, and at least 99% of the surface area of the anode and at least 99% of the surface area of the cathode are coated with the conductive polymer. Most preferably.

The liquid electrolyte is preferably a solvent containing a supporting electrolyte. Any conventional solvent is gamma-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof. can be used with exemplary solvents including However, it is preferred that no supporting salts are required. Examples of supporting salts include inorganic acid ammonium salts, inorganic acid amine salts, inorganic acid alkyl-substituted amide salts, organic ammonium salts, organic acid amide salts, organic acid alkyl-substituted amide salts, and derivatives thereof. Any gas absorbent or cathodic electrochemical depolarizer can be used. Examples of supporting additives include nitro derivatives of organic alcohols, acids, esters, o-, m-, p-nitroanisole, o-, m-, p-nitrobenzoic acid, o-, m-, p-nitrobenzene. Aromatic derivatives such as alcohols are included. In particular, hybrid capacitors contain up to 50% by weight of liquid electrolyte.

The separator is not particularly limited herein, and any commercially available separator can be used as long as it is a material used for a conductive separator and can be coated with or impregnated with a conductive polymer. can be used to implement the present invention. Alternatively, or in addition to the conductive polymer, the separator itself may be a conductive material. An exemplary separator of a conductive separator functions as a scaffold layer of a conductive polymer. The separator can be made in sheets of various sizes that can be wound on rolls, reels, etc., or it can be in paste or gel form. The anode foil can serve as a support for the separator. Here, the anode foil has an insulator layer formed on its surface, a conductive polymer coating on the insulator, and a conductive separator layer formed on the polymer coating. Working difficulties can be minimized when the anode is used as a support. A separator is a porous conductive layer that allows direct electrical contact between the anode conductive polymer layer and the cathode. The separator preferably has a pore volume that allows passage of the liquid electrolyte. Paper or other non-conducting materials such as polymers may be used as a support for the conducting polymer. Paper is an example of a separator due to its widespread use and availability. Unlike prior art capacitors, paper does not need to be carbonized for use as a conductive separator. In manufacturing prior art capacitors, the paper is often carbonized after formation of the working element to minimize the amount of polymer absorbed by the paper. In the present invention, carbonization is not required because the separator is coated with a conductive polymer or impregnated with a conductive polymer to form a conductive separator. The separator can be a fibrous material, such as paper fibers, which are physically entangled or crosslinked to form a continuous fibrous layer, such as a paper fibrous layer. The spaces between the fibers may be partially or completely filled with highly conductive components. A paper-based separator may be a dispersion of highly conductive component fibers, liquid or solid conductive fibers, crumbs, particles, or agglomerates thereof, either by modifying the finished paper layer or prior to formation of the paper layer. or by modifying paper with deposits of conductive fibers, flakes, particles. Conductive fibers, flakes, or particles may comprise conductive materials such as conductive polymers, carbon black, graphite, metals, etc., or may be modified with conductive materials such as conductive polymers, carbon black, graphite, metals, etc. It may also be a composite material consisting of a non-conductive core such as paper, plastic, or the like.

The conductive separator and the non-conductive separator may have a conductive coating or comprise the same material as the conductive separator impregnated with a conductor, although neither is required in the non-conductive separator.

In one embodiment, the separator has reactive groups, particularly on its surface. Here, the reactive group is suitable for reacting with the reactive group of the conductive layer, thereby cross-linking the conductive polymer on the separator with the conductive polymer thereon to increase the adhesion of the conductive polymer to the separator. can increase Particularly preferred reactive groups include reactive groups such as epoxy, hydroxyl, amino, carboxylic, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic, sulfone, nitro, acrylate. , imides, amides, carboxyls, carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimide itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturation, unsaturated Included are saturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates or quaternary ammonium salts, which can crosslink with reactive groups on the liquid electrolyte.

Particularly preferred separators have a length of the working element or a width suitable for the manufacturing process, examples for the practice of the invention being widths of 1.5 cm to 500 cm. Since the capacitance is a function of the overlap of the anode and cathode and is therefore directly related to the length and width of the cathode and anode, the length is selected based on the desired capacitance. Examples for practicing the invention include separators having a length of 0.1 m to 400 m and a thickness of 10 μm to 300 μm.

The conductive polymer is preferably selected from polyaniline, polypyrrole and polythiophene, or substituted derivatives thereof.

（式中、Ｒ^１及びＲ^２は、環のβサイトでの重合を阻害するように選択される）で表される。αサイトの重合のみが進行することが最も好ましい。そのため、Ｒ^１及びＲ^２が水素ではないことが好ましい。Ｒ^１及びＲ^２がα－ディレクターであることがより好ましい。そのため、アルキル結合よりもエーテル結合が好ましい。これらの基が小さく、立体干渉が起こらないことが最も好ましい。これらの理由より、Ｒ^１及びＲ^２は、まとめて、－Ｏ－（ＣＨ_２）_２－Ｏ－であることが最も好ましい。式１中、ＸはＳ又はＮであり、最も好ましいＸはＳである。特に好ましい導電性ポリマーは、重合３，４－ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）である。 Particularly preferred conductive polymers are those of formula I:

(wherein R ¹ and R ² are selected to inhibit polymerization at the β-site of the ring). Most preferably, only α-site polymerization proceeds. Therefore, it is preferred that R ¹ and R ² are not hydrogen. More preferably, R ¹ and R ² are α-directors. Therefore, an ether bond is preferable to an alkyl bond. Most preferably, these groups are small and do not cause steric interference. For these reasons, R ¹ and R ² taken together are most preferably -O-(CH ₂ ) ₂ -O-. In Formula 1, X is S or N, most preferably X is S. A particularly preferred conductive polymer is polymerized 3,4-polyethylenedioxythiophene (PEDOT).

