Ceramic composite material with superstructure laminated structure as well as preparation method and application of ceramic composite material

Abstract

The invention belongs to the field of a preparation technology and performance regulation and control of a ceramic composite material with a superstructure laminated structure, and discloses a ceramic composite material with a superstructure laminated structure as well as a preparation method and application of the ceramic composite material with the superstructure laminated structure. Comprising a negative dielectric layer and a positive dielectric layer, the negative dielectric layer and the positive dielectric layer are formed through lamination, and the ceramic composite material of the superstructure lamination structure has a double-layer lamination structure. The negative dielectric layer and the positive dielectric layer are laminated to form the double-layer laminated structure, the double-layer laminated structure has high dielectric constant and low loss capability, a simple, convenient and feasible new method is provided for preparation of the ceramic pulse capacitor, and by changing the element content of the material, the preparation efficiency of the ceramic pulse capacitor is improved. The dielectric property is effectively regulated and controlled; the prepared ceramic composite material with the superstructure laminated structure has important application value in the fields of pulse capacitors and the like.

Description

Technical Field

[0001] This invention belongs to the field of preparation technology and performance control of metalayered ceramic composite materials, specifically relating to a metalayered ceramic composite material, its preparation method and application. Background Technology

[0002] In recent years, with the trend of integration, miniaturization, and high frequency development of electronic components, higher requirements have been placed on the dielectric performance of ceramic pulse capacitors. In existing ceramic pulse capacitor designs, there is a coupling relationship between dielectric constant and loss; that is, a high dielectric constant is accompanied by high loss, and high loss will significantly reduce the efficiency of the pulse capacitor.

[0003] For example, the ceramic material disclosed in publication number CN113620696A has a dielectric constant range of 2750-3380, but its loss is relatively high, ranging from 1.2% to 3.2%. Typically, a loss tangent tanδ < 0.1 meets the requirements for capacitor use. For single-layer dielectric materials, achieving synergistic optimization of dielectric constant and dielectric loss faces significant challenges due to the mutual constraints of their intrinsic polarization mechanisms, inherent contradictions in their microstructure, and multi-scale defects.

[0004] Layered materials can achieve a certain degree of matching between dielectric constant and loss performance. At present, most layered materials are positive dielectric constant materials. For example, the dielectric constant of the layered positive dielectric constant materials in publication number CN120365052A is 4.1-5.8, but the loss is low, ranging from 0.0011% to 0.0016%. Therefore, neither of the above two materials meets the requirements of actual electronic components, that is, the need for high dielectric constant and low loss. Summary of the Invention To address the shortcomings of existing technologies, this invention provides a metalayered ceramic composite material, its preparation method, and its application. The aim is to effectively control its negative dielectric properties by changing the element content and the metalayer design, enabling the material to possess the advantages of high dielectric constant and low loss.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a metalayered ceramic composite material includes the following steps: The meta-layered ceramic composite material includes a negative dielectric layer and a positive dielectric layer, which are formed by stacking the negative dielectric layer and the positive dielectric layer, and the meta-layered ceramic composite material has a double-layered structure.

[0006] Preferably, both the positive dielectric layer and the negative dielectric layer are in sheet form.

[0007] Preferably, the negative dielectric layer is one of 25 wt% Ag / ZnO, 35 wt% Ag / ZnO, and 40 wt% Ag / ZnO; and the positive dielectric layer is one of ZnO, 10 wt% Ag / ZnO, and 20 wt% Ag / ZnO.

[0008] Preferably, the thickness of the negative dielectric layer is 1.1-1.3 mm; and the thickness of the positive dielectric layer is 1.8-2.1 mm.

[0009] Preferably, the metastructure stacked materials are ZnO-25 wt% Ag / ZnO, ZnO-35 wt% Ag / ZnO, ZnO-40wt% Ag / ZnO, 10 wt% Ag / ZnO-25 wt% Ag / ZnO, 10 wt% Ag / ZnO-35 wt% Ag / ZnO, 10 wt% Ag / ZnO-40 wt% One of Ag / ZnO, 20 wt% Ag / ZnO-25 wt% Ag / ZnO, 20 wt% Ag / ZnO-35 wt% Ag / ZnO, 20wt% Ag / ZnO-40 wt% Ag / ZnO.

[0010] Preferably, the meta-layered ceramic composite material is a double-layered structure with a negative dielectric layer on top and a positive dielectric layer on the bottom, or a double-layered structure with a positive dielectric layer on top and a negative dielectric layer on the bottom.

[0011] Preferably, the thickness of the meta-layered ceramic composite material is 3.000-3.500 mm.

