[go: up one dir, main page]

CN119503816A - High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof - Google Patents

High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof Download PDF

Info

Publication number
CN119503816A
CN119503816A CN202311082452.4A CN202311082452A CN119503816A CN 119503816 A CN119503816 A CN 119503816A CN 202311082452 A CN202311082452 A CN 202311082452A CN 119503816 A CN119503816 A CN 119503816A
Authority
CN
China
Prior art keywords
preparation
resorcinol
microspheres
silicon dioxide
formaldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311082452.4A
Other languages
Chinese (zh)
Inventor
黄世俊
翟苏宇
陈凯
罗建峰
朱光明
兰永强
肖旺钏
陈家茂
陈欣鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHAXIAN HONGSHENG PLASTIC CO Ltd
Sanming University
Original Assignee
SHAXIAN HONGSHENG PLASTIC CO Ltd
Sanming University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHAXIAN HONGSHENG PLASTIC CO Ltd, Sanming University filed Critical SHAXIAN HONGSHENG PLASTIC CO Ltd
Priority to CN202311082452.4A priority Critical patent/CN119503816A/en
Publication of CN119503816A publication Critical patent/CN119503816A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1611—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Veterinary Medicine (AREA)
  • Physics & Mathematics (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention relates to the technical field of carbon materials, in particular to a high-purity superfine electronic grade silicon dioxide microsphere, a preparation method and application thereof. The preparation method comprises the steps of reacting resorcinol, formaldehyde and tetraethyl silicate in an alcohol-containing aqueous solution for 5-60 min at 45-80 ℃ in a surfactant-free system by taking ammonia water as a catalyst to obtain primary microspheres, and burning the primary microspheres in air to obtain high-purity superfine electronic grade silicon dioxide microspheres. The silicon dioxide microsphere provided by the invention has high-purity superfine characteristics and meets the requirements of electronic-grade application.