R ¹ and R ² independently represent linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl, or unsubstituted or C1-C6 alkyl, C1-C6 alkoxy, halogen, or OR3 or R ¹ and R ² taken together are unsubstituted or C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl, 5-, 6-, or 7-membered ring containing two oxygen atoms Linear C1-C6 alkylene substituted with a heterocyclic structure. R3 preferably represents hydrogen, linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl, or C3-C8 cycloalkyl unsubstituted or substituted with C1-C6 alkyl, phenyl or benzyl is.

Various dopants can be introduced into the polymer during the polymerization process, as typically employed in the art. Dopants include aromatic sulfonic acids, aromatic polysulfonic acids, hydroxyl group-containing organic sulfonic acids, carboxyl hydroxyl group-containing organic sulfonic acids, alicyclic sulfonic acids and benzoquinone sulfonic acids, benzenedisulfonic acid, sulfosalicylic acid, sulfoisophthalic acid, camphor It can be derived from a variety of acids or salts including sulfonic acid, benzoquinone sulfonic acid, dodecylbenzene sulfonic acid, toluene sulfonic acid. Other suitable dopants include sulfoquinones, anthracene monosulfonic acids, substituted naphthalene monosulfonic acids, substituted benzenes, as exemplified in US Pat. No. 6,381,121, incorporated herein by reference. sulfonic acids, or heterocyclic sulfonic acids.

Binders and crosslinkers can also be included in the conductive polymer layer if desired. Suitable materials include poly(vinyl acetate), polycarbonate, poly(vinyl butyrate), polyacrylate, polymethacrylate, polystyrene, polyacrylonitrile, poly(vinyl chloride), polybutadiene, polyisoprene, polyether, polyester, silicone, and Pyrrole/acrylate copolymers, vinyl acetate/acrylate copolymers and ethylene/vinyl acetate copolymers are included.

A cross-linking agent is a material that forms intermolecular bonds with the reactive groups of the liquid electrolyte with or by the reactive groups of the solid electrolyte. Particularly preferred crosslinkers include silanes such as glycidylsilanes and organofunctional silanes, epoxides, ethers such as glycidyl ethers, epoxy crosslinkers, and hydrophilic coupling agents.

（式中、Ｘは、アミノ、エポキシ、無水物、ヒドロキシ、メルカプト、スルホネート、カルボキシレート、ホスホネート、ハロゲン、ビニル、メタクリロキシ、エステル、アルキル等の有機官能基であり、Ｒ_１は、アリール又はアルキル（ＣＨ_２）_ｍ（ここで、ｍは０～１４であり得る）であり、Ｒ_２は、個々に、アルコキシ、アシルオキシ、ハロゲン、アミン等の加水分解性官能基、又はこれらの加水分解物であり、Ｒ_３は、個々に、炭素数１～６のアルキル官能基であり、ｎは１～３である）によって定義される。 Organofunctional silanes have the formula:

(Wherein, X is an organic functional group such as amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, alkyl, etc., and R ₁ is aryl or alkyl ( CH ₂ ) _m (where m can be from 0 to 14) and R ₂ is individually a hydrolyzable functional group such as alkoxy, acyloxy, halogen, amine, or a hydrolyzate thereof. , R ₃ are individually alkyl functional groups of 1-6 carbon atoms and n is 1-3.

（式中、Ｙは、アルキル、アリール、スルフィド、又はメラミン等の、反応性官能基又は非反応性官能基を含有する任意の有機部であり、Ｒ_３、Ｒ_２、及びｎは上で定義した通りである）で定義される二脚状のものであってもよい。有機官能性シランは、シラン変性ポリブタジエン若しくはシラン変性ポリアミン等の多官能シラン又はポリマーシランであってもよい。 Organofunctional silanes have the formula:

(wherein Y is any organic moiety containing a reactive or non-reactive functional group such as alkyl, aryl, sulfide, or melamine, and R ₃ , R ₂ , and n are defined above) as defined above). The organofunctional silane may be a polyfunctional silane or polymeric silane, such as silane-modified polybutadiene or silane-modified polyamine.

Examples of said organofunctional silanes include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxy silane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, bis(triethoxysilyl)octane, and the like. These examples are used to illustrate the invention and should not be considered definitive.

（式中、Ｒ_１は、炭素数１～１４のアルキルであり、メチル、エチル、及びプロピルから選ばれることがより好ましく、Ｒ_２は、各々独立して、炭素数１～６のアルキル又は置換アルキルである）で定義されるグリシジルシランである。 A particularly preferred organofunctional silane has the formula:

(wherein R ₁ is an alkyl having 1 to 14 carbon atoms and is more preferably selected from methyl, ethyl and propyl; each R ₂ is independently an alkyl having 1 to 6 carbon atoms or a substituted is alkyl).

で定義される３－グリシドキシプロピルトリメトキシシランである。これは、本明細書中、便宜上、「シランＡ」と言う。 A particularly preferred glycidylsilane has the formula:

3-glycidoxypropyltrimethoxysilane as defined in It is referred to herein as "Silane A" for convenience.

The second cross-linking agent, which is an organic compound having at least two functional groups selected from epoxy and carboxylic acid, has a concentration in the conductive polymer dispersion of about 0.2% to about 10% by weight solids content. A range of 0.1% to about 10% by weight is preferred. More preferably, the glycidyl ether concentration can range from about 0.2% to about 5%, more preferably from about 0.2% to about 2%, by weight of the conductive polymer. be.

