CN113539689B - Silica lactone sol, preparation method and electrolyte for aluminum electrolytic capacitor - Google Patents
Silica lactone sol, preparation method and electrolyte for aluminum electrolytic capacitor Download PDFInfo
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- CN113539689B CN113539689B CN202010296097.0A CN202010296097A CN113539689B CN 113539689 B CN113539689 B CN 113539689B CN 202010296097 A CN202010296097 A CN 202010296097A CN 113539689 B CN113539689 B CN 113539689B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/145—Liquid electrolytic capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
In order to solve the problem that the conductivity of the lactone electrolyte added with glycol silica sol is greatly attenuated under high-temperature storage in the prior art, the invention provides the silica lactone sol, which takes the lactone compound as a solvent, disperses surface modified silica colloidal particles, controls the number of hydroxyl groups on each square nanometer surface of the surface modified silica to be less than 3, and controls the particle size of the surface modified silica to be 5-200 nm. The invention also provides a preparation method of the silica lactone sol. The invention also provides an electrolyte for the aluminum electrolytic capacitor, which comprises a main solvent, a main solute and the silica lactone sol. The silicon dioxide lactone sol provided by the invention obviously improves the sparking voltage of the lactone electrolyte, so that the conductivity of the lactone electrolyte is kept stable in high-temperature-resistant storage, and the lactone electrolyte can stably exist in the lactone electrolyte.
Description
Technical Field
The invention belongs to the field of electrolyte for aluminum electrolytic capacitors, and particularly relates to a silica lactone sol, a preparation method and electrolyte for an aluminum electrolytic capacitor.
Background
The sparking voltage is one of the important parameters of the working electrolyte of the aluminum electrolytic capacitor and directly determines the rated working voltage of the capacitor. The additives for increasing the sparking voltage are generally the following: (1) The macromolecular carboxylic acid is easy to be adsorbed by an alumina film, and the macromolecular carboxylic acid ionizes to generate anions in a solvent, and the anions are directionally adsorbed to the surface of the anode under the action of an electric field to form an adsorption layer. The adsorption layer has the function of shielding an electric field, and the electric field applied to the electrode is uniform, so that the edge effect is eliminated. Meanwhile, the adsorption layer has strong oxidation capacity and can also improve the sparking voltage; (2) Some electrolytes (such as adipic acid and the like) with good formation performance and some substances with strong oxidizability (such as ammonium dichromate, maleic acid and the like) are easy to release oxygen, can quickly repair the damage of a dielectric film, improve the formation performance and are more beneficial to improving the sparking voltage; (3) Phosphoric acid and its salts, such as phosphoric acid, hypophosphorous acid and ammonium dihydrogen phosphate, can repair dielectric film, prevent hydration, and ensure sparking voltage.
In the traditional electrolyte preparation materials, the most effective method for improving the sparking voltage of the electrolyte is to add macromolecular carboxylic acid to form an adsorption layer on the surface of an anode, but the macromolecular carboxylic acid inevitably increases the viscosity and the resistivity of the electrolyte, which is unfavorable for the service performance of a capacitor. The silica sol is applied to the working electrolyte of the aluminum capacitor due to the characteristics of small particle size, charged charge, uniform dispersion, high purity, high temperature resistance, strong adsorbability and the like. The high-purity silica sol can effectively improve the breakdown resistance of the aluminum foil, thereby improving the sparking voltage of the aluminum electrolytic capacitor. Compared with macromolecular carboxylic acid, the viscosity of the silica sol is low, so that the viscosity and the resistivity of the electrolyte cannot be influenced when the silica sol is added into the electrolyte. Compared with the flash-fire voltage booster of adipic acid, partial substances with stronger oxidability, phosphoric acid and salts thereof and the like, the effect of boosting the flash-fire voltage is better than that of the materials.
