A perovskite-structured material applicable to MLCC and its preparation method

Abstract

The present invention relates to a perovskite structure material that can be used for MLCC and a preparation method thereof. In addition to barium titanate, the raw materials required for the preparation also contain 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 barium titanate; the mass ratio of Gd₂O₃ to Pr₆O₁₁ is 2.0 - 2.3:1; the barium titanate is prepared by high-energy ball milling of raw material A and raw material B. Raw material A is anatase and rutile mixed crystal type titanium dioxide powder, and the ratio of anatase phase to rutile phase is 50% - 60%:40% - 50%. By selecting a specific ratio of anatase and rutile mixed crystal type titanium dioxide powder and combining it with the high-energy ball milling process, the present invention improves the particle uniformity of the prepared barium titanate, makes the particle size finer, and improves the dielectric properties of the ceramic.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic material preparation, and particularly relates to a solid-phase preparation method for ultrafine barium titanate powder and its product. Background Art

[0002] As a typical perovskite-type ferroelectric ceramic material, barium titanate is widely used in fields such as multilayer ceramic capacitors (MLCCs), sensors, and memories due to its excellent dielectric, ferroelectric, and piezoelectric properties.

[0003] Currently, the preparation methods for 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 industrial mainstream due to its simple process and low cost. However, its core problem lies in the uneven mixing of raw materials. The traditional solid-phase method uses mechanical mixing of barium carbonate and titanium dioxide. Titanium dioxide is mostly in a single crystal form (such as anatase or rutile), and the crystal form difference leads to inconsistent reaction activities, and agglomerated particles with uneven particle sizes are easily formed during the sintering process. The BaTiO3 powder obtained by the liquid-phase method usually has -OH defects, which cause pores to form during the sintering of multilayer ceramic capacitors, affecting the performance and stability of multilayer ceramic capacitors. In addition, multilayer ceramic capacitors also have requirements for small size, high tetragonality, and higher dielectric properties of barium titanate powder. However, the barium titanate powder prepared by the liquid-phase method is also difficult to meet the requirements of high-end MLCCs in terms of tetragonal phase.

[0004] Therefore, there are technical problems in the existing preparation of barium titanate powder, such as uneven particle size, small specific surface area, uncontrollable particle size, insufficient fineness, and 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 for MLCC and its preparation method.

[0006] The present invention relates to a perovskite structure material for MLCC. In addition to barium titanate, the raw materials required for preparation also contain 0.1wt% - 0.2wt% of ZnO, 0.2wt% - 0.6wt% of Gd2O3, and 0.1wt% - 0.3wt% of Pr6O 11 based on the mass of barium titanate; the barium titanate is selected by using raw material A and raw material B through high-energy ball milling. Raw material A is an anatase and rutile mixed crystal form titanium dioxide powder, where the ratio of anatase phase to rutile phase is 50% - 60%:40% - 50%, and raw material B is Ba(OH)2·8H2O powder.

[0007] Preferably, the mass ratio of Gd2O3 to Pr6O 11 is 2.0 - 2.3:1.

[0008] The present invention relates to a preparation method of a perovskite structure material that can be used in MLCC, comprising the following steps: (1) Selecting anatase and rutile mixed crystal type titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 50% - 60%: 40% - 50%.

[0009] (2) Mixing raw material A and raw material B in a molar ratio of 1: 1.010 - 1.015, and then performing high-energy ball milling. The ball milling uses binary mixed beads and high-energy ball mills at a speed of 800 - 1100 rpm for 2 - 3 h. Subsequently, smaller-sized quaternary mixed beads are used to high-energy ball mill at a speed of 2500 - 3200 rpm for 3 - 4 h to prepare barium titanate.