（式中、Ｘは、炭素数０～１４、好ましくは０～６のアルキル若しくは置換アルキル、アリール若しくは置換アリール、エチレンエーテル若しくは置換エチレンエーテル、エチレンエーテル基を２個～２０個有するポリエチレンエーテル若しくは置換ポリエチレンエーテル、又はこれらの組み合わせである）で定義される。特に好ましい置換基は、エポキシ基である。 A second cross-linking agent having at least two epoxy groups is referred to herein as an epoxy cross-linking compound and has the following formula:

(Wherein, X is alkyl or substituted alkyl, aryl or substituted aryl having 0 to 14 carbon atoms, preferably 0 to 6 carbon atoms, ethylene ether or substituted ethylene ether, polyethylene ether having 2 to 20 ethylene ether groups or substituted polyethylene ether, or a combination thereof). A particularly preferred substituent is an epoxy group.

Examples of epoxy cross-linking compounds containing 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 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, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl Ethers, maleimide-epoxy compounds, and the like.

（式中、Ｒ_３は、炭素数１～１４、好ましくは２～６のアルキル又は置換アルキル；エチレンエーテル、又は２個～２０個のエチレンエーテル基を有するポリエチレンエーテル；ヒドロキシ、若しくは、

、若しくは－（ＣＨ_２ＯＨ）_ｘＣＨ_２ＯＨ（ここで、Ｘは１～１４である）から選ばれる基で置換されたアルキルである）で定義されるグリシジルエーテルである。 A preferred epoxy cross-linking compound has the formula:

(wherein R ₃ is alkyl or substituted alkyl having 1 to 14 carbon atoms, preferably 2 to 6 carbon atoms; ethylene ether, or polyethylene ether having 2 to 20 ethylene ether groups; hydroxy, or

or -(CH ₂ OH) _x CH ₂ OH, where X is alkyl substituted with a group selected from 1 to 14).

ＥＧＤＧＥ：エチレングリコールジグリシジルエーテル

（式中、ｎは１～２２０の整数である）；
ＰＥＧＤＧＥ：ポリエチレングリコールジグリシジルエーテル

ＢＤＤＧＥ：１，４－ブタンジオールジグリシジルエーテル

（Ｒ＝（１：２）は、Ｒ基の１つが水素であり、他の２つがエポキシドであることを示す）；
ＧＤＧＥ：グリセロールジグリシジルエーテル

ソルビトール－ＤＧＥ：ソルビトールジグリシジルエーテル
で表される。 Particularly preferred glycidyl ethers are

EGDGE: ethylene glycol diglycidyl ether

(wherein n is an integer from 1 to 220);
PEGDGE: polyethylene glycol diglycidyl ether

BDDGE: 1,4-butanediol diglycidyl ether

(R=(1:2) indicates that one of the R groups is hydrogen and the other two are epoxides);
GDGE: glycerol diglycidyl ether

Sorbitol-DGE: represented by sorbitol diglycidyl ether.

An organic compound having at least two carboxyl functional groups is referred to herein as a carboxyl-bridged compound.

Examples of carboxyl bridging compounds 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, but are not limited to these. Particularly preferred organic acids are aromatic acids such as phthalic acid, especially ortho-phthalic acid, which reduce ESR.

A layer can be cross-linked within a layer by introducing a cross-linking agent that reacts with functional groups of a component of the conductive polymer or components contained within the layer of the conductive polymer layer, herein Such crosslinks are called intralayer crosslinks. A layer can be cross-linked with an adjacent layer by introducing into one layer a cross-linking agent that reacts with functional groups of a component of the conductive polymer in the adjacent layer or a component contained within the adjacent layer; Such crosslinks are referred to herein as interlayer crosslinks.

The solid electrolyte preferably comprises at least one additive selected from fibers, dopants, cross-linking agents, binders and nanoparticles, the additive comprising reactive groups of the solid electrolyte.

Particularly preferred nanoparticles are functionalized nanoparticles in which the surface of the nanoparticles has been derivatized to contain reactive groups.

A binder can also be incorporated into the conductive polymer layer if desired. Suitable binders include poly(vinyl acetate), polycarbonate, poly(vinyl butyrate), polyacrylate, polymethacrylate, polystyrene, polyacrylonitrile, poly(vinyl chloride), polybutadiene, polyisoprene, polyether, polyester, silicone, and Pyrrole/acrylate copolymers, vinyl acetate/acrylate copolymers and ethylene/vinyl acetate copolymers are included. In one embodiment, the binder comprises reactive groups of the solid electrolyte.

Conductive polymers, binders, dopants or other components of solid electrolytes may contain reactive groups such as epoxy, hydroxyl, amino, carboxylic acid groups, urethanes, phosphates, silanes, isocyanates, cyanates, nitros, peroxys, phosphinos, phosphonos, sulfonic acids. , sulfones, nitro, acrylates, imides, amides, carboxyls, carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ - _C22 fatty acid esters or amides, carboxylates or quaternary ammonium salts, which can crosslink with reactive groups on the liquid electrolyte. Liquid electrolytes contain reactive groups such as epoxy, hydroxyl, amino, carboxylic acid groups, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl , carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates or electrolyte solvents, anions, electrolytes and other additives with quaternary ammonium salts (which are capable of cross-linking with the reactive groups of the solid electrolyte). By bridging the liquid electrolyte with the solid electrolyte, other constituents of the liquid electrolyte are more difficult to remove from the liquid electrolyte while the electrolyte of the liquid electrolyte remains fluid, thereby enhancing performance at higher temperatures.