Description

High-purity superfine electronic grade silicon dioxide microsphere and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon materials, in particular to a high-purity superfine electronic grade silicon dioxide microsphere, a preparation method and application thereof.
Background
Silicon dioxide (SiO 2) is a nontoxic, odorless and pollution-free inorganic material, molecules are in a three-dimensional network structure, and a plurality of hydroxyl groups in different states exist on the surface of the silicon dioxide, so that the silicon dioxide has the characteristics of excellent dielectric property, low thermal expansion coefficient, high thermal conductivity and the like. The excellent physical properties, extremely high chemical stability and unique optical properties determine the special status of the polymer in the fields of aviation, aerospace, electronic information and the like, and the polymer has become the most basic, important and key raw material in many high-tech fields.
With the development of high-tech fields such as electronic industry, battery and energy storage, integrated circuits, optical fiber communication and the like, the demand for superfine silicon dioxide is also increasing, and higher requirements are also put forward for the content of impurities in the superfine silicon dioxide. There is also a great deal of research on the development of high purity ultrafine silica at home and abroad. Current research directions and related intellectual property have focused mainly on the following:
Firstly, high-quality high-purity quartz ore is used as a raw material, and high-purity or superfine silicon dioxide is obtained through processes such as acid washing purification, complexation, calcination or grinding, for example, patent CN201710367309.8, CN201610604327.9, CN201710367309.8 and the like;
And secondly, preparing silicon dioxide by a gas-phase method, such as CN201711123068.9 (chlorosilane vaporization combustion method), CN201811213512.0 (organosilicon slurry slag and siloxane mixed combustion method), CN201880005781.X (monochlorosilane or monosilane combustion method) and the like.
Thirdly, a method for removing metal ions at high temperature and high pressure by lime is developed based on a precipitation method, such as Tibetan medicine, but the method is high in operation difficulty and high in operation risk, wang Shengjin and the like adopt iron removing agents to reduce indissolvable ferric ions into ferrous ions which are easier to dissolve, and complex with EDTA to achieve the purpose of removing iron, but other metal ions are difficult to remove by the method, and the fineness of a product cannot meet the requirements. In addition, team personnel in the research center of the supergravity engineering of Beijing university also research the process for preparing nano silicon dioxide by the supergravity method, but the industrialized production is difficult at present.
Fourthly, a sol-gel method is reported as patent CN201610329438.3, but the microsphere prepared by the method has a single structure and larger particle size, and patent CN201611114914.6 dissolves end siloxane polyether into ethanol solution of ammonia water, then orthosilicate is added and stirred uniformly, a hydrothermal method is adopted to react at 100-120 ℃ to obtain a monodisperse submicron-sized silica microsphere dispersion liquid, and the dispersion liquid is fired under the protection of inert atmosphere at 650-700 ℃ to obtain the monodisperse submicron-sized silica microsphere, wherein the microsphere has a single pore structure and has a micron particle size.
The pore structure and the morphology structure of the silica microspheres prepared by other prior patents are single, the particle size is large, and the electronic-grade requirement is difficult to meet.
Disclosure of Invention
The invention aims to solve the technical problems of providing the high-purity superfine electronic grade silicon dioxide microsphere which meets the electronic grade requirement and further provides the preparation method and the application of the silicon dioxide microsphere.
In order to solve the technical problems, the invention provides a preparation method of high-purity superfine electronic grade silicon dioxide microspheres, which comprises the steps of taking ammonia water as a catalyst in a surfactant-free system, reacting resorcinol, formaldehyde and tetraethyl silicate in an alcohol-containing aqueous solution at 45-80 ℃ for 5-60 min to obtain primary microspheres, and burning the primary microspheres in air to obtain the high-purity superfine electronic grade silicon dioxide microspheres.
Further provides the high-purity superfine electronic grade silicon dioxide microsphere prepared by the preparation method.
Further provided are applications of the silica microspheres in preparing electronic packages, integrated circuits, copper-clad plates, battery separators, electrolytes, electrode materials, molding compounds, adsorption materials, drug transporters or catalysts.
The invention has the beneficial effects that under the condition of no surfactant, the high-purity superfine silica combined by shell and core mesopores/micropores can be prepared, the preparation efficiency is high, the process flow and the operation are simple and convenient, the mesoporous outer shell is beneficial to the adsorption and the entry of substances, the microporous inner shell is beneficial to the storage and the slow release of the substances, the flow speed of the substances is controlled, and the prepared silica has good application effects in the fields of electronic appliances, batteries, medicine operation and the like.
Drawings
FIG. 1 is a TEM photograph of silica microspheres prepared in example 1 of the present invention;
