CN107954712B - Low-loss giant dielectric CCTO ceramic material and preparation method thereof - Google Patents
Low-loss giant dielectric CCTO ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-loss giant dielectric CCTO ceramic material and a preparation method thereof, belonging to the technical field of advanced dielectric ceramic materials. The low-loss giant dielectric CCTO ceramic material is characterized by comprising the following components in parts by weight: 0.62-1.48 parts of calcium salt, 1.34-4.54 parts of copper salt or copper oxide, 1.5-2.5 parts of titanium dioxide, 0.012-0.15 part of graphene, 0.02-0.06 part of nano P-type semiconductor and 0.1-0.5 part of adhesive. The CCTO dielectric ceramic mixed and doped with the graphene and the nano P-type semiconductor has finer and uniform crystal grains, the dielectric constant is improved, most importantly, the dielectric loss is obviously reduced, and the comprehensive dielectric property is obviously improved. The process used in the invention is the traditional solid phase synthesis process, the process and equipment are simple, the process cost is low, and the large-scale production is easy to realize.
Description
Technical Field
The invention relates to the technical field of advanced dielectric ceramic materials, in particular to a low-loss giant dielectric CCTO ceramic material and a preparation method thereof.
Background
With the progress of electronic communication technology, the requirements of miniaturization, chip type and high quality factor of used components are further improved by the integration and high-speed development of electronic complete machines. Miniaturization and multilayer chip integration of high-frequency capacitors become the development trend of components. The electronic ceramic material with the ultrahigh dielectric constant has great significance for miniaturization and integration of the capacitor element.
CaCu3Ti4O12The compound (CCTO) has huge dielectric constant (approximately equal to 104-105), especially the dielectric constant value in a wide temperature region near room temperature is basically kept unchanged, and the compound has wide application prospect in the integrated electronic fields of high-density energy storage, pressure sensitive devices, high-density capacitors and the like. The CCTO ceramic is composed of semiconductor crystal grains of several micrometers to tens of micrometers and insulating crystal grain boundaries with nanometer-scale thickness. It is the internal grain boundary barrier insulating layer microcapacitance that results in the giant dielectric constant of CCTO.
The biggest problem faced in use of CCTO dielectric ceramics is excessive dielectric loss. Therefore, trying to reduce dielectric loss of CCTO ceramics is a key to the development of CCTO giant dielectric ceramic materials with practical value. CCTO dielectric loss results from electron displacement polarization inside the grains and tunneling current of the grain boundary layer. The current well-established methods for reducing loss are the following two approaches: (1) controlling the growth of crystal grains in the sintering process and reducing the size of the crystal grains; (2) the insulativity of the grain boundary layer is improved, the thickness of the grain boundary layer is increased, and the crystallization quality of the grain boundary is improved.
In order to achieve the above effects, the literature reports mostly adopt single or multiple elements with grain refining function such as Mg, Sr, Co, Cr, Sm, Zn, Al, etc. to dope so as to inhibit grain growth, and simultaneously adopt doped glass to subtract small interface defects and improve sintering density.
However, the following problems still exist in the preparation of high dielectric constant and low dielectric loss CCTO ceramic materials so far: (1) by adopting trace doping, the grain size can be effectively reduced, meanwhile, a crystal boundary barrier layer with an excessively thin CCTO (CCTO) is maintained, tunneling conduction is easy to generate, and loss is difficult to reduce; (2) the high-insulation phase ceramic with excessive doping can form a high-insulation grain boundary barrier layer, but the grain boundary is too thick, so that the overall dielectric constant is reduced too much, and the advantage of CCTO huge dielectric property is lost.
Therefore, research and development of more effective ways are urgently needed for industrial application of CCTO, and CCTO electronic ceramics with high dielectric constant and low dielectric loss can be obtained at the same time.
Disclosure of Invention
The invention aims to provide a low-loss and giant-dielectric CCTO ceramic material and a preparation method thereof, and aims to solve the problem that the existing CCTO electronic ceramic cannot have both giant dielectric constant and low dielectric loss.
