CN116376431A - Self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide and preparation method and application thereof - Google Patents

Self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide and preparation method and application thereof Download PDF

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CN116376431A
CN116376431A CN202310310446.3A CN202310310446A CN116376431A CN 116376431 A CN116376431 A CN 116376431A CN 202310310446 A CN202310310446 A CN 202310310446A CN 116376431 A CN116376431 A CN 116376431A
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self
repairing
molybdenum sulfide
hydrophobic
super
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史继富
吴金磊
杨志源
陈泽鑫
陈铭创
蔡婉珠
吴忠珏
郑旭
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Jinan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
    • H01G2/10—Housing; Encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides

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Abstract

The invention discloses a self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide and a preparation method and application thereof. According to the invention, the self-repairing super-hydrophobic protective packaging composite coating with ultraviolet light response is formed by taking the organic silica gel with the two-dimensional flaky molybdenum sulfide modified by the amino acid or the coupling agent as a substrate and taking the titanium dioxide super-hydrophobic coating with ultraviolet light response as a surface layer. According to the invention, the self-repairing super-hydrophobic mode is adopted for packaging the tantalum capacitor for the first time, innovation is realized in principle, the influence on the internal structure of the tantalum capacitor is very small, the yield is improved obviously, and the service life can reach more than 12 years according to the ageing experiment result.

Description

Self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide and preparation method and application thereof
Technical Field
The invention belongs to the field of electronic device packaging, and particularly relates to a self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide, and a preparation method and application thereof.
Background
Power electronics technology is increasingly important in the fields of power generation, distribution and utilization. Since more than 70% of the power is handled by the power electronics, the reliability of the power electronics is important, and among all electronic components, the capacitor is the weakest in terms of fault level and service life. Different types of capacitors to meet different electrical, thermal and mechanical constraints associated with their use. Thus, there are three different types of capacitors that can meet all user requirements: ceramics, films and electrolytic capacitors. The electrolytic capacitor has higher volume ratio capacitance, so the electrolytic capacitor is widely applied to the power electronics field and is mainly used for filtering and energy storage. The tantalum capacitor is used as one of electrolytic capacitors, has the advantages of small volume, large capacity, stable electrical property and high reliability, has stable market share and performance advantage in the field of high-end capacitors, and has better stability, wider working temperature range and longer service life than other capacitors. The solid tantalum capacitor anode is formed by sintering tantalum powder, and is led out by tantalum wires, ta 2 O 5 The cathode is PEDOT polymer or MnO as a dielectric layer 2 And bonding the capacitor with the negative electrode through graphite and silver paste, and finally molding an epoxy shell to protect the internal structure of the capacitor.
Although tantalum capacitors are encapsulated with an epoxy shell, moisture can still invade the device interior and cause the stability of the tantalum capacitor to be reduced, and people usually start from the internal structure of the capacitor based on the protection of the tantalum capacitor. PEDOT: residual ions in the PSS electrode cause accumulation of dielectric-cathode interface charges, so that an additional water washing process is required to improve the stability of the capacitor after each dispersion impregnation step; PEDOT treated by glycol is used for PSS electrode, ESR value and capacitance frequency performance are obviously improved, and leakage current of the capacitance is also obviously reduced; the PEDOT-PSS electrode after annealing and cooling is coated with a moisture protection layer, so that the capacitance of the moisture protection layer is improved to a certain extent in terms of moisture resistance and solvent resistance. The different dielectric thicknesses have a greater difference in the effect on tantalum capacitance, and thicker dielectric film capacitances generally behave more stably than thinner dielectric film capacitances. The high temperature characteristic of the tantalum capacitor is also a bottleneck for limiting the wide application of the capacitor, the temperature limitation of 105 ℃ is generally adopted internationally at present, and the temperature limitation of the tantalum capacitor can be increased to 125 ℃ through the shielding and pretreatment of dielectrics, the treatment of organic solid dielectrics and the improvement of an encapsulation layer.
These protection methods have good effects, but these methods are applied to the inside of the capacitor, so the influence on the capacitor itself needs to be carefully considered. However, repackaging the epoxy housing can avoid this effect. The super-hydrophobic phenomenon of lotus leaves is inspired, and the super-hydrophobic coating is applied to the field of tantalum capacitor packaging, but the durability of the super-hydrophobic coating is a practical problem which is very concerned by people. In recent years, materials from repair are receiving more and more attention, and when the materials are damaged, the materials can automatically repair physical damage under external stimuli such as heat, light, solvents and the like. In order to meet the demands of the super-hydrophobic material for use in different environments and prolonging the service life, the combination of the self-repairing function and the super-hydrophobic surface can obviously improve the service life of the coating. Therefore, a self-repairing hydrophobic coating based on tantalum capacitor packaging is designed and prepared, and the hydrophobic coating with the self-repairing function is applied to the surface of the epoxy shell.
