CN108530068B - Barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and preparation method thereof - Google Patents

Barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and preparation method thereof Download PDF

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CN108530068B
CN108530068B CN201710128540.1A CN201710128540A CN108530068B CN 108530068 B CN108530068 B CN 108530068B CN 201710128540 A CN201710128540 A CN 201710128540A CN 108530068 B CN108530068 B CN 108530068B
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郭旺
黄集权
江亚彬
薛锤兵
李国京
邓种华
兰海
陈剑
刘著光
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Anhui chenxinwei Industrial Technology Co.,Ltd.
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention discloses a barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and a preparation method thereof. The chemical general formula is La2‑x(Ba,Ca)xNiO4Wherein x is 0<x is less than or equal to 0.5. The preparation method adopts a solid-phase sintering method, and the method has the advantages of simple operation, good repeatability, high yield and no need of additional atmosphere for auxiliary sintering. XRD diffraction results show that the doped samples are all K2NiF4And (5) structure. And with La2NiO4Compared with the dielectric constant of the material, the dielectric constant of the material is obviously improved. In addition, ceramic samples with different dielectric properties can be obtained by adopting different doping ratios of Ba and Ca.

Description

Barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and preparation method thereof
Technical Field
The invention belongs to the field of dielectric medium information functions, and particularly relates to barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and a preparation method thereof.
Background
In recent years, the electronic industry is rapidly developing, and the trend of integration and miniaturization of electronic information technology is driving the increasing miniaturization, miniaturization and integration of electronic components, and the development of high reliability and low cost. In the field of ceramic capacitors, miniaturization, high capacity and excellent temperature stability have become inevitable trends. The multilayer ceramic capacitor (MLCC) can well meet the requirements of small volume, large capacity and the like. Furthermore, with the development of the ceramic manufacturing process, MLCCs are also developed to have more layers and thinner dielectric layers. However, the capacitance of the MLCC is related to the dielectric constant of the ceramic dielectric itself in addition to the thickness and the number of layers of the dielectric layer, and is proportional to the dielectric constant of the ceramic dielectric in the case where the thickness and the number of layers of the dielectric layer are not changed. In addition, in order to achieve a sufficiently good insulating property, the thickness of the ceramic dielectric layer between two adjacent electrodes is at least about 10 times the grain size, i.e., the thickness of the dielectric layer cannot be reduced without limit. In this case, it is also very useful to increase the dielectric constant of the ceramic material.
Dielectric ceramics which are well studied and applied at present are traditional ferroelectric materials (such as barium titanate, strontium titanate and the like), but the materials have the disadvantage of needing to show higher dielectric constant at lower testing temperature. For example xNd2O3-SrTiO3The ceramics will exhibit giant dielectric properties, but the dielectric constant is generally low in the range of 20-340 ℃, the dielectric constant is less than 500 in the temperature range of 20-160 ℃, the dielectric constant at the high temperature end does not exceed 16000, and the dielectric constant temperatureThe range of the dielectric constant is narrow, and the frequency stability of the dielectric constant is poor in the frequency range of 0.04-300 kHz. Because of the above limitations of conventional ferroelectrics, it is important to explore giant dielectric materials that work around room temperature.
Disclosure of Invention
Provided herein is a barium calcium co-doped substituted La with giant dielectric constant and frequency stability2NiO4Giant dielectric ceramic and a preparation method thereof. Researches show that the barium-calcium co-doped substituted La provided by the invention2NiO4Giant dielectric ceramic belongs to K2NiF4Form nickelate. As is known, K2NiF4Type nickelate and LuFe2O4LuFe with layered mixed valence structure2O4Materials exhibit a high dielectric constant and are ferroelectric materials due to the presence of charge ordered regions. The giant dielectric ceramic of the invention also has charge order phenomenon and very high dielectric constant.
