阅读说明：本技术 包含纳米涂层的固体电解质电容器 (Solid electrolyte capacitor comprising a nanocoating ) 是由 J.彼得齐勒克 L.杰巴拉 L.维尔克 于 2018-07-02 设计创作，主要内容包括：提供电容器,其包括固体电解质电容器元件、封装所述电容器元件的壳体材料、阳极端子、和阴极端子。在所述电容器元件、壳体材料、阳极端子、阴极端子、或其组合的至少一部分上设置纳米涂层。所述纳米涂层具有约2,000纳米或更小的平均厚度并且包含气相沉积的聚合物。(A capacitor is provided that includes a solid electrolyte capacitor element, a case material that encapsulates the capacitor element, an anode terminal, and a cathode terminal. Disposing a nanocoating on at least a portion of the capacitor element, the case material, the anode terminal, the cathode terminal, or a combination thereof. The nanocoating has an average thickness of about 2,000 nanometers or less and comprises a vapor deposited polymer.)

1. A capacitor, comprising:

a capacitor element comprising a sintered porous anode body, a dielectric overlying the anode body, and a solid electrolyte overlying the dielectric;

a case material encapsulating the capacitor element;

an anode terminal electrically connected to the anode body and including a portion located outside the casing material;

a cathode terminal electrically connected to the solid electrolyte and including a portion located outside the case material; and

a nanocoating disposed on at least a portion of the capacitor element, the housing material, the anode terminal, the cathode terminal, or a combination thereof, wherein the nanocoating has an average thickness of about 2,000 nanometers or less and comprises a vapor deposited polymer.

2. The capacitor of claim 1 wherein said vapor deposited polymer is formed by in situ polymerization of a precursor compound.

3. The capacitor of claim 2 wherein said precursor compound is a polyaromatic.

4. The capacitor of claim 3 wherein the polyaromatic hydrocarbon has the following overall structure:

wherein the content of the first and second substances,

R₁is alkyl, alkenyl, halogen, or haloalkyl; and

R₂、R₃、R₄、R₅and R₆Independently selected from hydrogen, alkyl, alkenyl, halogen, or haloalkyl, wherein R is₁、R₂、R₃、R₄、R₅Or R₆Optionally bonded to a second polyaromatic ring structure to form a dimer.

5. The capacitor of claim 3 wherein the polyaromatic hydrocarbon is 1, 4-dimethylbenzene, 1, 3-dimethylbenzene, 1, 2-dimethylbenzene, toluene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 1, 4-divinylbenzene, 1, 3-divinylbenzene, 1, 2-divinylbenzene, chloropolyarene, [2,2] para-cyclophane, or a combination thereof.

6. The capacitor of claim 1 wherein said precursor compound is a fluorocarbon.

7. The capacitor of claim 6 wherein said hydrofluorocarbon is CF₄、C₂F₄、C₂F₆、C₃F₆、C₃F₈Or a combination thereof.

8. The capacitor of claim 1 wherein said nanocoating comprises a polymer formed from a polyaromatic precursor compound and a fluorohydrocarbon precursor compound.

9. The capacitor of claim 1, wherein the nanocoating is disposed on the capacitor element.

10. The capacitor of claim 1, wherein the capacitor element comprises a front surface, a back surface, a top surface, a bottom surface, a first side surface, and a second side surface, and further wherein the capacitor element comprises an anode wire extending from the front surface of the capacitor element.

11. The capacitor of claim 10, wherein the nanocoating is disposed on the front surface, the back surface, the top surface, the bottom surface, the first side surface, the second side surface, or a combination thereof.

12. The capacitor of claim 11, wherein the nanocoating has a thickness on at least a portion of the front surface that is greater than a thickness of the nanocoating on at least a portion of the back surface, the top surface, the bottom surface, the first side surface, or the second side surface.

13. The capacitor of claim 1, wherein the nanocoating is disposed on the housing material.

14. The capacitor of claim 1, wherein a ratio of a thickness of the nanocoating at one region of the capacitor to a thickness of the nanocoating at another region of the capacitor is about 2 or greater.

15. The capacitor of claim 1 wherein said vapor deposited polymer is formed by: sputtering, plasma enhanced physical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer chemical vapor deposition, or combinations thereof.

16. The capacitor of claim 1 wherein said vapor deposited polymer is polymerized in the presence of a plasma.

17. The capacitor of claim 1 wherein said capacitor element further comprises a cathodic coating comprising a metal particle layer overlying said solid electrolyte, wherein said metal particle layer comprises a plurality of electrically conductive metal particles dispersed within a resinous polymer matrix.

18. The capacitor of claim 1 wherein said anode body comprises tantalum and said dielectric comprises tantalum pentoxide.

19. The capacitor of claim 1 wherein the solid electrolyte comprises a plurality of conductive polymer particles.

20. The capacitor of claim 19 wherein said conductive polymer particles comprise an extrinsic conductive polymer.

21. The capacitor of claim 20 wherein the extrinsic conductive polymer is poly (3, 4-ethylenedioxythiophene).

22. The capacitor of claim 20 wherein said particles further comprise a polymeric counterion.

23. The capacitor of claim 19 wherein said conductive polymer particles comprise an intrinsically conductive polymer.

24. The capacitor of claim 1 further comprising an outer polymer coating overlying said solid electrolyte and comprising pre-polymerized conductive polymer particles and a cross-linking agent.

25. A method of sealing a capacitor, the capacitor comprising: a capacitor element comprising a sintered porous anode body, a dielectric overlying the anode body, and a solid electrolyte overlying the dielectric; a case material encapsulating the capacitor element; an anode terminal electrically connected to the anode body and including a portion located outside the casing material; and a cathode terminal electrically connected to the solid electrolyte and comprising a portion located outside of the case material, the method comprising gas phase polymerizing a precursor compound to form at least one layer of a nanocoating on at least a portion of the capacitor element, case material, anode terminal, cathode terminal, or a combination thereof.

26. The method of claim 25, wherein the nanocoating has an average thickness of about 2,000 nanometers or less.

27. The method of claim 25, wherein the precursor compound is a polyaromatic hydrocarbon, a fluorinated hydrocarbon, or a combination thereof.

28. The method of claim 25 wherein the precursor compound is gas phase polymerized on the capacitor element.

29. The method of claim 25, wherein the precursor compound is gas phase polymerized on the shell material.

30. The method of claim 25, wherein the vapor phase polymerization comprises sputtering, plasma enhanced physical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer chemical vapor deposition, or a combination thereof.

31. The method of claim 25, wherein the gas phase polymerization occurs in the presence of a plasma.

32. The method of claim 25, wherein the gas phase polymerization occurs in the absence of a solvent.

33. The method of claim 25, wherein the gas phase polymerization occurs at a temperature of about 15 ℃ to about 35 ℃.

Background

A tantalum polymer capacitor is formed from a sintered tantalum anode having disposed thereon a solid electrolyte, a silver layer, and a carbon layer. However, one problem often associated with conventional solid electrolyte capacitors is that the silver layer tends to form ions when exposed to high humidity environments (e.g., 85% relative humidity), particularly at high temperatures (e.g., 85 ℃). These ions can migrate through the electrolyte and redeposit as silver on the anode surface, which in turn can lead to increased leakage currents. Accordingly, there is a need for improved solid electrolyte capacitors that can be used under humid conditions.

Disclosure of Invention

According to one embodiment of the present invention, there is disclosed a capacitor including: a capacitor element comprising a sintered porous anode body (anode body), a dielectric overlying the anode body, and a solid electrolyte overlying the dielectric; a case material encapsulating the capacitor element; an anode terminal electrically connected to the anode body and including a portion located outside the casing material; and a cathode terminal electrically connected to the solid electrolyte and including a portion located outside the case material. Further, a nanocoating is disposed on at least a portion of the capacitor element, the case material, the anode terminal, the cathode terminal, or a combination thereof. The nanocoating has an average thickness of about 2,000 nanometers or less and comprises a vapor deposited polymer.

Other features and aspects of the present invention are set forth in more detail below.

Drawings

A full and enabling disclosure of the present invention, including the best mode thereof, directed to one of ordinary skill in the art, is set forth more particularly in the remainder of the specification, which makes reference to the appended figures in which:

fig. 1 is a schematic view of one embodiment of a solid electrolytic capacitor of the present invention: wherein the nanocoating is disposed on the capacitor element;

fig. 2 is a schematic view of another embodiment of the solid electrolytic capacitor of the present invention: wherein the nanocoating is disposed on the shell material.

Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.

Detailed Description

It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied by way of exemplary explanation.

In general, the present invention relates to solid electrolyte capacitors comprising a capacitor element including a sintered porous anode body, an electrolyte overlying the anode body, and a solid electrolyte overlying the dielectric. The anode body is in electrical contact with an anode terminal and the solid electrolyte is in electrical contact with a cathode terminal. The capacitor element is further encapsulated by a housing material such that at least a portion of the anode and cathode terminations remain outside of the housing material. In particular, at least a portion of the capacitor element, the housing material, the anode terminal, and/or the cathode terminal comprises a nanocoating. The nanocoating comprises a vapor deposited polymer, typically formed by in situ polymerization of a gaseous precursor compound on a portion of the capacitor. The resulting nanocoating may comprise a single layer or multiple layers, e.g., 2-10 layers, in some embodiments 3-8 layers, and in some embodiments 4-6 layers, formed of the same or different materials. Regardless of the number of layers employed, the nanocoating typically has an average thickness of about 2,000 nanometers or less, in some embodiments from about 1 nanometer to about 1,000 nanometers, in some embodiments from about 10 nanometers to about 600 nanometers, and in some embodiments, from about 20 nanometers to about 400 nanometers.

By selectively controlling various aspects of the nanocoating, such as where it is applied, the material from which the nanocoating is formed, and the specific manner in which it is applied, the inventors have discovered that capacitors can be formed that: it is not highly sensitive to moisture and therefore can exhibit excellent electrical properties even when exposed to high humidity levels, for example, when contacted with an atmosphere having a relative humidity of about 40% or greater, in some embodiments about 45% or greater, in some embodiments about 50% or greater, and in some embodiments about 70% or greater (e.g., from about 85% to about 100%). Relative humidity can be determined, for example, according to ASTM E337-02, method A (2007). The humid atmosphere may be part of the internal atmosphere of the capacitor itself, or it may be the external atmosphere to which the capacitor is exposed during storage and/or use. The capacitor may, for example, exhibit a relatively low equivalent series resistance ("ESR") when exposed to a high humidity atmosphere (e.g., 85% relative humidity), such as about 200 milliohms, in some embodiments less than about 150 milliohms, in some embodiments from about 0.01 to about 125 milliohms, and in some embodiments, from about 0.1 to about 100 milliohms, measured at an operating frequency of 100 kHz. The capacitor may exhibit a DCL of only about 50 micro-amperes ("μ A") or less, in some embodiments about 40 μ A or less, in some embodiments about 20 μ A or less, and in some embodiments, from about 0.1 to about 10 μ A. The capacitor may also exhibit a high percentage of its wet capacitance, which enables it to have only a small loss and/or fluctuation of capacitance in the presence of atmospheric humidity. This performance characteristic is quantified by the "wet-to-dry capacitance percentage" which is determined by the equation:

wet to dry capacitance (dry capacitance/wet capacitance) x 100

The capacitor may exhibit a percentage wet to dry capacitance of about 50% or greater, in some embodiments about 60% or greater, in some embodiments about 70% or greater, and in some embodiments, about 80% to 100%. The dry capacitance can be about 30 nanofarads (rads)/square centimeter ("nF/cm²") or greater, and in some embodiments about 100nF/cm²Or greater, in some embodiments from about 200 to about 3,000nF/cm²And in some embodiments from about 400 to about 2,000nF/cm²Measured at a frequency of 120 Hz.

In particular, the ESR, DCL, and capacitance values may be maintained for a substantial amount of time, even at high temperatures. For example, the values may be maintained at a temperature of 50 ℃ to 250 ℃, and in some embodiments 70 ℃ to 200 ℃, and in some embodiments 80 ℃ to about 150 ℃ (e.g., 85 ℃), and at high humidity levels for about 100 hours or more, in some embodiments from about 300 hours to about 3,000 hours, and in some embodiments from about 400 hours to about 2,500 hours (e.g., 500 hours, 600 hours, 700 hours, 800 hours, 900 hours, 1,000 hours, 1,100 hours, 1,200 hours, or 2,000 hours). In one embodiment, for example, the values may be maintained at a temperature of 85 ℃ for 1,000 hours.

Various embodiments of the capacitor will now be described in more detail.

I.Capacitor element

A.Anode body

The capacitor element includes an anode including a dielectric formed on a sintered porous body. The porous anode body may be formed from a powder of: it comprises valve metals (i.e. metals capable of oxidation) or compounds based on valve metals, such as tantalum, niobium, aluminium, hafnium, titanium, alloys thereof, oxides thereof, nitrides thereof, etc. The powder typically has a tantalum salt (e.g., potassium (K) fluorotantalate) added thereto₂TaF₇) Sodium fluorotantalate (Na)₂TaF₇) Tantalum pentachloride (TaCl)₅) Etc.) with a reducing agent. The reducing agent may be provided in the form of a liquid, a gas (e.g., hydrogen), or a solid such as a metal (e.g., sodium), a metal alloy, or a metal salt. In one embodiment, for example, a tantalum salt (e.g., TaCl) may be added₅) At about 900 ℃ to about 2,000 ℃, in some embodiments about 1,000 ℃ to about 1,800 ℃, and atIn some embodiments, from about 1,100 ℃ to about 1,600 ℃ to form a vapor that can be reduced in the presence of a gaseous reducing agent (e.g., hydrogen). Additional details of such reduction reactions can be described inMaeshima et alWO 2014/199480. After reduction, the product may be cooled, pulverized, and washed to form a powder.

The specific charge of the powder typically varies from about 2,000 to about 800,000 microfaravolts per gram ("μ F V/g"), depending on the desired application. For example, in certain embodiments. The following highly charged powders may be used: it has a specific charge of about 100,000 to about 800,000 μ F V/g, in some embodiments about 120,000 to about 700,000 μ F V/g, and in some embodiments, about 150,000 to about 600,000 μ F V/g. In further embodiments, the following low charge powders may be employed: it has a specific charge of about 2,000 to about 100,000 μ F V/g, in some embodiments about 5,000 to about 80,000 μ F V/g, and in some embodiments, about 10,000 to about 70,000 μ F V/g. As is known in the art, the specific charge can be determined by: the capacitance is multiplied by the anodization voltage employed and then the product is divided by the weight of the anodized electrode body.

The powder may be a free-flowing, finely divided powder comprising primary particles. The primary particles of the powder typically have a median size (D50) of about 5 to about 500 nanometers, in some embodiments about 10 to about 400 nanometers, and in some embodiments about 20 to about 250 nanometers, as determined, for example, using a laser particle size distribution analyzer (e.g., LS-230) manufactured by BECKMAN COULTER Corporation, optionally after subjecting the particles to ultrasonic vibration for 70 seconds. The primary particles typically have a three-dimensional granular shape (e.g., nodular or angular). Such particles typically have a relatively low "aspect ratio," which is the average diameter or width divided by the average thickness ("D/T") of the particle. For example, the aspect ratio of the particles may be about 4 or less, in some embodiments about 3 or less, and in some embodiments, from about 1 to about 2. In addition to primary particles, the powder may also comprise other types of particles, such as secondary particles formed by aggregating (or agglomerating) the primary particles. Such secondary particles may have a median size (D50) of from about 1 to about 500 microns, and in some embodiments, from about 10 to about 250 microns.

Agglomeration of the particles may occur by heating the particles and/or by using a binder. For example, agglomeration may occur at a temperature of from about 0 ℃ to about 40 ℃, in some embodiments from about 5 ℃ to about 35 ℃, and in some embodiments, from about 15 ℃ to about 30 ℃. Similarly, suitable binders can include, for example, poly (vinyl butyral); poly (vinyl acetate); poly (vinyl alcohol); poly (vinyl pyrrolidone); cellulosic polymers such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and methylhydroxyethyl cellulose; atactic polypropylene, polyethylene; polyethylene glycols (e.g., Carbowax from Dow Chemical co.); polystyrene, poly (butadiene/styrene); polyamides, polyimides, and polyacrylamides, high molecular weight polyethers; copolymers of ethylene oxide and propylene oxide; fluoropolymers such as polytetrafluoroethylene, polyvinylidene fluoride, and fluoroolefin copolymers; acrylic polymers such as sodium polyacrylate, poly (lower alkyl acrylate), poly (lower alkyl methacrylate), and copolymers of lower alkyl acrylate and lower alkyl methacrylate; and fatty acids and waxes such as stearic acid and other soap fatty acids, vegetable waxes, microcrystalline waxes (purified paraffin wax), and the like.