Meanwhile, we also pay attention to two-dimensional flaky molybdenum disulfide, which has superior electronic, optical and mechanical properties, so that the molybdenum disulfide is paid attention to by scientific researchers. The edge positions and the plane positions of the molybdenum disulfide nano-sheets are different in polarity, the edge shows hydrophilicity, and the plane positions are hydrophobic. The self-repairing super-hydrophobic modified molybdenum disulfide packaging material is designed and prepared by introducing modified flaky molybdenum disulfide with an amino acid modified edge position on the basis of the original self-repairing coating.
Disclosure of Invention
In order to overcome the defects and the shortcomings of the prior art, the primary aim of the invention is to provide a preparation method of a self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide. Therefore, we propose an efficient tantalum capacitor packaging mode: modified two-dimensional flaky molybdenum disulfide is introduced, and the special structural property of the modified two-dimensional flaky molybdenum disulfide can effectively block water vapor, so that the protective performance of the coating is further improved.
The second aim of the invention is to provide the self-repairing super-hydrophobic protective packaging composite coating based on the two-dimensional molybdenum sulfide, which is prepared by the preparation method, wherein the water contact angle of the composite coating is less than or equal to 120 degrees, and the organic silica gel can be decomposed into small molecules with surface energy to be diffused to the surface of the coating by using ultraviolet irradiation for seconds, so that the surface energy of the surface layer is reduced, and self-repairing is performed.
The third purpose of the invention is to provide the application of the self-repairing super-hydrophobic protective packaging composite coating based on the two-dimensional molybdenum sulfide.
The primary purpose of the invention is realized by the following technical scheme:
a preparation method of a self-repairing super-hydrophobic protective packaging coating based on two-dimensional molybdenum sulfide comprises the following steps:
(1) Preparation of superhydrophobic solution: dissolving titanium dioxide in an organic solvent containing perfluorinated silane to obtain a super-hydrophobic solution;
(2) Modified molybdenum disulfide (MoS) 2 ) Is prepared from the following steps: preparing amino acid or coupling agent water solution, magnetically stirring, vacuum filtering, and drying the precipitate to obtain modified molybdenum disulfide (MoS) 2 )；
(3)Contains modified molybdenum disulfide (MoS) 2 ) Is prepared from the organic silicon solution: the modified molybdenum disulfide (MoS) prepared in the step (2) is treated 2 ) Mixing with organic silica gel, stirring at room temperature to obtain modified molybdenum disulfide (MoS) 2 ) Is a silicone solution of (a);
(4) Uniformly spraying the organic silicon solution containing the modified molybdenum disulfide in the step (3) on the surface to be sprayed, heating and forming, uniformly spraying the super-hydrophobic solution in the step (1), standing at room temperature, and after the organic solvent volatilizes, preparing the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide.
Preferably, the mass ratio of the titanium dioxide to the organic solvent in the step (1) is (1-5): 100; the mass ratio of the perfluorinated silane to the organic solvent is (1-10): 100.
Preferably, the titanium dioxide in step (1) is anatase; the perfluoro silane is 1H,2H perfluoro octyl trimethoxy silane, 1H,2H perfluoro octyl triethoxy silane any one of 1H,2H perfluoro dodecyl trimethoxy silane, the organic solvent is any one of ethanol, acetone, ethyl acetate and butyl acetate.
Preferably, the amino acid in the step (2) is any one of aspartic acid, lysine, alanine, tryptophan, proline and glutamic acid; or, the coupling agent is any one of KH550, KH540, KH792 and KH 602.
Preferably, the drying temperature in the step (2) is 60-100 ℃ and the drying time is 6-12h.
Preferably, the modified molybdenum disulfide (MoS) in step (3) 2 ) The addition mass of the catalyst is 0.5 to 2 percent of that of the organic silica gel.
Preferably, the organic silica gel in the step (3) is polysiloxane with a silicon-oxygen bond (-Si-O-Si-) as a framework.
Preferably, the heating temperature in the step (4) is 50-100 ℃, and the heating time is 1-6h.