Because the nano material has small particle size, high specific surface area and large surface energy and is in an energy unstable state, the nano powder is easy to agglomerate to cause sedimentation and delamination, so that the good characteristics of the nano powder can not be well exerted. The nano powder can be uniformly and stably dispersed in the solution only after special treatment, and can be added into the working electrolyte. At present, the silica sol applied to the field of the electrolyte of the aluminum electrolytic capacitor is generally nano-silica glycol sol, and the effect of improving flash fire is generally between 20 and 40V due to the difference of the electrolyte. The most widely applied liquid aluminum electrolytic capacitor working electrolyte in the market is mainly two solvent systems of ethylene glycol and gamma-butyrolactone, and the two solvent systems account for more than 95% of the liquid aluminum electrolytic capacitor working electrolyte market. The nano-silica glycol sol is widely used in working electrolyte using glycol solvent as a system. The nano-silica glycol sol has good effect of improving the sparking voltage, and can not affect other parameters of the capacitor. For the working electrolyte using a gamma-butyrolactone system, the existing method for increasing the voltage basically adds nano-silica glycol sol. The addition of the nano-silica glycol sol can improve the sparking voltage of the electrolyte, but the glycol is introduced into the gamma-butyrolactone solution. The introduction of ethylene glycol can cause a great reduction in the conductivity of the electrolyte during high-temperature storage, and the electrical performance of the capacitor is affected.
Disclosure of Invention
The invention aims to solve the technical problem that the conductivity of a lactone electrolyte added with silica glycol sol in the prior art is greatly attenuated under high-temperature storage, and provides a silica lactone sol, a preparation method and an electrolyte for an aluminum electrolytic capacitor.
The technical scheme adopted by the invention for solving the problems is as follows:
in one aspect, the invention provides a silica lactone sol comprising the following components:
a solvent and surface modified silica;
the solvent comprises a lactone compound, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
Optionally, the content of the solvent is 30% to 99% and the content of the surface-modified silica is 1% to 40% based on 100% of the total weight of the silica lactone sol.
Optionally, the lactone-type compound comprises gamma-butyrolactone and/or gamma-valerolactone.
Optionally, the content of the surface-modified silica is 5% to 20%.
Optionally, the surface modified silicon dioxide is prepared by reacting silicon powder, an alkaline catalyst, an alkyl reagent and water;
the alkaline catalyst comprises one or more of ammonia water, ethylenediamine, sodium hydroxide, sodium bicarbonate, sodium carbonate and silicate.
Optionally, the silane agent includes a silane coupling agent including one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloxy) propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane.
In another aspect, the present invention also provides a method for preparing the silica lactone sol described in any one of the above, comprising the steps of:
dissolving silicon powder in water, adding an alkaline catalyst, and filtering and concentrating to obtain silicon dioxide hydrosol;
adding a silane reagent into the silicon dioxide hydrosol to obtain surface modified silicon dioxide;
uniformly mixing the surface modified silica and a solvent lactone compound, and distilling to remove water to obtain silica lactone sol;
wherein, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
Optionally, the preparation method of the silica lactone sol comprises the following steps:
dissolving the required parts of silicon powder in water accounting for 300-2000% of the mass of the silicon powder, adding an alkaline catalyst, keeping the pH value at 9-10.5, the reaction temperature at 30-90 ℃ and the reaction time at 2-24 h, filtering and concentrating to obtain silicon dioxide hydrosol accounting for 5-35% of the mass of the silicon dioxide;
heating the silica hydrosol to 30-90 ℃, and adding an alkyl reagent with the silica content of 1-30% to obtain surface modified silica;
uniformly mixing the surface modified silicon dioxide and a solvent lactone compound, wherein the adding amount of the solvent is 50-900% of the mass of the silicon dioxide hydrosol, and distilling to remove water to obtain a silicon dioxide lactone sol;
wherein, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
In another aspect, the present invention also provides an electrolyte for an aluminum electrolytic capacitor, comprising a main solvent, a main solute, and the silica lactone sol described in any one of the above.
Optionally, the main solvent is a lactone compound.