FIG. 2 is a TEM photograph of silica microspheres prepared according to comparative example 1 of the present invention.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments in conjunction with the accompanying drawings.
The preparation method of the high-purity superfine electronic grade silicon dioxide microsphere comprises the steps of reacting resorcinol, formaldehyde and tetraethyl silicate in an alcohol-containing aqueous solution for 5-60 min at 45-80 ℃ in a surfactant-free system by taking ammonia water as a catalyst, and burning the primary microsphere in air to obtain the high-purity superfine electronic grade silicon dioxide microsphere, wherein the high-purity superfine electronic grade silicon dioxide microsphere comprises an inner layer with a micropore structure and an outer layer with a mesoporous structure.
In this embodiment, the reaction temperature is increased to 45-80 ℃ to accelerate the balling rate, and the time difference between hydrolysis/condensation of resorcinol and TEOS (tetraethyl silicate) and precipitation of particles is reduced to reduce the time ratio of homogeneous nucleation of TEOS, so as to promote the co-assembly of the TEOS hydrolysis condensation product and resorcinol/formaldehyde condensation product, i.e. the core-shell microspheres of silica coated phenolic resin/silica (i.e. the aforementioned primary microspheres), and further firing treatment is performed to form high-purity ultrafine electronic grade silica microspheres. That is, in this embodiment, since the phenolic resin is a condensation product of resorcinol and formaldehyde, which is co-assembled with silica (TEOS hydrolysis condensation product) on a core silica formed of TEOS homogeneous phase, the phenolic resin is removed during the subsequent firing to form the mesoporous structure of the outer layer, that is, the phenolic resin is a pore-forming agent formed of the mesoporous structure of the outer layer.
In a specific process, in a system of water, alcohol and ammonia water, the tetraethyl silicate can be rapidly hydrolyzed to form monodisperse silica microspheres, but the microspheres are mainly of a microporous structure, so that the application of the microspheres as electrode materials, electronic packaging and the like is limited. Therefore, the inventor designs a method for obtaining the silicon dioxide microsphere with the mesoporous structure by taking phenolic resin as a pore-forming template in a surfactant-free system. However, since the hydrolysis condensation rate of tetraethyl silicate is generally significantly higher than that of resorcinol-formaldehyde, if tetraethyl silicate, resorcinol and formaldehyde are added together into the water, alcohol and ammonia water system, tetraethyl silicate will be rapidly hydrolyzed and condensed to form silica microspheres, when resorcinol and formaldehyde are condensed until a sufficient amount of phenolic resin particles are precipitated, tetraethyl silicate in the system has been substantially reacted to form silica microspheres, phenolic resin particles can only be coated on the surface of silica individually to form phenolic resin coated silica microspheres, and the phenolic resin with the surface layer removed by subsequent firing can only obtain solid microporous silica microspheres, and it is difficult to obtain core-shell structure silica microspheres with a composite mesoporous structure and microporous structure. Thus, in one embodiment, the co-assembly of the outer silica with the resorcinol-formaldehyde condensation product and deposition onto the core can be accomplished by sequential addition of resorcinol, formaldehyde, and tetraethyl silicate to control the hydrolytic condensation of the tetraethyl silicate to produce the core and the outer silica, and to control the timing of the formation of the resorcinol and formaldehyde condensation product.
Meanwhile, the research also finds that by increasing the reaction temperature, the balling speed can be increased, the rapid preparation is realized, and the condensation process of resorcinol and formaldehyde is very sensitive to temperature. As the reaction temperature increases, the difference in the hydrolysis condensation rate of tetraethyl silicate and the condensation rate of resorcinol-formaldehyde will gradually decrease, which will result in an increase in the concentration of tetraethyl silicate and its soluble condensation products in the later stages of the system. Therefore, when the phenolic resin formed by resorcinol-formaldehyde condensation is deposited on the surface of the inner core, the hydrolysis condensation product of the residual TEOS in the system is co-assembled with the condensation product of resorcinol-formaldehyde by a heterogeneous nucleation mechanism under the action of NH 4 + and coated on the surface of the inner core to form a core-shell structure, and after the phenolic resin template is removed by a subsequent firing process, a mesoporous structure is formed in the outer layer of the silica microsphere, and the inner layer (namely the inner core) of the silica microsphere forms a microporous structure. On this basis, it can be seen that the reaction temperature is raised to 45-80 ℃ which is a key factor in obtaining the desired high-purity ultrafine electronic grade silica microspheres. Meanwhile, the raw materials do not contain or contain trace metal ions, so that the prepared silicon dioxide microspheres have lower metal content and can effectively meet the electronic-grade requirements.
In the present application, micropores and mesopores are generally defined in the art, that is, pore structures having pore diameters smaller than 2nm formed on the silica microspheres are called microporous structures, and pore structures having pore diameters of 2 to 50nm are called mesoporous structures (or mesoporous structures).
In a preferred embodiment, the preparation method comprises the steps of:
S1, adding resorcinol into an aqueous solution containing alcohol, adding ammonia water, and uniformly stirring to obtain a solution A;
S2, adding formaldehyde and tetraethyl silicate into the solution A, and reacting for 5-60 min at a reaction temperature of 45-80 ℃;
s3, separating the turbid liquid, and drying the precipitate to obtain primary microspheres (silica coated silica/phenolic resin microspheres);
And S4, carbonizing the primary microspheres to obtain the high-purity superfine electronic grade silicon dioxide microspheres.
In an alternative embodiment, the firing is performed in air, and the firing condition is 600-1200 ℃ for 1-6 hours.
In one embodiment, the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, octanol, pentanol, hexanol, heptanol, decanol, ethylene glycol, glycerol, propylene glycol, pentaerythritol, preferably ethanol. The volume ratio of water to alcohol is 1 (2-10), preferably 1 (5-8).
In one embodiment, the formaldehyde is selected from paraformaldehyde or an aqueous formaldehyde solution, preferably an aqueous formaldehyde solution, and the molar ratio of formaldehyde to resorcinol is (1.5-2): 1. In this embodiment, the formaldehyde and resorcinol are used as condensation raw materials for the phenolic resin to form a mesoporous structure in the outer layer of the silica microspheres during firing by using the phenolic resin as a pore-forming template. In order to form a stable crosslinked structure, the molar ratio of aldehyde to phenol is preferably controlled to be >1, i.e., the final concentration of resorcinol in the alcoholic aqueous solution (the concentration of the aforementioned solution A) is preferably 2 to 100mg/mL. In this embodiment, since the condensation process of resorcinol and formaldehyde is very temperature sensitive, the phenolic resin and silica particles can be co-assembled and co-deposited on the surface of the core by increasing the reaction temperature to significantly accelerate the reaction temperature of resorcinol and formaldehyde to ensure that when the resorcinol-formaldehyde condensation product precipitates as an example, the reaction system still contains sufficient residual TEOS and its soluble condensate or monomer.
In one embodiment, the molar ratio of the tetraethyl silicate to the resorcinol is (0.5-20): 1, namely, the molar ratio of the tetraethyl silicate and the resorcinol is controlled so that the tetraethyl silicate can be rapidly hydrolyzed to form a silicon dioxide core at the reaction temperature of 45-80 ℃, the resorcinol and formaldehyde can be condensed to form phenolic resin, the phenolic resin can be assembled together with condensation product silicon dioxide of the residual tetraethyl silicate in the system and other soluble condensation products and is coated on the surface of the silicon dioxide core to form a core-shell microsphere structure of the silicon dioxide/phenolic resin coated silicon dioxide, and in the subsequent firing process, the phenolic resin on the outer layer of the core-shell structure is removed to form the high-purity superfine electronic grade silicon dioxide microsphere.
In one embodiment, the molar ratio of the ammonia water to the resorcinol is (2-20): 1. In this embodiment, the ammonia acts to reduce the surface polarity of the silica monomer in addition to catalysis, to achieve the process of co-assembling and co-cladding the silica monomer and phenolic resin to the silica core, forming a core-shell structure.
The high-purity superfine electronic grade silicon dioxide microsphere prepared by the preparation method is characterized in that the particle size of the silicon dioxide microsphere is less than or equal to 1000nm, and the metal ion content of the silicon dioxide microsphere is less than or equal to 100ppm, namely the prepared silicon dioxide microsphere has the characteristic of high purity superfine, wherein the lower metal ion content can obviously reduce the corrosion of the silicon dioxide microsphere to devices, improve the use safety and service life of the devices, and the lower particle size can effectively improve the distribution uniformity of the silicon dioxide microsphere in materials, and improve the mechanical property and the electrochemical property.
The silica microspheres are applied to the preparation of electronic packages, integrated circuits, copper-clad plates, battery separators, electrolyte, electrode materials, molding compounds, adsorption materials, drug transporters or catalysts. The silicon dioxide microsphere prepared by the method has a microporous structure and a mesoporous structure, so that when the silicon dioxide microsphere is used as a medicine operation body/adsorption material, the mesoporous structure is favorable for adsorption and entry of substances, the microporous structure is favorable for storage and slow release of the substances, the flow speed, the release speed and the like of the substances can be controlled, and the silicon dioxide microsphere can also be used as a silicon-based anode material for preparing a battery electrode, so that the battery capacity is improved. Just because of the abundant pore structure and the unique core-shell structure, the porous ceramic has application potential in a plurality of emerging fields.
Example 1
The preparation method of the silicon dioxide microsphere with the core-shell structure comprises the following steps:
S1, adding resorcinol into a water/alcohol system, adding ammonia water (25%), and uniformly stirring;
s2, adding formaldehyde and tetraethyl silicate, and reacting for 60min at the temperature of 45 ℃ to obtain turbid liquid;
S3, separating and drying the turbid liquid to obtain silica coated silica/phenolic resin microspheres;
S4, firing the microspheres in the air at 700 ℃ for 4 hours to obtain silicon dioxide microspheres, as shown in figure 1;
the volume ratio of the water to the alcohol is 1:7;