The resulting powder may be compacted to form tablets using any conventional powder compaction equipment. For example, the following compression mold (press mold) may be employed: it is a one-station compaction press (compaction press) comprising a die and one or more punches (punch). Alternatively, a variety of anvil-type compaction presses may be used that use only a die and a single lower punch. One-station compaction dies are available in a number of basic types, for example: cam, crank (toggle)/toggle (knuckle), and eccentric (eccentric)/crankshaft (crank) presses with varying capabilities such as single-acting, double-acting, floating die (floating die), movable platen (movable plate), opposed piston (opposed ram), screw, impact, hot press, embossing (stamping, molding, post-casting, coining), or coining (sizing). The powder may be compacted around an anode lead, which may be in the form of a wire, sheet, or the like. The lead may extend longitudinally from the anode body and may be formed of any conductive material, such as tantalum, niobium, aluminum, hafnium, titanium, and the like, as well as conductive oxides and/or nitrides thereof. The connection of the leads can also be achieved using other known techniques, for example by: the lead wire is welded to the anode body or embedded within the anode body during formation (e.g., prior to compaction and/or sintering).

Any binder may be removed after pressing by: the sheet is heated under vacuum at a temperature (e.g., about 150 ℃ to about 500 ℃) for several minutes. Alternatively, the binder may also be removed by: contacting the sheet with an aqueous solution, e.g. inBishop et alIs described in us patent No.6,197,252. The sheet is then sintered to form a porous monolithic mass. The sheets are typically sintered at a temperature of from about 700 ℃ to about 1600 ℃, in some embodiments from about 800 ℃ to about 1500 ℃, and in some embodiments, from about 900 ℃ to about 1200 ℃, for a time of from about 5 minutes to about 100 minutes, and in some embodiments, from about 8 minutes to about 15 minutes. This may occur in one or more steps. Sintering may, if desired, occur in an atmosphere that limits the transfer of oxygen atoms to the anode. For example, sintering may occur in a reducing atmosphere, such as in a vacuum, inert gas, hydrogen, and the like. The reducing atmosphere may be at a pressure of from about 10 torr to about 2000 torr, in some embodiments from about 100 torr to about 1000 torr, and in some embodiments, from about 100 torr to about 930 torr. Mixtures of hydrogen and other gases (e.g., argon or nitrogen) may also be used.

B.Dielectric medium

The anode is also covered with a dielectric. The dielectric may be formed by: anodizing the sintered anode such that a dielectric layer is formed on and/or within the anode. For example, a tantalum (Ta) anode may be anodized to tantalum pentoxide (Ta)₂O₅). Typically, anodization is carried out by initially applying a solution to the anode, for example by dipping the anodeIn an electrolyte. A solvent such as water (e.g., deionized water) is typically employed. In order to enhance ion conductivity, a compound capable of dissociating in the solvent to form ions may be used. Examples of such compounds include, for example, acids such as those described below for the electrolyte. For example, the acid (e.g., phosphoric acid) may constitute from about 0.01 wt% to about 5 wt%, in some embodiments from about 0.05 wt% to about 0.8 wt%, and in some embodiments, from about 0.1 wt% to about 0.5 wt% of the anodizing solution. Blends of acids may also be used if desired.

Passing an electric current through the anodizing solution to form the dielectric layer. The value of the forming voltage governs the thickness of the dielectric layer. For example, the power supply may be initially set to a constant current mode until the desired voltage is reached. The power supply can then be switched to potentiostatic mode to ensure that the desired dielectric thickness is formed over the entire surface of the anode. Of course, other known methods, such as pulsed or step (step) potentiostatic methods, may also be used. The voltage at which anodization occurs typically ranges from about 4 to about 250V, and in some embodiments from about 5 to about 200V, and in some embodiments, from about 10 to about 150V. During oxidation, the anodizing solution may be maintained at an elevated temperature, such as about 30 ℃ or higher, in some embodiments from about 40 ℃ to about 200 ℃, and in some embodiments, from about 50 ℃ to about 100 ℃. The anodization may also be performed at ambient temperature or lower. The resulting dielectric layer may be formed on the surface of the anode and within the pores thereof.

Although not required, in certain embodiments, the dielectric layer may have a differential thickness in the anode due to: having a first portion overlying the outer surface of the anode and a second portion overlying the inner surface of the anode. In such embodiments, the first portion is selectively formed such that its thickness is greater than the thickness of the second portion. However, it should be understood that the thickness of the dielectric layer need not be uniform in a particular area. Certain portions of the dielectric layer adjacent to the outer surface may, for example, be substantially thinner than certain portions of the layer at the inner surface, and vice versa. However, the dielectric layer may be formed such that at least a portion of the layer at the outer surface has a greater thickness than at least a portion at the inner surface. While the exact difference in these thicknesses may vary depending on the particular application, the ratio of the thickness of the first portion to the thickness of the second portion is typically from about 1.2 to about 40, in some embodiments from about 1.5 to about 25, and in some embodiments, from about 2 to about 20.

To form dielectric layers having differential thicknesses. A multi-stage process is typically employed. In various stages of the process, the sintered anode is anodized ("anodized") to form a dielectric layer (e.g., tantalum pentoxide). During the first stage of anodization, a relatively small formation voltage is typically employed to ensure that a desired dielectric thickness is achieved for the inner region, such as a formation voltage in the range of about 1 to about 90 volts, in some embodiments about 2 to about 50 volts, and in some embodiments, about 5 to about 20 volts. Thereafter, the sintered body may then be anodized in a second stage of the process to increase the thickness of the dielectric to a desired level. This is typically accomplished by anodization in the electrolyte at a higher voltage than employed during the first stage, for example, at a formation voltage in the range of about 50 to about 350 volts, in some embodiments about 60 to about 300 volts, and in some embodiments, about 70 to about 200 volts. During the first and/or second stages, the electrolyte may be maintained at a temperature in the range of from about 15 ℃ to about 95 ℃, in some embodiments from about 20 ℃ to about 90 ℃, and in some embodiments, from about 25 ℃ to about 85 ℃.

The electrolytes employed during the first and second stages of the anodization process may be the same or different. Typically, however, it is desirable to employ a different solution to help better facilitate obtaining a higher thickness at the outer portion of the dielectric layer. For example, it may be desirable for the electrolyte employed in the second stage to have a lower ionic conductivity than the electrolyte employed during the first stage to prevent formation of a significant amount of oxide film on the inner surface of the anode. In this regard, the electrolyte employed during the first stage may comprise acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid (boric acid), borinic acid (borinic acid), and the like. Such electrolytes can have a conductivity of from about 0.1 to about 100mS/cm, in some embodiments from about 0.2 to about 20mS/cm, and in some embodiments, from about 1 to about 10mS/cm, as measured at a temperature of 25 ℃. The electrolyte employed during said second stage typically comprises a salt of a weak acid such that the hydronium ion concentration is increased in the pores due to charge channels therein. Ion transport or diffusion allows weak acid anions to move into the pores as necessary to balance the charge. As a result, the concentration of the predominant conductive species (hydronium ions) is reduced in the establishment of a balance between hydronium ions, acid anions, and undissociated acids, thereby forming a less conductive species. The reduction in the concentration of the conductive species results in a relatively high voltage drop in the electrolyte, which hinders further anodization in the interior, while in the region of continued high conductivity a thicker oxide layer builds up on the outside for higher formation voltages. Suitable weak acid salts can include, for example, ammonium or alkali metal salts (e.g., sodium, potassium, etc.) of boric acid, acetic acid, oxalic acid, lactic acid, adipic acid, and the like. Particularly suitable salts include sodium tetraborate and ammonium pentaborate. Such electrolytes typically have a conductivity of from about 0.1 to about 20mS/cm, in some embodiments from about 0.5 to about 10mS/cm, and in some embodiments, from about 1 to about 5mS/cm, as measured at a temperature of 25 ℃.

If desired, the various stages of anodization may be repeated for one or more cycles to achieve the desired dielectric thickness. Furthermore, the anode may also be rinsed or washed with additional solvent (e.g., water) after the first and/or second stages to remove the electrolyte.