The preparation method of the invention organically combines ball milling, spheroidizing or spray granulation, cold isostatic pressing, solid phase sintering and the like. Wherein, the ball milling can uniformly mix different raw materials and can grind coarse raw materials into fine particles with regular shapes; the powder can be converted into spheroidized particles consisting of nano powder with the characteristics of high activity, high fluidity and the like through spheroidizing or spray granulation, so that the low-temperature densification of the ceramic is facilitated; the density of the biscuit can be greatly improved by cold isostatic pressing. Through the organic combination of the above means and the solid-phase sintering method, the synthesis of the high-density nickelate giant dielectric ceramic is ensured, the performance of the ceramic is effectively improved, and the method has important significance for obtaining ceramic materials with high dielectric adjustable performance.
In order to solve the technical problems, the invention adopts the technical scheme that:
barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic in which a part of La is substituted by Ba and Ca and has a chemical formula of La2-x(Ba,Ca)xNiO4Wherein x is in the range of 0<x≤0.5。
Preferably, 0.1 < x < 0.5. As an illustrative example, the barium calcium co-doped substituted La2NiO4The chemical formula of the giant dielectric ceramic is any one of the following formulas: la1.5(Ba,Ca)0.5NiO4、La1.6(Ba,Ca)0.4NiO4、La1.7(Ba,Ca)0.3NiO4、La1.8(Ba,Ca)0.2NiO4、La1.9(Ba,Ca)0.1NiO4。
Wherein the ratio of Ba and Ca may be (1-3): 1, preferably 1: 1.
preferably, the barium calcium co-doped substituted La2NiO4The giant dielectric ceramic has K2NiF4And (5) structure.
The invention also provides the barium-calcium co-doped substituted La2NiO4The preparation method of the giant dielectric ceramic adopts a solid-phase sintering method and comprises the following steps:
(1) preparing mixed powder: the raw material La is added2O3、BaCO3、CaCO3Placing NiO in a ball mill for ball milling, drying and sieving to obtain mixed powder;
(2) preparation of Pre-fired La2-x(Ba,Ca)xNiO4Powder: putting the mixed powder in the step (1) into a high-temperature tube furnace for presintering to obtain presintered La2-x(Ba,Ca)xNiO4Powder;
(3) secondary ball milling: pre-burning La2-x(Ba,Ca)xNiO4Ball-milling the powder in a ball mill, drying and sieving to obtain La2-x(Ba,Ca)xNiO4Powder;
(4) and (3) granulation: to La2-x(Ba,Ca)xNiO4Adding a binder into the powder, drying, sieving and granulating;
(5) tabletting and forming: pressing the powder obtained in the step (4) into a blank on a press machine, and carrying out cold isostatic pressing to obtain a sample piece;
(6) plastic discharging: heating the sample piece in the step (5) and then preserving heat, and performing plastic removal on the sample piece to obtain a ceramic blank;
(7) and (3) sintering: and (4) placing the ceramic blank in the step (6) into a high-temperature tube furnace for sintering, and cooling along with the furnace to obtain the product.
According to the present invention, in the step (1),
the raw material La2O3、BaCO3、CaCO3The molar ratio of NiO can be (3-19): 1: 1: (4-20), as an illustrative example, a molar ratio of (19: 1: 1: 20), (9: 1: 1: 1), (51: 9: 9: 60), (4: 1: 1: 5), or (3: 1: 1: 4);
the ball milling medium used in the ball milling is a mixture of polyvinyl butyral (PVB), oleic acid and ethanol;
the concentration of the polyvinyl butyral (PVB) and the oleic acid can be 0.1 to 0.5wt%, and is more preferably 0.45 wt%;
the volume ratio of the total volume of the polyvinyl butyral (PVB) and the oleic acid to the volume of the ethanol is (3-1): 1; more preferably 2: 1;
the ball milling time is 18-24 hours, for example, 24 hours;
the sieving is performed by a sieve with 120 meshes and 150 meshes, preferably a sieve with 150 meshes;
according to the present invention, in the step (2),
the pre-sintering is performed at 900-1200 ℃, preferably at 1050-1100 ℃, for example at 1100 ℃;
the pre-sintering time is 1-5 hours, preferably 1-3 hours, and as an exemplary implementation, the pre-sintering time is 3 hours;
according to the present invention, in the step (3),
