TWI506031B - Ferric salt oxidant, solid electrolytic capacitor, and method for fabricating the same - Google Patents

Description

Iron salt oxidant composition, solid capacitor, and method of manufacturing same

This invention relates to an iron salt oxidizing agent composition and a solid state capacitor.

Capacitors are electronic components that are widely used in various electronic products. With the development of technology, electronic products tend to be smaller and lighter. The capacitors used in them are miniaturized, large-capacity, and used at high frequencies. Characteristics such as lower low impedance.

Capacitors can be divided into traditional liquid capacitors and newly developed solid capacitors depending on the electrolyte type. Although the conventional liquid capacitor satisfies the demand for large capacity at a low cost, since the electrolyte used is a liquid, there are disadvantages such as low conductivity and high temperature resistance. Although liquid electrolytes can be added with hydrogen absorbing agents to reduce the possibility of explosion, they do not solve the problem at all.

The solid electrolyte is composed of a conductive polymer, has a higher conductivity than a liquid electrolyte used in a conventional electrolytic capacitor, and has moderate high-temperature insulating properties. In the current manufacture of solid capacitors, polymerization is generally carried out using reactive monomers and iron salt oxidants to obtain conductive high scores. child. However, since the general iron salt oxidizing agent is a strong acid, it is easy to cause the dielectric layer (for example, alumina) of the capacitor anode aluminum foil to be corroded and damaged, resulting in an increase in leakage current and a reduction in withstand voltage.

Based on the above, the development of a novel iron salt oxidizing agent composition to avoid corrosion of the dielectric layer by the iron salt oxidant and improve the leakage current and withstand voltage characteristics of the capacitor is an important subject of the current solid capacitor technology.

According to an embodiment of the invention, an iron salt oxidizing agent composition is provided. The iron salt oxidizing agent composition comprises: an iron-containing compound; and a promoter. Wherein, the accelerator has the structure shown in formula (I):

Wherein R ¹ and R ⁴ are independently C _1-10 alkyl group, C _2-10 alkenyl group, C _2-10 alkoxyalkyl group, C _5-12 aromatic An aryl group, or a C _5-12 alkaryl group, or R ¹ and R ^{4 are} joined together to form a C _2-5 heterocyclic group together with the oxygen atom to which they are respectively attached. ; R ² and R ³ are independently hydrogen, hydroxy, C _1-10 alkoxy group, C _1-10 alkyl group, C _2-10 alkenyl group, C _{2 - 10} alkenyloxy (alkenyloxy group), C _2-10 alkoxyalkyl (alkoxyalkyl), C _2-10 alkoxyalkoxy group (alkoxyalkoxy), C _5-12 aromatic group (aryl group), C _5-12 aryl An aryloxy group, a C _5-12 alkaryl group, or a C _5-12 alkaryloxy group; and, A is a C _2-15 divalent aliphatic group Or, C _5-15 divalent aryl group; and n is 0, 1, or 2.

According to another embodiment of the present invention, the present invention also provides A solid capacitor formed by the iron salt oxidizing agent composition. The solid capacitor includes: a capacitor element; and an electrolyte disposed in the capacitor element. Here, the electrolyte is formed by polymerizing a conductive polymer monomer coated on a capacitor element and the above iron salt oxidizing agent composition.

According to another embodiment of the present invention, the present invention also provides the above solid The method for manufacturing a capacitor includes: providing a capacitor element; and impregnating the capacitor element with a conductive polymer monomer, and the iron salt oxidant composition, and polymerizing the conductive polymer monomer to form an electrolyte The capacitor is on the prime.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

10‧‧‧Capacitance

12‧‧‧Anode metal foil

14‧‧‧Cathed metal foil

16‧‧‧Isolation paper

18‧‧‧Metal oxide layer

20‧‧‧ Electrolytes

1 is a partial cross-sectional structural view of a solid capacitor according to an embodiment of the present invention.