C.Solid electrolyte

As described above, a solid electrolyte overlies the dielectric and generally serves as the cathode of the capacitor. The solid electrolyte may include materials such as conductive polymers (e.g., polypyrrole, polythiophene, polyaniline, etc.), manganese dioxide, etc., as known in the art. Typically, however, the solid electrolyte comprises one or more layers comprising extrinsic and/or intrinsic conductive polymer particles. One benefit of using such particles is that they can be used to generate ionic species (e.g., Fe) during conventional in situ polymerization processes²⁺Or Fe³⁺) The presence of dielectric breakdown at high electric fields, which may be due to ion migration, is minimized. Thus, by applying the conductive polymer as pre-polymerized particles, rather than via in-situ polymerization, the resulting capacitor may exhibit a relatively high "breakdown voltage". The solid electrolyte may be formed from one or more layers, if desired. When multiple layers are employed, the following is possible: one or more of the layers comprises a conductive polymer formed by in situ polymerization. However, when it is desired to achieve a very high breakdown voltage, the present inventors have found that the solid electrolyte is mainly formed of the above-described conductive particles, and it is generally free of a conductive polymer formed via in-situ polymerization. Regardless of the number of layers employed, the resulting solid electrolyte typically has a total thickness of from about 1 micrometer (μm) to about 200 μm, in some embodiments from about 2 μm to about 50 μm, and in some embodiments, from about 5 μm to about 30 μm.

Thiophene polymers are particularly suitable for use in the solid electrolyte. In certain embodiments, for example, "extrinsic" conducting thiophene polymers having repeating units of the following formula (III) may be employed in the solid electrolyte:

wherein the content of the first and second substances,

R₇is linear or branched C₁-C₁₈Alkyl radicals (for example methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, etc.); c₅-C₁₂Cycloalkyl radicals (e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc.); c₆-C₁₄Aryl radicals (e.g., phenyl, naphthyl, etc.); c₇-C₁₈Aralkyl radicals (e.g., benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2-6, 3-4-, 3, 5-xylyl, yl, etc.); and

q is an integer from 0 to 8, in some embodiments from 0 to 2, and in one embodiment 0. In one embodiment, "q" is 0 and the polymer is poly (3, 4-ethylenedioxythiophene). One commercially suitable example of a monomer suitable for forming such a polymer is 3, 4-ethylenedioxythiophene, available from Heraeus under the name Clevios TMM.

Polymers of formula (III) are generally considered to be "extrinsic" conductive in the sense that they typically require the presence of a separate counterion that is not covalently bound to the polymer. The counter ion may be a monomeric or polymeric anion that counteracts the charge of the conductive polymer. The polymeric anion may for example be an anion as follows: polymeric carboxylic acids (e.g., polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.); polymeric sulfonic acids (e.g., polystyrene sulfonic acid ("PSS"), polyvinyl sulfonic acid, etc.); and so on. The acids may also be copolymers, such as copolymers of vinyl carboxylic and vinyl sulfonic acids with other polymerizable monomers such as acrylates and styrene. Similarly, suitable monomeric anions include, for example, the following anions: c₁-C₂₀Alkane sulfonic acids (e.g., dodecanesulfonic acid); aliphatic perfluorosulfonic acids (e.g., trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, or perfluorooctanesulfonic acid); aliphatic C₁-C₂₀Carboxylic acids (e.g., 2-ethyl-hexylcarboxylic acid); aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid or perfluorooctanoic acid); optionally is covered with C₁-C₂₀Alkyl-substituted aromatic sulfonic acids (e.g., benzenesulfonic acid, o-toluenesulfonic acid, p-toluenesulfonic acid, or dodecylbenzenesulfonic acid); cycloalkanesulfonic acids (e.g. camphorsulfonic acid or tetrafluoro sulfonic acid)Borate, hexafluorophosphate, perchlorate, hexafluoroantimonate, hexafluoroarsenate or hexachloroarsenate); and so on. Particularly suitable counter anions are polymeric anions such as polymeric carboxylic or sulfonic acids (e.g., polystyrene sulfonic acid ("PSS")). The molecular weight of such polymeric anions typically ranges from about 1,000 to about 2,000,000, and in some embodiments from about 2,000 to about 500,000.

The following intrinsically conductive polymers may also be used: having a positive charge on the backbone, the positive 5 charge being at least partially offset by an anion covalently bound to the polymer. For example, one example of a suitable intrinsically conductive thiophene polymer may have a repeating unit of the following formula (IV):

wherein the content of the first and second substances,

r is (CH)₂)_a-O-(CH₂)_b；

a is from 0 to 10, in some embodiments from 0 to 6, and in some embodiments from 1 to 4 (e.g., 1);

b is 1 to 18, in some embodiments 1 to 10, and in some embodiments 2 to 6 (e.g., 2,3, 4, or 5);

z is an anion, e.g. SO₃ ^-、C(O)O^-、BF₄ ^-、CF₃SO₃ ^-、SbF₆ ^-、N(SO₂CF₃)₂ ^-、C₄H₃O₄ ^-、ClO₄ ^-Etc.;

x is a cation, such as hydrogen, an alkali metal (e.g., lithium, sodium, rubidium, cesium, or potassium), ammonium, or the like.

In one embodiment, Z in formula (IV) is a sulfonate ion such that the intrinsically conductive polymer comprises repeating units of the following formula (V):

wherein R and X are defined above. In formula (IV) or (V), a is preferably 1 and b is preferably 3 or 4. Similarly, X is preferably sodium or potassium.

The polymer may be a copolymer comprising other types of repeating units, if desired. In such embodiments, the repeat units of formula (IV) typically constitute about 50 mole% or more, in some embodiments from about 75 mole% to about 99 mole%, and in some embodiments, from about 85 mole% to about 95 mole% of the total amount of repeat units in the copolymer. Of course, the polymer may also be a homopolymer to the extent that it comprises 100 mole% of recurring units of formula (IV). Specific examples of such homopolymers include poly (4- (2, 3-dihydrothieno [3,4-b ]][1,4]II

En-2-ylmethoxy) -1-butane-sulfonate) and poly (4- (2, 3-dihydrothieno [3, 4-b)][l,4]II

Lnt-2-ylmethoxy) -l-propanesulfonate).

Regardless of the specific nature of the polymer, the resulting conductive polymer particles typically have an average size (e.g., diameter) of about 1 to about 80 nanometers, in some embodiments about 2 to about 70 nanometers, and in some embodiments, about 3 to about 60 nanometers. The diameter of the particles can be determined using known techniques, such as by ultracentrifuge, laser diffraction, and the like. The shape of the particles may likewise vary. In one embodiment, for example, the particles are spherical in shape. However, it should be understood that other shapes such as sheets, rods, discs, strips, tubes, irregular shapes, etc. are also contemplated by the present invention.

Although not required, the conductive polymer particles may be applied in the form of a dispersion. The concentration of the conductive polymer in the dispersion may vary depending on the desired viscosity of the dispersion and the particular manner in which the dispersion is applied to the capacitor element. Typically, however, the polymer constitutes from about 0.1 to about 10 weight percent, in some embodiments from about 0.4 to about 5 weight percent, and in some embodiments, from about 0.5 to about 4 weight percent of the dispersion. The dispersion may also include one or more components for enhancing the overall properties of the resulting solid electrolyte. For example, the dispersion may comprise a binder to further enhance the adhesive properties of the polymer layer and also to increase the stability of the particles within the dispersion. The binder may be organic in nature, for example polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyacrylate, polyacrylamide, polymethacrylate, polymethacrylamide, polyacrylonitrile, styrene/acrylate, vinyl acetate/acrylate and ethylene/vinyl acetate copolymers, polybutadiene, polyisoprene, polystyrene, polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysulfone, melamine formaldehyde resins, epoxy resins, silicone resins or cellulosics. Cross-linking agents may also be employed to enhance the adhesive ability of the binder. Such crosslinking agents may include, for example, melamine compounds, masked isocyanates or crosslinkable polymers, such as polyurethanes, polyacrylates or polyolefins, and subsequent crosslinking. Dispersing agents may also be employed to facilitate the ability to apply the layer to the anode. Suitable dispersing agents include solvents such as aliphatic alcohols (e.g., methanol, ethanol, isopropanol, and butanol), aliphatic ketones (e.g., acetone and methyl ethyl ketone), aliphatic carboxylic acid esters (e.g., ethyl acetate and butyl acetate), aromatic hydrocarbons (e.g., toluene and xylene), aliphatic hydrocarbons (e.g., hexane, heptane, and cyclohexane), chlorinated hydrocarbons (e.g., dichloromethane and dichloroethane), aliphatic nitriles (e.g., acetonitrile), aliphatic sulfoxides and sulfones (e.g., dimethyl sulfoxide and sulfolane), aliphatic carboxylic acid amides (e.g., methylacetamide, dimethylacetamide, and dimethylformamide), aliphatic and araliphatic ethers (e.g., diethyl ether and anisole), water, and mixtures of any of the foregoing solvents. A particularly suitable dispersing agent is water.