[0010] (3) Incorporating 0.1wt% - 0.2wt% of ZnO, 0.2wt% - 0.6wt% of Gd2O3, and 0.1wt% - 0.3wt% of Pr6O into the barium titanate obtained in step (2), then performing ball milling to obtain a slurry, drying, adding a binder for granulation, compressing, degumming, and sintering at 1100 - 1200 °C for 2 - 4 h to obtain a perovskite structure material that can be used in MLCC. 11

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

[0012] In step (2), the quaternary mixed beads are quaternary mixed beads containing 0.05 mm, 0.1 mm, 0.3 mm, and 0.6 mm.

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

[0014] Preferably, in step (3), the mass ratio of Gd2O3 to Pr6O 11 is 2.0 - 2.3:1.

[0015] Preferably, in step (3), the binder 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 type titanium dioxide powder and combining it with the high-energy ball milling process, the difficulty of high-energy ball milling synthesis can be reduced. The rutile phase can synthesize tetragonal crystals at a lower temperature, making the reaction in the subsequent high-energy ball milling synthesis process more controllable, improving the particle uniformity of the prepared barium titanate, and making the particle size smaller.

[0017] Barium titanate is prepared by high-energy ball milling process. The high-energy ball milling triggers the mechanical and chemical activation processes among the raw material powders, causing interfacial reactions at the nanoscale. In the first stage of ball milling, a binary mixed bead is used to crush and refine the raw material powders into nanosized powders and disperse them evenly. Anatase TiO2 participates in the synthesis reaction first to form barium titanate microcrystals. In the second stage of ball milling, a quaternary mixed bead is used to promote grain growth, enhance the uniformity of powder size, and obtain finer particle size.

[0018] Barium titanate prepared by using mixed crystal type titanium dioxide powder and by high-energy ball milling method has higher reaction activity and requires a lower sintering temperature for sintering to prepare barium titanate ceramics. It can be sintered at 1100 - 1200 °C, reducing the sintering temperature by nearly 100 °C or more compared with the conventional method. Sintering is promoted by doping ZnO, and doping composite rare earth oxides Gd2O3 and Pr6O 11 , and optimizing their ratio improves the dielectric properties of the ceramics.

[0019] The average particle size of the barium titanate powder prepared by the present invention is in the range of 150 - 185 nm, 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 relative dielectric constant at room temperature of the perovskite structure material prepared for MLCC is above 4160, and the highest reaches 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 will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0021] Figure 1 It is a schematic process flow diagram of the preparation of the perovskite structure material for MLCC disclosed in the embodiments of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0022] The technical solutions of the present invention will be clearly and completely described below in conjunction with the drawings. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention.

[0023] There are technical problems in the preparation of existing barium titanate powder, such as uneven particle size, small specific surface area, uncontrollable particle size, not being fine enough, and the dielectric properties of the ceramics prepared from barium titanate need to be further improved.

[0024] For the above technical problems, a perovskite structure material applicable to MLCC according to an embodiment of the present invention, in addition to barium titanate, the raw materials required for preparation also contain 0.1wt%-0.2wt% of ZnO, 0.2wt%-0.6wt% of Gd2O3, and 0.1wt%-0.3wt% of Pr6O 11 based on the mass of barium titanate; the barium titanate is prepared by high-energy ball milling of raw material A and raw material B. Raw material A is anatase and rutile mixed crystal type titanium dioxide powder, where the ratio of anatase phase to rutile phase is 50% - 60%:40% - 50%, and raw material B is Ba(OH)2·8H2O powder.

[0025] In one embodiment, the mass ratio of Gd2O3 to Pr6O 11 is 2.0 - 2.3:1.

[0026] The perovskite structure material applicable to MLCC of the present invention is prepared by high-energy ball milling using anatase and rutile mixed crystal type titanium dioxide powder with a ratio of anatase phase to rutile phase of 50% - 60%:40% - 50%. By selecting this specific ratio of anatase and rutile mixed crystal type titanium dioxide powder, since the density of TiO2 in the anatase phase is lower than that of TiO2 in the rutile structure, the difficulty of high-energy ball milling synthesis can be reduced, and the rutile phase can synthesize tetragonal crystals at a lower temperature, making the reaction in the subsequent high-energy ball milling synthesis process more controllable, improving the particle uniformity of the prepared barium titanate, and making the particle size finer.

