CN104143442A - Capacitor - Google Patents

Abstract

The invention provides a capacitor. The capacitor comprises a compound crystal shown in the formula I. A crystal compound belongs to the triclinic crystal system, according to a P-1 space group, a is equal to 1.09091, b is equal to 1.16257, c is equal to 1.94343, alpha is equal to 81.38 degrees, beta is equal to 84.47 degrees, gamma is equal to 65.29 degrees and V is equal to 2.2122.

Description

A kind of capacitor

Technical field

The present invention relates to a kind of capacitor, there is the low and little excellent specific property of the initial disqualification rate of leakage current of equivalent series resistance.

Background technology

Along with the high frequency of electronic equipment, in the capacitor as one of electronic unit, require the large value capacitor in the impedance operator excellence of high frequency region.Recently, in order to reduce the impedance of this high frequency region, start electrolytic capacitor to using the high electroconductive polymer of conductivity and study and carry out goods.Electrolytic capacitor possesses: anode foils, the dielectric overlay film forming on the surface of anode foils and the electroconductive polymer layer forming on dielectric overlay film.The surface process of anode foils is roughened, and is formed with multiple holes.As the method that forms electroconductive polymer layer, except chemical polymerization and electrolysis polymerization, also comprise and make preformed electroconductive polymer particle be impregnated in the dispersion method of capacitor element.With regard to chemical polymerization, sometimes because the existence of oxidant damages dielectric overlay film.In addition, for chemical polymerization and electrolysis polymerization, be difficult to be formed uniformly electroconductive polymer layer.So, can form electroconductive polymer layer compared with heavy back, use a large amount of electroconductive polymers.Little molecular organic compound, it is simple that particularly little molecular organic compound crystal has preparation compared with polymer, and coating is even, rate of finished products is high, and feature easily and effectively, therefore still needs application organic micromolecule compound, particularly organic micromolecule compound crystal current electrolysis condenser.

Require to have small size and high capacitance for electronic instrument as the capacitor of portable phone and PC.In these capacitors, tantalum capacitor is preferred, because with respect to its size, capacitance is large and performance good.In addition, in recent years, require electronic device to operate under low-voltage and high-frequency, and there is low noise, and for solid electrolyte capacitators, also require lower equivalent parallel resistance (ESR).In this tantalum capacitor, the sintered body of tantalum powder is generally used as anode part.By this powder forming, then sintering, thus make described powder integration and make the electrode that is called as sintered body.This sintered body inside is formed the structure of 3 D complex by electricity and the powder particle of mechanical link each other, comprise the surface on internal void surface at this sintered body, forms dielectric film layer, floods the material of conduct to electrode, thereby prepares a kind of capacitor.As long as dielectric film layer is evenly attached to inner surface or the outer surface of described sintered body, the capacitance of the capacitor of manufacturing just depends primarily on the contact condition to electrode material and dielectric film layer on microcosmic.In order to improve the capacitance of tantalum capacitor, must improve the quality of sintered body or use the sintered body that has increased surface area by broken tantalum powder.

Summary of the invention

The general manufacture method of electrolytic capacitor comprises following steps: the step of the multiple holes that prepare to have surperficial anode foils, form on the surface of anode foils and the dielectric overlay film forming on the surface of anode foils; The first dispersion solution that anode foils is impregnated in contain the first electroconductive polymer particle and the first solvent, forms the step of the first electroconductive polymer layer on the surface of dielectric overlay film; And, the second dispersion solution that anode foils is impregnated in contain the second electroconductive polymer particle and the second solvent, form the step of the second electroconductive polymer layer that covers the first electroconductive polymer layer, wherein, compared with described the first dispersion solution, the pH of described the second dispersion solution and 7 differs farther.

The object of this invention is to provide the capacitor that a kind of unit mass capacitance is large, leakage current is little and moisture-proof is high; A kind of sintered body that can be used as the electrode material of this capacitor and can obtain the apparent ratio of high-capacitance; A kind of material as this sintered body is preferred, in shaping operation, show good fluidity, promote progressive forming and niobium powder that can steady production capacitor; Manufacture method with described capacitor, described sintered body and described niobium powder.

The invention provides a kind of capacitor, a kind of capacitor, it comprises that an electrode, one are to electrode and dielectric material, described electrode is for comprising that volume is 10mm ³niobium sintered body, described dielectric material comprises niobium oxide, described is organic semiconductor to electrode, it comprises the organic compound of following structure:

I，

Described crystalline compounds belongs to anorthic system, P-1 space group, a=1.09091, b=1.16257, c=1.94343, α=81.38 °, β=84.47 °, γ=65.29 °, V=2.2122.

Embodiment

Below by embodiment, the invention will be further described.It should be understood that described in the embodiment of the present invention that preparation method is only used for illustrating the present invention, instead of limitation of the present invention, right under design prerequisite of the present invention

Preparation method's of the present invention simple modifications all belongs to the scope of protection of present invention.All raw materials of using in embodiment and solvent are all purchased from Sigma Biochemical and Organic Compounds for Research and Diagnostic Clinical Reagents company.

In powder X-ray x ray diffraction (XRD), use Cu K α 1 as X ray tube, at room temperature use powder x-ray diffraction device RINT2200/Ultima+ (RIGAKU) or X'Pert Pro MPD (PANalytical) to measure within the scope of the 2 θ angles of diffraction of 2 ° to 35 °.For used each diffraction instrument, measuring condition is as follows.