In addition to those mentioned above, further ingredients may be used in the dispersion. For example, conventional fillers having dimensions of from about 10 nanometers to about 100 micrometers, in some embodiments from about 50 nanometers to about 50 micrometers, and in some embodiments, from about 100 nanometers to about 30 micrometers may be used. Examples of such fillers include calcium carbonate, silicates, silica, calcium sulfate or barium sulfate, aluminum hydroxide, glass fibers or spheres (bulb), wood flour, cellulose powder, carbon black, conductive polymers, and the like. The filler may be introduced into the dispersion in powder form, but may also be present in another form, such as fibers.

Surface-active substances such as ionic or nonionic surfactants can also be employed in the dispersion. In addition, adhesives such as organofunctional silanes or their hydrolyzates, for example 3-glycidoxypropyltrialkoxysilane, 3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane, may be used. The dispersion may also contain conductivity-enhancing additives such as ether group-containing compounds (e.g., tetrahydrofuran), lactone group-containing compounds (e.g., gamma-butyrolactone or gamma-valerolactone), amide or lactam group-containing compounds (e.g., caprolactam, N-methylcaprolactam, N-dimethylacetamide, N-methylacetamide, N-Dimethylformamide (DMF), N-methylformamide, N-methylformanilide, N-methylpyrrolidone (NMP), N-octylpyrrolidone, or pyrrolidone), sulfones and sulfoxides (e.g., sulfolane (tetramethylene sulfone) or Dimethylsulfoxide (DMSO)), sugars or sugar derivatives (e.g., sucrose, glucose, fructose, or lactose), sugar alcohols (e.g., sorbitol or mannitol), Furan derivatives (e.g., 2-furancarboxylic acid or 3-furancarboxylic acid), alcohols (e.g., ethylene glycol, glycerol, diethylene glycol, or triethylene glycol).

The dispersion can be applied using a variety of known techniques, such as by spin coating, dipping, pouring, drop-wise application, injection, spraying, knife coating, brushing, printing (e.g., ink jet, screen, or pad printing), or dip coating. The viscosity of the dispersion is typically from about 0.1 to about 100,000mPas (at 100 s)^-1Measured at a shear rate of), in some embodiments from about 1 to about 10,000mPas, in some embodiments from about 10 to about 1,500mPas, and in some embodiments, from about 100 to about 1000 mPas.

i.Inner layer

The solid electrolyte is typically formed from one or more "internal" layers of conductive polymer. The term "inner" in this context refers to one or more layers overlying the dielectric, whether directly or via additional layers (e.g., a pre-coat layer). One or more inner layers may be employed. For example, the solid electrolyte typically comprises 2 to 30, in some embodiments 4 to 20, and in some embodiments about 5 to 15 inner layers (e.g., 10 layers). The inner layer may, for example, comprise intrinsic and/or extrinsic conductive polymer particles such as described above. For example, such particles may constitute about 50 wt% or more, in some embodiments about 70 wt% or more, and in some embodiments, about 90 wt% or more (e.g., 100 wt%) of the inner layer. In an alternative embodiment, the inner layer may comprise an in situ polymerized conductive polymer. In such embodiments, the in situ polymerized polymer may constitute about 50 wt.% or more, in some embodiments about 70 wt.% or more, and in some embodiments, about 90 wt.% or more (e.g., 100 wt.%) of the inner layer.

ii.Outer layer

The solid electrolyte may also include one or more optional "outer" layers of conductive polymer overlying the inner layer and formed of different materials. For example, the outer layer may comprise particles of an intrinsically conductive polymer. In one embodiment, the outer layer is formed primarily of such extrinsic conductive polymer particles in that they constitute about 50% or more, in some embodiments about 70% or more, and in some embodiments about 90% or more (e.g., 100% by weight) of the respective outer layer. One or more outer layers may be used. For example, the solid electrolyte may comprise 2 to 30, in some embodiments 4 to 20, and in some embodiments about 5 to 15 outer layers, each of which may optionally be formed from a dispersion of the extrinsic conductive polymer particles.

D. Outer polymer coating

An outer polymer coating may also overlie the solid electrolyte. The outer polymer coating typically comprises one or more layers formed from pre-polymerized conductive polymer particles such as described above (e.g., a dispersion of extrinsic conductive polymer particles). The outer coating may be able to penetrate further into the edge region of the capacitor body (body) to improve the adhesion to the dielectric and to result in a mechanically stronger component (part), which may lead to a reduction of the equivalent series resistance and the leakage current. The particles used in the outer coating typically have a larger size than those employed in the solid electrolyte, since they are generally intended to improve the degree of edge coverage rather than impregnating the interior of the anode body. For example, the ratio of the average size of the particles employed in the outer polymer coating to the average size of the particles employed in any dispersion of the solid electrolyte is typically from about 1.5 to about 30, in some embodiments from about 2 to about 20, and in some embodiments, from about 5 to about 15. For example, the particles employed in the dispersion of the outer coating may have an average size of from about 80 to about 500 nanometers, in some embodiments from about 90 to about 250 nanometers, and in some embodiments, from about 100 to about 200 nanometers.

If desired, a cross-linking agent may also be employed in the outer polymer coating to promote the degree of adhesion to the solid electrolyte. Typically, the cross-linking agent is applied prior to application of the dispersion used in the outer coating. Suitable crosslinking agents are described, for example, in U.S. patent publication No.2007/0064376 to Merker et al and include, for example, amines (e.g., diamines, triamines, oligomeric amines, polyamines, etc.); polyvalent metal cations, such as salts or compounds of Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce or Zn,

compounds, sulfonium compounds, and the like. Particularly suitable examples include, for example1, 4-diaminocyclohexane, 1, 4-bis (amino-methyl) cyclohexane, ethylenediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 12-dodecanediamine, N, N-dimethylethylenediamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetramethyl-1, 4-butanediamine, and the like, and mixtures thereof.

The crosslinking agent is typically applied from a solution or dispersion having a pH of 1 to 10, in some embodiments 2 to 7, in some embodiments 3 to 6, as measured at 25 ℃. Acidic compounds may be employed to help achieve the desired pH level. Examples of the solvent or dispersant for the crosslinking agent include water or organic solvents such as alcohols, ketones, carboxylic esters, and the like. The crosslinking agent may be applied to the capacitor object by any known process, such as spin coating, dipping, casting, drop-wise application, spray application, vapor deposition, sputtering, sublimation, blade coating, painting, or printing, such as ink-jet, screen, or pad printing. Once applied, the crosslinking agent can be dried prior to application of the polymer dispersion. The process can then be repeated until the desired thickness is achieved. For example, the total thickness of the entire outer polymer coating, including the crosslinker and the dispersion layer, may range from about 1 to about 50 μm, in some embodiments from about 2 to about 40 μm, and in some embodiments, from about 5 to about 20 μm.

E.Cathode coating

The capacitor element may also employ a cathode coating overlying the solid electrolyte and other optional layers (e.g., an outer polymer coating), if desired. The cathodic coating may comprise a layer of metal particles comprising a plurality of electrically conductive metal particles dispersed within a resinous polymer matrix. The particles typically constitute from about 50 wt% to about 99 wt%, in some embodiments from about 60 wt% to about 98 wt%, and in some embodiments from about 70 wt% to about 95 wt% of the layer, while the resinous polymer matrix typically constitutes from about 1 wt% to about 50 wt%, in some embodiments from about 2 wt% to about 40 wt%, and in some embodiments, from about 5 wt% to about 30 wt% of the layer.