The present invention discloses an iron salt oxidizing agent composition and a solid state capacitor prepared using the same. The iron salt oxidant composition is characterized by In addition to containing an iron-containing compound, it further comprises an accelerator having a polar terminal functional group and a non-polar terminal functional group to achieve an interface corrosion inhibiting function. Therefore, when a cryptophore is impregnated into the iron salt oxidant composition, the hydrophilic end of the promoter can generate hydrogen bonds or ionic bonds with the iron-containing compound, and the hydrophobic end is adsorbed on the non-polar capacitive element dielectric layer (for example, The metal oxide) surface protects the surface of the dielectric layer from corrosion by the iron-containing compound, so that the resulting solid capacitor has low leakage current and high withstand voltage characteristics.

The iron salt oxidizing agent composition of the present invention may comprise an iron-containing compound; and an accelerator. Wherein, the iron-containing compound may be an aromatic sulfonic acid iron salt, for example, iron p-toluenesulfonate, iron benzenesulfonate, iron naphthalenesulfonate, Or iron methoxybenzenesulfonate. Further, the promoter is a phosphorus-containing compound having a polar terminal functional group and a non-polar terminal functional group, and may have a structure represented by the formula (I):

Wherein R ¹ and R ⁴ are independently C _1-10 alkyl group, C _2-10 alkenyl group, C _2-10 alkoxyalkyl group, C _5-12 aromatic An aryl group, or a C _5-12 alkaryl group, or R ¹ and R ^{4 are} joined together to form a C _2-5 heterocyclic group together with the oxygen atom to which they are respectively attached. ; R ² and R ³ are independently hydrogen, hydroxy, C _1-10 alkoxy group, C _1-10 alkyl group, C _2-10 alkenyl group, C _{2 - 10} alkenyloxy (alkenyloxy group), C _2-10 alkoxyalkyl (alkoxyalkyl), C _2-10 alkoxyalkoxy group (alkoxyalkoxy), C _5-12 aromatic group (aryl group), C _5-12 aryl An aryloxy group, a C _5-12 alkaryl group, or a C _5-12 alkaryloxy group; and, A is a C _2-15 divalent aliphatic group Or, C _5-15 divalent aryl group; and n is 0, 1, or 2.

According to an embodiment of the present invention, R ¹ and R ⁴ may each independently be a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , isobutyl group, tertbutyl group, pentyl group, hexyl group, vinyl group, propenyl group, allyl group ), butenyl, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl ( Butoxyethyl group), phenyl (phenyl), biphenyl group, naphthyl group, 2-methyl-phenyl group, 3-methylphenyl (3-methylphenyl) -phenyl group), 4-methyl-phenyl group, 2,6-dimethyl-phenyl group, 2,4-dimethylphenyl ( 2,4-dimethyl-phenyl group), or 3,4-dimethyl-phenyl group.

According to an embodiment of the present invention, R ² and R ³ may each independently be a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. ), isobutyl group, tertbutyl group, pentyl group, hexyl group, methoxy group, ethoxy group, propoxy group (propoxy group), isopropoxy group, butoxy group, isobutoxy group, tertbutoxy group, pentyloxy group, hexyloxy Hexyloxy group, vinyl group, propenyl group, allyl group, butenyl, vinyloxy group, propenyloxy group , allyloxy group, butenyloxy, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, propoxyethyl ( Propoxyethyl group), butoxyethyl group, methoxymethoxy, ethoxymethoxy g Roup), ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, phenyl group, biphenyl group, naphthyl Naphthyl), 2-methyl-phenyl group, 3-methyl-phenyl group, 4-methyl-phenyl group, 2, 2,6-dimethyl-phenyl group, 2,4-dimethyl-phenyl group, 3,4-dimethylphenyl (3, 4-dimethyl-phenyl group), phenoxy group, biphenoxy group, naphthoxy group, 2-methyl-phenoxy group, 3 -3-methyl-phenoxy group, 4-methyl-phenoxy group, 2,6-dimethyl-phenoxy group , 2,4-dimethyl-phenoxy group, or 3,4-dimethyl-phenoxy group.

According to an embodiment of the present invention, when n is 1 or 2, A can be independently ,or (The group is bonded to the adjacent two oxygen atoms by a carbon atom indicated by *).