the ball milling medium used in the ball milling is ethanol, preferably absolute ethanol;
the prefired La2-x(Ba,Ca)xNiO4The volume ratio (g: mL) of the powder mass to the ball-milling medium is 1: (10-15), more preferably 1: 15;
the ball milling time is 16-24 hours, for example, 18 hours;
the sieving is performed by a sieve with 120 meshes and 150 meshes, preferably a sieve with 150 meshes;
according to the present invention, in the step (4),
the binder is a 1-5wt% aqueous polyvinyl alcohol solution, and as an illustrative example, a 5wt% aqueous polyvinyl alcohol solution is used;
the dosage of the polyvinyl alcohol aqueous solution is La2-x(Ba,Ca)xNiO45-8wt% of the powder;
the sieving is double-layer sieving, such as 40-mesh and 100-mesh sieving;
according to the present invention, in the step (5),
the tabletting is dry-pressing;
the pressure used for dry pressing is 15-20MPa, preferably 15 MPa;
the dry pressing and pressure maintaining time is 4-6min, preferably 6 min;
the pressure of the cold isostatic pressing is 190-200MPa, and preferably 200 MPa;
the pressure maintaining time of the cold isostatic pressing is 1-3min, preferably 2 min;
the sample piece is cylindrical, the diameter of the sample piece is 12mm, and the thickness of the sample piece is about 1-2 mm;
according to the present invention, in the step (6),
the temperature is raised to 450-600 ℃ in the plastic removal process, and 500 ℃ is preferred;
the time for the heat preservation is 1-2 hours, for example, 1 hour;
the heating rate in the plastic discharging process is 2-5 ℃/min, preferably 2 ℃/min; according to the present invention, in the step (7),
the sintering temperature is 1200-1400 ℃, preferably 1250-1300 ℃, for example 1300 ℃;
the sintering time is 2-3 hours, preferably 3 hours;
according to the invention, in the sintering process, the temperature rise rate is preferably controlled to be 5 ℃/min during temperature rise, and the temperature is preferably reduced to the temperature of the pre-sintering in the step (2) at the rate of 2 ℃/min during temperature reduction;
preferably, a layer of padding is laid below the ceramic blank in the sintering process;
preferably, the composition of the mat is the same as the calcined powder.
The invention has the beneficial effects that:
the invention has K2NiF4La of structure2NiO4Carrying out micro-ion substitution of different elements due to Ba2+、Ca2+Are all mixed with La3+Strong interfacial polarization is formed in the ceramic, giant dielectric phenomenon can be generated, the coulomb effect among the ceramic limits the movement of electrons to a certain degree, high loss generated by doping ions is reduced, and giant dielectric ceramic material La with dielectric constant as high as 4451410 is obtained2-x(Ba,Ca)xNiO4。
The barium-calcium co-doped substituted La prepared by the invention2NiO4Giant dielectric ceramic material La2-x(Ba,Ca)xNiO4Has high dielectric constant and good temperature stability of dielectric constant, and can be used in a wide frequency range such as 103-106Hz maintains a giant dielectric constant. The preparation method is simple, good in repeatability, high in yield, free of additional atmosphere auxiliary sintering and easy to prepare. In addition, La with different doping ratios can be obtained by changing the doping content of Ba and Ca by changing the dosage of the raw materials2-x(Ba,Ca)xNiO4Further, the dielectric property of the material system can be regulated and controlled.
Drawings
FIG. 1 is comparative example 1 La of the present invention2NiO4Ceramic samples and examples 1-5La2-x(Ba,Ca)xNiO4(0.1. ltoreq. X. ltoreq.0.5) an X-ray diffraction pattern of the ceramic sample.
FIG. 2 is comparative example 1 La of the present invention2NiO4Ceramic samples and examples 1-5La2-x(Ba,Ca)xNiO4(x is more than or equal to 0.1 and less than or equal to 0.5) the dielectric constant of the ceramic sample is plotted against the frequency.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
The invention is further illustrated by the following examples
Unless otherwise indicated, the starting materials, reagents and the like used in the following examples are all commercially available. Or alternatively, can be prepared by methods known in the art.