the molar ratio of the ammonia water to the resorcinol is 11:1;
the concentration of resorcinol in the solution is 5mg/mL;
The molar ratio of formaldehyde to resorcinol is 2:1;
The molar ratio of the tetraethyl silicate to the resorcinol is 3.4:1.
Through detection, the obtained silicon dioxide is of a shell-core structure, the inner layer is compact, the outer layer is loose, the average size of the silicon dioxide microsphere is about 135nm, the average mesoporous pore diameter is about 8nm, and the metal ion content is 52ppm. According to fig. 1, the product is spherical, has a core-shell structure, and has a compact inner layer and a loose outer layer.
Comparative example 1
The preparation method of the silicon dioxide microsphere with the core-shell structure comprises the following steps:
S1, adding resorcinol into a water/alcohol system, adding ammonia water (25%), and uniformly stirring;
S2, adding formaldehyde and tetraethyl silicate, and reacting for 24 hours at the temperature of 25 ℃ to obtain turbid liquid;
s3, separating and drying the turbid liquid to obtain silica coated phenolic resin microspheres;
s4, firing the microspheres in the air at 700 ℃ for 4 hours to obtain silicon dioxide microspheres, as shown in figure 2;
the volume ratio of the water to the alcohol is 1:7;
the molar ratio of the ammonia water to the resorcinol is 11:1;
the concentration of resorcinol in the solution is 5mg/mL;
The molar ratio of formaldehyde to resorcinol is 2:1;
The molar ratio of the tetraethyl silicate to the resorcinol is 3.4:1.
The detection shows that the silica microsphere has a solid structure, the average size is about 166nm, the pore diameter is mainly micropores, and the metal ion content is 60ppm. According to fig. 2, the product is spherical, uniform in inner and outer structure, compact and free of obvious core-shell structure.
Example 2
The preparation method of the silicon dioxide microsphere with the core-shell structure comprises the following steps:
s1, adding resorcinol into a water/alcohol system, adding ammonia water, and uniformly stirring;
s2, adding formaldehyde and tetraethyl silicate, and reacting for 30min at the temperature of 60 ℃ to obtain turbid liquid;
S3, separating and drying the turbid liquid to obtain silica coated silica/phenolic resin microspheres;
s4, firing the microspheres in the air at 700 ℃ for 4 hours to obtain silicon dioxide microspheres;
the volume ratio of the water to the alcohol is 1:7;
the molar ratio of the ammonia water to the resorcinol is 11:1;
the concentration of resorcinol in the solution is 5mg/mL;
The molar ratio of formaldehyde to resorcinol is 2:1;
the molar ratio of the tetraethyl silicate to the resorcinol is 4:1.
The average size of the silica microspheres was found to be about 108nm, the average mesoporous pore size was found to be about 14nm, and the metal ion content was found to be 53ppm.
Example 3
The preparation method of the silicon dioxide microsphere with the core-shell structure comprises the following steps:
s1, adding resorcinol into a water/alcohol system, adding ammonia water, and uniformly stirring;
s2, adding formaldehyde and tetraethyl silicate, and reacting for 60 minutes at a temperature of 60 ℃ to obtain turbid liquid;
S3, separating and drying the turbid liquid to obtain silica coated silica/phenolic resin microspheres;
s4, firing the microspheres in the air at 700 ℃ for 4 hours to obtain silicon dioxide microspheres;
the volume ratio of the water to the alcohol is 1:7;
the molar ratio of the ammonia water to the resorcinol is 11:1;
the concentration of resorcinol in the solution is 5mg/mL;
The molar ratio of formaldehyde to resorcinol is 2:1;
the molar ratio of the tetraethyl silicate to the resorcinol is 4:1.
The average size of the silica microspheres is about 112nm, the average mesoporous pore diameter is about 13nm, and the metal ion content is 48ppm.
Example 4
The preparation method of the silicon dioxide microsphere with the core-shell structure comprises the following steps:
s1, adding resorcinol into a water/alcohol system, adding ammonia water, and uniformly stirring;
S2, adding formaldehyde and tetraethyl silicate, and reacting for 30min at the temperature of 75 ℃ to obtain turbid liquid;
S3, separating and drying the turbid liquid to obtain silica coated silica/phenolic resin microspheres;
s4, firing the microspheres in the air at 700 ℃ for 4 hours to obtain silicon dioxide microspheres;
the volume ratio of the water to the alcohol is 1:7;
the molar ratio of the ammonia water to the resorcinol is 11:1;
the concentration of resorcinol in the solution is 5mg/mL;
The molar ratio of formaldehyde to resorcinol is 2:1;
the molar ratio of the tetraethyl silicate to the resorcinol is 4:1.
The average size of the silica microspheres was found to be about 83nm, the average mesoporous pore size was found to be about 15nm, and the metal ion content was found to be 49ppm.
In summary, the high-purity ultrafine silicon dioxide combined by shell, core and mesopores/micropores can be prepared under the condition of no surfactant, the preparation efficiency is high, the process flow and the operation are simple and convenient, the mesoporous shell is favorable for the adsorption and the entry of substances, the microporous inner shell is favorable for the storage and the slow release of substances, the flow speed of the substances is controlled, and the prepared silicon dioxide has good application effects in the fields of electronic appliances, batteries, medicine operation and the like, and particularly can be used as a silicon-based anode material for preparing battery electrodes, and the capacity of the battery is improved.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent changes made by the specification and drawings of the present invention, or direct or indirect application in the relevant art, are included in the scope of the present invention.