The second object of the invention is achieved by the following technical scheme:
a self-repairing super-hydrophobic protective packaging coating based on two-dimensional molybdenum sulfide is prepared by the preparation method.
The third object of the invention is achieved by the following technical scheme:
an application of a self-repairing super-hydrophobic protective packaging coating based on two-dimensional molybdenum sulfide in a tantalum capacitor.
Specifically, the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide is applied to the surface of the tantalum capacitor epoxy shell.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the current common encapsulation method for the epoxy shell of the electronic device, the method for encapsulating the epoxy shell of the electronic device has the advantages that the self-repairing super-hydrophobic protection encapsulation coating based on the two-dimensional molybdenum sulfide is adopted for encapsulating the epoxy shell for the first time, which is not reported in the prior literature and patents, and the modified titanium dioxide surface layer and the organic silica gel have excellent hydrophobicity, so that the self-repairing super-hydrophobic protection encapsulation coating based on the two-dimensional molybdenum sulfide is applied to the tantalum capacitor and has very good protection sealing performance.
(2) When the surface energy of the coating is increased after a certain time or damage, the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide prepared by the invention irradiates the surface layer by ultraviolet light, and due to the photoresponse effect of titanium dioxide, the organic silica gel at the bottom layer is decomposed into small molecules with low surface energy and is diffused to the surface layer, so that the surface energy of the coating is reduced, and the good hydrophobic protective property of the coating is maintained.
(3) According to the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide, the flaky two-dimensional molybdenum disulfide is added during preparation, and because the flaky two-dimensional molybdenum disulfide has the characteristics of middle hydrophobicity and edge hydrophilicity, the amino acid is used for modifying the molybdenum disulfide to change the edge characteristics of the flaky two-dimensional molybdenum disulfide from hydrophilicity to hydrophobicity; the modified molybdenum disulfide is added into the organic silica gel, and because of the special two-dimensional flaky structure of the molybdenum disulfide, the path of water vapor invasion can be greatly prolonged, so that the hydrophobic protection of the coating can be further improved.
(4) According to the invention, the self-repairing super-hydrophobic protective packaging coating is adopted for packaging the tantalum capacitor for the first time, innovation is realized in principle, the influence on the internal structure of the tantalum capacitor is very small, the yield is improved obviously, and the service life of the tantalum capacitor can reach more than 12 years by coating the self-repairing super-hydrophobic protective packaging coating according to the ageing experiment result.
Drawings
FIG. 1 is a schematic diagram of a tantalum capacitor encapsulated by a self-repairing super-hydrophobic protective encapsulation coating based on two-dimensional molybdenum sulfide prepared by the invention;
FIG. 2 is a graph showing the effect of the amount of perfluorosilane added in example 2 on the wettability of a two-dimensional molybdenum sulfide-based self-repairing superhydrophobic protective encapsulation coating;
FIG. 3 is a graph showing water contact angles of the blank, silicone gel and pva groups of example 3 at different illumination times;
fig. 4 (a) and 4 (b) are SEM images of molybdenum disulfide, fig. 4 (c) is an SEM image of modified molybdenum disulfide organosilica gel, and fig. 4 (d) is an SEM image of molybdenum disulfide organosilica gel;
FIG. 5 shows the surface morphology of the blank, the silicone gel and the PVA coating of example 5 before and after irradiation, wherein FIG. 5 (a) shows an SEM image before irradiation of the blank, FIG. 5 (b) shows an SEM image after irradiation of the blank, FIG. 5 (c) shows an SEM image before irradiation of the silicone gel, FIG. 5 (d) shows an SEM image after irradiation of the silicone gel, FIG. 5 (e) shows an SEM image before irradiation of the PVA group, and FIG. 5 (f) shows an SEM image after irradiation of the PVA group;
FIG. 6 is an FTIR spectrum analysis before and after illumination of the surface coatings of the blank, silicone gel and PVA groups described in example 6;
FIG. 7 is the tantalum capacitance acceleration test parameters (before illumination) for the blank, silicone gel, and PVA groups described in example 7;
FIG. 8 is the tantalum capacitance acceleration test parameters (after illumination) for the blank, silicone gel, and PVA groups described in example 8;
FIG. 9 is a FTIR spectrum of alanine, lysine and aspartic acid modified molybdenum disulfide described in example 9;
FIG. 10 is a Raman spectrum of alanine, lysine and aspartic acid modified molybdenum disulfide described in example 10;
fig. 11 is a graph showing the effect of the amount of modified molybdenum disulfide added on the protective properties of tantalum capacitors described in example 11.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