Comparative example 1
(1) Preparing mixed powder: placing 9.774g of lanthanum oxide and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, ball milling for 24 hours, drying, and sieving with a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La2NiO4Powder: placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to presintered at 1050 ℃ for 3 hours to obtain presintered La2NiO4Powder;
(3) secondary ball milling: pre-burning La2NiO4Placing the powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the powder into a planetary ball mill for ball milling for 18 hours, drying the powder, and screening the dried powder through a 150-mesh screen to obtain La2NiO4Powder;
(4) and (3) granulation: to 2g La2NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, sieving by a 40-mesh and 100-mesh sieve, and granulating;
(5) tabletting and forming: keeping the pressure of the powder in the step (4) on a press machine for 6min at 15MPa to press the powder into a blank, and keeping the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible2NiO4And (3) padding, finally placing the ceramic blank on the padding, and sintering in a high-temperature tube furnace. Sintering at 1250 ℃ for 3 hours in air atmosphere to obtain the compact ceramic. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1050 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling2NiO4Ceramic samples.
Example 1
(1) Preparing mixed powder: placing 9.286g of lanthanum oxide, 0.296g of barium carbonate, 0.15g of calcium carbonate and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, placing in a planetary ball mill for ball milling for 24 hours, drying, and sieving with a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La1.9(Ba,Ca)0.1NiO4The powder of (2): placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to pre-sinter for 3 hours at 1100 ℃ to obtain pre-sintered La1.9(Ba,Ca)0.1NiO4Powder;
(3) secondary ball milling: placing the presintered powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 18 hours, drying the mixture, and screening the dried mixture through a 150-mesh screen to obtain La1.9(Ba,Ca)0.1NiO4Powder;
(4) and (3) granulation: to 2g La1.9(Ba,Ca)0.1NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, and then sieving by a 40-mesh and 100-mesh sieve for granulation;
(5) tabletting and forming: maintaining the pressure of the powder in the step (4) on a press machine at 15MPa for 6min to obtain a blank, and maintaining the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
（7）and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible1.9(Ba,Ca)0.1NiO4And (4) padding, finally placing the blank body on the padding, and sintering in a high-temperature tube furnace. Sintering at 1300 ℃ for 3 hours in an air atmosphere to obtain dense ceramics. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1100 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling1.9(Ba,Ca)0.1NiO4Ceramic samples.
Example 2
(1) Preparing mixed powder: placing 8.797g of lanthanum oxide, 0.592g of barium carbonate, 0.3g of calcium carbonate and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, placing in a planetary ball mill for ball milling for 24 hours, drying, and then sieving by a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La1.8(Ba,Ca)0.2NiO4The powder of (2): placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to pre-sinter for 3 hours at 1100 ℃ to obtain pre-sintered La1.8(Ba,Ca)0.2NiO4Powder;
(3) secondary ball milling: placing the presintered powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 18 hours, drying the mixture, and screening the dried mixture through a 150-mesh screen to obtain La1.8(Ba,Ca)0.2NiO4Powder;
(4) and (3) granulation: to 2gLa1.8(Ba,Ca)0.2NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, and then sieving by a 40-mesh and 100-mesh sieve for granulation;
(5) tabletting and forming: maintaining the pressure of the powder in the step (4) on a press machine at 15MPa for 6min to obtain a blank, and maintaining the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible1.8(Ba,Ca)0.2NiO4And (4) padding, finally placing the blank body on the padding, and sintering in a high-temperature tube furnace. Sintering at 1300 ℃ for 3 hours in an air atmosphere to obtain dense ceramics. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1100 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling1.8(Ba,Ca)0.2NiO4Ceramic samples.