The conductive metal particles can be formed from a wide variety of different metals such as copper, nickel, silver, nickel, zinc, tin, lead, copper, aluminum, molybdenum, titanium, iron, zirconium, magnesium, and the like, as well as alloys thereof. Silver is a particularly suitable conductive metal for use in the layer. The metal particles often have a relatively small size, such as an average size of about 0.01 to about 50 microns, in some embodiments about 0.1 to about 40 microns, and in some embodiments, about 1 to about 30 microns. Typically, only one layer of metal particles is employed, although it will be understood that multiple layers may be employed (if so desired). The total thickness of such layers is typically in the range of about 1 μm to about 500 μm, in some embodiments about 5 μm to about 200 μm, and in some embodiments, about 10 μm to about 100 μm.

The resinous polymer matrix typically comprises a polymer which may be thermoplastic or thermosetting in nature. Typically, however, the polymer is selected such that it can act as a barrier to electromigration of silver ions, and also such that it contains a relatively small amount of polar groups to minimize the extent of water adsorption in the cathode coating. In this regard, the present inventors have found that vinyl acetal polymers are particularly suitable for this purpose, such as polyvinyl butyral, polyvinyl formal, and the like. Polyvinyl butyrals, for example, can be formed by reacting polyvinyl alcohol with an aldehyde (e.g., butyraldehyde). Since the reaction is typically not complete, the polyvinyl butyral will generally have a residual hydroxyl content. However, by minimizing this content, the polymer may have a lesser degree of strongly polar groups that would otherwise result in a high degree of moisture absorption and silver ion migration. For example, the residual hydroxyl content in the polyvinyl acetal may be about 35 mole% or less, in some embodiments about 30 mole% or less, and in some embodiments, from about 10 mole% to about 25 mole%. One commercially available example of such a polymer is available under the name "BH-S" (polyvinyl butyral) from Sekisui Chemical co.

To form the cathode coating, a conductive paste is typically applied to the capacitor overlying the solid electrolyte. One or more organic solvents are typically employed in the paste. A wide variety of different organic solvents such as glycols (e.g., propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol, ethoxydiglycol, and dipropylene glycol) can generally be employed; glycol ethers (glycol ethers) (e.g., methyl glycol ether (glycol ether), ethyl glycol ether (glycol ether), and isopropyl glycol ether (glycol ether)); ethers (e.g., diethyl and tetrahydrofuran); alcohols (e.g., benzyl alcohol, methanol, ethanol, n-propanol, isopropanol, and butanol); a triglyceride; ketones (e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone); esters (e.g., ethyl acetate, butyl acetate, diethylene glycol ether acetate, and methoxypropyl acetate); amides (e.g., dimethylformamide, dimethylacetamide, dimethyloctanoic/decanoic fatty acid amide, and N-alkylpyrrolidones); nitriles (e.g., acetonitrile, propionitrile, butyronitrile, and benzonitrile); sulfoxides or sulfones (e.g., dimethyl sulfoxide (DMSO) and sulfolane); and the like, and mixtures thereof. The organic solvent typically comprises from about 10% to about 70%, in some embodiments from about 20% to about 65%, and in some embodiments, from about 30% to about 60% by weight of the paste. Typically, the metal particles constitute from about 10 wt% to about 60 wt%, in some embodiments from about 20 wt% to about 45 wt%, and in some embodiments, from about 25 wt% to about 40 wt% of the paste, and the resinous polymer matrix constitutes from about 0.1 wt% to about 20 wt%, in some embodiments, from about 0.2 wt% to about 10 wt%, and in some embodiments, from about 0.5 wt% to about 8 wt% of the paste.

The paste may have a relatively low viscosity, allowing it to be easily handled and applied to the capacitor element. The viscosity may, for example, range from about 50 to about 3,000 centipoise, in some embodiments from about 100 to about 2,000 centipoise, and in some embodiments, from about 200 to about 1,000 centipoise, as measured, for example, with a Brookfield DV-1 viscometer (cone plate) operating at a speed of 10rpm and a temperature of 25 ℃. If desired, thickeners or other viscosity modifiers may be employed in the paste to increase or decrease viscosity. Further, the thickness of the applied paste may also be relatively thin and still achieve the desired properties. For example, the paste may have a thickness of about 0.01 to about 50 microns, in some embodiments about 0.5 to about 30 microns, and in some embodiments, about 1 to about 25 microns. Once applied, the metal paste may optionally be dried to remove certain components, such as the organic solvent. For example, drying may occur at a temperature of from about 20 ℃ to about 150 ℃, in some embodiments from about 50 ℃ to about 140 ℃, and in some embodiments, from about 80 ℃ to about 130 ℃.

F.Other Components (component)

The capacitor may also contain other layers as known in the art, if desired. In certain embodiments, for example, a carbon layer (e.g., graphite) may be disposed between the solid electrolyte and the silver layer, which can help further limit contact of the silver layer with the solid electrolyte. Additionally, a pre-coat layer overlying the dielectric and including an organometallic compound (e.g., a silane compound) may be employed in certain embodiments.

II.Terminal with a terminal body

Once the capacitor element is formed, terminals may be provided to the capacitor. For example, the capacitor may include an anode terminal to which an anode lead of the capacitor element is electrically connected and a cathode terminal to which a cathode of the capacitor element is electrically connected. Any conductive material may be used to form the terminals, such as conductive metals (e.g., copper, nickel, silver, nickel, zinc, tin, palladium, lead, copper, aluminum, molybdenum, titanium, iron, zirconium, magnesium, and alloys thereof). Particularly suitable conductive metals include, for example, copper alloys (e.g., copper-zirconium, copper-magnesium, copper-zinc, or copper-iron), nickel, and nickel alloys (e.g., nickel-iron). The thickness of the terminals is typically selected to minimize the thickness of the capacitor. For example, the thickness of each of the terminals may range from about 0.05 to about 1 millimeter, in some embodiments from about 0.05 to about 0.5 millimeters, and from about 0.07 to about 0.2 millimeters. One exemplary electrically conductive material is a copper-iron alloy metal sheet available from wieland (germany). If desired, the surfaces of the terminals may be plated with nickel, silver, gold, tin, etc., as is known in the art to ensure that the final component is mountable to a circuit board. In one embodiment, both surfaces of each of the terminals are plated with nickel and silver slashes (flash), respectively, while the mounting surface is also plated with a tin solder layer. Such surface coatings (e.g., tin) may be applied over the entire surface of the terminal or, alternatively, selectively applied only at those locations that are external to and in contact with the housing material.

III.Shell material

The capacitor element is also encapsulated with a housing material such that at least a portion of the anode and cathode terminations are exposed for mounting on a circuit board. In certain embodiments, the shell material may comprise an epoxy composition comprising: one or more inorganic oxide fillers and a resinous material comprising one or more epoxy resins optionally crosslinked with a co-reactant (hardener). To help improve the overall moisture resistance of the shell material, the inorganic oxide filler content is maintained at a high level, for example, about 75% or more by weight of the composition, in some embodiments about 76% or more by weight, and in some embodiments, from about 77% to about 90% by weight. The properties of the inorganic oxide filler can vary, such as silica, alumina, zirconia, magnesium oxide, iron oxides (e.g., yellow iron oxyhydroxide), titanium oxides (e.g., titanium dioxide), zinc oxides (e.g., zinc borate), copper oxides, zeolites, silicates, clays (e.g., smectite clays), and the like, as well as composites thereof (e.g., alumina-coated silica particles) and mixtures thereof. However, regardless of the particular filler employed, a substantial portion, if not all, of the inorganic oxide filler is typically in the form of vitreous silica, which is believed to further improve the moisture resistance of the housing material due to its high purity and relatively simple chemical form. The vitreous silica may, for example, constitute about 30% by weight or more, in some embodiments from about 35% by weight to about 90% by weight, and in some embodiments, from about 40% by weight to about 80% by weight of the total weight of the filler employed in the composition, as well as from about 20% by weight to about 70% by weight, in some embodiments from about 25% by weight to about 65% by weight, and in some embodiments, from about 30% by weight to about 60% by weight of the total composition. Of course, other forms of silica, such as quartz, fumed silica, cristobalite, and the like, may also be employed in combination with the vitreous silica.