The invention provides a silicon dioxide lactone sol, which takes a lactone compound as a solvent, surface modified silicon dioxide is added, the number of hydroxyl groups on each square nanometer surface of the surface modified silicon dioxide is controlled to be less than 3, the particle size of the surface modified silicon dioxide is 5-200 nm, the uniformity and stability of the surface modified silicon dioxide dispersed in the lactone solvent are ensured, the conductivity of the lactone electrolyte added with the nano silicon dioxide glycol sol is greatly reduced under high-temperature storage due to the fact that the nano silicon dioxide glycol sol contains glycol, the flashover voltage of the lactone electrolyte is improved by preparing the silicon dioxide lactone sol, the conductivity of the lactone electrolyte can be kept stable in high-temperature storage, and the silicon dioxide lactone sol can stably exist in the lactone electrolyte.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an electrolyte for an aluminum electrolytic capacitor, which comprises the following components:
in one aspect, the invention provides a silica lactone sol additive comprising the following components:
a solvent and surface modified silica;
the solvent comprises lactone compounds, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
The silicon dioxide lactone sol provided by the invention takes the lactone compound as a solvent, the surface modified silicon dioxide is added, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is controlled to be less than 3, the particle size of the surface modified silicon dioxide is 5-200 nm, and the uniformity and the stability of the surface modified silicon dioxide dispersed in the lactone solvent are ensured. The nanometer silicon dioxide glycol sol contains glycol, so that the conductivity of the lactone electrolyte added with the nanometer silicon dioxide glycol sol is greatly reduced under high-temperature storage, the sparking voltage of the lactone electrolyte is improved by preparing the silicon dioxide lactone sol, the conductivity of the lactone electrolyte can be kept stable under high-temperature storage, and the silicon dioxide lactone sol can stably exist in the lactone electrolyte.
In some embodiments of the present invention, the solvent is present in an amount of 30% to 99% and the surface-modified silica is present in an amount of 1% to 40%, based on 100% by weight of the silica lactone sol.
In some embodiments of the invention, the lactone-based compound comprises gamma-butyrolactone and/or gamma-valerolactone.
Preferably, the purity of the gamma butyrolactone is of electronic grade.
In some embodiments of the invention, the surface modified silica is present in an amount of 5% to 20%.
In some embodiments of the invention, the surface modified silica is prepared by reacting silica powder, a basic catalyst, an alkyl reagent and water;
the alkaline catalyst comprises one or more of ammonia water, ethylenediamine, sodium hydroxide, sodium bicarbonate, sodium carbonate and silicate.
Wherein, the purity of the silicon powder is more than or equal to 99 percent, the granularity is 200-500 meshes, the water is deionized water, and the pure water with the ion content of 3ppb is preferred.
In some embodiments of the invention, the alkyl reagent comprises a silane coupling agent, preferably an aromatic group or aromatic alkyl group containing silane coupling agent.
The silane coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane.
In some embodiments of the present invention, the surface modified silica is present in the silica lactone sol in an amount of 20%.
The invention also provides a preparation method of the silica lactone sol, which comprises the following steps:
dissolving silicon powder in water, adding an alkaline catalyst, and filtering and concentrating to obtain silicon dioxide hydrosol;
adding a silane reagent into the silicon dioxide hydrosol to obtain surface modified silicon dioxide;
uniformly mixing the surface modified silicon dioxide and a solvent lactone compound, and distilling to remove water to obtain the silicon dioxide lactone sol;
wherein, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
In some embodiments of the present invention, the method for preparing the silica lactone sol comprises the following steps:
dissolving the required silicon powder in water accounting for 300-2000% of the mass of the silicon powder, adding an alkaline catalyst, keeping the pH value at 9-10.5, the reaction temperature at 30-90 ℃ and the reaction time at 2-24 h, and filtering and concentrating to obtain silicon dioxide hydrosol with the mass fraction of 5-35% of silicon dioxide;
heating the silica hydrosol to 30-90 ℃, and adding an alkyl reagent with the silica content of 1-30% to obtain surface modified silica;
uniformly mixing the surface modified silicon dioxide and a solvent lactone compound, wherein the adding amount of the solvent is 50-900% of the mass of the silicon dioxide hydrosol, and distilling to remove water to obtain a silicon dioxide lactone sol;
wherein the number of hydroxyl groups per square nanometer surface of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
The solution after the silicon powder reaction can be filtered by a PE filter membrane of 10um, and then the filtrate passes through a resin column of anion-cation resin to remove ions, so as to obtain the silica hydrosol.
The invention also provides an electrolyte for an aluminum electrolytic capacitor, which comprises a main solvent, a main solute and the silica lactone sol.
In some embodiments of the invention, the primary solvent is a lactone-type compound.
The present invention will be further illustrated by the following examples. It is to be understood that the present invention is not limited to the following embodiments, and methods are regarded as conventional methods unless otherwise specified. Materials are commercially available from the open literature unless otherwise specified.
Example 1
This example illustrates the silica lactone sol and the method of making the same disclosed herein.