Example 3
(1) Preparing mixed powder: placing 8.308g of lanthanum oxide, 0.888g of barium carbonate, 0.45g of calcium carbonate and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, placing in a planetary ball mill for ball milling for 24 hours, drying, and sieving with a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La1.7(Ba,Ca)0.3NiO4The powder of (2): placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to pre-sinter for 3 hours at 1100 ℃ to obtain pre-sintered La1.7(Ba,Ca)0.3NiO4Powder;
(3) secondary ball milling: placing the presintered powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 18 hours, drying the mixture, and screening the dried mixture through a 150-mesh screen to obtain La1.7(Ba,Ca)0.3NiO4Powder;
(4) and (3) granulation: to 2g La1.7(Ba,Ca)0.3NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, and then sieving by a 40-mesh and 100-mesh sieve for granulation;
(5) tabletting and forming: maintaining the pressure of the powder in the step (4) on a press machine at 15MPa for 6min to obtain a blank, and maintaining the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible1.7(Ba,Ca)0.3NiO4And (4) padding, finally placing the blank body on the padding, and sintering in a high-temperature tube furnace. Sintering at 1300 ℃ for 3 hours in an air atmosphere to obtain dense ceramics. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1100 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling1.7(Ba,Ca)0.3NiO4Ceramic samples.
Example 4
(1) Preparing mixed powder: placing 7.819g of lanthanum oxide, 1.184g of barium carbonate, 0.6g of calcium carbonate and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, placing in a planetary ball mill for ball milling for 24 hours, drying, and sieving with a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La1.6(Ba,Ca)0.4NiO4The powder of (2): placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to pre-sinter for 3 hours at 1100 ℃ to obtain pre-sintered La1.6(Ba,Ca)0.4NiO4Powder;
(3) secondary ball milling: placing the presintered powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 18 hours, drying the mixture, and screening the dried mixture through a 150-mesh screen to obtain La1.6(Ba,Ca)0.4NiO4Powder;
(4) and (3) granulation: to 2gLa1.6(Ba,Ca)0.4NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, and then sieving by a 40-mesh and 100-mesh sieve for granulation;
(5) tabletting and forming: maintaining the pressure of the powder in the step (4) on a press machine at 15MPa for 6min to obtain a blank, and maintaining the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible1.6(Ba,Ca)0.4NiO4And (4) padding, finally placing the blank body on the padding, and sintering in a high-temperature tube furnace. Sintering at 1300 ℃ for 3 hours in an air atmosphere to obtain dense ceramics. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1100 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling1.6(Ba,Ca)0.4NiO4Ceramic samples.
Example 5
(1) Preparing mixed powder: placing 7.331g of lanthanum oxide, 1.48g of barium carbonate, 0.75g of calcium carbonate and 2.241g of nickel oxide in a ball milling tank, adding 10ml (0.45wt% of PVB +0.45wt% of oleic acid) and 5ml of absolute ethyl alcohol, placing in a planetary ball mill for ball milling for 24 hours, drying, and sieving with a 150-mesh sieve to obtain mixed powder;
(2) preparation of Pre-fired La1.5(Ba,Ca)0.5NiO4The powder of (2): placing the mixed powder in the step (1) into an alumina crucible, and placing the alumina crucible into a high-temperature tube furnace to pre-sinter for 3 hours at 1100 ℃ to obtain pre-sintered La1.5(Ba,Ca)0.5NiO4Powder;
(3) secondary ball milling: placing the presintered powder into a ball milling tank, adding 15ml of absolute ethyl alcohol, placing the mixture into a planetary ball mill for ball milling for 18 hours, drying the mixture, and screening the dried mixture through a 150-mesh screen to obtain La1.5(Ba,Ca)0.5NiO4Powder;
(4) and (3) granulation: to 2gLa1.5(Ba,Ca)0.5NiO4Adding 1ml of polyvinyl alcohol aqueous solution with the concentration of 5wt% into the powder, drying, and then sieving by a 40-mesh and 100-mesh sieve for granulation;
(5) tabletting and forming: maintaining the pressure of the powder in the step (4) on a press machine at 15MPa for 6min to obtain a blank, and maintaining the pressure for 2min by using a cold isostatic pressing machine at 200MPa to obtain a cylindrical sample piece with the diameter of 12mm and the thickness of about 1-2 mm;
(6) plastic discharging: heating the sample piece in the step (5) to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 1 hour to remove plastics from the ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into an alumina crucible, and paving a layer of La serving as a component in the crucible1.5(Ba,Ca)0.5NiO4And (4) padding, finally placing the blank body on the padding, and sintering in a high-temperature tube furnace. Sintering at 1300 ℃ for 3 hours in an air atmosphere to obtain dense ceramics. In the sintering process, the temperature is controlled at 5 ℃/min during temperature rising, the temperature is reduced to 1100 ℃ at the speed of 2 ℃/min during temperature reduction, and then the La is obtained after furnace cooling1.5(Ba,Ca)0.5NiO4Ceramic samples.