Diffraction instrument: RINT2200/Ultima+ (RIGAKU)

Tube current: 40mA, tube voltage: 40kV, sweep speed: 4 °/minute

Diffraction instrument: X'Pert Pro MPD (PANalytical)

Tube current: 40 mA, tube voltage: 45kV, sweep speed: 40.1 °/minute

Although 2 θ values generally illustrate 0.2 ° of about scholar's error, may cause larger error due to measuring condition etc.Use thermogravimetric/differential thermal analyzer TG/SDTA851e (TG/DTA) (Mettler Toledo) or differential scanning calorimeter DSC821e (DSC), in the dry nitrogen air-flow of 40ml/ minute and under the intensification degree speed of 10 DEG C/min, carry out heat analysis.

Embodiment 1:

Be the sodium of 10 times of fluoro potassium niobates to packing 5,000 grams in nickel crucible at 80 DEG C of abundant vacuum drying fluoro potassium niobates and mole, and make it under argon atmospher, carry out the reduction reaction of 20 hours at 1,000 DEG C.After reacting completely, reduzate is cooling, wash with water successively, with 95% sulfuric acid scrubbing, then wash with water, vacuumize is also used the oxidation aluminium pot ball mill that contains silica alumina ball to pulverize 40 hours.Crushed products is flooded and stirred in the 3:2 (by mass) of 50% nitric acid and 10% aqueous hydrogen peroxide solution mixed solution.Then, crushed products water is fully washed, until pH value reaches 7, to remove impurity, then vacuumize.The particle mean size of raw material niobium powder is 1.2 microns.

In niobium tank, place 500 grams of this raw material niobium powder and add wherein 50 grams of polybutyl methacrylates and 1 liter of toluene.In addition, add zirconia ball and use shaking mixer by contents mixed 1 hour.Removing after zirconia ball, this mixture is being placed in circular cone drier and 1 × 10 ²vacuumize under the condition of Pa and 80 DEG C.

Subsequently, by this niobium powder at 250-400 DEG C 1 × 10 ^-2pa heating 12 hours, to decompose and to remove polybutyl methacrylate, then 4 × 10 ^-3under the decompression of Pa 1,150 DEG C of sintering 2 hours.Until being reduced to 30 DEG C or lower, product temperature then uses roll pelletizer fragmentation by cooling niobium powder sintering agglomerate, to obtain particle mean size as the broken powder of the niobium of 100 microns.

The broken powder of this niobium, by passing into nitrogen through the nitrogen treatment at 300 DEG C, 2 hours adding to depress, obtains the niobium powder of approximately 450 grams.Nitrogen content is 0.22%.

Pack the niobium powder (approximately 0.1 gram) so obtaining into tantalum device automatic forming machine (TAP-2R, manufactured by Seiken) hopper in, and with automatic forming together with the niobium silk of 0.3mm φ, carry out the molded article that manufacturing dimension is about 0.3cm × 0.18cm × 0.45cm.This molded article is 4 × 10 ^-3in the vacuum of Pa, leave standstill 30 minutes at 1,250 DEG C, to obtain sintered body.Prepare this sintered body of 100, and each uses 0.1% phosphate aqueous solution electrochemical shaping 200 minutes under 20V voltage, to form from the teeth outwards oxide dielectric film.

Subsequently, repeat this sintered body to be immersed in and in 60% manganese nitrate aqueous solution, then to make it in 220 DEG C of heating operation of 30 minutes, to form manganese dioxide layer as to electrode layer on oxide dielectric film.This to electrode layer on, stack gradually carbon-coating and silver stick with paste layer.After lead frame being installed thereon, this device is shaped with epoxy resin as a whole, to manufacture chip capacitor.Average electrical capacity and the average leakage current (hereinafter referred is " LC ") of the apparent ratio of capacitance of this capacitor and chip capacitor (n=100) represent in table 1.LC value is the 1 minute value at room temperature measuring of voltage by applying 6.3V.

Embodiment 2: the preparation of formula I compound crystal

106g benzaldehyde, 400g ortho-fluorophenyl amine, 450g hydrochloric acid (approximately 30%) and 800ml water are heated 6 hours at 120-140 DEG C in autoclave.Reactant mixture is poured in 1kg ice and 500g sodium hydroxide solution (30%).Separate organic layer and the ortho-fluorophenyl amine with toluene excessive separation.Residue is cleaned to filter cake from toluene recrystallization and with cold ethanol.Obtain formula I compound; Productive rate: 41%.Accurately take with assay balance by above-claimed cpd, load weighted compound is put into agate mortar in fume hood and fully ground it is mixed, then sample is packed in platinum crucible.For late phase reaction is carried out smoothly, put into box type furnace in 90 DEG C of pre-burnings, grinding.Finally constant temperature 5h at 70 DEG C, through Slow cooling stage by stage to room temperature.Finally, obtain colourless bulk crystals in crucible bottom.This crystal is carried out to its crystal structure of crystallographic analysis, and its crystallographic parameter is described above.The capacity of the capacitor of the present invention of use formula I compound crystal is 676 μ F, and LC is 19 μ A.

Claims (3)

1. a capacitor, it comprises that an electrode, one are to electrode and dielectric material, described electrode is for comprising that volume is 10mm ³niobium sintered body, described dielectric material comprises niobium oxide, described is organic semiconductor to electrode, it comprises the organic compound of following structure:

I，

Described crystalline compounds belongs to anorthic system, P-1 space group, a=1.09091, b=1.16257, c=1.94343, α=81.38 °, β=84.47 °, γ=65.29 °, V=2.2122.

2. capacitor as described in claim 1, is characterized in that, described electrode is contained to organic sulfonic acid root anion as dopant.

3. a compound crystal, it has suc as formula the structure shown in I:

I，

Described crystalline compounds belongs to anorthic system, P-1 space group, a=1.09091, b=1.16257, c=1.94343, α=81.38 °, β=84.47 °, γ=65.29 °, V=2.2122.