Solid electrolytes may include fibers suitable for facilitating absorption of liquid electrolytes. Particularly suitable fibers are fibers and nanofibers made from polymers such as polyacrylonitrile, cellulose, polyethylene oxide, polymethyl methacrylate, polyamide, polyaniline, polyvinyl alcohol, nanofibers derived from cellulose, conductive fibers such as polyaniline, polythiophene, polypyrrole, and the like. It is a nanofiber electrospun from a flexible polymer. Fibers with a length of 100 nm or less and a diameter of 50 nm or less are preferred. Microfibers or nanofibers prepared by milling can also be used. Hollow fibers and fibers with higher electrolyte absorption properties are preferred.

As at least one component of the liquid electrolyte, also referred to as impregnated electrolyte, any conventionally known electrolytic solution can be employed, including a component having reactive groups. However, liquid electrolytes preferably include solvents such as non-aqueous solvents or aprotic solvents, organic salts, cations, anions, electrolytes, and other compounds. Particularly preferred additives in liquid electrolytes include ethers, amides, oxazolidinones, nitriles, glycols, glymes, glycerol, lactones, carbonates, sulfones, or polyols.

In liquid electrolytes, organic salts refer to salts in which at least one of the base and acid constituents of the salt is organic. γ-Butyrolactone or sulfolane, or mixtures thereof, are reliable, low resistivity, and particularly suitable non-aqueous solvents. Organic amine salts are preferred for the practice of this invention. Organic amine salts refer to salts of organic amines with organic or inorganic acids. Among organic amine salts, it is preferable to use salts of organic amines and organic acids, examples of which include triethylamine borodisalicylate, ethyldimethylamine phthalate, and mono-1,2,3,4-tetramethylimidazoly. phthalate, mono 1,3-dimethyl-2-ethylimidazolinium phthalate, and mixtures thereof.

Particularly preferred additives for liquid electrolytes include polyols, glycerin, polyethylene glycol, poly(ethylene glycol) diacrylate, tetramethylammonium phthalate, γ-butyrolactone, ethylated γ-butyrolactone, propylated γ-butyrolactone, and β-butyrolactone. Piolactone, dimethoxyethane (DME), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), ethylene glycol diethyl ether (DEE), and diethylene glycol diethyl ether, polyethylene glycol dimethyl ether, and at least one other organic solvent. be done. Other additives include hyperbranched polyglycidols, hyperbranched polyalkylene glycols, poly(allyl glycidyl ether), poly(ethoxyethyl glycidyl ether), copolymers of methyl glycidyl ether and allyl glycidyl ether, methyl glycidyl ether and n- Copolymers with butyl glycidyl ether, polymerized glycidyl ether monomers such as methyl glycidyl ether Hyperbranched copolymers containing glycidol, poly(ethylene glycol) methyl ether acrylate, methoxypolyethyleneglycolamine, O-(carboxymethyl)-O'-methylpolyethylene Glycol, methoxypoly(ethylene glycol), polyethylene glycol monomethyl ether, methoxypolyethylene glycol maleimide, and poly(ethylene glycol) methyl ether methacrylate.

Examples of aprotic solvents in liquid electrolytes include ethers, amides, oxazolidinones, lactones, nitriles, carbonates, sulfones, and other organic solvents. Examples of ethers include monoethers such as ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, tetrahydrofuran, and 3-methyltetrahydrofuran; diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl. ethers and the like; and triethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether. Examples of amides include formamides such as N-methylformamide, N,N-dimethylformamide, N-ethylformamide, and N,N-diethylformamide; acetamides such as N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide and the like; propionamides such as N,N-dimethylpropionamide and the like; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone and the like; and hexamethylphosphorylamide and the like. . Examples of oxazolidinone include N-methyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone and the like. Examples of lactones include γ-butyrolactone, α-acetyl-γ-butyrolactone, β-butyrolactone, γ-valerolactone, δ-valerolactone, and the like. Examples of nitriles include acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, benzonitrile, and the like. Examples of carbonates include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and the like. Examples of sulfones include sulfolane and dimethylsulfone. Examples of other organic solvents include 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, aromatic solvents (toluene, xylene, etc.), and paraffinic solvents (linear paraffins, isoparaffins, etc.).

Aprotic solvents may be used alone or in combination of two or more in the liquid electrolyte. Of these, lactones and sulfones are preferred, γ-butyrolactone and sulfolane are more preferred, and γ-butyrolactone is particularly preferred.

In one embodiment, the solvent has a boiling point greater than 200° C. and a dielectric constant greater than 35.

The liquid electrolyte preferably contains a cation represented by Formula II and an anion.

In Formula II, R ¹ -R ³ are each C _1-3 alkyl and R ⁴ -R ⁷ are each C _1-3 alkyl or a hydrogen atom. Examples of C _1-3 alkyl include methyl, ethyl, n-propyl and isopropyl.

Examples of cations are 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethyl-imidazolinium, 1,2,3- trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, and 1,2,3-triethylimidazolinium. , 3,4-tetramethylimidazolinium and 1-ethyl-2,3-dimethylimidazolinium are more preferred.

Examples of anions in liquid electrolytes include anions of various organic and/or inorganic acids commonly used in electrolytes. In the case of divalent or higher organic acids and/or inorganic acids, the anion is preferably a monoanion.