La of comparative example 1 and examples 1 to 5 of the present invention2-x(Ba,Ca)xNiO4The X-ray diffraction results of the ceramic samples are shown in FIG. 1, from La2NiO4And La2-x(Ba,Ca)xNiO4The XRD characteristic diffraction peak of the ceramic sample can be seen: the structure of the compound obtained after sintering is a single tetragonal phase.
The dielectric constant versus frequency curves for the comparative example 1 and examples 1-5 ceramic samples of the present invention are shown in FIG. 2, from which it can be seen that: the test frequency was 10 at 28 ℃3-106In Hz, the dielectric constant of the ceramic sample gradually increases with increasing Ba and Ca content.
The results of the dielectric constant test of the ceramic samples of comparative example 1 and examples 1 to 5 according to the present invention at a frequency of 2KHz at room temperature (28 ℃ C.) are shown in Table 1 below, and it can be seen from the results of Table 1 that the ceramic samples of examples La2-x(Ba，Ca)xNiO4After doping, its dielectric properties are comparable to La2NiO4The dielectric constant is greatly improved relative to La especially when the doping amount is x =0.52NiO4Approximately 10 times higher.
TABLE 1
Figure DEST_PATH_IMAGE002
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. Barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic, characterized in that a part of the element La is substituted by the elements Ba and Ca, and the chemical formula is La2-x(Ba,Ca)xNiO4Wherein x is in the range of 0<x≤0.5；
The barium calcium co-doped substituted La2NiO4The giant dielectric ceramic has K2NiF4Structure;
the barium calcium co-doped substituted La2NiO4The giant dielectric ceramic is prepared by adopting a solid-phase sintering method, and comprises the following steps:
(1) preparing mixed powder: the raw material La is added2O3、BaCO3、CaCO3Placing NiO in a ball mill for ball milling, drying and sieving to obtain mixed powder;
(2) preparation of Pre-fired La2-x(Ba,Ca)xNiO4Powder: putting the mixed powder in the step (1) into a high-temperature tube furnace for presintering to obtain presintered La2-x(Ba,Ca)xNiO4Powder;
(3) secondary ball milling: pre-burning La2-x(Ba,Ca)xNiO4Ball-milling the powder in a ball mill, drying and sieving to obtain La2-x(Ba,Ca)xNiO4Powder;
(4) and (3) granulation: to La2-x(Ba,Ca)xNiO4Adding a binder into the powder, drying, sieving and granulating;
(5) tabletting and forming: pressing the powder obtained in the step (4) into a blank on a press machine, and carrying out cold isostatic pressing to obtain a sample piece;
(6) plastic discharging: heating the sample piece in the step (5) and then preserving heat, and performing plastic removal on the sample piece to obtain a ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into a high-temperature tube furnace for sintering, and cooling along with the furnace to obtain a product;
in the step (2), the pre-sintering is performed at 900-1200 ℃;
the pre-sintering time is 1-5 hours;
in the step (7), the sintering temperature is 1200-1400 ℃;
the sintering time is 2-3 hours.
2. The barium calcium co-doped substituted La of claim 12NiO4Giant dielectric ceramic is characterized in that x is within the range of 0.1-0.5.
3. The barium calcium co-doped substituted La of claim 22NiO4Giant dielectric ceramic, characterized in that the barium calcium co-doped substitutes La2NiO4The chemical formula of the giant dielectric ceramic is any one of the following formulas: la1.5(Ba,Ca)0.5NiO4、La1.6(Ba,Ca)0.4NiO4、La1.7(Ba,Ca)0.3NiO4、La1.8(Ba,Ca)0.2NiO4、La1.9(Ba,Ca)0.1NiO4；
The ratio of Ba to Ca is (1-3): 1.
4. the barium calcium co-doped substituted La of any one of claims 1 to 32NiO4The preparation method of the giant dielectric ceramic is characterized by adopting a solid-phase sintering method and comprising the following steps of:
(1) preparing mixed powder: the raw material La is added2O3、BaCO3、CaCO3Placing NiO in a ball mill for ball milling, drying and sieving to obtain mixed powder;
(2) preparation of Pre-fired La2-x(Ba,Ca)xNiO4Powder: putting the mixed powder in the step (1) into a high-temperature tube furnace for presintering to obtain presintered La2-x(Ba,Ca)xNiO4Powder;
(3) secondary ball milling: will be provided withPrefired La2-x(Ba,Ca)xNiO4Ball-milling the powder in a ball mill, drying and sieving to obtain La2-x(Ba,Ca)xNiO4Powder;
(4) and (3) granulation: to La2-x(Ba,Ca)xNiO4Adding a binder into the powder, drying, sieving and granulating;
(5) tabletting and forming: pressing the powder obtained in the step (4) into a blank on a press machine, and carrying out cold isostatic pressing to obtain a sample piece;
(6) plastic discharging: heating the sample piece in the step (5) and then preserving heat, and performing plastic removal on the sample piece to obtain a ceramic blank;
(7) and (3) sintering: placing the ceramic blank in the step (6) into a high-temperature tube furnace for sintering, and cooling along with the furnace to obtain a product;
in the step (2), the pre-sintering is performed at 900-1200 ℃;
the pre-sintering time is 1-5 hours;
in the step (7), the sintering temperature is 1200-1400 ℃;
the sintering time is 2-3 hours.
5. The method according to claim 4, wherein, in the step (1),
the raw material La2O3、BaCO3、CaCO3The molar ratio of NiO is (3-19): 1: 1: (4-20);
the ball milling medium used in the ball milling is a mixture of polyvinyl butyral (PVB), oleic acid and ethanol;
the concentration of the polyvinyl butyral (PVB) and the oleic acid is 0.1 to 0.5 weight percent;
the volume ratio of the total volume of the polyvinyl butyral (PVB) and the oleic acid to the volume of the ethanol is (3-1): 1;
the ball milling time is 18-24 hours;
the sieving is a sieve with 120 meshes and 150 meshes.
6. The method according to claim 4 or 5, wherein in the step (3), the ball milling medium used in the ball milling is ethanol;
the prefired La2-x(Ba,Ca)xNiO4The volume ratio of the powder mass to the ball milling medium is 1 g: (10-15) mL;
the ball milling time is 16-24 hours;
the sieving is performed by a sieve with 120-150 meshes;
the prefired La2-x(Ba,Ca)xNiO4The volume ratio of the powder mass to the ball milling medium is 1 g: (10-15) mL;
the ball milling time is 16-24 hours;
the sieving is a sieve with 120 meshes and 150 meshes.
7. The method according to claim 4 or 5, wherein in the step (4), the binder is a 1-5wt% aqueous solution of polyvinyl alcohol;
the dosage of the polyvinyl alcohol aqueous solution is La2-x(Ba,Ca)xNiO45-8wt% of the powder;
the sieving is double-layer sieving.
8. The production method according to claim 4 or 5, wherein in the step (5), the tablet is formed into a dry-pressed shape;
the pressure used for dry pressing is 15-20 MPa;
the pressure maintaining time of the dry pressing is 4-6 min;
the pressure of the cold isostatic pressing is 190-200 MPa;
the pressure maintaining time of the cold isostatic pressing is 1-3 min;
the sample piece is cylindrical, the diameter is 12mm, and the thickness is 1-2 mm.
9. The preparation method according to claim 4 or 5, wherein in the step (6), the temperature is raised to 450-600 ℃ in the plastic removal process;
the heat preservation time is 1-2 hours;
the heating rate in the plastic discharging process is 2-5 ℃/min.
10. The production method according to claim 4 or 5, wherein in the step (7), during the sintering, the temperature is raised at a rate of 5 ℃/min, and during the temperature lowering, the temperature is lowered at a rate of 2 ℃/min to the temperature for the pre-firing in the step (2);
laying a layer of padding below the ceramic blank in the sintering process;
the components of the padding are the same as those of the pre-sintered powder.
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