According to an embodiment of the present invention, the accelerator according to the present invention may be

Further, in the iron salt oxidizing agent group according to an embodiment of the present invention The weight ratio of the promoter to the iron-containing compound may be between 0.01 and 0.49, such as between 0.01 and 0.45, between 0.01 and 0.40, or between 0.01 and 0.35. If the weight ratio is less than 0.01, the concentration of the promoter adsorbed on the dielectric layer is insufficient, the protective effect is lowered, and the effect of improving the leakage current and withstand voltage characteristics is not obvious; if the weight ratio is higher than 0.49, the iron salt oxidant combination is easily formed. The viscosity of the material rises, the fluidity deteriorates, and it cannot penetrate into the pores formed by the dielectric layer, resulting in a decrease in the properties of the capacitor (capacitance value (Cs), energy consumption coefficient (DF), and equivalent series resistance (ESR)).

According to other embodiments of the present invention, the iron salt oxidizing agent composition Further comprising a solvent, and the iron-containing compound and the promoter are uniformly dispersed In the solvent. Wherein, the solvent may be an alcohol solvent such as methanol, ethanol, butanol, or a combination thereof. Further, the weight ratio of the solvent to the iron-containing compound may be between 0.2 and 2.0, such as between 0.2 and 1.5.

According to other embodiments of the present invention, the iron salt oxidizing agent composition It may further comprise a polyol. Due to the interaction between the polyol and the iron salt oxidant molecule, and the compatibility of the polyol with the accelerator is good, the addition of a small amount of polyol can increase the dispersibility of the promoter in the iron salt oxidant and improve the interface corrosion resistance of the accelerator. . For example, the polyol can be, for example, glycerol, polyethylene glycol, or a combination thereof. Further, the weight ratio of the polyol to the iron-containing compound may be between 0.01 and 0.70.

The invention also provides a capacitor, which can comprise a capacitor And an electrolyte is disposed in the capacitor element. Here, the electrolyte is formed by polymerizing a conductive polymer monomer coated on a capacitor element and an iron salt oxidizing agent composition of the present invention. For example, the capacitive element refers to a semi-finished product of a capacitor, that is, a capacitor that has not been coated with an electrolyte. The manufacturing method of the capacitor element can be, for example, nailing an anode metal foil (for example, aluminum foil) and a cathode metal foil (for example, aluminum foil) to a guide pin, separating the two electrodes by a separator paper, and winding the two electrodes and the separator paper. Wrap it and finally fix it with tape. The capacitor element may be further subjected to an oxidation treatment by applying a voltage to an aqueous solution of 1-20% diammonium adipate to form a dielectric layer on the surface (the voltage may be, for example, 10 V to 100 V), and washed with pure water. Next, it was dried at 120 ° C for 30 minutes, and the separator paper was carbonized at 250 ° C, and cooled for use.

The conductive polymer monomer can be a reactive monomer which can form a conductive polymer after polymerization. For example, the reactive monomer may have the structure shown by formula (II)

Wherein, X ¹ and X ² are independently O or S; Y is ,or And R is independently hydrogen or C _1-6 alkyl. According to an embodiment of the present invention, the monomer having the structure represented by the formula (II) may be ,or . In addition, the conductive polymer monomer can be dissolved in a solvent before use to obtain a conductive polymer monomer solution having a solid content of 10 to 60%, and then the solution is used for impregnation of the capacitor element. The solvent can be an alcohol solvent such as methanol, ethanol, butanol, or a combination thereof.

Please refer to FIG. 1 , which is a partially enlarged schematic view of a solid capacitor according to an embodiment of the invention. The capacitor element 10 comprises an anode metal foil 12 (such as aluminum foil) and a cathode metal foil 14 (such as aluminum foil), separated by a separator paper 16 between the anode metal foil 12 and the cathode metal foil 14, and at the anode metal. A metal oxide layer 18 (e.g., aluminum oxide (Al ₂ O ₃ )) is formed on the foil 12, and the metal oxide layer 18 may include a plurality of grooves. After the electrolyte 20 is formed in the capacitor element, the electrolyte 20 is filled into the recess formed by the metal oxide layer 18.

