CN112011149A - High-dielectric quasicrystal composite material substrate and preparation method thereof - Google Patents
High-dielectric quasicrystal composite material substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high dielectric quasicrystal composite material which can be used as a high-temperature energy storage capacitor, a chemical sensor and a novel solid-state ionic electrolyte and a preparation method thereof. The high-dielectric quasicrystal composite material consists of one of Al65Cu23Fe12, Al70Pd21Mn9, Cd57Yb10 and Al63Cu24Fe13, sodium bismuth titanate with a composite perovskite structure and liquid graphene phenolic resin. The composite material substrate has the advantages of good mechanical property, light weight, easy processing, high dielectric constant and the like, and can be widely applied to the fields of high-temperature energy storage, chemical sensors and the like.
Description
Technical Field
The invention relates to a composite material substrate and a preparation method thereof, in particular to a high-dielectric quasicrystal composite material substrate and a preparation method thereof.
Background
A quasi-crystal, also known as a "quasicrystal" or "pseudocrystal," is a solid structure between a crystalline and an amorphous crystal, having an atomic arrangement of long range order similar to that of a crystal, but a quasi-crystal does not possess translational symmetry of a crystal, and may possess macroscopic symmetry not allowed by a crystal. Quasicrystals are unique in property, hard and elastic, and have poor electrical and thermal conductivity unlike most metals; has good thermoelectric effect, can convert electric energy into heat energy, and can prepare ideal thermoelectric materials. All hundreds of quasicrystals discovered before 2000 contained at least 3 metal elements, such as Al65Cu23Fe12, Al70Pd21Mn9, etc., but recently only 2 metal elements were found to form quasicrystals, such as Cd57Yb 10.
The perovskite material has the same crystal structure as calcium titanate (CaTiO3), the structural formula of the perovskite material is ABX3, A, B is positive ions, and X is negative ions, and the unique crystal structure enables the perovskite material to have a plurality of unique physicochemical properties, such as light absorption, electrocatalysis and the like. "Scientific Reports" journal 2015, volume 5, page 12699, paper Origin of organic giant differential performance in novel Perovsite: Bi0.5-xLaxNa0.5-xLixTi1-yMyO3(M is Mg2+ and Ga3+) reports that A/B co-doping modification design is carried out on Bi0.5Na0.5TiO3 ceramic with a perovskite structure, so that novel materials with extremely high dielectric constants are obtained, the extension of the perovskite material concept is greatly expanded, and the perovskite material has great application potential in the fields of high-temperature energy storage capacitors, chemical sensors, novel solid-state ion electrolytes and the like.
The Chinese patent with the publication number of CN103382240B discloses a barium titanate/polymer composite material with high dielectric constant and a preparation method thereof; the composite material comprises the following components in percentage by volume: the dielectric ceramic material comprises 1-60% of a mononuclear, 3-30% of an inner shell and 20-80% of an outer shell, wherein the mononuclear is barium titanate ceramic particles, the inner shell is polyamide with a high dielectric constant, and the outer shell is polymethyl methacrylate with a low dielectric constant. The invention also relates to a preparation method of the composite material, wherein the mononuclear in the composite material is firstly subjected to surface treatment by using aminosilane, an organic functional group is introduced, and then the aminosilane is sequentially dispersed into different monomer solutions to obtain the composite material with a core-shell covalent bond connection structure, and the composite material has the characteristics of high dielectric constant, low dielectric loss and uniform distribution of inorganic particles.
The existing high-dielectric composite material substrate has the following problems: (1) is fragile, difficult to process and poor in mechanical property; (2) insufficient heat resistance and low peeling strength at high temperature; (3) the preparation conditions are strict, and the requirements on equipment, process and operating environment are high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-dielectric quasicrystal composite material which can be used as a high-temperature energy storage capacitor, a chemical sensor and a novel solid-state ionic electrolyte, and a preparation method thereof.