[0027] Barium titanate is prepared by high-energy ball milling. During the high-energy ball milling process, mechanical and chemical activation processes between raw material powders will be triggered, 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. The longer the ball milling time, the more severely the lattice structure is damaged. This damage will reduce the sintering temperature of barium titanate during 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. Since ZnO has a relatively low melting point, adding it to perovskite structure ceramics can act as a flux to promote sintering and improve dielectric properties. If the content of ZnO is less than 0.1Wt%, it will be difficult to obtain the above effects. If it exceeds 0.2wt%, the sintering performance will be reduced, and the preferred content is 0.1wt%-0.2wt%.

[0029] Gd2O3 and Pr6O 11 are both rare earth doping components. Gd2O3 increases the dielectric constant of the ceramic, but adding too much will increase the dielectric loss. Pr6O 11For the stable temperature characteristics, adding too much will cause an increase in dielectric loss. The preferred content is 0.2 wt% - 0.6 wt% of Gd2O3 and 0.1 wt% - 0.3 wt% of Pr6O 11 0.1 wt% - 0.3 wt%.

[0030] The simultaneous addition of Gd2O3 and Pr6O 11 has a mutual synergistic effect. When the mass ratio of Gd2O3 to Pr6O 11 is controlled to be 2.0 - 2.3:1, the dielectric constant can be significantly improved more than adding only one of them, thus enhancing the dielectric properties.

[0031] As Figure 1 shown, a preparation method of a perovskite structure material for MLCC according to an embodiment of the present invention includes the following steps: (1) Select anatase and rutile mixed crystal type titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 50% - 60%:40% - 50%.

[0032] (2) Mix raw material A and raw material B according to the molar ratio of 1:1.010 - 1.015, and then perform high-energy ball milling. The ball milling uses binary mixed beads and high-energy ball milling is carried out at a speed of 800 - 1100 rpm for 2 - 3 h. Subsequently, smaller-sized quaternary mixed beads are used to perform high-energy ball milling at a speed of 2500 - 3200 rpm for 3 - 4 h to prepare barium titanate.

[0033] (3) Incorporate 0.1 - 0.2 wt% of ZnO, 0.2 wt% - 0.6 wt% of Gd2O3, and 0.1 wt% - 0.3 wt% of Pr6O 11 into the barium titanate obtained in step (2), then perform ball milling to obtain a slurry, dry it, add a binder for granulation, pressing, degumming, and sinter at 1100 - 1200 °C for 2 - 4 h to obtain a perovskite structure material for MLCC.

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

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

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

[0037] In one embodiment, the mass ratio of Gd2O3 to Pr6O 11 in step (3) is 2.0 - 2.3:1.

[0038] The anatase phase and rutile phase ratio of the perovskite structure material of the MLCC is 50% - 60%: 40% - 50% of the mixed crystal type titanium dioxide powder, which is prepared by high-energy ball milling. By selecting the titanium dioxide powder of the anatase and rutile mixed crystal type with this specific ratio, since the density of TiO2 in the anatase phase is lower than that of TiO2 in the rutile structure, the difficulty of high-energy ball milling synthesis can be reduced, and the rutile phase can synthesize tetragonal crystals at a lower temperature, making the reaction in the subsequent high-energy ball milling synthesis process more controllable, improving the particle uniformity of the prepared barium titanate, and making the size finer.

[0039] The molar ratio of the anatase and rutile mixed crystal type titanium dioxide powder to Ba(OH)2·8H2O is 1: 1.010 - 1.015. The appropriate molar ratio of the titanium dioxide powder to Ba(OH)2·8H2O can ensure complete reaction and synthesize barium titanate. During the ball milling process, there will be a certain loss of Ba(OH)2·8H2O, so its proportion is appropriately increased during the synthesis process.