The titanium dioxide powder was dissolved in an organic solvent of 1H,2H perfluorooctyltriethoxysilane in a ratio of 1:100 to the organic solvent to give a superhydrophobic solution, 2mmol of amino acid (lysine, aspartic acid, alanine) and 12.5mmol of MoS2 were added to 100ml of deionized water and stirred in a magnetic stirrer for 12 hours. The solution was filtered by vacuum filtration and the black precipitate was dried at 60℃for 12 hours. Then, three amino acid modified MoS were obtained 2 . Respectively adding 0.05 g, 0.1 g, 0.15 g and 0.2g of amino acid modified molybdenum disulfide (two-dimensional sheet) into a beaker containing 10g of organic silica gel, stirring for 1h at room temperature to obtain modified molybdenum disulfide organic silicon solution containing different proportions, uniformly spraying 2mL of modified molybdenum disulfide organic silicon solution on a tantalum capacitor epoxy shell, and heating at 50 ℃ for 10h; after the organic silica gel is heated and molded, 2mL of super-hydrophobic solution is taken and evenly sprayed on the surface of the organic silica gel, and then the organic silica gel is placed at room temperature for 24 hours, so that the encapsulation is completed after the organic solvent is completely volatilized, and the tantalum capacitor containing the self-repairing super-hydrophobic protective encapsulation coating based on the two-dimensional molybdenum sulfide is prepared.
Example 2
In order to explore the influence of the addition of perfluorosilane on the wettability of the superhydrophobic coating, comparative experiments of different proportions were set up. As can be seen from FIG. 2, when M Titanium dioxide ：M Perfluoro silane When the ratio is 1:3, the prepared self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide has optimal wettability, a proper amount of perfluorinated silane is used for modifying titanium dioxide to maximize the coating performance, if less fluorinated silane is used for modification, the surface energy of the surface layer is lower, the super-hydrophobic performance is not enough to be achieved, and if excessive fluorinated silane is used for modification, insufficient dissolution of an organic solvent is caused, so that the hydrophobicity of the coating is reduced.
Example 3
To facilitate the test characterization, all experimental coatings were applied to the glass substrate and the loss of the coating was simulated by uv irradiation. In order to compare with the performance of the organosilicon substrate, a blank group and a PVA group are arranged in the experiment, the organosilicon group and the PVA group are embedded with an organosilicon coating and a PVA coating between the substrate and the titanium dioxide coating, and the blank group is directly coated with a super-hydrophobic coating on the tantalum capacitor epoxy shell.
As can be seen from fig. 3, the titanium dioxide coating modified by 1h,2h perfluoro octyl triethoxysilane has good superhydrophobicity, the initial water contact angle is 161.3 °, under the irradiation of ultraviolet light, the electrons in the valence band of the titanium dioxide are excited to the conduction band, the electrons and holes migrate to the surface, electron-hole pairs are generated on the surface, the electrons react with titanium, and the holes react with surface oxo-ions to form trivalent titanium ions and oxygen vacancies respectively. At this time, water in the air is dissociated and adsorbed in the oxygen vacancies to become chemically adsorbed water, which can further adsorb moisture in the air to form a physical adsorption layer. With the increase of the illumination time, the hydrophobicity of the surface coating is reduced, and the hydrophobicity of the blank group and the PVA group is disappeared after 120s of ultraviolet light irradiation, but the water contact angle of the organic silica gel group is still kept at about 160 degrees, which indicates that the organic silica gel group still has good protection hydrophobicity after being damaged.
Example 4
FIGS. 4 (a) and 4 (b) are Mo synthesized by hydrothermal method S2 SEM images of (a). The SEM can observe that the synthesized molybdenum disulfide is a nanosphere composed of a plurality of nano sheets, the unique structure can be used for protecting the outer coating of the capacitor, and the laminated nano sheets can prolong the path of water vapor invasion to a limited extent, so that the function of prolonging the service life of a device is achieved.
Molybdenum disulfide is easy to agglomerate due to the action of Van der Waals force, and is not easy to disperse in a resin matrix, so that the wide application of the molybdenum disulfide in the composite material is limited. The molybdenum disulfide subjected to covalent modification through KH550 enables the surface of the nano-sheet to generate more active sites, so that the dispersibility of the nano-sheet and a matrix can be increased. The dispersibility of the functionalized molybdenum disulfide in the organic silicon is far better than that of the molybdenum disulfide in the organic silicon, and as shown in fig. 4 (c) and 4 (d), the modified molybdenum disulfide can be uniformly dispersed in the organic silicon matrix.
Example 5
As shown in FIGS. 5 (a) to 5 (f) which show the surface morphology of the coating of the blank group, the organic silica gel group and the PVA group before and after illumination, it can be seen that the coating is mainly composed of TiO before ultraviolet illumination 2 Large particles formed by agglomeration are piled up to form a large number of air pockets, resulting in a rough surface. After ultraviolet light irradiation, the surface morphology of the blank group and the PVA group is not changed too much, which indicates that the influence of the surface morphology of the composite structure on the wettability is relatively weak. The surface of the organic silica gel group is dense due to the fact that air pockets are filled with upwards-diffused small molecules to different degrees, but the surface of the organic silica gel group is rough, and the upwards-diffused small molecules are supposed to be low-surface-energy small molecules formed by decomposing organic silica gel.
Example 6
To confirm the composition of these upwardly diffusing small molecules in example 5, we performed fourier transform infrared spectroscopy (FTIP). The spectra before and after illumination of the surface coating of the blank group, the silicone gel group and the PVA group are sequentially analyzed as shown in fig. 6. Wherein the wettability of the coating surface changes from hydrophobic to hydrophilic after 120S of illumination, 1238cm -1 、1200cm -1 、1147cm -1 The peak represents the stretching vibration peak of the fluorocarbon bond, and the intensity of the stretching vibration peak of the fluorocarbon bond is greatly reduced after illumination. The organic silica gel group can detect 2962cm on the surface layer after illumination -1 、1256cm -1 、1064cm -1 And 1014cm -1 These three represent silicone C-H, CH _3 And Si-O characteristic peaks, confirming that the upwardly diffusing small molecules belong to the organosilicon. When the surface energy of the coating is increased due to damage, the upward-diffused small molecules can timely reduce the surface energy, so that the hydrophobicity of the coating can be better kept. Wherein Si-O and CH _2 A slight blue shift occurs, which is the decomposition of the organosilicon small molecules with the surface TiO 2 The interaction between them resulting from the interactionOnly the physical filling and no chemical reaction takes place. 3370cm -1 、1639cm -1 The hydroxyl vibration peak of PVA is not detected after illumination, which indicates that PVA with a composite structure cannot diffuse to the surface layer.
Example 7
Tantalum capacitors have four important parameters, namely leakage current, capacitance, loss factor and ESR. When device performance decreases or fails, the rate of change of the device parameters increases accordingly. The change rate of four parameters of the tantalum capacitor after the double 85 test is shown in fig. 7, wherein leakage current is a parameter of interest to people, and the blank group, the blank group and the PVA group are not as good as the organosilicon group in the protection performance of the device, and secondly, the PVA is hydrophilic, so that when the moisture absorbed by the PVA is not saturated before 764h, the environment facing the device is worse than that of the blank group, and when the PVA absorbs water and is saturated, the influence on the parameters of the device is larger than that of the blank group. The three experimental groups did not differ much in terms of the rate of change of capacitance. The loss factor change rate and ESR value change rate of the device are similar to the leakage current change rate, the protection of the organic silicon group on the device is superior to that of a blank group and a pva group, and the influence on the device parameters after the pva group is saturated by water absorption is larger than that of the blank group.
Example 8
As shown in fig. 8, the silicone is decomposed into small molecules with low surface energy after illumination and diffuses to the surface layer, thereby preventing the surface layer from being further damaged. After the acceleration experiment of 1004h, the protective performance of the organosilicon group is still twice as high as that of the blank group in terms of the leakage current change rate. The loss factor change rate and the ESR value change rate are smaller than the device parameters before illumination, so that the protection performance of the device after illumination of the coating is improved.
Example 9
Modification of MoS with alanine, lysine and aspartic acid 2 Respectively called Ala-MoS 2 、Lys-MoS 2 And Asp-MoS 2 . The original MoS is given as shown in FIG. 9 2 Sample and modified MoS 2 FTIR spectra of the samples. From the spectrum, the Ala-MoS 2 、Lys-MoS 2 And Asp-MoS 2 Three modified MoS 2 Peaks of molybdenum sulfide bonds (467 cm) -1) At the same time, an amino group unique to the amino acid was also detected (1610 cm -1 ) Prove that all three amino acids are successfully grafted to MoS _2 And (3) upper part.
Example 10
As shown in FIG. 10, we modified MoS for alanine, lysine and aspartic acid _2 Raman spectroscopy characterization was performed. MoS for three amino acid blots _2 ,A 1g The mode stays at 402cm -1 While
Figure BDA0004148240860000081
Mode transition to 373cm -1 This may be amino acids and MoS 2 The polar attraction between the edges.
Example 11
The self-repairing hydrophobic coating of the functional molybdenum disulfide based on tantalum capacitor packaging is prepared by introducing the functional flaky molybdenum disulfide with the edge position modified by amino acid on the basis of the original self-repairing coating, so that the hydrophobicity and mechanical property of the coating are effectively improved. We set the addition amounts of different proportions, and from FIG. 11, it can be seen that the performance is optimal when the addition amount of modified molybdenum disulfide is 1.5%. After the acceleration experiment for 1004h, the leakage current change rate of the tantalum capacitor is 75.9% at the minimum, and the protective performance is two thirds higher than that of the tantalum capacitor without adding modified molybdenum disulfide. The minimum change rate of the ESR value of the tantalum capacitor is 14.7%, and the protective performance is doubled compared with that of the tantalum capacitor without modified molybdenum disulfide. This indicates that the addition of modified molybdenum disulfide improves the overall performance of the self-healing coating system.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide is characterized by comprising the following steps of:
(1) Preparation of superhydrophobic solution: dissolving titanium dioxide in an organic solvent containing perfluorinated silane to obtain a super-hydrophobic solution;
(2) Preparation of modified molybdenum disulfide: preparing an amino acid or coupling agent aqueous solution, magnetically stirring, vacuum filtering the solution, and drying the precipitate to obtain modified molybdenum disulfide;
(3) Preparation of modified molybdenum disulfide-containing organosilicon solution: mixing the modified molybdenum disulfide prepared in the step (2) with organic silica gel, and stirring at room temperature to obtain an organic silicon solution containing the modified molybdenum disulfide;
(4) Uniformly spraying the organic silicon solution containing the modified molybdenum disulfide in the step (3) on the surface to be sprayed, heating and forming, uniformly spraying the super-hydrophobic solution in the step (1), standing at room temperature, and after the organic solvent volatilizes, preparing the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide.
2. The preparation method of the self-repairing super-hydrophobic protective packaging coating based on two-dimensional molybdenum sulfide according to claim 1, wherein the mass ratio of titanium dioxide to organic solvent in the step (1) is (1-5): 100; the mass ratio of the perfluorinated silane to the organic solvent is (1-10): 100.
3. The method for preparing a two-dimensional molybdenum sulfide-based self-repairing superhydrophobic protective encapsulation coating according to claim 1, wherein the titanium dioxide in step (1) is anatase; the perfluoro silane is 1H,2H perfluoro octyl trimethoxy silane, 1H,2H perfluoro octyl triethoxy silane any one of 1H,2H perfluoro dodecyl trimethoxy silane, the organic solvent is any one of ethanol, acetone, ethyl acetate and butyl acetate.
4. The method for preparing the two-dimensional molybdenum sulfide-based self-repairing superhydrophobic protective packaging coating according to claim 1, wherein the amino acid in the step (2) is any one of aspartic acid, lysine, alanine, tryptophan, proline and glutamic acid; or, the coupling agent is any one of KH550, KH540, KH792 and KH 602.
5. The method for preparing the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide according to claim 1, wherein the drying temperature in the step (2) is 60-100 ℃ and the drying time is 6-12h.
6. The preparation method of the two-dimensional molybdenum sulfide-based self-repairing super-hydrophobic protective packaging coating, which is characterized in that the addition mass of the modified molybdenum disulfide in the step (3) is 0.5% -2% of that of organic silica gel.
7. The method for preparing the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide according to claim 1, wherein the organic silica gel in the step (3) is polysiloxane with a silicon-oxygen bond as a framework.
8. The preparation method of the self-repairing super-hydrophobic protective packaging coating based on the two-dimensional molybdenum sulfide according to claim 1, wherein the heating temperature in the step (4) is 50-100 ℃, and the heating time is 1-6h.
9. A self-repairing superhydrophobic protective packaging coating based on two-dimensional molybdenum sulfide, characterized in that the coating is prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the two-dimensional molybdenum sulfide-based self-repairing superhydrophobic protective encapsulation coating according to claim 9 in tantalum capacitors.
CN202310310446.3A 2023-03-28 2023-03-28 Self-repairing super-hydrophobic protective packaging composite coating based on two-dimensional molybdenum sulfide and preparation method and application thereof Pending CN116376431A (en)

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