Claims (10)

1.高纯超细电子级二氧化硅微球的制备方法，其特征在于，在无表面活性剂体系中，以氨水为催化剂，间苯二酚、甲醛和硅酸四乙酯在含醇水溶液中，45～80℃反应5～60min，得初级微球；将所述初级微球在空气中灼烧获得高纯超细电子级二氧化硅微球。1. A method for preparing high-purity ultrafine electronic grade silica microspheres, characterized in that, in a surfactant-free system, with ammonia water as a catalyst, resorcinol, formaldehyde and tetraethyl silicate are reacted in an alcohol-containing aqueous solution at 45-80° C. for 5-60 minutes to obtain primary microspheres; the primary microspheres are burned in air to obtain high-purity ultrafine electronic grade silica microspheres. 2.根据权利要求1所述制备方法，其特征在于，所述高纯超细电子级二氧化硅微球包括具有微孔结构的内层，和具有介孔结构的外层。2. The preparation method according to claim 1, characterized in that the high-purity ultrafine electronic-grade silica microspheres include an inner layer with a microporous structure and an outer layer with a mesoporous structure. 3.根据权利要求1所述制备方法，其特征在于，所述醇选自甲醇、乙醇、丙醇、丁醇、辛醇、戊醇、己醇、庚醇、葵醇、乙二醇、丙三醇、丙二醇、季戊四醇中的至少一种。3. The preparation method according to claim 1, characterized in that the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, octanol, pentanol, hexanol, heptanol, hemptanol, ethylene glycol, glycerol, propylene glycol and pentaerythritol. 4.根据权利要求1所述制备方法，其特征在于，所述甲醛选自多聚甲醛或甲醛水溶液，所述甲醛与间苯二酚的摩尔比为(1.5～2)：1。4. The preparation method according to claim 1, characterized in that the formaldehyde is selected from paraformaldehyde or formaldehyde solution, and the molar ratio of formaldehyde to resorcinol is (1.5-2):1. 5.根据权利要求1所述制备方法，其特征在于，在所述含醇水溶液中，水与醇的体积比为1：(2～10)。5. The preparation method according to claim 1, characterized in that, in the alcohol-containing aqueous solution, the volume ratio of water to alcohol is 1:(2-10). 6.根据权利要求1所述制备方法，其特征在于，所述间苯二酚在所述含醇水溶液中的终浓度为2～100mg/mL。6. The preparation method according to claim 1, characterized in that the final concentration of the resorcinol in the alcohol-containing aqueous solution is 2 to 100 mg/mL. 7.根据权利要求1所述制备方法，其特征在于，所述氨水与间苯二酚的摩尔比为(2～20)：1。7. The preparation method according to claim 1, characterized in that the molar ratio of the ammonia water to resorcinol is (2-20):1. 8.根据权利要求1所述制备方法，其特征在于，所述硅酸四乙酯与间苯二酚的摩尔比为(0.5～20)：1。8. The preparation method according to claim 1, characterized in that the molar ratio of tetraethyl silicate to resorcinol is (0.5-20):1. 9.一种由权利要求1至8任一项所述制备方法所制备得到的高纯超细电子级二氧化硅微球，其特征在于，所述二氧化硅微球的粒径≤1000nm，所述二氧化硅微球的金属离子含量≤100ppm。9. A high-purity ultrafine electronic grade silica microsphere prepared by the preparation method according to any one of claims 1 to 8, characterized in that the particle size of the silica microsphere is ≤1000nm, and the metal ion content of the silica microsphere is ≤100ppm. 10.如权利要求9所述二氧化硅微球在制备电子封装体、集成电路、覆铜板、电池隔板、电解液、电极材料、模塑料、吸附材料、药物转运体或催化剂上的应用。10. Use of the silica microspheres as claimed in claim 9 in the preparation of electronic packaging, integrated circuits, copper-clad laminates, battery separators, electrolytes, electrode materials, molding compounds, adsorption materials, drug transporters or catalysts.
CN202311082452.4A 2023-08-25 2023-08-25 High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof Pending CN119503816A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311082452.4A CN119503816A (en) 2023-08-25 2023-08-25 High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311082452.4A CN119503816A (en) 2023-08-25 2023-08-25 High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN119503816A true CN119503816A (en) 2025-02-25