The technical scheme for solving the technical problems is as follows:
a low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.62-1.48 parts of calcium salt, 1.34-4.54 parts of copper salt or copper oxide, 1.5-2.5 parts of titanium dioxide, 0.012-0.15 part of graphene, 0.02-0.06 part of nano P-type semiconductor and 0.1-0.5 part of adhesive.
According to the invention, the graphene and the nano P-type semiconductor are added into the prepared CCTO ceramic raw material for co-doping, so that the technical problem of development of the CCTO giant dielectric ceramic material with giant dielectric constant and low dielectric loss is effectively solved.
On one hand, the graphene is introduced in the processes of material preparation and pre-sintering in the early period, and is of an ordered network structure formed by single-layer carbon atoms with hexagonal periodic arrangement, the thickness of the graphene is less than 1nm, the graphene has good atomic density and excellent mechanical property in a surface, and the nano ultrathin structural characteristics and the blocking effect of a carbon material on ceramic sintering enable the graphene to play the roles of improving the CCTO ceramic sintering dynamics, regulating and controlling the microstructure, refining crystal grains and modifying crystal boundaries in the CCTO ceramic sintering process, so that the function of dielectric properties of the CCTO ceramic is optimized; and the graphene can be oxidized and removed in the sintering process, no new impurities are introduced, and the giant dielectric constant of the CCTO ceramic is maintained and improved. Specifically, the graphene is used as a sintering process control agent, the CCTO crystal grains are inhibited from growing, and the CCTO ceramics with uniform and fine crystal grains are obtained, so that the dielectric constant of the CCTO ceramics is improved, and the dielectric loss is reduced; meanwhile, the graphene nanosheets play a role in isolation and blocking in the sintering process, atomic diffusion in the sintering process is limited, the thickness of a crystal boundary layer is reduced, and the crystallization quality of the crystal boundary is improved, so that the dielectric constant is improved.
On the other hand, the CCTO ceramic obtained by sintering generally has oxygen vacancies and is generally intrinsic n-type semiconductor characteristics, and an "n-I-n" structure of "n-type semiconductor-grain boundary insulating layer (I) -n-type semiconductor" is formed in the internal microstructure thereof due to the insulating characteristics of the grain boundary. The thinning of the grain boundary layer can effectively improve the dielectric constant of the crystal boundary layer, but the too thin thickness of the grain boundary layer can easily cause tunneling conduction, so that the leakage current and the loss are increased. The nano P-type semiconductor is introduced into the ingredients, and enters the crystal boundary layer of the CCTO to form a novel n-P-n crystal grain-crystal boundary blocking microstructure with the bidirectional cut-off characteristic, so that the generation of leakage current can be prevented, the tunneling conductance of the crystal boundary is effectively reduced, and the dielectric loss of the CCTO ceramic is reduced.
Further, in a preferred embodiment of the present invention, the calcium salt is calcium nitrate or calcium carbonate.
Further, in a preferred embodiment of the present invention, the copper salt is copper nitrate, and the copper oxide is copper oxide or cuprous oxide.
Further, in a preferred embodiment of the present invention, the graphene is a single-layer or multi-layer graphene.
Further, in a preferred embodiment of the present invention, the nano P-type semiconductor is P-type ZnO or P-type copper zinc tin sulfide.
Further, in the preferred embodiment of the present invention, the P-type ZnO is Na-doped or N-doped P-type ZnO, and the P-type copper zinc tin sulfide is an intrinsic P-type semiconductor.
Further, in a preferred embodiment of the present invention, the adhesive is paraffin wax or polyvinyl alcohol.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing calcium salt, copper salt or copper oxide, titanium dioxide and graphene according to the formula ratio, adding deionized water or alcohol which is 2-4 times of the weight of the materials as a solvent and grinding balls which are 2-4 times of the weight of the materials, and performing ball milling for 1.5-3 hours at a rotation speed of 200-400r/min to prepare a primary ball grinding material;
(2) drying the primary ball grinding material, then continuously grinding the material through a 100-sand 120-mesh sieve, and then presintering the material for 4 to 6 hours at the temperature of between 750 and 900 ℃ to prepare a presintering material;
(3) grinding the pre-sintered material, adding a nano P-type semiconductor with a formula amount, and then ball-milling for 5-7 hours according to the weight ratio of balls to solvent to materials of 2-4: 1 to prepare a secondary ball grinding material;
(4) drying the secondary ball grinding material, then continuously grinding, sieving with a 100-200 mesh sieve, adding a formula amount of adhesive, granulating, and pressing into a wafer under the condition of 20-50 MPa; and
(5) and sintering the wafer at 950-1200 ℃ for 2-10 hours to obtain the low-loss giant dielectric CCTO ceramic material, wherein the sintering atmosphere is one or more of air, oxygen, nitrogen and argon.
Further, in a preferred embodiment of the present invention, the preparation method further includes:
(6) and (3) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste, drying, and sintering in air at 550-650 ℃ for 30-60 min.
The invention has the following beneficial effects:
compared with the CCTO ceramic obtained by the same process, the CCTO dielectric ceramic obtained by mixing and doping the graphene and the nano P-type semiconductor has finer and uniform crystal grains (the size of the crystal grains ranges from 0.5 to 5 microns), and the dielectric constant is improved (from 1 to 2 multiplied by 10)4Increased to 5 × 104) Most importantly, the dielectric loss is significantly reduced (loss tangent is reduced from 0.07 to<0.03), the comprehensive dielectric property is obviously improved. The process used in the invention is the traditional solid phase synthesis process, the process and equipment are simple, the process cost is low, and the large-scale production is easy to realize.
Drawings
FIG. 1 is a scanning electron micrograph of undoped CCTO ceramic;
FIG. 2 is a scanning electron micrograph of graphene-doped CCTO ceramic;
FIG. 3 is a scanning electron micrograph of graphene/P-type ZnO co-doped CCTO ceramic of example 1 of the present invention;
fig. 4 is a scanning electron microscope photograph of the graphene/nano CZTS co-doped CCTO ceramic in example 6 of the present invention;
fig. 5 is an XRD of undoped, CCTO ceramics of examples 1 and 6 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.025 part of nano P-type ZnO and 0.12 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ for 6 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.025 parts of P-type ZnO, and placing the mixture into a ball milling tank for ball milling for 6 hours to prepare a secondary ball grinding material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.12 part of paraffin for granulation, sieving by a 100-mesh sieve, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1050 ℃ for 3 hours in a mixed gas atmosphere of 40% by volume of oxygen and 60% by volume of argon;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 7X 104 and a loss tangent of 0.028 at 1 kHz.
Example 2:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.62 part of calcium carbonate, 1.34 parts of copper oxide, 1.5 parts of titanium dioxide, 0.0124 part of graphene, 0.025 part of nano P-type ZnO and 0.12 part of polyvinyl alcohol.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.62 part of calcium carbonate, 1.34 parts of copper oxide, 1.5 parts of titanium dioxide and 0.0124 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol which is 2 times of the weight of the materials as a solvent and grinding balls which are 2 times of the weight of the materials, and carrying out ball milling for 3 hours at a rotating speed of 200r/min to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving with a 100-mesh sieve, and presintering in air at 750 ℃ for 6 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.025 parts of ZnO, and placing the mixture into a ball milling tank to be ball milled for 7 hours according to the ratio of balls to solvent to material to 2:2:1 to prepare a secondary ball grinding material;
(4) transferring and drying the secondary ball grinding material, grinding, sieving by a 100-mesh sieve, adding 0.12 part of polyvinyl alcohol for granulation, sieving, and pressing into a wafer with the diameter of 15mm under the condition of 20 MPa;
(5) sintering the wafer obtained in the step (4) at a temperature of 1080 ℃ for 4 hours in an air atmosphere;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 550 ℃ for 60 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed. The test result shows that: the sample obtained under these conditions had a dielectric constant of 5.6X 10 at 1kHz4Loss tangent 0.03.
Example 3:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
1.48 parts of calcium carbonate, 4.54 parts of copper oxide, 2.5 parts of titanium dioxide, 0.15 part of graphene, 0.025 part of nano P-type ZnO and 0.12 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 1.48 parts of calcium carbonate, 4.54 parts of copper oxide, 2.5 parts of titanium dioxide and 0.15 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol which is 3 times of the weight of the materials as a solvent and grinding balls which are 3 times of the weight of the materials, and carrying out ball milling for 1.5 hours at a rotating speed of 400r/min to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving with a 110-mesh sieve, and presintering in air at 900 ℃ for 5 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.025 parts of P-type ZnO, and placing the mixture into a ball milling tank to be ball-milled for 6 hours according to the ratio of balls to solvent to material of 4:4:1 to prepare a secondary ball grinding material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material by a 150-mesh sieve, adding 0.12 part of molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 50 MPa;
(5) sintering the wafer obtained in the step (4) at 1200 ℃ for 2 hours in the atmosphere of air;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in the air at 650 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 5.2X 10 at 1kHz4Loss tangent 0.045.
Example 4:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium nitrate, 1.49 parts of copper nitrate, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.05 part of nano P-type ZnO and 0.12 part of paraffin. The nano P-type ZnO of this example is N-doped P-type ZnO.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium nitrate, 1.49 parts of copper nitrate, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling at the rotating speed of 300r/min for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving with a 120-mesh sieve, and presintering in air at 850 ℃ for 4.5 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.05 part of P-type ZnO, and placing the mixture into a ball milling tank to be ball-milled for 6 hours according to the ratio of balls to solvent to material of 4:4:1 to prepare a secondary ball grinding material;
(4) transferring, drying and grinding the secondary ball grinding material, sieving the ground material by a 200-mesh sieve, adding 0.12 part of molten paraffin for granulation and sieving, and pressing the mixture into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 950 ℃ for 10 hours in a mixed gas of 20% by volume of oxygen and 80% by volume of nitrogen;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 5.5X 10 at 1kHz4Loss tangent 0.031.
Example 5:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of cuprous oxide, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.025 part of nano P-type ZnO and 0.12 part of paraffin. The nano P-type ZnO of this example is Na doped P-type ZnO.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of cuprous oxide, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ for 6 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.05 part of P-type ZnO, and placing the mixture into a ball milling tank to be ball-milled for 6 hours according to the ratio of balls to solvent to material of 4:4:1 to prepare a secondary ball grinding material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.12 part of molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at a temperature of 1080 ℃ for 4 hours in an air atmosphere;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the dielectric constant of the sample obtained under these conditions at 1kHz was 4.8X 104Loss tangent 0.029.
Example 6:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.032 part of P-type copper-zinc-tin-sulfur compound and 0.12 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ for 6 hours to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.032 parts of P-type copper-zinc-tin-sulfur compound nano powder, and placing the mixture in a ball milling tank for ball milling for 6 hours to prepare a secondary ball milling material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.12 part of molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1020 ℃ for 4 hours in an argon atmosphere;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 6.6X 10 at 1kHz4Loss tangent 0.035.
Example 7:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
1.23 parts of calcium carbonate, 3.49 parts of copper oxide, 1.8 parts of titanium dioxide, 0.0124 part of graphene, 0.032 part of P-type copper zinc tin sulfide compound and 0.12 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 1.23 parts of calcium carbonate, 3.49 parts of copper oxide, 1.8 parts of titanium dioxide and 0.0124 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.032 parts of P-type copper-zinc-tin-sulfur compound nano powder, and placing the mixture in a ball milling tank for ball milling for 6 hours to prepare a secondary ball milling material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.12 part of molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1020 ℃ for 4 hours in a mixed gas atmosphere of 15% by volume of oxygen and 85% by volume of argon;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 5.5X 10 at 1kHz4Loss tangent 0.04.
Example 8:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide, 0.15 part of graphene, 0.032 part of P-type copper-zinc-tin-sulfur compound and 0.12 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide and 0.15 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ to obtain a presintering material;
(3) taking out the pre-sintered material, grinding the pre-sintered material appropriately, adding 0.032 parts of P-type copper-zinc-tin-sulfur compound nano powder, and placing the mixture in a ball milling tank for ball milling for 6 hours to prepare a secondary ball milling material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.12 molten paraffin for granulation, sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1020 ℃ for 4 hours in the atmosphere of air;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the dielectric constant of the sample obtained under these conditions at 1kHz was 4.5X 104Loss tangent 0.046.
Example 9:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.06 part of P-type copper-zinc-tin-sulfur compound and 0.5 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ to obtain a presintering material;
(3) taking out the pre-sintered material, properly grinding, adding 0.06 part of P-type copper-zinc-tin-sulfur compound nano powder, placing the mixture in a ball milling tank, and carrying out ball milling for 6 hours to prepare a secondary ball grinding material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.5 molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1020 ℃ for 4 hours in a nitrogen atmosphere;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 4X 104 and a loss tangent of 0.042 at 1 kHz.
Example 10:
the low-loss giant dielectric CCTO ceramic material comprises the following components in parts by weight:
0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide, 0.0258 part of graphene, 0.06 part of P-type copper-zinc-tin-sulfur compound and 0.1 part of paraffin.
The preparation method of the low-loss giant dielectric CCTO ceramic material comprises the following steps:
(1) mixing 0.63 part of calcium carbonate, 1.49 parts of copper oxide, 2 parts of titanium dioxide and 0.0258 part of graphene powder according to a formula, pouring the mixture into a ball milling tank, adding deionized water or alcohol with the weight 4 times that of the materials as a solvent and grinding balls with the weight 4 times that of the materials, and carrying out ball milling for 2 hours to obtain a primary ball grinding material;
(2) taking out the primary ball-milled material, drying, grinding, sieving, and presintering in air at 850 ℃ to obtain a presintering material;
(3) taking out the pre-sintered material, properly grinding, adding 0.06 part of P-type copper-zinc-tin-sulfur compound nano powder, placing the mixture in a ball milling tank, and carrying out ball milling for 6 hours to prepare a secondary ball grinding material;
(4) transferring, drying, grinding and sieving the secondary ball grinding material, adding 0.1 molten paraffin for granulation and sieving, and pressing into a wafer with the diameter of 15mm under the condition of 40 MPa;
(5) sintering the wafer obtained in the step (4) at 1020 ℃ for 4 hours in the atmosphere of air;
(6) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste on the polished ceramic wafer, drying the polished ceramic wafer, and sintering the polished ceramic wafer in air at 580 ℃ for 30 min;
(7) and (4) testing the ceramic wafer obtained by sintering in the step (6) after the double-sided silver-backed electrode is formed.
The test result shows that: the sample obtained under these conditions had a dielectric constant of 5.5X 10 at 1kHz4Loss tangent 0.044.
The results of the tests of examples 1-10 above were compared with the properties of the existing CCTO ceramics and are shown in Table 1.
TABLE 1
| Examples | Dielectric constant/104(1kHz) | Loss tangent tg delta (1kHz) |
| 1 | 7 | 0.028 |
| 2 | 5.6 | 0.03 |
| 3 | 5.2 | 0.045 |
| 4 | 5.5 | 0.031 |
| 5 | 4.8 | 0.29 |
| 6 | 6.6 | 0.035 |
| 7 | 5.5 | 0.04 |
| 8 | 4.5 | 0.046 |
| 9 | 4 | 0.042 |
| 10 | 6 | 0.044 |
| Comparative example | 1～2 | 0.07 |
As can be seen from Table 1, the dielectric constants of the CCTO ceramics prepared by the examples of the present invention are all significantly higher than those of the comparative examples, and the maximum dielectric constant can be increased to 7 × 104The loss tangent value can be reduced to 0.028, and the comprehensive dielectric property is obviously improved.
In addition, as can be seen from the comparison between fig. 1 and fig. 2 to 4, the ceramic grains become finer and more uniform after the mixed doping with graphene and nano P-type semiconductor according to the present invention, especially the CCTO ceramic of example 1 represented by fig. 2, the grains of which are the finest. As seen in fig. 5: the X-ray diffraction peaks of the doped and undoped CCTO ceramics correspond to the CCTO characteristic peak, no impurity peak of other phases appears, and the diffraction peak position does not obviously move. The doped graphene, the P-type ZnO and the P-type copper zinc tin sulfide compound do not form a second phase with obvious size in CCTO, and only exist in the CCTO ceramic grain boundary in an ultrathin layer form.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A low-loss giant dielectric CCTO ceramic material is characterized by comprising the following components in parts by weight:
0.62-1.48 parts of calcium salt, 1.34-4.54 parts of copper salt or copper oxide, 1.5-2.5 parts of titanium dioxide, 0.012-0.15 part of graphene, 0.02-0.06 part of nano P-type semiconductor and 0.1-0.5 part of adhesive;
the graphene is single-layer or multi-layer graphene;
the nano P-type semiconductor is P-type ZnO or a P-type copper-zinc-tin-sulfur compound;
the low-loss giant dielectric CCTO ceramic material is prepared by the following method:
(1) mixing calcium salt, copper salt or copper oxide, titanium dioxide and graphene according to the formula ratio, adding deionized water or alcohol which is 2-4 times of the weight of the materials as a solvent and grinding balls which are 2-4 times of the weight of the materials, and performing ball milling for 1.5-3 hours at a rotation speed of 200-400r/min to prepare a primary ball grinding material;
(2) drying the primary ball grinding material, then continuously grinding the material through a 100-sand 120-mesh sieve, and then pre-burning the material for 4 to 6 hours at the temperature of 750 to 900 ℃ to prepare a pre-burning material;
(3) grinding the pre-sintered material, adding a nano P-type semiconductor with a formula amount, and then ball-milling for 5-7 hours according to the weight ratio of balls to solvent to materials of 2-4: 1 to prepare a secondary ball grinding material;
(4) drying the secondary ball grinding material, then continuously grinding, sieving with a 100-200-mesh sieve, adding a formula amount of adhesive, granulating, and pressing into a wafer under the condition of 20-50 MPa; and
(5) and sintering the wafer at 950-1200 ℃ for 2-10 hours to obtain the low-loss giant dielectric CCTO ceramic material, wherein the sintering atmosphere is one or more of air, oxygen, nitrogen and argon.
2. The low-loss, macropolydielectric CCTO ceramic material of claim 1, wherein the calcium salt is calcium nitrate or calcium carbonate.
3. The low-loss, macrocrystalline CCTO ceramic material of claim 1, wherein the copper salt is cupric nitrate and the copper oxide is cupric oxide or cuprous oxide.
4. The low-loss, giant dielectric CCTO ceramic material of claim 1, wherein the P-type ZnO is Na-doped or N-doped P-type ZnO, and the P-type copper zinc tin sulfide compound is an intrinsic P-type semiconductor.
5. The low-loss, macropolydielectric CCTO ceramic material of claim 1, wherein the binder is paraffin wax or polyvinyl alcohol.
6. The method of preparing a low-loss, giant dielectric CCTO ceramic material according to any one of claims 1-5, comprising:
(1) mixing calcium salt, copper salt or copper oxide, titanium dioxide and graphene according to the formula ratio, adding deionized water or alcohol which is 2-4 times of the weight of the materials as a solvent and grinding balls which are 2-4 times of the weight of the materials, and performing ball milling for 1.5-3 hours at a rotation speed of 200-400r/min to prepare a primary ball grinding material;
(2) drying the primary ball grinding material, then continuously grinding the material through a 100-sand 120-mesh sieve, and then pre-burning the material for 4 to 6 hours at the temperature of 750 to 900 ℃ to prepare a pre-burning material;
(3) grinding the pre-sintered material, adding a nano P-type semiconductor with a formula amount, and then ball-milling for 5-7 hours according to the weight ratio of balls to solvent to materials of 2-4: 1 to prepare a secondary ball grinding material;
(4) drying the secondary ball grinding material, then continuously grinding, sieving with a 100-200-mesh sieve, adding a formula amount of adhesive, granulating, and pressing into a wafer under the condition of 20-50 MPa; and
(5) and sintering the wafer at 950-1200 ℃ for 2-10 hours to obtain the low-loss giant dielectric CCTO ceramic material, wherein the sintering atmosphere is one or more of air, oxygen, nitrogen and argon.
7. The method of preparing a low-loss, giant dielectric CCTO ceramic material according to claim 6, further comprising:
(6) and (3) polishing the ceramic wafer prepared in the step (5) to be smooth, coating silver paste, drying, and sintering in air at 550-650 ℃ for 30-60 min.
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