[0040] Barium titanate is prepared by high-energy ball milling process. During the high-energy ball milling process, mechanical and chemical activation processes between raw material powders will be triggered, causing interfacial reactions at the nanoscale. In the first stage of ball milling, binary mixed beads are used, with larger sizes. The ball milling mainly crushes and refines the raw material powders into nanoscale powders and disperses them evenly. Since the density of TiO2 in the anatase phase is lower, it is easier to participate in the synthesis reaction first during the high-energy ball milling process to form barium titanate microcrystals. In the second stage of ball milling, quaternary mixed beads are used. The high-speed collision mechanical energy of the combination of large and small mixed beads is continuously stored inside the microcrystals, promoting grain growth, enhancing the uniformity of the powder size, and obtaining finer particle sizes. The mechanical energy absorbed by the raw materials causes defects in the crystals. The longer the ball milling time, the more severely the lattice structure is damaged. This damage will reduce the sintering temperature of the formed barium titanate during the subsequent sintering process and is more conducive to improving the dielectric properties of barium titanate ceramics. To achieve the above effects, the binary mixed beads of the present invention are preferably binary mixed beads containing 0.8 mm and 1.2 mm, and the quaternary mixed beads are quaternary mixed beads containing 0.05 mm, 0.1 mm, 0.3 mm, and 0.6 mm, and the ball milling ball-to-material ratio is 4 - 5:1. The two types of mixed beads cooperate with each other, and through two-stage ball milling, the final barium titanate powder has higher reaction activity.

[0041] The barium titanate prepared by using the mixed crystal type titanium dioxide powder of the present invention and prepared by high-energy ball milling has higher reaction activity and requires a lower sintering temperature for sintering to prepare barium titanate ceramics. It can be sintered at 1100 - 1200 °C, reducing the sintering temperature by nearly 100 °C or more compared with the conventional method. By doping a specific proportion of rare earth oxide Gd2O3 and Pr6O 11, it can greatly improve the dielectric constant and enhance the dielectric properties.

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

[0043] Example 1: A preparation method of a perovskite structure material for MLCC, comprising the following steps: (1) Selecting anatase and rutile mixed crystal type titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 50%:50%.

[0044] (2) Mixing raw material A and raw material B in a molar ratio of 1:1.010, then performing high-energy ball milling. The ball milling uses binary mixed beads and high-energy ball mills at a speed of 900 rpm for 2 h. Subsequently, smaller-sized quaternary mixed beads are used to high-energy ball mill at a speed of 2500 rpm for 4 h to prepare barium titanate.

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

[0046] (3) Incorporate 0.1 wt% of ZnO, 0.2 wt% of Gd2O3, and Pr6O 11 0.1 wt% into the barium titanate obtained in step (2), then perform ball milling to obtain a slurry, dry it, add a PVA solution binder for granulation, molding, degumming, and then sinter at 1100 °C for 4 h to obtain a perovskite structure material for MLCC.

[0047] Example 2: A preparation method of a perovskite structure material for MLCC, comprising the following steps: (1) Selecting anatase and rutile mixed crystal type titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 55%:45%.

[0048] (2) Mixing raw material A and raw material B in a molar ratio of 1:1.011, then performing high-energy ball milling. The ball milling uses binary mixed beads and high-energy ball mills at a speed of 1000 rpm for 3 h. Subsequently, smaller-sized quaternary mixed beads are used to high-energy ball mill at a speed of 3000 rpm for 3 h to prepare barium titanate.

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

[0050] (3) Incorporate the barium titanate from step (2) with 0.15 wt% ZnO, 0.4 wt% Gd2O3, and 0.2 wt% Pr6O 11 , then perform ball milling to obtain a slurry, dry it, add a PVA solution binder for granulation, compaction, degumming, and sinter at 1150 °C for 3 h to obtain a perovskite-structured material for MLCC.

[0051] Example 3: A method for preparing a perovskite-structured material for MLCC, comprising the following steps: (1) Select anatase and rutile mixed-crystalline titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, where the ratio of anatase phase to rutile phase in raw material A is 60%:40%.