The preparation of the silica lactone sol comprises the following components:
(1) Silicon powder 5g
(2) 15g of pure water
(3) Sodium hydroxide
(4) Gamma- (2,3-epoxypropoxy) propyltrimethoxysilane 1.26g
(5) 25g of gamma-butyrolactone
The preparation method comprises the following steps:
(1) Adding 5g of silicon powder into an aqueous solution at 55 ℃, stirring for 1h, pouring out the upper-layer aqueous solution after precipitation, washing twice to remove impurities attached to the surface of the silicon powder;
(2) Adding 15g of pure water into the silicon powder, adding sodium hydroxide, and adjusting the pH value of the solution to 9, wherein the reaction temperature is kept at 30 ℃ for 24 hours;
(3) Filtering the reacted solution by using a 10-micrometer PE filter membrane to obtain 21.4g of milky white filtrate, and collecting unreacted silicon powder for the next experiment;
(4) Slowly passing the filtrate through a resin column filled with anion and cation resin to obtain 93g of silica hydrosol;
(5) Heating the silica hydrosol to 50 ℃, slowly adding 1.26g of gamma- (2,3-epoxy propoxy) propyl trimethoxy silane with the silica content of 5%, and reacting for 5 hours at 50 ℃ to obtain surface modified silica;
(6) Adding 25g of gamma-butyrolactone into the surface modified silicon dioxide, and removing water by reduced pressure distillation to obtain the nano silicon dioxide gamma-butyrolactone sol marked as S1.
Example 2
This example illustrates the silica lactone sol and the method of making the same disclosed herein.
The preparation of the silica lactone sol comprises the following components:
(1) Silicon powder 5g
(2) 50g of pure water
(3) Sodium hydroxide
(4) 2.52g of gamma-aminopropyltriethoxysilane
(5) 25g of gamma-butyrolactone
The preparation method comprises the following steps:
(1) Adding 5g of silicon powder into an aqueous solution at 70 ℃, stirring for 1h, pouring out an upper-layer aqueous solution after precipitation, washing twice to remove impurities attached to the surface of the silicon powder;
(2) Adding 50g of pure water into the silicon powder, adding sodium hydroxide, and adjusting the pH value of the solution to 9, wherein the reaction temperature is kept at 60 ℃ for 6 hours;
(3) Filtering the reacted solution by using a 10-micrometer PE filter membrane to obtain 56.1g of milky white filtrate, and collecting unreacted silicon powder for the next experiment;
(4) Slowly passing the filtrate through a resin column filled with anion and cation resin to obtain 72.3g of silica hydrosol;
(5) Heating the hydrosol to 65 ℃, slowly adding 2.52g of gamma-aminopropyl triethoxysilane with the silicon dioxide content of 10%, and reacting for 8h at 65 ℃ to obtain surface modified silicon dioxide;
(6) Adding 25g of gamma-butyrolactone into the surface modified silicon dioxide, and removing water by reduced pressure distillation to obtain the nano silicon dioxide gamma-butyrolactone sol marked as S2.
Example 3
This example illustrates the silica lactone sol and the method of making the same disclosed herein.
The preparation of the silica lactone sol comprises the following components:
(1) Silicon powder 5g
(2) 90g of pure water
(3) Sodium hydroxide
(4) Phenyltrimethoxysilane 3.78g
(5) 25g of gamma-butyrolactone
The preparation method comprises the following steps:
(1) Adding 5g of silicon powder into an aqueous solution at 90 ℃, stirring for 1h, pouring out an upper-layer aqueous solution after precipitation, washing twice to remove impurities attached to the surface of the silicon powder;
(2) Adding 90g of pure water into the silicon powder, adding sodium hydroxide, and adjusting the pH value of the solution to 9, wherein the reaction temperature is kept at 60 ℃ for reaction for 10 hours;
(3) Filtering the reacted solution by using a 10-micrometer PE filter membrane to obtain 96.4g of milky white filtrate, and collecting unreacted silicon powder for the next experiment;
(4) Slowly passing the filtrate through a resin column filled with anion and cation resin to obtain 105g of silica hydrosol;
(5) Heating the silica hydrosol to 90 ℃, slowly adding 3.78g of phenyltrimethoxysilane with the silica content of 15%, and reacting at 90 ℃ for 12h to obtain surface modified silica;
(6) Adding 25g of gamma-butyrolactone into the surface modified silicon dioxide, and distilling under reduced pressure to remove water in the surface modified silicon dioxide to obtain the nano silicon dioxide gamma-butyrolactone sol marked as S3.