Organic and inorganic acids are exemplified by carboxylic acids, phenols, mono- and di-alkyl phosphates containing C _1-15 alkyl, sulfonic acids, inorganic acids, and the like. Examples of carboxylic acids include aliphatic polycarboxylic acids such as saturated polycarboxylic acids, especially oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and Bivalent to tetravalent including unsaturated polycarboxylic acids, especially maleic acid, fumaric acid, and itaconic acid, and aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. and S _- containing polycarboxylic acids such as thiodipropionic acid; _and aliphatic hydroxycarboxylic acids such as glycolic acid, lactic acid, tartaric acid, and castor oil fatty acid. acids; aromatic hydroxycarboxylic acids such as salicylic acid and mandelic acid; aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid C _1-30 monocarboxylic acids, including unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and oleic acid; and aromatic monocarboxylic acids such as benzoic acid, cinnamic acid, and naphthoic acid; Examples of phenols include _C1-15 alkylphenols such as phenol, cresol, xylenol, ethylphenol, n- or isopropylphenol, and isododecylphenol, methoxyphenols such as eugenol and guaiacol, α-naphthol, β-naphthol, and monohydric phenols, including phenols and naphthols, including cyclohexylphenol; and polyhydric phenols, including catechol, resorcin, pyrogallol, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and the like. Examples of mono- and di-alkyl phosphates containing C _1-15 alkyl are mono- and di-methyl phosphate, mono- and di-ethyl phosphate, mono- and di-isopropyl phosphate, mono- and di-butyl Phosphate, mono- and di-(2-ethylhexyl) phosphate, mono- and di-isodecyl phosphate and the like. Examples of sulfonic acids include _C1-15 alkylbenzenesulfonic acids such as p-toluenesulfonic acid, nonylbenzenesulfonic acid, and dodecylbenzenesulfonic acid, sulfosalicylic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include phosphoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoroarsenic acid, and the like. Other examples include the imide anion of trifluoromethanesulfonylimide and the like, and the methide anion of trifluoromethanesulfonylmethide and the like.

The electrolyte in the liquid electrolyte is represented by a combination of cations and anions, preferably the following: 1,2,3,4-tetramethylimidazolinium/phthalate monoanion, 1-ethyl-2, 3-dimethylimidazolinium/phthalate monoanion, 1,2,3,4-tetramethylimidazolinium/maleate monoanion, 1-ethyl-2,3-dimethylimidazolinium cation/maleate monoanion, 1 , 2,3,4-tetramethylimidazolinium/diethylphosphate anion, 1-ethyl-2,3-dimethylimidazolinium cation/diethylphosphate anion, 1,2,3,4-tetramethylimidazolinium/dibutyl Phosphate anion, 1-ethyl-2,3-dimethylimidazolinium cation/dibutyl phosphate anion, 1,2,3,4-tetramethylimidazolinium/diisopropyl phosphate anion, and 1-ethyl-2,3-dimethylimidazo linium cation/diisopropyl phosphate anion, most preferably 1,2,3,4-tetramethylimidazolinium/phthalate monoanion, 1-ethyl-2,3-dimethylimidazolinium/phthalate monoanion, 1 , 2,3,4-tetramethylimidazolinium/maleate monoanion, and 1-ethyl-2,3-dimethylimidazolinium cation/maleate monoanion.

The concentration of the organic salt in the non-aqueous solvent is not limited to a specific concentration, and a commonly used concentration can be appropriately adopted. This concentration can be, for example, 5% to 50% by weight.

The capacitor may contain other adjuvants, coatings, and congeners known in the art without departing from this invention. Non-limiting summaries include protective layers, multiple capacitance levels, terminals, leads, and the like.

A particular feature of the present invention is the ability to provide high voltage capacitors. By utilizing the conductive separators described above, capacitors with a rated voltage capability of 15V to 250V can be obtained. Further, the capacitor can be made as large as having a diameter of 10 mm to 30 mm and as large as having a length of 15 mm to 50 mm or larger.

Comparative Study Observation of components in a commercial product such as a capacitor with a working element of about 10 mm in diameter and about 8 mm in length makes it possible to understand the deficiencies in prior art hybrid capacitors. The prior art process of forming a polymer layer after winding results in concentrated conductive polymer around the final turn of the winding and at the bottom of the winding, resulting in non-uniform coverage of the foil and separator. You can see it with your own eyes. In the exemplary case, less than 40% of the foil is coated with a conductive polymer, making at least 60% of the foil useless in terms of contributing fully to the capacitance. FIG. 5 is a diagram schematically showing the difference between the prior art and the present invention. In FIG. 5, the prior art anode, labeled A, is coated only on the outer regions and has no conductive polymer coating at all in the center, while the example of the present invention, labeled B, has a conductive polymer over the entire surface. coated with a flexible polymer.

Example 1 (E-1)
Anodized aluminum anode foils and aluminum cathode foils having the sizes and rated capacitances shown in Table 1 were heat treated at 300°C ± 5°C for 30 minutes ± 5 minutes. A first edge forming treatment was performed by immersing the anode foil in 5% oxalic acid at 30° C.±5° C. and a voltage of 5 mA/cm ² . The foil was washed for a minimum of 5 minutes and dried at 125°C ± 5°C for 25-30 minutes. The anode foil is heat treated at 300° C.±5° C. for 30 min±5 min, then second edge formed in 1% ammonium citrate at 50° C.±5° C., voltage of 1.5 mA/cm ² . followed by washing for at least 5 minutes and drying at 125° C.±5° C. for 25-30 minutes. The anode and cathode were immersed in a solution containing 4935 ml ± 50 ml deionized water, 15 ml ± 0.5 ml acetic acid, and 50 ml ± 1 ml 3-glycidoxypropyltrimethoxysilane at a pH of 3.0 ± 1.0. Silanized for 15-30 seconds. The anode and cathode foils were again heat treated at 300° C.±5° C. for 30 min±5 min. The anode is again anodized in 0.1% ammonium phosphate at 55° C.±5° C. and a voltage of 1.5 mA/cm ² to oxidize the ends, then washed for at least 5 minutes, 125 C.±5.degree. C. for 25-30 minutes. The silanization was repeated for 15-30 seconds, followed by air drying for 15-20 minutes. The silane was cured at 125°C ± 5°C for 15 minutes ± 3 minutes. A conductive polymer layer was applied by passing the anode and cathode through a slurry containing poly-3,4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) at a speed of 3 mm/sec, followed by initial was dried at 80°C for about 10 minutes, then at 150°C for about 10 minutes, and then the coating was cooled to room temperature. The polymer coating was repeated three times with drying between coatings. The percentage of projected real surface area covered with polymer was observed to be approximately 100% for all components including the cathode foil, anode foil, and separator. All components were found to be flexible, crack-free and suitable for winding as axial capacitors. These components are stable in long-term storage. The capacitors were tested and the results are shown in Table 1.