Family

ID=94665864

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311082452.4A Pending CN119503816A (en) 2023-08-25 2023-08-25 High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN119503816A (en)

Similar Documents

Publication Publication Date Title
TWI411575B (en) A non-thermofusible granular phenol resin and a method for producing the same, and a thermosetting resin composition, a filler for semiconductor and a bonding agent for a semiconductor (1)
CN105498821B (en) It is a kind of for composite material of catalytic degradation nitrogen oxides and its preparation method and application
Zhang et al. Recent advances in carbon nanospheres: synthetic routes and applications
CN104961121B (en) Preparation method of nitrogen-doped core-shell hollow carbon
KR101714096B1 (en) Porous carbon and method for producing the same
KR100551602B1 (en) HMC capsule structure containing metal nanoparticles in the hollow and its manufacturing method
Cui et al. Preparation of SiO 2 aerogel from rice husk ash
CN102923687A (en) Middle-pore carbon material and its preparation method
CN103183342A (en) Controllable synthesis method of phosphorus-doped graphitized carbon spheres with hollow structures
CN105350113B (en) A kind of preparation method and products obtained therefrom of azotized carbon nano fiber
CN107032321A (en) The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application
Xu et al. Synthesis of multiple Ag nanoparticles loaded hollow mesoporous carbon spheres for highly efficient and recyclable catalysis
CN101768351A (en) Method for preparing mesoporous nano particle-enhanced nylon composite material
Ma et al. Preparation of submicron monodisperse melamine resin microspheres and nitrogen-doped carbon microspheres derived from them
CN119503816A (en) High-purity ultrafine electronic grade silicon dioxide microspheres and preparation method and application thereof
DK201901553A1 (en) Vanadium-based catalyst and preparation method therefor
CN115155554A (en) A kind of nanometer hollow mesoporous carbon ball supported platinum nanoparticle catalyst and preparation method thereof
CN115072723B (en) Method for preparing nano silicon carbide by sol-gel method
CN115232620B (en) A method for preparing quantum dot aerogels through gelation induced by trace amounts of water
CN101462737A (en) Preparation of ordered mesoporous carbon material and Ir-containing composite material thereof
Zhang et al. Preparation of functionalized SiO2 microspheres by one step method
KR101215034B1 (en) Method of forming carbon nanocapsuleses
CN108726500A (en) A method of preparing porous carbon materials using bivalent metal ion soft template
CN118545725B (en) A preparation method of embedded silicon-carbon material
WO2015192731A1 (en) Silicon-based monobasic or multibasic oxide aerogel material and preparation method therefor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination