Perovskite structure material capable of being used for MLCC and preparation method of perovskite structure material

Abstract

The invention relates to a perovskite structure material capable of being used for an MLCC and a preparation method of the perovskite structure material, and the perovskite structure material is prepared from the following raw materials in addition to barium titanate: 0.1 wt%-0.2 wt% of ZnO, 0.2 wt%-0.6 wt% of Gd2O3 and 0.1 wt%-0.3 wt% of Pr6O11 based on the mass of the barium titanate; the mass ratio of the Gd2O3 to the Pr6O11 is (2.0 to 2.3): 1; the barium titanate is prepared from a raw material A and a raw material B through a high-energy ball milling method, the raw material A is anatase and rutile mixed crystal type titanium dioxide powder, and the proportion of an anatase phase to a rutile phase is (50%-60%): (40%-50%). By selecting anatase and rutile mixed crystal type titanium dioxide powder in a specific proportion and combining with a high-energy ball milling process, the particle uniformity of the prepared barium titanate is improved, the size is smaller, and the dielectric property of the ceramic is improved.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic material preparation, and in particular to a solid phase preparation method of ultrafine barium titanate powder and a product thereof. Background Art

[0002] Barium titanate, as a typical perovskite ferroelectric ceramic material, is widely used in multilayer ceramic capacitors (MLCC), sensors, memory and other fields due to its excellent dielectric, ferroelectric and piezoelectric properties.

[0003] At present, the preparation methods of barium titanate powder mainly include solid phase method, liquid phase method (such as hydrothermal method, sol-gel method) and gas phase method. Among them, the solid phase method has become the mainstream of the industry due to its simple process and low cost, but its core problem is that the raw materials are not mixed evenly. The traditional solid phase method uses barium carbonate and titanium dioxide to mechanically mix. Titanium dioxide is mostly a single crystal form (such as anatase or rutile). The difference in crystal form leads to inconsistent reaction activity, and it is easy to form agglomerated particles with uneven particle size during sintering. The BaTiO3 powder obtained by the liquid phase method usually has -OH defects, which causes multilayer ceramic capacitors to form pores during sintering, affecting the performance and stability of multilayer ceramic capacitors. In addition, multilayer ceramic capacitors also put forward requirements for barium titanate powder such as small size, high tetragonality, and higher dielectric properties, and barium titanate powder prepared by the liquid phase method is also difficult to meet the requirements of high-end MLCC in the tetragonal phase.

[0004] Therefore, the existing preparation of barium titanate powder has technical problems such as uneven particle size, small specific surface area, uncontrollable particle size, and insufficient fineness. The dielectric properties of ceramics prepared with barium titanate need to be further improved. Summary of the invention

[0005] In view of the above technical problems, the present invention provides a perovskite structure material that can be used for MLCC and a preparation method thereof.

[0006] The present invention relates to a perovskite structural material that can be used for MLCC. The raw materials required for preparation include, in addition to barium titanate, 0.1wt%-0.2wt% ZnO, Gd 2 O 3 0.2wt%-0.6wt%,Pr 6 O 11 0.1wt%-0.3wt%; the barium titanate is prepared by high-energy ball milling using raw materials A and B, wherein raw material A is anatase and rutile mixed crystal titanium dioxide powder, wherein the ratio of anatase phase to rutile phase is 50%-60%:40%-50%, and raw material B is Ba(OH) 2 8H 2 O powder.

[0007] Preferably, the Gd2 O 3 With Pr 6 O 11 The mass ratio is 2.0~2.3:1.

[0008] The present invention relates to a method for preparing a perovskite structural material that can be used for MLCC, comprising the following steps: (1) selecting anatase and rutile mixed crystal titanium dioxide powder as raw materials A and Ba(OH) 2 8H 2 O powder is raw material B, wherein the ratio of anatase phase to rutile phase of raw material A is 50%~60%:40%~50%.

[0009] (2) Raw material A and raw material B are mixed in a molar ratio of 1:1.010-1.015 and then subjected to high-energy ball milling. Binary mixed beads are used for ball milling, and the high-energy ball milling is performed at a speed of 800-1100 rpm for 2-3 hours. Subsequently, smaller quaternary mixed beads are used for high-energy ball milling at a speed of 2500-3200 rpm for 3-4 hours to prepare barium titanate.

[0010] (3) Add the barium titanate from step (2) into ZnO 0.1wt%-0.2wt%, Gd 2 O 3 0.2wt%-0.6wt%,Pr 6 O 11 After the content of 0.1wt%-0.3wt%, ball milling is performed to obtain a slurry, which is then dried, and a binder is added to granulate, press and debond, and then sintered at 1100-1200°C and kept warm for 2-4h to obtain a perovskite structural material that can be used for MLCC.

[0011] Preferably, the binary mixed beads in step (2) are binary mixed beads comprising 0.8 mm and 1.2 mm.

[0012] The quaternary mixed beads in step (2) are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm.

[0013] Preferably, the ball-to-material ratio in the step (2) is 4-5:1.

[0014] Preferably, in step (3), the Gd 2 O 3 With Pr 6 O 11 The mass ratio is 2.0~2.3:1.

[0015] Preferably, the adhesive in step (3) is a PVA solution.

[0016] The beneficial effects of the present invention are as follows: by selecting a specific ratio of anatase and rutile mixed crystal titanium dioxide powder and combining it with a high-energy ball milling process, the difficulty of high-energy ball milling synthesis can be reduced, and the rutile phase can be synthesized into tetragonal crystals at a lower temperature, so that the reaction of the subsequent high-energy ball milling synthesis process is more controllable, and the particle uniformity of the prepared barium titanate is improved and the size is smaller.

[0017] Barium titanate is prepared by high-energy ball milling. High-energy ball milling triggers mechanical and chemical activation processes between raw material powders, causing interfacial reactions on the nanoscale. In the first stage of ball milling, two-component mixed beads are used to crush and refine the raw material powder into nano-sized powders and evenly disperse them. The anatase phase TiO 2 It is the first to participate in the synthesis reaction to form barium titanate microcrystals. The second stage of ball milling uses quaternary mixed beads to promote grain growth, enhance the uniformity of powder size and obtain a finer particle size.

[0018] Barium titanate prepared by high-energy ball milling using mixed-crystal titanium dioxide powder has higher reactivity and requires a lower sintering temperature to prepare barium titanate ceramics. The sintering can be completed at 1100-1200°C, which is nearly 100°C lower than the conventional method. Sintering is promoted by doping ZnO and composite rare earth oxide Gd is doped. 2 O 3 With Pr 6 O 11 , and preferably their ratio improves the dielectric properties of the ceramic.

[0019] The barium titanate powder prepared by the present invention has an average particle size of 150-185nm, a D99 / D50 range of 1.15-1.31, a uniform particle size distribution, fine particles, and high purity. The room temperature relative dielectric constant of the prepared perovskite structure material that can be used for MLCC is above 4160, and the highest is 4500. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0021] Figure 1 The present invention is a schematic diagram of a process flow diagram for preparing a perovskite structural material that can be used for MLCC according to an embodiment of the present invention. DETAILED DESCRIPTION

[0022] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] The existing preparation of barium titanate powder has technical problems such as uneven particle size, small specific surface area, uncontrollable particle size, and insufficient fineness. The dielectric properties of ceramics prepared with barium titanate need to be further improved.

[0024] In view of the above technical problems, a perovskite structural material that can be used for MLCC according to an embodiment of the present invention comprises, in addition to barium titanate, 0.1wt%-0.2wt% ZnO, Gd 2 O 3 0.2wt%-0.6wt%,Pr 6 O 11 0.1wt%-0.3wt%; the barium titanate is prepared by high-energy ball milling using raw materials A and B, wherein raw material A is anatase and rutile mixed crystal titanium dioxide powder, wherein the ratio of anatase phase to rutile phase is 50%-60%:40%-50%, and raw material B is Ba(OH) 2 8H 2 O powder.

[0025] In one embodiment, the Gd 2 O 3 With Pr 6 O 11 The mass ratio is 2.0~2.3:1.

[0026] The perovskite structural material that can be used for MLCC of the present invention is prepared by high-energy ball milling using a mixed-crystal titanium dioxide powder having an anatase phase and a rutile phase ratio of 50% to 60%:40% to 50%. By selecting the mixed-crystal titanium dioxide powder of anatase and rutile in this specific ratio, due to the anatase phase TiO 2 The density is higher than that of rutile TiO 2 The temperature is low, which can reduce the difficulty of high-energy ball milling synthesis, and the rutile phase can synthesize tetragonal crystals at a lower temperature, making the reaction of the subsequent high-energy ball milling synthesis process more controllable, and the prepared barium titanate particles have improved uniformity and smaller size.

[0027] Barium titanate is prepared by high-energy ball milling. The high-energy ball milling process will trigger mechanical and chemical activation processes between the raw material powders, causing interfacial reactions at the nanoscale. Mechanical energy is continuously stored inside the microcrystals, promoting grain growth. The mechanical energy absorbed by the raw materials causes defects in the crystals. As the ball milling time increases, the lattice structure is more severely damaged. This damage will reduce the sintering temperature of barium titanate in the subsequent sintering process, and is more conducive to improving the dielectric properties of barium titanate ceramics.

[0028] Doping is an effective way to improve the dielectric properties of barium titanate ceramics. ZnO has a low melting point and can be added to perovskite structure ceramics as a flux to promote sintering and improve dielectric properties. It will be difficult to achieve the above effect if the ZnO content is lower than 0.1wt%, and the sintering performance will be reduced if it exceeds 0.2wt%. The content is preferably 0.1wt%-0.2wt%.

[0029] G 2 O 3 With Pr 6 O 11 Both are rare earth doping components. Gd2O3 increases the dielectric constant of ceramics, but excessive addition increases the dielectric loss. 6 O 11 When the temperature characteristics are stabilized, adding too much will increase the dielectric loss. The content is preferably Gd 2 O 3 0.2wt%-0.6wt%,Pr 6 O 11 0.1wt%-0.3wt%.

[0030] G 2 O 3 With Pr 6 O 11 Adding them simultaneously has a synergistic effect. 2 O 3 With Pr 6 O 11 When the mass ratio is 2.0~2.3:1, the dielectric constant can be greatly improved and the dielectric performance can be improved more than adding one of them alone.

[0031] like Figure 1 As shown, a method for preparing a perovskite structural material that can be used for MLCC in an embodiment of the present invention comprises the following steps: (1) selecting anatase and rutile mixed crystal titanium dioxide powder as raw material A and Ba(OH) 2 8H 2 O powder is raw material B, wherein the ratio of anatase phase to rutile phase of raw material A is 50%~60%:40%~50%.

[0032] (2) Raw material A and raw material B are mixed in a molar ratio of 1:1.010-1.015 and then subjected to high-energy ball milling. Binary mixed beads are used for ball milling, and the high-energy ball milling is performed at a speed of 800-1100 rpm for 2-3 hours. Subsequently, smaller quaternary mixed beads are used for high-energy ball milling at a speed of 2500-3200 rpm for 3-4 hours to prepare barium titanate.

[0033] (3) Adding the barium titanate from step (2) to ZnO 0.1-0.2wt%, Gd 2 O 3 0.2wt%-0.6wt%,Pr 6 O 11 After the content of 0.1wt%-0.3wt%, ball milling is performed to obtain a slurry, which is then dried, and a binder is added to granulate, press and debond, and then sintered at 1100-1200°C and kept warm for 2-4h to obtain a perovskite structural material that can be used for MLCC.

[0034] In one embodiment, the binary hybrid beads in step (2) are binary hybrid beads comprising 0.8 mm and 1.2 mm.

[0035] In one embodiment, the quaternary mixed beads in step (2) are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm.

[0036] In one embodiment, the ball-to-material ratio in the step (2) is 4-5:1.

[0037] In one embodiment, the Gd 2 O 3 With Pr 6 O 11 The mass ratio is 2.0~2.3:1.

[0038] The perovskite structural material of MLCC uses a mixed-crystal titanium dioxide powder with a ratio of 50% to 60% of anatase phase to 40% to 50% of rutile phase and is prepared by high-energy ball milling. By selecting this specific ratio of anatase and rutile mixed-crystal titanium dioxide powder, due to the anatase phase TiO 2 The density is higher than that of rutile TiO 2 The temperature is low, which can reduce the difficulty of high-energy ball milling synthesis, and the rutile phase can synthesize tetragonal crystals at a lower temperature, making the reaction of the subsequent high-energy ball milling synthesis process more controllable, and the prepared barium titanate particles have improved uniformity and smaller size.

[0039] Anatase and rutile mixed crystal titanium dioxide powder and Ba(OH) 2 8H 2O is 1:1.010~1.015, titanium dioxide powder and Ba(OH) 2 8H 2 The appropriate molar ratio of O can ensure the complete reaction and synthesize barium titanate. During the ball milling process, Ba(OH) 2 8H 2 O will have a certain loss, so its proportion will be appropriately increased during the synthesis process.

[0040] High-energy ball milling process is used to prepare barium titanate. During the high-energy ball milling process, mechanical and chemical activation processes between raw material powders are induced, causing interfacial reactions at the nanoscale. In the first stage of ball milling, two-component mixed beads are used, which are larger in size. Ball milling mainly crushes and refines the raw material powder into nano-sized powders and evenly disperses them. 2 The density is lower, and it is easier to participate in the synthesis reaction first in the high-energy ball milling process to form barium titanate microcrystals. The second stage of ball milling uses quaternary mixed beads. The high-speed collision mechanical energy of large and small mixed beads is continuously stored inside the microcrystals, which promotes grain growth, enhances the uniformity of powder size, and obtains a finer particle size. The mechanical energy absorbed by the raw material causes defects in the crystal. As the ball milling time increases, the lattice structure is more severely damaged. This damage will cause the formation of barium titanate to reduce the sintering temperature in the subsequent sintering process, and is more conducive to improving the dielectric properties of barium titanate ceramics. To achieve the above effect, the binary mixed beads of the present invention are preferably binary mixed beads comprising 0.8mm and 1.2mm, and the quaternary mixed beads are quaternary mixed beads comprising 0.05mm, 0.1mm, 0.3mm and 0.6mm, and the ball-to-material ratio of ball milling is 4~5:1. The two types of mixed beads cooperate with each other, and the final barium titanate powder has higher reactivity through two-stage ball milling.

[0041] The barium titanate prepared by using the mixed crystal titanium dioxide powder of the present invention and the high-energy ball milling method has higher reactivity, and the sintering temperature required for sintering the barium titanate ceramic is lower, and the sintering can be completed at 1100-1200°C, which is nearly 100°C lower than the conventional method. 2 O 3 With Pr 6 O 11 , which can significantly increase the dielectric constant and improve dielectric performance.

[0042] In one embodiment, the adhesive in step (3) is a PVA solution.

[0043] Example 1: A method for preparing a perovskite structural material that can be used for MLCC, comprising the following steps: (1) selecting anatase and rutile mixed crystal titanium dioxide powder as raw material A and Ba(OH) 28H 2 O powder is raw material B, in which the ratio of anatase phase to rutile phase of raw material A is 50%:50%.

[0044] (2) Raw material A and raw material B were mixed in a molar ratio of 1:1.010 and then subjected to high-energy ball milling. Binary mixed beads were used for ball milling and the high-energy ball milling was performed at 900 rpm for 2 h. Subsequently, smaller quaternary mixed beads were used for high-energy ball milling at 2500 rpm for 4 h to prepare barium titanate.

[0045] The binary mixed beads are binary mixed beads comprising 0.8 mm and 1.2 mm, the quaternary mixed beads are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm, and the ball-to-material ratio of the ball milling is 4:1.

[0046] (3) Add the barium titanate from step (2) into ZnO 0.1wt%, Gd 2 O 3 0.2wt%,Pr 6 O 11 After the concentration of 0.1wt%, ball milling is performed to obtain a slurry, which is then dried and granulated with a PVA solution binder. After pressing and debonding, the sintering is performed at 1100°C and kept warm for 4 hours to obtain a perovskite structural material that can be used for MLCC.

[0047] Example 2: A method for preparing a perovskite structural material that can be used for MLCC, comprising the following steps: (1) selecting anatase and rutile mixed crystal titanium dioxide powder as raw materials A and Ba(OH) 2 8H 2 O powder is raw material B, in which the ratio of anatase phase to rutile phase of raw material A is 55%%:45%.

[0048] (2) Raw material A and raw material B were mixed in a molar ratio of 1:1.011 and then subjected to high-energy ball milling. Binary mixed beads were used for ball milling and the high-energy ball milling was performed at a speed of 1000 rpm for 3 h. Subsequently, smaller quaternary mixed beads were used for high-energy ball milling at a speed of 3000 rpm for 3 h to prepare barium titanate.

[0049] The binary mixed beads are binary mixed beads comprising 0.8 mm and 1.2 mm, the quaternary mixed beads are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm, and the ball-to-material ratio of the ball mill is 4.5:1.

[0050] (3) Add the barium titanate from step (2) into ZnO 0.15wt%, Gd 2 O 3 0.4wt%,Pr 6 O 11After the concentration of 0.2wt%, ball milling is performed to obtain a slurry, which is then dried and granulated with a PVA solution binder, pressed and debonded, and then sintered at 1150°C for 3 hours to obtain a perovskite structural material that can be used for MLCC.

[0051] Example 3: A method for preparing a perovskite structural material that can be used for MLCC, comprising the following steps: (1) selecting anatase and rutile mixed crystal titanium dioxide powder as raw material A and Ba(OH) 2 8H 2 O powder is raw material B, wherein the ratio of anatase phase to rutile phase of raw material A is 60%:40%.

[0052] (2) Raw material A and raw material B were mixed in a molar ratio of 1:1.012 and then subjected to high-energy ball milling. Binary mixed beads were used for ball milling and the high-energy ball milling was performed at a speed of 1100 rpm for 2 h. Subsequently, smaller quaternary mixed beads were used for high-energy ball milling at a speed of 3200 rpm for 3 h to prepare barium titanate.

[0053] The binary mixed beads are binary mixed beads comprising 0.8 mm and 1.2 mm, the quaternary mixed beads are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm, and the ball-to-material ratio of the ball milling is 5:1.

[0054] (3) Add the barium titanate prepared in step (2) into ZnO 0.2wt%, Gd 2 O 3 0.6wt%,Pr 6 O 11 After the concentration of 0.27wt%, ball milling is performed to obtain a slurry, which is then dried and granulated with a PVA solution binder. After pressing and debonding, the sintering is performed at 1200°C and kept warm for 2h to obtain a perovskite structural material that can be used for MLCC.

[0055] Comparative Example 1: The perovskite structural material that can be used for MLCC in Comparative Example 1 is different from that in Example 1 only in that the ratio of anatase phase to rutile phase in the titanium dioxide powder in step (1) is 40%:60%.

[0056] Comparative Example 2: The perovskite structural material that can be used for MLCC in Comparative Example 2 is different from that in Example 1 only in that the binary mixed beads in step (2) are changed to 0.8 mm single beads, and the quaternary mixed beads are 0.3 mm and 0.6 mm binary mixed beads.

[0057] Comparative Example 3: The preparation method of the perovskite structural material that can be used for MLCC in Comparative Example 3 is different from that in Example 1 only in that: Step (2) uses binary mixed beads for high-energy ball milling at 900 rpm for 1 h, and then uses smaller quaternary mixed beads for high-energy ball milling at 2500 rpm for 2 h.

[0058] Comparative Example 4: The preparation method of the perovskite structure material that can be used for MLCC in Comparative Example 4 is different from that in Example 1 only in that: in step (3), barium titanate is doped with ZnO 0.05wt%, Gd 2 O 3 0.2wt%.

[0059] Comparative Example 5: The preparation method of the perovskite structure material that can be used for MLCC in Comparative Example 5 is different from that in Example 1 only in that: in step (3), barium titanate is doped with ZnO 0.1wt%, Gd 2 O 3 0.1wt%,Pr 6 O 11 0.05wt%.

[0060] Comparative Example 6: The preparation method of the perovskite structure material that can be used for MLCC in Comparative Example 6 is different from that in Example 1 only in that: in step (3), barium titanate is doped with ZnO 0.1wt%, Gd 2 O 3 0.2wt%,Pr 6 O 11 0.6wt%.