[0012] Preferably, the positive dielectric layer / negative dielectric layer is prepared according to the following steps: The silver / zinc oxide or zinc oxide precursor powder is obtained by pre-calcining, grinding and granulating, pressing and molding and high-temperature sintering.

[0013] Preferably, the method for fabricating the positive dielectric layer / negative dielectric layer includes the following steps: S1. Take ZnO powder, Ag2O powder and combustion aid, ball mill, dry and pre-calcine, discard the combustion aid to obtain pre-calcineed ZnO powder and Ag2O powder, i.e. precursor powder; S2. PVA glue is added to the silver / zinc oxide precursor powder in step S1, and the powder is ground and granulated to obtain particles with quicksand characteristics; then it is ground and pressed to obtain sheet material. S3. The sheet material from step S2 is then sintered at high temperature to obtain the final product.

[0014] Preferably, in step S1, the total mass of ZnO powder and Ag2O powder is 30-35g; the combustion aid accounts for 2-3% of the mass fraction of ZnO powder; the ball milling conditions are as follows: anhydrous ethanol and milling beads are added to ZnO powder, Ag2O powder, Bi2O3 powder, and SiO2 powder for ball milling, and the amount of anhydrous ethanol added is 30-120mL; the diameter of the milling beads is 1-4mm; the mass is 30-100g; the ball milling time is 3-8h; the rotation speed of the ball mill is set to 300-800 rpm; the drying temperature is 80-150℃; the pre-calcination conditions are as follows: starting from room temperature, heating to 550℃ at 3.5℃ / min, holding for 2-2.5h, and then cooling down with the furnace.

[0015] Preferably, in step S2, PVA accounts for 2-8 wt% of ZnO powder and Ag2O powder; the ground powder passes through a 600-1200 sieve; the pressing conditions are an air pressure of 2-8 MPa and a holding pressure of 1-5 min.

[0016] Preferably, in step S3, the high-temperature sintering conditions are as follows: starting from room temperature, heating to 550°C at 3.5°C / min, holding for 2 hours, then continuing to heat to 950°C at 3°C / min, holding for 2 hours, and then cooling down with the furnace.

[0017] Preferably, the combustion aid is Bi2O3 powder and SiO2 powder.

[0018] A metalayered ceramic composite material is prepared by the above-described method.

[0019] The above-mentioned meta-layered ceramic composite material is used in the fabrication of silver-zinc oxide ceramic pulse capacitors and high-dielectric field-effect transistors.

[0020] A silver-zinc oxide ceramic pulse capacitor includes a ceramic composite material with a meta-layered structure as described above.

[0021] A high-dielectric field-effect transistor comprising a ceramic composite material with a meta-layered structure as described above.

[0022] Compared with the prior art, the beneficial effects of the present invention are: Because this invention proposes to stack a negative dielectric layer and a positive dielectric layer to form a double-layer stacked structure, this double-layer stacked structure has both a high dielectric constant and low loss capability, providing a simple and easy new method for the preparation of ceramic pulse capacitors. Furthermore, by changing the content of material elements, its dielectric properties can be effectively controlled. The meta-stacked ceramic composite material prepared by this invention has important application value in the fields of pulse capacitors and the like. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the double-layer stacked structure in this invention; Figure 2 The dielectric constant test results are shown for silver / zinc oxide ceramic composites with pure zinc oxide, silver content of 10 wt%, and silver content of 20 wt%. Figure 3 The graph shows the dielectric constant test results of silver / zinc oxide ceramic composites with silver contents of 25 wt%, 35 wt%, and 40 wt%. Figure 4 The loss tangent test results are shown in the figure for silver / zinc oxide ceramic composite materials with pure zinc oxide and silver content of 10 wt%, 20 wt%, 25 wt%, 35 wt%, and 40 wt%. Figure 5 The dielectric constant test results are shown in the figure for the design of a silver / zinc oxide ceramic composite metalayer with pure zinc oxide and silver content of 25 wt%, 35 wt%, and 40 wt%. Figure 6 The loss tangent test results are shown in the figure for the superstructure design of silver / zinc oxide ceramic composites with pure zinc oxide and silver content of 25 wt%, 35 wt%, and 40 wt%. Figure 7 The dielectric constant test results are shown for the superstructured designs of silver / zinc oxide ceramic composites with silver contents of 10 wt%, 25 wt%, 35 wt%, and 40 wt%. Figure 8 The loss tangent test results are shown for the superstructure design of silver / zinc oxide ceramic composites with silver contents of 10 wt%, 25 wt%, 35 wt%, and 40 wt%. Figure 9 The dielectric constant test results are shown for the superstructured designs of silver / zinc oxide ceramic composites with silver contents of 20 wt%, 25 wt%, 35 wt%, and 40 wt%. Figure 10 The loss tangent test results are shown for the superstructure design of silver / zinc oxide ceramic composites with silver contents of 20 wt%, 25 wt%, 35 wt%, and 40 wt%. Detailed Implementation To make the technical means, creative features, objectives and effects of this invention easier to understand, the following embodiments are described in detail with reference to the accompanying drawings. It should be noted that the description of these embodiments is for the purpose of helping to understand this invention, but does not constitute a limitation of this invention.