Example 2 (E-2)
Example 1 was repeated except that the polymer was applied by spraying the slurry at the same coverage as in Example 1.

Example 3 (E-3)
A sample was prepared using the same anode and cathode as in Example 1, except that the conductive polymer was added by the prior art method described in US Pat. Table 1 shows the results.

In Table 1, _VR is the rated voltage and CV is the capacitance times volts. In the example, the capacitance for the same anode and cathode sizes was almost three times higher for E-1 than for E-3.

The results obtained for E-1 were successfully applied to the fabrication of axial capacitors of various case sizes. The CV for capacitors from 40V to 63V was almost three times higher for E-1 than for E-3. Lifetime tests have demonstrated that the prototypes produced have high stability at elevated temperatures for several hours at rated voltage. Prototypes achieved low ESR and temperature dependent suppression along with high CV values. 6 to 10 are diagrams showing electrical performance. FIG. 6 shows the ESR improvement as a function of temperature for a 20 mm diameter, 27 mm long axial capacitor with a rated voltage of 40V. FIG. 7 shows the ESR improvement as a function of temperature for a 10 mm diameter, 20 mm long axial capacitor with a rated voltage of 40V. FIG. 8 shows the ESR improvement as a function of time at 125° C. for a 10 mm diameter, 20 mm long axial capacitor with a rated voltage of 40V. FIG. 9 shows the ESR improvement as a function of time at 105° C. for a series of comparative hybrid 40V capacitors of the prior art versus a series of capacitors of the present invention. FIG. 10 shows the ESR improvement as a function of time at 105° C. for a comparative hybrid 63V capacitor versus the capacitor of the present invention.

A series of capacitors were prepared to determine the shift in ESR as a function of frequency. A control axial electrolytic capacitor was prepared, a fully asymmetric capacitor as described herein, a symmetric capacitor designated HAC-1 having a conductive polymer on both sides of the anode and a single layer of polymer over the dielectric; A symmetrical capacitor designated HAC-3 was also prepared with a conductive polymer on both sides of the anode and three polymer layers coated on the dielectric. FIG. 18 is a graph showing the benefits of being asymmetric and using additional coating layers to add conductivity to the conductive polymer layer.

Crosslinked Examples To test the effect of internal crosslinking on polymer adhesion, three groups of samples were prepared on glass clay plates.

In group 1, the glass plywood was coated with the conductive polymer slurry, then dried at 80°C for 15 minutes and cured at 150°C for 15 minutes.

In group 2, the glass plate was treated with the 3-glycidoxypropyltrimethoxysilane solution and then dried at 125° C. for 15 minutes. The griddle was then coated with a conductive polymer slurry, then dried at 80°C for 15 minutes and cured at 150°C for 15 minutes.

In group 3, the glass plate was treated with the 3-glycidoxypropyltrimethoxysilane solution and then dried at 125° C. for 15 minutes. The griddle was then coated with a conductive polymer slurry, then dried at 80°C for 15 minutes and cured at 150°C for 15 minutes. The samples were treated with a silane solution and then dried at 125°C for 15 minutes.

Samples of groups 1-3 were placed in a container, partially immersed with the conductive polymer coating in the electrolyte, sealed, and stored at elevated temperature under various conditions. Test 1 is a 48 hour test at room temperature, Test 2 is a 96 hour test at 125°C and Test 3 is a 24 hour test at 150°C. After testing, all samples were rinsed with deionized water.

In each test, the portion immersed in the electrolyte in the Group 1 sample delaminated to the height of the immersion. At room temperature after immersion in the electrolyte, the conducting polymer does not effectively adhere to the surface. If this were introduced into a hybrid capacitor, the capacitor would likely have very poor ESR stability.

Group 2 showed moderate stability. Conductive layers soaked in electrolyte adhered more strongly to the glass slab than Group 1, and nearly all the polymer remained adhered under room temperature conditions. However, after storage in hotter electrolytes, a significant portion of the conductive polymer layer detached below the immersion level. Group 3 showed the best adhesion even under the most severe conditions of Test 3. In this case, the polymer layer was reinforced at the sub-particle level and chemically bonded to the surface.

FIG. 22 shows the results of ESR measurement performed on a hybrid capacitor winding with a diameter of 10 mm and a length of 20 mm (D10×L20). In FIG. 22, a hybrid capacitor (E-4) has a silane pretreated anode with a conductive polymer coating, a conductive separator using paper impregnated with a conductive polymer slurry and then cured, and a carbon It was assembled from coated cathodes. Hybrid Capacitor (E-5) represents a hybrid prototype in which all polymer layers on all materials were post-treated with silane to fully cross-link the conducting polymer pathways.

The results clearly show that much higher stability and better performance are obtained in prototypes applying the full cross-linking approach.

The present invention has been described with reference to preferred embodiments without being limited thereto. Those skilled in the art will recognize additional embodiments and modifications not specifically described herein but within the scope of the invention as more particularly set forth in the appended claims. be.