In order to realize the purpose of the invention, the following technical scheme is adopted: a high-dielectric quasicrystal composite material substrate is formed by compounding a quasicrystal material, a composite perovskite material and resin, and is characterized in that the quasicrystal material is used as a reinforcing phase, the composite perovskite material is used as a functional phase, the resin is used as a base material, the quasicrystal material accounts for 5-10% by mass, the composite perovskite material accounts for 5-10% by mass, the resin accounts for 80-90% by mass, the porosity of the substrate is less than 3%, the quasicrystal is one of Al65Cu23Fe12, Al70Pd21Mn9, Cd57Yb10 and Al63Cu24Fe13, the composite perovskite is sodium bismuth titanate, the resin is liquid graphene phenolic resin, and the content of graphene is 0.5-5% by mass.
The preparation method of the high-dielectric quasicrystal composite material is characterized by comprising the following steps in sequence:
(1) quenching an Al metal melt containing 50-55% of Cu and Fe or 55-60% of Pd and Mn or a Cd metal melt containing 20-25% of Yb by mass, converting the Al metal melt into metastable quasi-crystals by one step, and fully crushing and grinding the metastable quasi-crystals to obtain quasi-crystal powder with the average particle size of less than 100 nm;
(2) fully crushing and grinding sodium bismuth titanate with a composite perovskite structure to obtain perovskite powder with the average particle size of less than 100 nm;
(3) fully and uniformly mixing the quasi-crystal powder, the perovskite powder and the resin according to the mass proportion to obtain mixture slurry;
(4) and pouring the mixture slurry in a mold, drying and curing in a vacuum oven, and cooling to room temperature along with the furnace after heat preservation to obtain the quasi-crystal composite material.
Detailed Description
The present invention is further described in the following examples in connection with specific embodiments thereof, it is to be understood that these examples are intended only for the purpose of illustration and not as a definition of the limits of the invention, since various equivalent modifications of the invention will become apparent to those skilled in the art upon reading the present disclosure and are intended to be covered by the appended claims.
Example 1
A high-dielectric quasicrystal composite material substrate comprises 5% of Al65Cu23Fe12 quasicrystal, 5% of composite perovskite material, 90% of graphene phenolic resin, 1% of porosity and 1% of graphene in graphene phenolic. The preparation method of the high-dielectric quasicrystal composite material comprises the following steps:
(1) quenching Al metal melt containing 50% of Cu and Fe, converting the Al metal melt into metastable quasicrystal by one step, and fully crushing and grinding the metastable quasicrystal to obtain quasicrystal powder with the average grain diameter of less than 100 nm;
(2) fully crushing and grinding the sodium bismuth titanate with the composite perovskite structure, wherein the average particle size is 80 nm;
(3) fully and uniformly mixing the quasi-crystal powder, the perovskite powder and the resin according to the mass proportion to obtain mixture slurry;
(4) and pouring the mixture slurry in a mold, drying and curing in a vacuum oven, and cooling to room temperature along with the furnace after heat preservation to obtain the quasi-crystal composite material.
Through tests, the dielectric constant of the composite substrate at normal temperature is within 2300-5200, the degree of change along with temperature and frequency is small, the composite substrate is superior to data reported by the current published documents, and the composite substrate has remarkable novelty and practicability.
Example 2
A high-dielectric quasicrystal composite material substrate comprises 8% of Al70Pd21Mn9 quasicrystal, 5% of composite perovskite material, 87% of graphene phenolic resin, 1% of porosity and 1% of graphene in graphene phenolic. The preparation method of the high-dielectric quasicrystal composite material comprises the following steps:
(1) quenching Al metal melt containing 60 wt% of Pd and Mn, converting the Al metal melt into metastable quasicrystal by one step, and fully crushing and grinding the metastable quasicrystal to obtain quasicrystal powder with the average grain diameter of less than 100 nm;
(2) fully crushing and grinding the sodium bismuth titanate with the composite perovskite structure, wherein the average particle size is 80 nm;
(3) fully and uniformly mixing the quasi-crystal powder, the perovskite powder and the resin according to the mass proportion to obtain mixture slurry;
(4) and pouring the mixture slurry in a mold, drying and curing in a vacuum oven, and cooling to room temperature along with the furnace after heat preservation to obtain the quasi-crystal composite material.
Through tests, the dielectric constant of the composite substrate at normal temperature is within 2500-6000, the degree of change along with temperature and frequency is small, the degree of change is superior to data reported by the current published documents, and the composite substrate has remarkable novelty and practicability.
Example 3
A high-dielectric quasi-crystal composite material substrate is provided, wherein Cd57Yb10 quasi-crystal accounts for 10% by mass, a composite perovskite material accounts for 10% by mass, graphene phenolic resin accounts for 80% by mass, porosity is 2%, and graphene content in graphene phenolic is 2%. The preparation method of the high-dielectric quasicrystal composite material comprises the following steps:
(1) quenching Al metal melt containing 20 wt% of Pd and Mn, converting the Al metal melt into metastable quasicrystal by one step, and fully crushing and grinding the metastable quasicrystal to obtain quasicrystal powder with the average grain diameter of less than 70 nm;
(2) fully crushing and grinding sodium bismuth titanate Bi0.5Na0.5TiO3 with a composite perovskite structure to obtain a powder with an average particle size of 60 nm;
(3) fully and uniformly mixing the quasi-crystal powder, the perovskite powder and the resin according to the mass proportion to obtain mixture slurry;
(4) and pouring the mixture slurry in a mold, drying and curing in a vacuum oven, and cooling to room temperature along with the furnace after heat preservation to obtain the quasi-crystal composite material.
Through tests, the dielectric constant of the composite substrate at normal temperature is 3000-6000, the degree of change along with temperature and frequency is small, the degree of change is superior to data reported by the current published documents, and the composite substrate has remarkable novelty and practicability.
The above description is only three specific embodiments of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the protection scope of the present invention. Any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention, without departing from the content of the technical solution of the present invention, still belong to the protection scope of the technical solution of the present invention.
Claims (2)
1. A high-dielectric quasicrystal composite material substrate is formed by compounding a quasicrystal material, a composite perovskite material and resin, and is characterized in that the quasicrystal material is used as a reinforcing phase, the composite perovskite material is used as a functional phase, the resin is used as a base material, the quasicrystal material accounts for 5-10% by mass, the composite perovskite material accounts for 5-10% by mass, the resin accounts for 80-90% by mass, the porosity of the substrate is less than 3%, the quasicrystal is one of Al65Cu23Fe12, Al70Pd21Mn9, Cd57Yb10 and Al63Cu24Fe13, the composite perovskite material is sodium bismuth titanate, the resin is liquid graphene phenolic resin, and the content of graphene is 0.5-5% by mass.
2. A preparation method of a high dielectric quasicrystal composite material is characterized by comprising the following steps in sequence:
(1) quenching an Al metal melt containing 50-55% of Cu and Fe or 55-60% of Pd and Mn or a Cd metal melt containing 20-25% of Yb by mass, converting the Al metal melt into metastable quasi-crystals by one step, and fully crushing and grinding the metastable quasi-crystals to obtain quasi-crystal powder with the average particle size of less than 100 nm;
(2) fully crushing and grinding sodium bismuth titanate with a composite perovskite structure to obtain perovskite powder with the average particle size of less than 100 nm;
(3) fully and uniformly mixing the quasi-crystal powder, the perovskite powder and the resin according to the mass proportion to obtain mixture slurry;
(4) and pouring the mixture slurry in a mold, drying and curing in a vacuum oven, and cooling to room temperature along with the furnace after heat preservation to obtain the quasi-crystal composite material.
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