Embodiments of the present invention also provide a manufacturing method of a solid capacitor The method includes providing a capacitor element and forming an electrolyte in the capacitor element. According to an embodiment of the invention, the method of forming the electrolyte may include: simultaneously immersing the cryptophore in the conductive polymer monomer and the iron salt oxidant composition, and performing a heating process on the impregnated capacitor element. The monomer is polymerized. According to another embodiment of the present invention, the method of forming the electrolyte may include: impregnating the modulating element with the conductive polymer monomer; and then performing a first heating process on the argon element; and then impregnating the crypto-ene element with The iron salt oxidant composition; and performing a second heating process on the capacitor element. According to still another embodiment of the present invention, the method of forming the electrolyte may include: impregnating the oleooxide element with the iron salt oxidant composition; and then performing a first heating process on the capacitor element; and then impregnating the capacitor element with the capacitor element The conductive polymer monomer; and performing a second heating process on the capacitor element.

It is worth noting that the capacitive element is impregnated with the iron salt oxygen. In the case of a chemical composition, the iron salt oxidizing agent composition must contain both the iron compound and the accelerator. In other words, the cryptotrophin is impregnated with the iron-containing compound (for example, iron salt of p-toluenesulfonate) in the presence of the promoter. Therefore, when the october element is impregnated into the iron salt oxidant composition, the hydrophilic end of the promoter may generate hydrogen bonds or ionic bonds with the iron-containing compound, and the hydrophobic end adsorbs on the surface of the non-polar capacitive element dielectric layer. In this way, the promoter can achieve the function of interface corrosion, and the surface of the protective dielectric layer is not corroded by the iron-containing compound.

In order to achieve the above and other objects, features, and advantages of the present invention The points can be more clearly understood, and the following examples are used to illustrate the invention. An iron salt oxidizing agent composition, and a solid capacitor prepared using the same.

Preparation of iron salt oxidant composition

Example 1: 100 parts by weight of iron p-toluenesulfonate (manufactured and sold by Junyu Co., Ltd.) and 66.7 parts by weight of ethanol were added to a reaction flask. Next, the reaction flask was heated to about 70 ° C, and stirred at a rotation speed of 400 rpm for 30 minutes to dissolve iron p-toluenesulfonate. After dropping to room temperature, the insoluble matter was removed by filtration through a 1 μm filter membrane, and the filtrate was collected to obtain an iron salt oxidizing agent composition (1).

Example 2: 100 parts by weight of iron p-toluenesulfonate (manufactured and sold by Junyu Co., Ltd.), 65 parts by weight of ethanol, and 1.7 parts by weight of triethyl phosphate (TEP) were placed in a reaction flask. Next, the reaction flask was heated to about 70 ° C, and stirred at a rotation speed of 400 rpm for 30 minutes to dissolve iron p-toluenesulfonate. After dropping to room temperature, the insoluble matter was removed by filtration through a 1 μm filtration membrane, and the filtrate was collected to obtain an iron salt oxidizing agent composition (2).

Example 3: This was carried out in the same manner as in Example 2 except that ethanol was changed from 65 parts by weight to 58.3 parts by weight, and triethyl phosphate was changed from 1.7 parts by weight to 8.3 parts by weight. An iron salt oxidizing agent composition (3) is obtained.

Example 4: This was carried out in the same manner as in Example 2 except that ethanol was changed from 65 parts by weight to 50 parts by weight, and triethyl phosphate was changed from 1.7 parts by weight to 16.7 parts by weight. An iron salt oxidizing agent composition (4) is obtained.

Example 5: This was carried out in the same manner as in Example 2 except that ethanol was changed from 65 parts by weight to 33.3 parts by weight, and triethyl phosphate was changed from 1.7 parts by weight to 33.3 parts by weight. An iron salt oxidizing agent composition (5) is obtained.

Example 6 This was carried out as described in Example 4 except that triethyl phosphate was changed from 16.7 parts by weight to 8.3 parts by weight, and 8.3 parts by weight of polyethylene glycol (having a molecular weight of about 600) was added to the reaction flask. An iron salt oxidizing agent composition (6) is obtained.

Example 7 This was carried out as described in Example 5 except that triethyl phosphate was changed from 33.3 parts by weight to 16.7 parts by weight, and 16.7 parts by weight of glycerin was added to the reaction flask. An iron salt oxidizing agent composition (7) is obtained.

Example 8: Performed as described in Example 2 except that triethyl phosphate was changed to resorcinol-bis-bis(2,6-dimethylphenyl)phosphate (tetrakis (2,6-) Dimethylphenyl)1,3-phenylene biphosphate, TDPB) (manufactured and sold by Haoyuan Industrial Co., Ltd., structure is ). An iron salt oxidizing agent composition (8) is obtained.

Example 9: 100 parts by weight of iron p-toluenesulfonate (manufactured by Junyi Co., Ltd.)

And sold), 63.3 parts by weight of ethanol, and 3.3 parts by weight of OP1312 (phosphorus ester derivative, manufactured and sold by Haoyuan Industrial Co., Ltd.) were added to a reaction bottle. Next, the reaction flask was heated to about 70 ° C, and stirred at a rotation speed of 400 rpm for 30 minutes to dissolve iron p-toluenesulfonate. After dropping to room temperature, the insoluble matter was removed by filtration through a 1 μm filter membrane, and the filtrate was collected to obtain an iron salt oxidizing agent composition (9).

Example 10: Performed as described in Example 4 except that triethyl phosphate was changed to ADK STAP FP-700 (manufactured and sold by Changchun Chemical, the chemical structure was ). An iron salt oxidizing agent composition (10) is obtained.

Example 11: The procedure described in Example 4 was followed except that triethyl phosphate was changed to tributyl phosphate (TBP). An iron salt oxidizing agent composition (11) is obtained.

Example 12: The procedure described in Example 2 was carried out except that ethanol was changed from 65 parts by weight to 17.3 parts by weight, and triethyl phosphate was changed from 1.7 parts by weight to 49.4 parts by weight. An iron salt oxidizing agent composition (12) is obtained.

Referring to Table 1, the composition and weight ratio of the iron salt oxidizing agent compositions (1) to (12) prepared in Examples 1-12 are shown.

Preparation of capacitive elements

Preparation Example 1: Capacitance element formed by high voltage

The anode aluminum foil and the cathode aluminum foil are respectively pinned to the guide pins, separated by a separation paper between the two electrodes, and the two electrodes are wound with the release paper, and finally fixed by tape to obtain unformed capacitance elements. Next, the unformed occidental element is oxidized by applying a voltage of 80 V to a 10% aqueous solution of diammonium adipate to form a dielectric layer (material is alumina (Al ₂ O ₃ )), which is washed with pure water. Subsequently, it was dried at 120 ° C for 30 minutes, and heated at 250 ° C for 3 hours to carbonize the release paper, and cooled to obtain a converted hydroxy element (1).

Preparation Example 2: Capacitance element formed by low voltage

This was carried out in the manner described in Preparation Example 1, except that the unformed cryptophore was subjected to oxidation treatment by applying a voltage of 10 V to a 10% aqueous solution of diammonium adipate. The obtained capacitive element (2) is obtained.

Preparation of EDOT solution

Preparation Example 3: 100 parts by weight of 3,4-ethylenedioxythiophene (EDOT) (manufactured and sold by Junyi Co., Ltd.), and 300 parts by weight of ethanol were added to a reaction flask at a rotation speed. Stir at 400 rpm for 5 minutes to obtain an EDOT solution.

Preparation of solid capacitors

Example 13-24

Next, the above-described hydrated element (1) was impregnated into the above EDOT solution for 30 minutes. After taking out the capacitor element, it was dried at 80 ° C for 30 minutes. Next, a plurality of occluders impregnated in the EDOT solution and dried were subjected to impregnation in the iron salt oxidizing agent compositions (1) to (12) described in Examples 1-12, respectively. After the impregnation is completed, it is dried at 60 ° C for 30 minutes, at 90 ° C for 30 minutes, and at 120 ° C for 30 minutes. After cooling, solid capacitors I-XII were obtained (three for each capacitor). Then, after passing the 120 ° C power-on aging test (10 V, 15 V, and 20 V were applied at 120 ° C and maintained for 1 hour, respectively), the capacitance characteristics of the solid capacitor I-XII were included (including Capacitance value (Cs), energy consumption coefficient (DF) and equivalent series resistance (ESR) test, leakage current analysis, and withstand voltage analysis are shown in Table 2.

Example 25-26

Take 90 parts by weight of ethanol and 10 parts by weight of triethyl phosphate Triethyl phosphate (TEP) was added to a reaction flask. Next, the reaction flask was stirred at a number of revolutions of 400 rpm for 5 minutes to obtain a triethyl phosphate solution.

Take 90 parts by weight of ethanol and 10 parts by weight of ADK STAP FP-700 was added to a reaction vial. Next, the reaction flask was stirred at a rotation speed of 400 rpm for 5 minutes to obtain an ADK STAP FP-700 solution.

Next, the formed capacitive element (1) is impregnated into the above EDOT solution for 30 minutes. After taking out the capacitor element, it was dried at 80 ° C for 30 minutes. Next, the october element impregnated in the EDOT solution and dried was impregnated in the iron salt oxidizing agent composition (1) (excluding the accelerator) described in Example 1. After the impregnation is completed, it is dried at 60 ° C for 30 minutes, at 90 ° C for 30 minutes, and at 120 ° C for 30 minutes. Next, the obtained plurality of occluders were further impregnated into the triethyl phosphate solution or the ADK STAP FP-700 solution, and taken out and dried at 80 ° C for 30 minutes. After cooling, solid capacitors XIII and XIV (three each) were obtained. Then, after passing the 120 ° C power-on aging test (10 V, 15 V, and 20 V were applied at 120 ° C and maintained for 1 hour, respectively), the capacitance characteristics (including the capacitance value (Cs), the capacitance values (Cs) were included for the solid capacitors XIII and XIV. Energy consumption factor (DF) and equivalent series resistance (ESR) tests, leakage current analysis, and withstand voltage analysis are shown in Table 2.

Remarks: The capacitance value test, the energy consumption coefficient test, and the equivalent series resistance test are measured by LCR Meter 4263B manufactured by Hewlett Packard (HP). Capacitance (measured at frequency 120Hz) >20μF is qualified (O), otherwise it is unqualified (X); energy consumption coefficient (DF) (measured at frequency 120Hz) <10% is qualified (O) Conversely, it is unqualified (X); and, equivalent series resistance (ESR) (measured at a frequency of 100 kHz) <40mΩ is qualified (O), and vice versa (X). Leakage current and withstand voltage are measured by a Chroma capacitor leakage current/IR meter model 1120. The leakage current is measured after charging for 60 seconds at 16V, and the withstand voltage is increased by 1V per minute until the voltage collapses.

As can be seen from Table 2, when a phosphate compound is added as an accelerator in the iron salt oxidizing agent composition, and the solid salt capacitor is produced by using the iron salt oxidizing agent composition, the leakage current of the obtained capacitor can be lowered, and the withstand voltage can be improved. The withstand voltage of the solid capacitor obtained by the present invention can be increased by 19.6% to 95.7% according to different added concentrations and the use of different accelerators (compared to the solid capacitor fabricated by the iron salt oxidant composition without the accelerator added). (Solid Capacitor I)). Further, from Examples 25 to 26, a solid capacitor produced by impregnating an EDOT solution and an iron salt of p-toluenesulfonate (the iron salt oxidizing agent composition (1) described in the examples) and drying it can be obtained. Further, if the phosphoric acid ester compound is further impregnated and dried (that is, the accelerator is not added at the same time when the iron salt of p-toluenesulfonate is impregnated), there is no significant effect in reducing the leakage current of the solid capacitor and increasing the withstand voltage. Further, as is clear from Table 2, the solid capacitors VI and VII prepared by adding the iron salt oxidizing agent compositions (6) and (7) of the polyol have a withstand voltage increase ratio of 80%. The reason is that the interaction between the polyol and the iron salt oxidant molecule is large and the compatibility is good, and the dispersibility of the promoter (phosphate compound) in the iron salt oxidant can be increased, and the function of the interface interface corrosion of the promoter can be further improved.

Example 27-28

Next, the above-formed accommodating element (2) was impregnated into the above EDOT solution for 30 minutes. After taking out the capacitor element, it was dried at 80 ° C for 30 minutes. Next, a plurality of occluders impregnated in the EDOT solution and dried are subjected to impregnation in the iron salt oxidizing agent compositions (1) and (4), respectively. After the impregnation is completed, it is dried at 60 ° C for 30 minutes, at 90 ° C for 30 minutes, and at 120 ° C for 30 minutes. After cooling, the solid capacitors XV and XVI are obtained respectively (each type of electricity Three containers were prepared separately. Then, after passing the 120 ° C power-on aging test (10 V, 15 V, and 20 V were applied at 120 ° C and maintained for 1 hour, respectively), the capacitance characteristics (including the capacitance value (Cs), the capacitance values (Cs) were included for the solid capacitors XV and XVI. Energy consumption coefficient (DF) and equivalent series resistance (ESR) test, and leakage current analysis, the results are shown in Table 3.

Remarks: Capacitance (measured at frequency 120Hz) >500μF Eligible (O), and vice versa (X); energy consumption factor (DF) (measured at frequency 120Hz) <10% is qualified (O), and vice versa (X); and, equivalent Series resistance (ESR) (measured at a frequency of 100 kHz) <10 mΩ is acceptable (O), and vice versa (X).

It can be seen from Table 3 that for a capacitor element that is reduced to a voltage, The use of the iron salt oxidizing agent composition of the present invention for the preparation of a solid capacitor can also reduce the leakage current of the resulting solid capacitor.

Based on the above, the iron salt oxidizing agent composition of the present invention, Since the hydrophobic end of the promoter easily reacts with the surface of the metal oxide dielectric layer, self-assembly forms a protective film, thereby blocking contact between the iron-containing compound and the metal oxide dielectric layer, thereby reducing the yield. The leakage current of the solid capacitor increases the withstand voltage characteristics. In addition, the accelerator is molecular-sized, so it does not block the corrosion pores of the alumina, resulting in capacitance. Decline. When used in a capacitor processing plant, it only needs to use the original equipment and process for production without increasing the production process.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

10‧‧‧Capacitance

12‧‧‧Anode metal foil

14‧‧‧Cathed metal foil

16‧‧‧Isolation paper

18‧‧‧Metal oxide layer

20‧‧‧ Electrolytes

Claims (19)