[0024] This invention is based on the following principle: the multilayer material is considered as a capacitor in series in terms of electrical properties; such as... Figure 1Theoretically, a laminated material structure is equivalent to two capacitors connected in series (C1 and C2), with each layer of material equivalent to one capacitor. Therefore, the total capacitance of a double-layer laminated material ( ) is represented as: (1) In the field of dielectric materials research, C1 and C2 are usually positive values. Therefore, the value of Ct is less than the capacitance value of either C1 or C2. Assuming C1 is negative and C2 is positive... It will increase significantly; if the absolute value of the negative value of C1 is equivalent to the value of C2, theoretically, The value will tend towards infinity. The emergence of negative dielectric materials makes it possible to achieve and control high dielectric constant and low loss. The negative dielectric constant of ceramic composite materials can be controlled through the material's composition and structural design. These materials combine high dielectric constant, low loss, and high temperature resistance, and are attracting much attention as high-performance structural ceramics.

[0025] In addition, the following situations need to be explained in this invention: (1) In the chemical formula of this invention, "-" refers to a superstructure stack; " / " refers to a composite; "10 wt% Ag / ZnO-25wt% Ag / ZnO" means that the material is formed by a superstructure stack of silver / zinc oxide ceramic composite material with a silver content of 10 wt% and silver / zinc oxide ceramic composite material with a silver content of 25 wt%.

[0026] (2) PVA stands for polyvinyl alcohol.

[0027] (3) Except for the inconsistent thickness of the two layers, the double-layer stacked structure is identical in all other aspects. For example, when the top or bottom cross section of the double-layer stacked structure is rectangular, the length of the rectangle in the upper layer is equal to the length of the rectangle in the lower layer, the width of the rectangle in the upper layer is equal to the width of the rectangle in the lower layer, and the other shapes are the same. That is, when the negative dielectric layer and the upper dielectric layer are stacked, their corresponding surfaces completely overlap when they come into contact.

[0028] Based on the above principles, the following meta-layered structure is designed: namely, Example 1 A method for preparing a metalayered ceramic composite material includes the following steps: S1 Preparation of silver / zinc oxide precursor powder: Mix 30g of zinc oxide powder, 0.6g of bismuth oxide powder, and 0.09g of silicon dioxide powder; add 50mL of anhydrous ethanol; use 50g of 3mm and 1mm diameter grinding balls for ball milling, mill for 4 hours at a speed of 300 rpm; dry at 80℃. Then, pre-calcine to remove bismuth oxide and silicon dioxide. Specifically, place the dried powder in a crucible, heat in a muffle furnace from room temperature (25℃) at a rate of 3.5℃ / min to 550℃, hold for 2 hours, and then cool to room temperature with the furnace to successfully obtain the zinc oxide precursor powder.

[0029] S2 Preparation of silver / zinc oxide flake ceramic material: The zinc oxide precursor powder obtained above is placed in a mortar and ground, during which 5 wt% PVA glue is added. The mixture is sieved through 800 mesh and 1000 mesh sieves, and the portion that passes through 800 mesh but not through 1000 mesh is collected. The mixture is repeatedly ground and sieved until it becomes a quicksand-like substance with a particle size range of 13~18μm. The mixture is then placed in a mold with a diameter of 12.5mm and pressed into shape under a pressure of 5MPa for 2min to obtain zinc oxide flake ceramic material, i.e., ZnO.

[0030] Examples 2-6 are basically the same as Example 1, except that the reactants contain not only zinc oxide powder but also silver oxide powder (the specific amount is shown in Table 1). The precursor powder is silver / zinc oxide precursor powder, and the final sheet is silver / zinc oxide sheet ceramic material. The results are shown in Table 2 after characterization by Agilent E4991A test table. Table 1 In addition, the silver / zinc oxide sheet ceramic materials prepared in Examples 1-6 have the following effects: The parameters (including thickness and final yield) of the positive or negative dielectric layer in Examples 1-6 are shown in Table 2.

[0031] Table 2 Then, Examples 1-3 and Examples 4-6 were operated in the following manner to finally obtain a metastructured ceramic composite material: As shown in Table 2, ZnO, 10 wt% Ag / ZnO, and 20 wt% Ag / ZnO are all positive dielectric layers because their dielectric constants are positive; 25 wt% Ag / ZnO, 35 wt% Ag / ZnO, and 40 wt% Ag / ZnO are all negative dielectric layers because their dielectric constants are negative. S4 The positive dielectric layer and negative dielectric layer prepared in step S3 are stacked together (i.e., Examples 7-15), and the ceramic composite material of the meta-stacked structure has a double-layer stacked structure; then the Agilent E4991A test table is used to characterize Examples 7-15 to obtain Table 3.

[0032] Table 3 This invention provides a method for controlling the dielectric properties of zinc oxide or silver / zinc oxide ceramic composite materials obtained by the above preparation method, that is, controlling the dielectric properties of the ceramic composite material by changing the element content and structure of the ceramic composite material.

[0033] As shown in Table 3, by changing the element content (mainly the mass of zinc oxide and silver oxide) and structure (establishing a double-layer stacked structure formed by stacking negative dielectric layer and positive dielectric layer), the dielectric properties and loss tangent of the ceramic composite material can be effectively controlled, thus obtaining a high dielectric material while reducing loss. Therefore, the material has good performance.

[0034] Depend on Figure 2-3 As shown, the dielectric properties of the ceramic composite material can be effectively controlled by changing the element content and structure of the ceramic composite material.

[0035] Depend on Figure 5 , 7 As shown in Figures 9 and 1, the dielectric properties of the ceramic composite material can be effectively controlled by changing the element content and structure of the ceramic composite material.

[0036] Depend on Figure 6 , 8 As shown in Figures 1 and 10, the dielectric loss of the ceramic composite material can be effectively reduced by changing its structure.

[0037] This invention prepares a ceramic composite material with dielectric properties through a high-temperature sintering method. The microstructure of the material is controlled by adjusting the silver content, and a meta-layer design is employed to achieve high dielectric properties while reducing losses. This ceramic composite material has significant application value in fields such as pulse capacitors and high-dielectric field-effect transistors.

[0038] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Various modifications or variations that can be made by those skilled in the art without creative effort within the scope of the appended claims are still within the scope of protection of this patent.

Claims

1. A method for producing a ceramic composite material of superlattice structure, characterized by, The method comprises the following steps: The ceramic composite material of the superlattice structure comprises a negative dielectric layer and a positive dielectric layer, and the negative dielectric layer and the positive dielectric layer are stacked together, and the ceramic composite material of the superlattice structure has a double-layer stacked structure.

2. The method according to claim 1, wherein: The positive dielectric layer and the negative dielectric layer are both in the form of a sheet.

3. The method according to claim 1, wherein: The negative dielectric layer is one of 25 wt% Ag / ZnO, 35 wt% Ag / ZnO and 40 wt% Ag / ZnO; and the positive dielectric layer is one of ZnO, 10 wt% Ag / ZnO and 20 wt% Ag / ZnO.

4. The method of claim 3, wherein: The superlattice material is one of ZnO-25 wt% Ag / ZnO, ZnO-35 wt% Ag / ZnO, ZnO-40 wt% Ag / ZnO, 10 wt% Ag / ZnO-25 wt% Ag / ZnO, 10 wt% Ag / ZnO-35 wt% Ag / ZnO, 10 wt% Ag / ZnO-40 wt% Ag / ZnO, 20 wt% Ag / ZnO-25 wt% Ag / ZnO, 20 wt% Ag / ZnO-35 wt% Ag / ZnO and 20 wt% Ag / ZnO-40 wt% Ag / ZnO.

5. The method of claim 4, wherein: The thickness of the ceramic composite material of the superlattice structure is 3.000-3.500 mm.

6. The method of claim 5, wherein: The positive dielectric layer / negative dielectric layer is prepared by the following steps: The silver-containing / zinc oxide or zinc oxide precursor powder is pre-burned, ground and granulated, pressed and molded, and subjected to high-temperature sintering process to obtain the positive dielectric layer / negative dielectric layer.

7. A ceramic composite material of a superlattice structure, prepared by the method of any one of claims 1-6.

8. Use of the ceramic composite material of the superlattice structure of claim 7 in the production of silver-zinc oxide ceramic pulse capacitors and high-dielectric field effect transistors.

9. A silver zinc oxide ceramic pulse capacitor characterized by, The ceramic composite material of the superlattice structure of claim 7.

10. A high dielectric field effect transistor, characterized by, The ceramic composite material of the superlattice structure of claim 7.

Images