Comparative example 1
This comparative example is intended to illustrate the silica lactone sols disclosed herein.
A silica glycol sol of model CS2 manufactured by Fushan drugs Ltd is denoted by D1.
Comparative example 2
This comparative example is intended to illustrate by comparison the silica lactone sols disclosed herein.
The comparative silica lactone sols were prepared comprising the following components:
(1) Silicon powder 5g
(2) 15g of pure water
(3) Sodium hydroxide
(4) 25g of gamma-butyrolactone
The preparation method comprises the following steps:
(1) Adding 5g of silicon powder into an aqueous solution at 55 ℃, stirring for 1h, pouring out the upper-layer aqueous solution after precipitation, washing twice to remove impurities attached to the surface of the silicon powder;
(2) Adding 15g of pure water into the silicon powder, adding sodium hydroxide, and adjusting the pH value of the solution to 9, wherein the reaction temperature is kept at 30 ℃ for 24 hours;
(3) Filtering the reacted solution by using a 10-micrometer PE filter membrane to obtain 21.4g of milky white filtrate, and collecting unreacted silicon powder for the next experiment;
(4) Slowly passing the filtrate through a resin column filled with anion and cation resin to obtain 93g of silica hydrosol;
(5) Adding 25g of gamma-butyrolactone into the silica hydrosol, and performing reduced pressure distillation to remove water to obtain a system gel marked as D2.
Comparative example 3
This comparative example is for comparative illustration of the silica lactone sol and the method of preparing the same disclosed in the present invention.
The preparation of the silica lactone sol comprises the following components:
(1) 5g of silicon powder
(2) 50g of pure water
(3) Sodium hydroxide
(4) 1.92g of gamma-aminopropyltriethoxysilane
(5) 25g of gamma-butyrolactone
The preparation method comprises the following steps:
(1) Adding 5g of silicon powder into an aqueous solution at 70 ℃, stirring for 1h, pouring out an upper-layer aqueous solution after precipitation, washing twice to remove impurities attached to the surface of the silicon powder;
(2) Adding 50g of pure water into the silicon powder, adding sodium hydroxide, and adjusting the pH value of the solution to 8, wherein the reaction temperature is kept at 60 ℃ for 1 hour;
(3) Filtering the reacted solution by using a 10-micrometer PE filter membrane to obtain 46.1g of milky filtrate, and collecting unreacted silicon powder for the next experiment;
(4) Slowly passing the filtrate through a resin column filled with anion and cation resin to obtain 52.3g of silica hydrosol;
(5) Heating the hydrosol to 65 ℃, slowly adding 1.92g of gamma-aminopropyl triethoxysilane with the silicon dioxide content of 12%, and reacting for 8h at 65 ℃ to obtain surface modified silicon dioxide;
(6) Adding 25g of gamma-butyrolactone into the surface modified silicon dioxide, and removing water by reduced pressure distillation to obtain the nano silicon dioxide gamma-butyrolactone sol marked as D3.
Performance testing
Testing parameters of surface-modified silica
1. Determination of the number of surface hydroxyl groups:
10.0g of nano SiO with a solid content of 20% are weighed 2 The hydrosol was placed in a 200mL beaker, and 25mL of absolute ethanol and 75mL of 20% NaCl solution were added. After stirring, the pH was adjusted to 4.0 with 0.1mol/L HCl solution or 0.1mol/L NaOH. Then, 0.1mol/L NaOH solution was slowly added to raise the pH to 9.0, and the pH was maintained for 20 seconds. Calculate each (nm) according to equation (1) 2 The number (N) of hydroxyl groups on the surface area of the nano SiO 2:
formula (1)
In the formula (1), C is the concentration of NaOH (0.1 mol/L), V is the volume of NaOH (mL) of 0.1mol/L consumed when the pH is raised from 4.0 to 9.0, and NA is the Alvardea constantS is nano SiO 2 Specific surface area (nm) 2 In g), m is nano SiO 2 Mass (g) of (c).
2. The particle size distribution of the modified silicon dioxide is tested by a dynamic light flash nanometer particle size analyzer, and the average particle size is calculated.
The test results obtained are shown in table 1.
TABLE 1
| Numbering | Number of hydroxyl groups on square nano surface | Average particle size/nm |
| S1 | 1.2 | 26 |
| S2 | 2.3 | 65 |
| S3 | 1.5 | 34 |
| D1 | 1.4 | 28 |
| D2 | / | / |
| D3 | 3.6 | 219 |
Heating the gamma-butyrolactone solution, adding an imidazole phthalate salt into the gamma-butyrolactone solution, and dissolving the imidazole phthalate salt in a stirring state. And adding the prepared additives S1-S3 and the comparative samples D1-D3 into gamma-butyrolactone and main solute imidazole phthalate to prepare working electrolyte of the aluminum electrolytic capacitor, wherein the working electrolyte is marked as SS1, SS2, SS3, DD1, DD2 and DD3. The amounts added are shown in Table 2. The capacitor used to verify additive performance was of the size 47f/100V, 10 x 13mm, and 143Vf capacity.
TABLE 2
1. And (3) respectively taking the electrolytes SS1 to SS3 to be tested and the electrolytes DD1 to DD3 to be tested, and testing the conductivity and the sparking voltage at the temperature of 30 ℃.
(1) Electrical conductivity of
And (4) carrying out conductivity test on the electrolytes SS1 to SS3 and the electrolytes DD1 to DD3 by using a conductivity detector.
(2) Sparking voltage
Respectively placing electrolytes SS1 to SS3 to be detected and electrolytes DD1 to DD3 into a clean and dry beaker, and respectively connecting the positive electrode and the negative electrode with the optical foil by using a crocodile clip, wherein the optical foil is immersed in the liquid level by about 1 cm. And the part of the foil immersed in the liquid surface can not be attached to the cup wall, and the distance between the two electrode plates is more than 2cm.
Turning on a power switch of a spark voltmeter, setting the gear of a voltage stepping switch to be 800V, simultaneously turning on computer test software, entering a test system, inputting the name and the batch number of a test project, setting the current required by constant current boosting to be 20mA, starting the test system to test, and starting the test.
When the voltage rises to the point that the spark occurs on the optical foil or the voltage drops (more than or equal to 2V), reading the first peak voltage of the test curve, namely the sparking voltage of the electrolyte; and when the voltage rises to the point that the spark occurs on the optical foil or the voltage drops (more than or equal to 2V), reading the time under the first peak voltage of the test curve, wherein the time is the sparking time of the electrolyte.
The test results obtained are shown in table 3.
TABLE 3
2. Respectively taking electrolytes SS1 to SS3 to be tested and electrolytes DD1 to DD3 to be tested, and testing the conductivity, the conductivity change rate, the flash voltage and the moisture under the high-temperature storage condition of 125 ℃, wherein the testing process of the high-temperature storage is as follows: and placing the electrolyte to be tested into a steel cylinder, sealing the bottle opening, baking in an oven, and taking out the electrolyte for a fixed time to test electrical performance parameters.
The test results obtained are shown in tables 4 and 5.
TABLE 4
TABLE 5
As can be seen from tables 4 and 5, the conductivities, the conductivity change rates and the sparking voltages of the electrolytes SS1 to SS3 are relatively stable even when the electrolytes are stored at 125 ℃ for 1500 hours, while the conductivities of the electrolytes DD1 to DD2 are significantly reduced when the electrolytes are stored at 125 ℃ for 250 hours, which shows that the silica lactone sol added in the invention has excellent high-temperature storage resistance, and the conductivities and the sparking voltages are relatively stable under long-time high-temperature storage; the moisture can influence the conductivity, and the conductivity is relatively stable under the condition of long-time high-temperature storage under the condition that the moisture of the electrolytes SS1 to SS3 is equivalent to that of the electrolyte DD 1; when the number of hydroxyl groups on the surface of each square nanometer of the electrolyte DD3 surface modified silicon dioxide is more than 3, the conductivity is greatly reduced compared with the electrolytes SS 1-SS 3 along with the increase of the storage time.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. The electrolyte of the aluminum electrolytic capacitor is characterized by comprising a main solvent, a main solute and a silica lactone sol, wherein the silica lactone sol comprises the following components:
a solvent and surface modified silica;
the solvent comprises a lactone compound, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm; the content of the solvent is 30-99% and the content of the surface modified silica is 1-40% based on 100% of the total weight of the silica lactone sol.
2. The aluminum electrolytic capacitor electrolyte of claim 1, wherein the lactone-based compound comprises gamma-butyrolactone and/or gamma-valerolactone.