An iron salt oxidizing agent composition comprising: an iron-containing compound; and an accelerator, wherein the accelerator has the structure represented by the formula (I): Wherein R ¹ and R ⁴ are independently C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkoxyalkyl, C _5-12 aryl, or C _5-12 alkaryl, or R ¹ and R ^{4 are} bonded together to form a C _2-5 heterocyclic group together with the oxygen atom to which they are respectively attached; R ² and R ³ are independently hydrogen, hydroxy, C _1-10 alkoxy, C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkenyloxy, C _2-10 alkoxyalkyl, C _2-10 alkoxyalkoxy, C _5-12 aryl, C _5-12 aryloxy a C _5-12 alkaryl group, or a C _{5-12 alkaryloxy} group; and, A is a C _2-15 divalent aliphatic group, or a C _5-15 divalent aryl group; and, n is 0 1, or 2, wherein the weight ratio of the promoter to the iron-containing compound is between 0.01 and 0.49. The iron salt oxidizing agent composition according to claim 1, wherein the iron-containing compound is an aromatic sulfonic acid iron salt. The iron salt oxidizing agent composition according to claim 1, wherein the iron-containing compound is iron p-toluenesulfonate, iron salt of methanesulfonate, iron salt of benzenesulfonate or methoxybenzenesulfonic acid. Iron salt. The iron salt oxidizing agent composition according to claim 1, wherein R ¹ and R ⁴ are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentane. Base, hexyl, vinyl, propenyl, allyl, butenyl, methoxymethyl, ethoxymethyl, ethoxyethyl, propoxyethyl, or butoxyethyl. The iron salt oxidizing agent composition according to claim 1, wherein R1 and R4 are independently phenyl, biphenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methyl Phenylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, or 3,4-dimethylphenyl. The iron salt oxidizing agent composition according to claim 1, wherein R ² and R ³ are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentane. Base, hexyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, vinyl, propenyl, alkene Propyl, butenyl, vinyloxy, propyleneoxy, allyloxy, butenyloxy, methoxymethyl, ethoxymethyl, ethoxyethyl, propoxyethyl, butoxyethyl, Methoxymethoxy, ethoxymethoxy, ethoxyethoxy, propoxyethoxy, or butoxyethoxy. The iron salt oxidizing agent composition according to claim 1, wherein R ² and R ³ are independently phenyl, biphenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4 -methylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, or 3,4-dimethylphenyl, phenoxy, biphenyloxy, naphthyloxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, or 3,4 - dimethylphenyl. The iron salt oxidizing agent composition according to claim 1, wherein the A system is ,or . An iron salt oxidizing agent composition as claimed in claim 1 Also contains: a polyol. The iron salt oxidizing agent composition of claim 9, wherein the polyol comprises glycerin or polyethylene glycol. The iron salt oxidizing agent composition of claim 9, wherein the weight ratio of the polyol to the iron-containing compound is between 0.01 and 0.70. The iron salt oxidizing agent composition according to claim 1, wherein the accelerator is , , A solid capacitor comprising: a capacitor element; and an electrolyte disposed in the capacitor element, wherein the electrolyte is composed of a conductive polymer monomer coated on a capacitor element, and described in claim 1 The iron salt oxidizing agent composition is formed by polymerization. The solid capacitor of claim 13, wherein the conductive polymer monomer has the structure shown in formula (II): Wherein X ¹ and X ² are independently O or S; Y is ,or And R is independently hydrogen or C _1-6 alkyl. The solid capacitor according to claim 13, wherein the single system is ,or . A method of manufacturing a solid capacitor, comprising: providing a capacitor element; and impregnating the capacitor element with a conductive polymer monomer, and the iron salt oxidant composition of claim 1 and polymerizing the conductive polymerization The monomer is formed to form an electrolyte on the capacitor element. The method of manufacturing a solid capacitor according to claim 16, wherein the step of impregnating the conductive polymer monomer with the conductive polymer monomer and the iron salt oxidizing agent, and polymerizing the conductive polymer monomer comprises : immersing the cryptophore in the conductive polymer monomer and the iron salt oxidant composition; and performing a heating process on the impregnated capacitor element. The method of manufacturing a solid capacitor according to claim 16, wherein the step of impregnating the conductive polymer monomer with the conductive polymer monomer and the iron salt oxidizing agent, and polymerizing the conductive polymer monomer comprises : immersing the crypto-function element in the conductive polymer monomer; after the modulating element is impregnated into the conductive polymer monomer, performing a first heating process on the capacitor element; after performing the first heating process, Capacitance element is impregnated with the iron a salt oxidizing agent composition; and after the capacitor element is impregnated with the iron salt oxidizing agent composition, the second heating process is performed on the capacitor element. The method of manufacturing a solid capacitor according to claim 16, wherein the step of impregnating the conductive polymer monomer with the conductive polymer monomer and the iron salt oxidizing agent, and polymerizing the conductive polymer monomer comprises : immersing the octophan element in the iron salt oxidant composition; after the octophan element is impregnated into the iron salt oxidant composition, performing a first heating process on the capacitor element; after performing the first heating process, The capacitor element is impregnated with the conductive polymer monomer; and after the capacitor element is impregnated into the conductive polymer monomer, the capacitor element is subjected to a second heating process.