The resinous material typically constitutes about 0.5% to about 25%, in some embodiments about 1% to about 24%, and in some embodiments, about 10% to about 23% by weight of the composition. In general, any of a wide variety of different types of epoxy resins may be employed in the present invention. Examples of suitable epoxy resins include, for example, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac epoxy resins, o-cresol novolac epoxy resins, brominated epoxy resins and biphenyl type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, cresol novolac epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins, cyclopentadiene type epoxy resins, heterocyclic epoxy resins, and the like. However, to help provide the desired degree of moisture resistance, it is particularly desirable to employ an epoxy phenol novolac ("EPN") resin, which is a glycidyl ether of a novolac resin. These resins can be prepared, for example, by: reacting a phenol with an excess of formaldehyde in the presence of an acidic catalyst to produce the novolac resin. The novolac epoxy resin is then prepared by reacting the novolac resin with epichlorohydrin in the presence of sodium hydroxide. Specific examples of the novolac epoxy resin include phenol-novolac epoxy resins, cresol-novolac epoxy resins, naphthol-phenol co-condensed novolac epoxy resins, naphthol-cresol co-condensed novolac epoxy resins, brominated phenol-novolac epoxy resins, and the like. Regardless of the type of resin selected, the resulting novolac epoxy resins typically have more than two oxirane groups and can be used to produce cured coating compositions with high crosslink densities, which can be particularly suitable for enhancing moisture resistance. One such novolac epoxy resin is poly [ (phenyl glycidyl ether) -co-formaldehyde ]. Other suitable resins are commercially available from Huntsman under the trade name ARALDITE (e.g., GY289, EPN 1183, EP 1179, EPN 1139, and EPN 1138).

The epoxy resin may optionally be crosslinked with a co-reactant (hardener) to further improve the mechanical properties of the composition and also, as indicated above, to improve its overall moisture resistance. Examples of such co-reactants may include, for example, polyamides, amidoamines (e.g., aromatic amidoamines such as aminobenzamide, aminobenzanilide, and aminobenzenesulfonamide), aromatic diamines (e.g., diaminodiphenylmethane, diaminodiphenylsulfone, and the like), aminobenzoates (e.g., trimethylene glycol di-p-aminobenzoate and neopentyl glycol di-p-aminobenzoate), aliphatic amines (e.g., triethylene tetramine, isophorone diamine), alicyclic amines (e.g., isophorone diamine), imidazole derivatives, guanidines (e.g., tetramethyl guanidine), carboxylic anhydrides (e.g., methyl hexahydrophthalic anhydride), carboxylic acid hydrazides (e.g., adipic acid hydrazide), novolak resins (e.g., phenol novolak, cresol novolak, and the like), and the like, Carboxylic acid amides, and the like, and combinations thereof. Novolac resins may be particularly suitable for use in the present invention.

In addition to the components described above, it is understood that still other additives, such as photoinitiators, viscosity modifiers, suspension aids, pigments, stress reducers, coupling agents (e.g., silane coupling agents), stabilizers, and the like, may also be employed in the epoxy composition used to form the shell. When employed, such additives typically constitute from about 0.1 to about 20 weight percent of the total composition.

The specific manner in which the housing material is applied to the capacitor object may vary as desired. In a specific embodiment, the capacitor element is placed in a mold and the housing material is applied to the capacitor element such that it occupies a space defined by the mold and exposes at least a portion of the anode and cathode terminals. The shell material may be initially provided in the form of a single or multiple compositions. For example, a first composition may comprise the epoxy resin and a second composition may comprise the co-reactant. Regardless, once it is applied, the shell material may be heated or allowed to stand at ambient temperature so as to allow the epoxy resin to crosslink with the co-reactants, which thereby causes the epoxy composition to cure and harden into the desired shape of the shell. For example, the composition may be heated to a temperature of from about 15 ℃ to about 150 ℃, in some embodiments from about 20 ℃ to about 120 ℃, and in some embodiments, from about 25 ℃ to about 100 ℃.

The resulting packaged capacitor can have a wide variety of different configurations. Referring to fig. 1-2, an embodiment of a capacitor 30 is shown that includes a housing material 28 having a top surface 35 and an opposing bottom surface 29, a front surface 37 and an opposing back surface 31, and first and second opposing side surfaces (one of which is not shown). The case material 28 encapsulates the capacitor element 33.

Capacitor 30 also includes a cathode terminal 72 that is provided in initial electrical contact with the solid electrolyte of capacitor element 33. In this particular embodiment, cathode terminal 72 includes a first constituent portion 73 in electrical contact with the lower surface of capacitor element 33 and substantially parallel to the lower surface of capacitor element 33. Cathode terminal 72 also includes a second constituent portion 75 that may be bent such that it is substantially perpendicular to first constituent portion 73 and in electrical contact with the rear surface of capacitor element 33. The second component 75 may be contained (housed) in the interior of the capacitor and encapsulated by the housing material 28, or alternatively extend outwardly from the housing material 28. Cathode terminal 72 may be electrically connected to capacitor element 33 using any technique known in the art, such as, for example, mechanical welding, laser welding, conductive adhesive, and the like. For example, a conductive paste (not shown) may be provided between the first constituent portion 73 and the lower surface of the capacitor element 33 and/or between the second constituent portion 75 and the rear surface of the capacitor element 33. The conductive paste may then be cured. For example, heat and pressure may be applied using a hot press to ensure that the electrolytic capacitor element 33 is sufficiently adhered to the cathode terminal 72 by the glue.

Capacitor 30 also includes an anode terminal 62 provided in contact with the anode body of capacitor element 33. More specifically, the anode terminal 62 in this embodiment includes a first constituent portion 63 disposed substantially perpendicular to a second constituent portion 65. First constituent portion 63 is in electrical contact with anode lead 16 extending from the anode body of capacitor element 33. Although by no means required, the first and second components 63 and 65 in the illustrated embodiment are contained within the interior of the capacitor and encapsulated by the housing material 28. However, the anode terminal 62 also includes a third component 64 that extends outwardly from the housing material 28. Anode lead 16 may be electrically connected to first component 63 using any technique known in the art, such as, for example, mechanical welding, laser welding, conductive adhesive, and the like. For example, a laser may be used to weld the anode lead 16 to the anode terminal 62. Lasers typically include resonators including: a lasing medium capable of releasing photons by stimulated emission and an energy source to excite an element of the lasing medium. One type of suitable laser is one in which the lasing medium is composed of Yttrium Aluminum Garnet (YAG) doped with neodymium (Nd). The excited particles being neodymium ions Nd³⁺. The energy source may provide continuous energy to the laser medium to emit a continuous laser beam, or multiple energy discharges to emit a pulsed laser beam.

IV.Nano-coating

As indicated above, a nanocoating is provided on the capacitor to help improve its sensitivity to moisture and high temperatures. Depending on the desired properties, the nanocoating may be disposed on at least a portion of the capacitor element, the housing material, the anode terminal, and/or the cathode terminal. The nanocoating may be continuous in that it covers substantially all of the surface on which it is disposed, or it may alternatively be discontinuous such that it covers only a portion of the surface. In certain embodiments, for example, the nanocoating may be disposed on one or more surfaces of the capacitor element, such as a top surface, a bottom surface, a back surface, a front surface, a first side surface, and/or a second side surface. Referring again to fig. 1, one example of such a capacitor 30 is shown, wherein a nanocoating 80 is disposed on the capacitor element 33 such that it covers a top surface, a bottom surface, a back surface, a front surface, a first side surface, and a second side surface of the capacitor element. The nanocoating 80 may also be disposed in contact with the anode lead wire 16. Alternatively, fig. 2 shows another embodiment of the capacitor 30 in which the nanocoating 80 is disposed on the casing material 28 such that it covers the top surface 35, the bottom surface 29, the back surface 31, the front surface 37, the first side surface, and/or the second side surface of the casing material 28.

The nanocoating typically has an average thickness of about 2,000 nanometers or less, in some embodiments from about 1 nanometer to about 1,000 nanometers, in some embodiments from about 10 nanometers to about 600 nanometers, and in some embodiments, from about 20 nanometers to about 400 nanometers. However, the thickness of the nanocoating need not be the same at all locations of the capacitor. In certain embodiments, for example, it may be desirable to establish a relatively thick coating at certain areas, while other areas remain relatively thin. In such embodiments, the ratio of the thickness of the nanocoating at one region to the thickness of the nanocoating at another (another) region may be about 2 or greater, in some embodiments about 3 or greater, and in some embodiments, from about 4 to about 10. As shown in fig. 1, for example, a thicker region may be located on at least a portion of the front surface of the capacitor element (e.g., at or near lead wire 16) to help protect the wire during the soldering process, while a thinner region may be located on at least a portion of the top, bottom, back, first side, and/or second side surfaces. The thicker regions may, for example, have a thickness of about 100 nanometers to about 2,000 nanometers or less, in some embodiments about 150 nanometers to about 1,000 nanometers, and in some embodiments about 200 nanometers to about 600 nanometers, while the thinner regions may have a thickness of about 1 to about 100 nanometers, in some embodiments about 10 nanometers to about 80 nanometers, and in some embodiments about 20 nanometers to about 60 nanometers.