3. The aluminum electrolytic capacitor electrolyte of claim 1, wherein the surface modified silica is present in an amount of 5% to 20%.
4. The aluminum electrolytic capacitor electrolyte of claim 1, wherein the surface modified silica is prepared by reacting silicon powder, an alkaline catalyst, an alkyl reagent and water;
the alkaline catalyst comprises one or more of ammonia water, ethylenediamine, sodium hydroxide, sodium bicarbonate, sodium carbonate and silicate.
5. The aluminum electrolytic capacitor electrolyte of claim 4, wherein the alkyl reagent comprises a silane coupling agent comprising one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane.
6. The aluminum electrolytic capacitor electrolyte of claim 1, wherein the preparation method of the silica lactone sol comprises the following steps:
dissolving silicon powder in water, adding an alkaline catalyst, and filtering and concentrating to obtain silicon dioxide hydrosol;
adding a silane reagent into the silicon dioxide hydrosol to obtain surface modified silicon dioxide;
uniformly mixing the surface modified silicon dioxide and a solvent lactone compound, and distilling to remove water to obtain the silicon dioxide lactone sol;
wherein, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
7. The aluminum electrolytic capacitor electrolyte of claim 6, wherein the preparation method of the silica lactone sol comprises the following steps:
dissolving the required silicon powder in water accounting for 300-2000% of the mass of the silicon powder, adding an alkaline catalyst, keeping the pH value at 9-10.5, the reaction temperature at 30-90 ℃ and the reaction time at 2-24 h, and filtering and concentrating to obtain silicon dioxide hydrosol with the mass fraction of 5-35% of silicon dioxide;
heating the silica hydrosol to 30-90 ℃, and adding an alkyl reagent with the silica content of 1-30% to obtain surface modified silica;
uniformly mixing the surface modified silicon dioxide and a solvent lactone compound, wherein the adding amount of the solvent is 50-900% of the mass of the silicon dioxide hydrosol, and distilling to remove water to obtain a silicon dioxide lactone sol;
wherein, the number of hydroxyl groups on the surface of each square nanometer of the surface modified silicon dioxide is less than 3, and the particle size of the surface modified silicon dioxide is 5-200 nm.
8. The aluminum electrolytic capacitor electrolyte of claim 1, wherein the primary solvent is a lactone-based compound.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10241999A (en) * | 1997-03-03 | 1998-09-11 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
| JP2003203827A (en) * | 2003-02-12 | 2003-07-18 | Nippon Chemicon Corp | Electrolytic solution for electrolytic capacitor |
| CN103897435A (en) * | 2014-03-30 | 2014-07-02 | 苏州奈微纳米科技有限公司 | Surface modified silicon dioxide and preparation method thereof |
| CN104326477A (en) * | 2014-10-10 | 2015-02-04 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of ultra-high pure silica sol for capacitor |
| CN106414328A (en) * | 2014-06-03 | 2017-02-15 | Az电子材料（卢森堡）有限公司 | Method for producing surface-modified silica nanoparticles, and surface-modified silica nanoparticles |
| WO2020027124A1 (en) * | 2018-08-01 | 2020-02-06 | 日本ケミコン株式会社 | Electrolytic solution for electrolytic capacitor, and electrolytic capacitor |
-
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- 2020-04-15 CN CN202010296097.0A patent/CN113539689B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10241999A (en) * | 1997-03-03 | 1998-09-11 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
| JP2003203827A (en) * | 2003-02-12 | 2003-07-18 | Nippon Chemicon Corp | Electrolytic solution for electrolytic capacitor |
| CN103897435A (en) * | 2014-03-30 | 2014-07-02 | 苏州奈微纳米科技有限公司 | Surface modified silicon dioxide and preparation method thereof |
| CN106414328A (en) * | 2014-06-03 | 2017-02-15 | Az电子材料（卢森堡）有限公司 | Method for producing surface-modified silica nanoparticles, and surface-modified silica nanoparticles |
| CN104326477A (en) * | 2014-10-10 | 2015-02-04 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of ultra-high pure silica sol for capacitor |
| WO2020027124A1 (en) * | 2018-08-01 | 2020-02-06 | 日本ケミコン株式会社 | Electrolytic solution for electrolytic capacitor, and electrolytic capacitor |
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