[0061] The barium titanate prepared in Examples 1-3 and Comparative Examples 1-6 and the perovskite structural materials that can be used for MLCC were tested, and the average particle size of the barium titanate was observed using a scanning electron microscope and the image analysis program was used to calculate the average particle size of the barium titanate. The width of the particle size distribution curve was statistically calculated using minitable software and expressed as D99 / D50, where D50 refers to the particle size equivalent to 10% of the total volume when the particle size is accumulated from small particles, and D99 refers to the particle size equivalent to 99% of the total volume when the volume is accumulated from small particles. The relative dielectric constants of these capacitors were measured at a frequency of 1KHz, 1V and a room temperature of 25°C. The results are shown in Table 1.

[0062] Table 1: Material performance data of examples and comparative examples:

[0063] It can be found from Table 1 that the average particle size of the barium titanate prepared by the present invention is 150-185nm, the D99 / D50 range is between 1.15-1.31, the particle size distribution is uniform, the particles are fine, and the purity is high. The room temperature relative dielectric constant of the prepared perovskite structure material that can be used for MLCC is above 4160, and the highest is 4500. After adjusting the crystal form of titanium dioxide powder and changing the ball milling conditions, the uniformity of the obtained barium titanate particle size distribution becomes worse, and the powder particle size also increases; after changing the type and proportion of the doping components, the relative dielectric constant decreases significantly.

[0064] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

Claims

1. A perovskite structural material that can be used for MLCC, characterized in that: The raw materials required for the preparation include, in addition to barium titanate, ZnO 0.1wt%-0.2wt%, Gd2O3 0.2wt%-0.6wt%, Pr6O 11 0.1wt%-0.3wt%; the barium titanate is prepared by high-energy ball milling using raw materials A and B, wherein raw material A is anatase and rutile mixed crystal titanium dioxide powder, wherein the ratio of anatase phase to rutile phase is 50%~60%:40%~50%, and raw material B is Ba(OH)2·8H2O powder.

2. A perovskite structural material that can be used for MLCC according to claim 1, characterized in that: The Gd2O3 and Pr6O 11 The mass ratio is 2.0~2.3:

1.

3. A method for preparing a perovskite structural material that can be used for MLCC, characterized in that: The following steps are involved: (1) Anatase and rutile mixed crystal titanium dioxide powder is selected as raw material A and Ba(OH)2·8H2O powder is selected as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 50%~60%:40%~50%; (2) Raw material A and raw material B are mixed in a molar ratio of 1:1.010~1.015 and then subjected to high-energy ball milling, wherein the ball milling adopts binary mixed beads and the high-energy ball milling is carried out at a speed of 800~1100rpm for 2-3h, and then the high-energy ball milling is carried out at a speed of 2500~3200rpm for 3-4h to prepare barium titanate; (3) The barium titanate prepared in step (2) is doped with ZnO 0.1wt%-0.2wt%, Gd2O3 0.2wt%-0.6wt%, Pr6O 11 After the content of 0.1wt%-0.3wt%, ball milling is performed to obtain a slurry, which is then dried, and a binder is added to granulate, press and debond, and then sintered at 1100-1200°C and kept warm for 2-4h to obtain a perovskite structural material that can be used for MLCC.

4. The method for preparing a perovskite structural material that can be used for MLCC according to claim 3, characterized in that: The binary mixed beads in step (2) are binary mixed beads comprising 0.8 mm and 1.2 mm.

5. The method for preparing a perovskite structural material that can be used for MLCC according to claim 3, characterized in that: The quaternary mixed beads in step (2) are quaternary mixed beads comprising 0.05 mm, 0.1 mm, 0.3 mm and 0.6 mm.

6. The method for preparing a perovskite structural material that can be used for MLCC according to claim 3, characterized in that: In step (2), the ball-to-material ratio of ball milling is 4-5:

1.

7. The method for preparing a perovskite structural material that can be used for MLCC according to claim 3, characterized in that: In step (3), Gd2O3 and Pr6O 11 The mass ratio is 2.0~2.3:

1.

8. The method for preparing a perovskite structural material that can be used for MLCC according to claim 3, characterized in that: The adhesive in step (3) is a PVA solution.

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