Regardless of their specific location and thickness, the nanocoating is typically formed using vapor deposition techniques. Suitable techniques for depositing the nanocoating can include, for example, physical vapor deposition ("PVD"), such as sputtering, plasma enhanced physical vapor deposition ("PEPVD"), and the like; chemical vapor deposition ("CVD") such as plasma enhanced chemical vapor deposition ("PECVD"), atomic layer chemical vapor deposition ("ALCVD"), and the like; and combinations of various techniques. Generally, such processes involve polymerizing precursor compounds to form polymeric nanocoating in situ on the capacitor. For example, the precursor compounds may be provided in a gaseous state and then polymerized in situ to deposit the nanocoating. The precursor compound may also be provided in a liquid or solid state, in which case it is typically vaporized (gasified) to a gaseous compound and then polymerized in situ to deposit the nanocoating. In any event, the present inventors have found that the use of such gas phase polymerisation techniques can result in very thin and uniform thickness coatings which are more accurately located. Further, gas phase polymerization can occur in the absence of solvents (e.g., organic alcohols, etc.) that can have an adverse effect on electrical properties. Likewise, gas phase polymerization may also occur at relatively ambient temperatures, for example, at temperatures of from about 15 ℃ to about 35 ℃, and in some embodiments, from about 20 ℃ to about 30 ℃.

Among the different techniques that can be employed, plasma enhanced polymerization is particularly suitable for use in the present invention. Plasma-enhanced polymerization, for example, is typically carried out in a reactor that generates a plasma, which may include ionized gaseous ions, electrons, atoms, and/or neutral species. The reactor typically includes a chamber, an optional vacuum system, and one or more energy sources, although any suitable type of reactor configured to generate a gas plasma may be used. The energy source may include any suitable device configured to convert one or more gases into a gas plasma, such as a heater, a radio frequency generator, a microwave generator, and the like. To form the layer of the nanocoating, the capacitor or capacitor element may be placed, for example, in a chamber of a reactor and the chamber may be pumped to 10 using a vacuum system^-3-a pressure in the range of 10 mbar. One or more gases may then be pumped into the chamber and a source of energyThe gas plasma may be generated. Thereafter, the precursor compounds may be introduced into the chamber containing the gas plasma. When introduced in this manner, the precursor compounds are typically ionized and/or decomposed to produce a wide variety of active species in the plasma that polymerize to produce the polymer forming the layer of the nanocoating. During such a process, the plasma drive frequency may be 1kHz-1GHz, the plasma power may be 100-250W, the mass flow rate may be 5-100 seconds per cubic centimeter (sccm), the operating pressure may be 10-100 mTorr, and the coating time may be 10 seconds-20 minutes. Of course, one skilled in the art will readily appreciate that the specific conditions will depend on the size and geometry of the plasma chamber.

Any of a wide variety of precursor compounds can be generally gas phase polymerized to form the nanocoating according to the present invention. In one embodiment, for example, the precursor compound may be a polyaromatic compound having the following overall (general) structure:

wherein the content of the first and second substances,

R₁is alkyl, alkenyl, halogen (e.g., chloro, fluoro, bromo, etc.), or haloalkyl (e.g., CF)₂) (ii) a And

R₂、R₃、R₄、R₅and R₆Independently selected from hydrogen, alkyl, alkenyl, halogen, or haloalkyl, wherein R is₁、R₂、R₃、R₄、R₅Or R₆One or more of (e.g. R)₁And/or R₄) May optionally be bonded to additional polyaromatic rings (e.g., alkyl functionality attached to the ring structure) to form a dimer. In certain embodiments, the alkyl group may include a linear or branched hydrocarbon radical having from 1 to 3 carbon atoms, and in some embodiments from 1 to 2 carbon atoms. Examples include methyl, ethyl, n-propyl and isopropyl. The alkenyl group may likewise comprise a group having 2 or 3 carbon atoms and a carbon-carbon double bondLinear or branched hydrocarbon radicals of (1). One example is vinyl. For example, R₁Can be methyl or vinyl (e.g., methyl), R₂Can be hydrogen, methyl or vinyl (e.g., hydrogen); r₃Can be hydrogen, methyl or vinyl (e.g., hydrogen); r₄Can be hydrogen, methyl or vinyl (e.g., hydrogen or methyl); r₅Can be hydrogen, methyl or vinyl (e.g., hydrogen); and/or R₆Can be hydrogen, methyl, or vinyl (e.g., hydrogen). Particularly suitable para-ylene compounds include, for example, 1, 4-dimethylbenzene ("p-xylene" or "para-ylene N"), 1, 3-dimethylbenzene, 1, 2-dimethylbenzene, toluene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 1, 4-divinylbenzene, 1, 3-divinylbenzene, 1, 2-divinylbenzene, chlorinated polyaromatics ("polyaromatic C" or "polyaromatic D"), and the like. As indicated above, the polyaromatic compound may also be a dimer in which one or more of the above-mentioned "R groups" of the arene structure are bonded to groups of another arene structure. An example of such polyaromatic dimers is [2,2]Para-cyclophane.

In addition to polyaromatics, other compounds may be used to form the nanocoating. For example, the precursor compound may be a fluoro hydrocarbon, which is a hydrocarbon material comprising fluorine atoms. Particularly suitable hydrofluorocarbon compounds include, for example, perfluoroalkanes, perfluoroolefins, perfluoroalkynes, fluoroalkanes, fluoroolefins, fluoroalynes, and the like. Typically, such compounds contain up to 10 carbon atoms, in some embodiments up to 5 carbon atoms. Examples of such compounds include, for example, CF₄、C₂F₄、C₂F₆、C₃F₆、C₃F₈And the like.

The nanocoating may be formed from various types of precursor compounds, if desired. For example, in one embodiment, a blend of polyaromatic and fluorocarbon precursor compounds may be used in one or more layers of the nanocoating. Alternatively, the polyaromatic hydrocarbon compound may be used in one layer of the nanocoating and the fluorinated hydrocarbon may be used to form a separate and distinct layer of the nanocoating. Regardless, when such components are employed, it is typically desirable that the molar ratio of the polyaromatic precursor compound to the fluorinated hydrocarbon is from about 5:95 to about 50:50, in some embodiments from about 10:90 to about 40:60, and in some embodiments, from about 20:80 to about 40: 60. The molar ratio can be easily adjusted by, for example, changing the flow rate of the precursor compounds into the plasma chamber.

The invention may be better understood by reference to the following examples.

Test procedure

Capacitor with a capacitor element

Capacitance can be measured using a Keithley 3330Precision LCZ meter with Kelvin leads with a 2.2 volt DC bias and a 0.5 volt peak-to-peak sinusoidal signal. The operating frequency may be 120Hz and the temperature may be 23 ℃ ± 2 ℃. In some cases, the "wet-to-dry" capacitance can be determined. "dry capacitance" refers to the capacitance of the part before application of the solid electrolyte, graphite, and silver layers, while "wet capacitance" refers to the capacitance of the part after formation of the dielectric, measured with a 10 volt DC bias and a 0.5 volt peak-to-peak sinusoidal signal after 30 seconds of electrolyte soak with a 1mF tantalum cathode in 14% nitric acid.

Equivalent Series Resistance (ESR)

The equivalent series resistance can be measured using a Keithley 3330Precision LCZ meter with Kelvin leads, a 2.2 volt DC bias, and a 0.5 volt peak-to-peak sinusoidal signal. The operating frequency may be 100kHz and the temperature may be 23 ℃ ± 2 ℃.

Leakage current

The leakage current can be measured using a leakage test meter at a temperature of 23 ℃ ± 2 ℃ and at rated voltage after a minimum of 60 seconds.

Humidity test

The humidity test can be carried out at a temperature of 85 ℃ and a relative humidity of 85% and at a nominal voltage. The recovery time after the test conditions may be 6-24 hours.