Claims (61)

is a capacitor,
an anode comprising a first dielectric and an anode conductive polymer layer on the first dielectric;
a cathode;
a separator between the anode conductive polymer layer and the cathode, the separator comprising a separator conductive polymer layer, at least one of the anode conductive polymer layer or the separator conductive polymer layer being contiguous; a separator bridging the layer;
an active element comprising
a liquid electrolyte;
at least one of the anode, the separator, or the cathode further comprising a reactive group ;
a first reactive group of the reactive group is crosslinked with a second reactive group of the reactive group;
wherein the first reactive group and the second reactive group are in adjacent layers;
capacitor. 2. The separator of claim 1, wherein the separator comprises one of said reactive groups , said reactive group reacting with a second reactive group of said reactive groups in said separator conductive polymer layer. capacitor. 2. The capacitor of claim 1, wherein said adjacent layer of one of said adjacent layers is said anode conductive polymer layer. 2. The capacitor of claim 1, wherein said adjacent layer of one of said adjacent layers is said separator conductive polymer layer. 2. The capacitor of claim 1, wherein said cathode comprises a cathode conductive layer, said adjacent layer of one of said adjacent layers being said cathode conductive layer . wherein at least one of said reactive groups is epoxy, hydroxyl, amino, carboxylic acid group, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic acid, sulfone, nitro, acrylate, imides, amides, carboxyls, carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or 2. The capacitor of claim 1 selected from the group consisting of amides, carboxylates, and quaternary ammonium salts. said reactive group is epoxy, hydroxyl, amino, carboxylic acid group, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic acid Anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates, and 7. The capacitor of claim 6, selected from the group consisting of quaternary ammonium salts. 2. The capacitor of claim 1, wherein said liquid electrolyte resides between said anode conductive polymer layer and said cathode. 9. The capacitor of claim 8, comprising up to 50% by weight of said liquid electrolyte. 2. The anode conductive polymer layer of claim 1, wherein the anode conductive polymer layer covers at least 80% of the surface area of the first dielectric, or at least 80% of the cathode surface area comprises a cathode conductive polymer layer. capacitor. 11. The method of claim 10, wherein the anode conductive polymer layer covers at least 90% of the surface area of the first dielectric or the cathode conductive polymer layer covers at least 90% of the surface area of the cathode. Capacitor as described. 2. The capacitor of claim 1, comprising multiple anode leads or multiple cathode leads. 2. The capacitor of claim 1, wherein at least one of said anode or said cathode comprises a valve metal. 14. The capacitor of claim 13, wherein said valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides thereof. 15. The capacitor of claim 14, wherein said valve metal is aluminum. 2. The capacitor of claim 1, wherein at least one of said anode, said cathode, or said separator has a conductive polymer coating of at least 0.1 mg/cm ² to 10 mg/cm ² or less. 2. The capacitor of claim 1, having a voltage rating of at least 15 volts up to 250 volts. 2. The capacitor of claim 1, wherein adjacent conductive polymer layers are in physical contact. at least one of the anode conductive polymer layer, the separator conductive polymer layer, or the cathode conductive layer on the cathode is selected from the group consisting of silanes, epoxides, ethers, epoxy crosslinkers, and hydrophilic coupling agents. 2. The capacitor of claim 1, crosslinked by a crosslinker. 20. The capacitor of claim 19, wherein said silane is selected from the group consisting of glycidylsilanes and organofunctional silanes. The organofunctional silane has the formula:

(Wherein, X is an organic functional group,
Y is any organic moiety containing reactive or non-reactive functional groups;
R ₁ is aryl or alkyl (CH ₂ ) _m (where m is 0-14);
R ₂ is individually a hydrolyzable functional group,
21. The capacitor of claim 20, wherein R ₃ is individually an alkyl functional group of 1-6 carbon atoms, and n is 1-3. 22. The capacitor of claim 21, wherein X is selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, and alkyl. The organofunctional silane is 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyl 21. The method of claim 20 selected from the group consisting of trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane. capacitor. The organofunctional silane has the formula:

wherein R ₁ is C 1-14 alkyl, and R ₂ is each independently C 1-6 alkyl or substituted alkyl. capacitor. The organofunctional silane has the formula:

21. The capacitor of claim 20, defined as: The epoxy crosslinker has the formula:

(Wherein, X is alkyl or substituted alkyl, aryl or substituted aryl having 0 to 14 carbon atoms, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups) 20. The capacitor of claim 19, defined as: The epoxy cross-linking agent is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol. Glycidyl ether, glycerol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetra methylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2,7,8-diepoxyoctane, 1,2,5 20. The capacitor of claim 19 selected from the group consisting of ,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, or maleimide-epoxy compounds. 20. The capacitor of Claim 19, wherein said ether is a glycidyl ether. wherein said ether is of the formula:

(wherein R ₃ is alkyl or substituted alkyl having 1 to 14 carbon atoms, ethylene ether, polyethylene ether having 2 to 20 ethylene ether groups; hydroxy,

or -(CH ₂ OH) _x CH ₂ OH, where X is alkyl substituted with a group selected from 1-14. Said ether is:

(wherein n is an integer from 1 to 220);

20. The capacitor of claim 19 selected from the group consisting of A method of forming a capacitor, the method comprising forming a working element, wherein forming the working element comprises:
forming an anode comprising a first dielectric and an anode conductive polymer layer on the first dielectric;
forming a cathode;
forming a separator comprising a separator conductive polymer layer;
a layered structure comprising said anode, said cathode and said separator, said separator forming a layered structure between said anode and said cathode; and forming a winding of said layered structure. and
Impregnating the wound body with a liquid electrolyte;
cross-linking at least one of the anode conductive polymer layer or the separator conductive polymer layer with an adjacent layer; and
at least one of the anode, the separator, or the cathode further comprising a reactive group ;
a first reactive group of the reactive group is crosslinked with a second reactive group of the reactive group;
wherein the first reactive group and the second reactive group are in adjacent layers;
Method. 32. The method of forming a capacitor of claim 31, wherein at least one of the anode conductive polymer layer or the separator conductive polymer layer is crosslinked prior to forming the winding. 32. The separator of claim 31, wherein the separator comprises one of said reactive groups , said reactive group reacting with a second reactive group of said reactive groups in said separator conductive polymer layer. How to form a capacitor. 32. The method of forming a capacitor of claim 31, wherein said adjacent layer of one of said adjacent layers is said anode conductive polymer layer. 32. The method of forming a capacitor of claim 31, wherein said adjacent layer of one of said adjacent layers is said separator conductive polymer layer. 32. The method of forming a capacitor of claim 31, wherein said cathode includes a cathode conductive layer, said adjacent layer of one of said adjacent layers being said cathode conductive layer . wherein at least one of said reactive groups is epoxy, hydroxyl, amino, carboxylic acid group, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic acid, sulfone, nitro, acrylate, imides, amides, carboxyls, carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or 32. The method of forming a capacitor of Claim 31 selected from the group consisting of amides, carboxylates, and quaternary ammonium salts. said reactive group is epoxy, hydroxyl, amino, carboxylic acid group, urethane, phosphate, silane, isocyanate, cyanate, nitro, peroxy, phosphino, phosphono, sulfonic acid, sulfone, nitro, acrylate, imide, amide, carboxyl, carboxylic acid Anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates and maleimidoitaconates, allyl alcohol esters, dicyclo-pentadiene unsaturated groups, unsaturated C ₁₂ -C ₂₂ fatty acid esters or amides, carboxylates, and 38. The method of forming a capacitor of claim 37, wherein the capacitor is selected from the group consisting of quaternary ammonium salts. 32. The method of forming a capacitor of claim 31, wherein said liquid electrolyte resides between said anode conductive polymer layer and said cathode. 40. The method of forming a capacitor of claim 39, comprising up to 50% by weight of said liquid electrolyte. 32. The method of claim 31, wherein the anode conductive polymer layer covers at least 80% of the surface area of the first dielectric, or at least 80% of the cathode surface area comprises a cathode conductive polymer layer. How to form a capacitor. 42. The method of claim 41, wherein the anode conductive polymer layer covers at least 90% of the surface area of the first dielectric or the cathode conductive polymer layer covers at least 90% of the surface area of the cathode. A method of forming the described capacitor. 32. The method of forming a capacitor of claim 31 including multiple anode leads or multiple cathode leads. 32. The method of forming a capacitor of claim 31, wherein at least one of said anode or said cathode comprises a valve metal. 45. The method of forming a capacitor of claim 44, wherein said valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides thereof. 46. The method of forming a capacitor of claim 45, wherein the valve metal is aluminum. 32. The method of forming a capacitor of claim 31, wherein at least one of said anode, said cathode, or said separator has a conductive polymer coating of at least 0.1 mg/ ^cm2 to 10 mg/ ^cm2 or less. 32. The method of forming a capacitor of claim 31, having a voltage rating of at least 15 volts to 250 volts or less. 32. The method of forming a capacitor of claim 31, wherein adjacent conductive polymer layers are in physical contact. at least one of the anode conductive polymer layer, the separator conductive polymer layer, or the cathode conductive layer on the cathode is selected from the group consisting of silanes, epoxides, ethers, epoxy crosslinkers, and hydrophilic coupling agents. 32. The method of forming a capacitor of claim 31, wherein the capacitor is cross-linked by a cross-linking agent. 51. The method of forming a capacitor of claim 50, wherein said silane is selected from the group consisting of glycidylsilanes and organofunctional silanes. The organofunctional silane has the formula:

(Wherein, X is an organic functional group,
Y is any organic moiety containing reactive or non-reactive functional groups;
R ₁ is aryl or alkyl (CH ₂ ) _m (where m is 0-14);
R ₂ is individually a hydrolyzable functional group,
52. The method of forming a capacitor of claim 51, wherein R ₃ is individually an alkyl functional group of 1-6 carbon atoms, and n is 1-3. 53. The method of forming a capacitor of claim 52, wherein X is selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, and alkyl. . The organofunctional silane is 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyl 52. The method of claim 51 selected from the group consisting of trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane. method of forming a capacitor. The organofunctional silane has the formula:

wherein R ₁ is C 1-14 alkyl, and R ₂ is each independently C 1-6 alkyl or substituted alkyl. method of forming a capacitor. The organofunctional silane has the formula:

52. The method of forming a capacitor of claim 51, defined as: The epoxy crosslinker has the formula:

(Wherein, X is alkyl or substituted alkyl, aryl or substituted aryl having 0 to 14 carbon atoms, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups) 51. A method of forming a capacitor as defined in claim 50. The epoxy cross-linking agent is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol. Glycidyl ether, glycerol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol diglycidyl ether, 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, 51. The method of forming a capacitor of claim 50 selected from the group consisting of 6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, or maleimide-epoxy compounds. 51. The method of forming a capacitor of claim 50, wherein said ether is a glycidyl ether. wherein said ether is of the formula:

(wherein R ₃ is alkyl or substituted alkyl having 1 to 14 carbon atoms, ethylene ether, polyethylene ether having 2 to 20 ethylene ether groups; hydroxy,

or —(CH ₂ OH) _x CH ₂ OH, wherein X is alkyl substituted with a group selected from 1 to 14. how to. Said ether is:

(wherein n is an integer from 1 to 220);

51. The method of forming a capacitor of claim 50 selected from the group consisting of:

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