[0052] (2) Mix raw material A and raw material B in a molar ratio of 1:1.012, then perform high-energy ball milling. The ball milling uses a binary mixed bead and high-energy ball mills at a speed of 1100 rpm for 2 h, and then uses a smaller-sized quaternary mixed bead to high-energy ball mill at a speed of 3200 rpm for 3 h to prepare barium titanate.

[0053] The binary mixed bead is a binary mixed bead containing 0.8 mm and 1.2 mm, and the quaternary mixed bead is a quaternary mixed bead containing 0.05 mm, 0.1 mm, 0.3 mm, and 0.6 mm. The ball-to-material ratio for ball milling is 5:1.

[0054] (3) Incorporate the barium titanate from step (2) with 0.2 wt% ZnO, 0.6 wt% Gd2O3, and 0.27 wt% Pr6O 11 , then perform ball milling to obtain a slurry, dry it, add a PVA solution binder for granulation, compaction, degumming, and sinter at 1200 °C for 2 h to obtain a perovskite-structured material for MLCC.

[0055] Comparative Example 1: The difference between the perovskite-structured material for MLCC in Comparative Example 1 and that in Example 1 is only that: in step (1), the ratio of anatase phase to rutile phase in the titanium dioxide powder is 40%:60%.

[0056] Comparative Example 2: The difference between the perovskite-structured material for MLCC in Comparative Example 2 and that in Example 1 is only that: in step (2), the binary mixed bead is changed to a single 0.8 mm bead, and the quaternary mixed bead uses a binary mixed bead of 0.3 mm and 0.6 mm.

[0057] Comparative Example 3: The preparation method of the perovskite structure material for MLCC in Comparative Example 3 is only different from that in Example 1 in that: in step (2), a binary mixed bead is used for high-energy ball milling at 900 rpm for 1 h, and then a quaternary mixed bead with a smaller size is used for high-energy ball milling at 2500 rpm for 2 h.

[0058] Comparative Example 4: The preparation method of the perovskite structure material for MLCC in Comparative Example 4 is only different from that in Example 1 in that: in step (3), 0.05 wt% of ZnO and 0.2 wt% of Gd2O3 are doped into barium titanate.

[0059] Comparative Example 5: The preparation method of the perovskite structure material for MLCC in Comparative Example 5 is only different from that in Example 1 in that: in step (3), 0.1 wt% of ZnO, 0.1 wt% of Gd2O3, and Pr6O 11 0.05 wt% are doped into barium titanate.

[0060] Comparative Example 6: The preparation method of the perovskite structure material for MLCC in Comparative Example 6 is only different from that in Example 1 in that: in step (3), 0.1 wt% of ZnO, 0.2 wt% of Gd2O3, and Pr6O 11 0.6 wt% are doped into barium titanate.

[0061] The barium titanate and the perovskite structure material for MLCC prepared in Examples 1-3 and Comparative Examples 1-6 were tested. The average particle size of barium titanate was observed using a scanning electron microscope and measured using an image analysis program. The width of the particle size distribution curve was statistically analyzed using minitable software, represented by 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 1 kHz, a voltage of 1 V, and a room temperature of 25 °C. The results are shown in Table 1.

[0062] Table 1: Material property data prepared in Examples and Comparative Examples:

[0063]

[0064] As can be seen from Table 1, the average particle size of the barium titanate prepared by the present invention is 150 - 185 nm, 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 perovskite structure material prepared for MLCC has a relative dielectric constant at room temperature of more than 4160, up to 4500 at most. After adjusting the crystal form of the titanium dioxide powder and changing the ball milling conditions, the uniformity of the particle size distribution of the obtained barium titanate becomes worse, and the particle size of the powder also increases; after changing the types and proportions of the doping components, the relative dielectric constant decreases significantly.

[0065] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

Claims

1. A preparation method of a perovskite structure material that can be used for MLCC, characterized in that, It includes the following steps: (1) Select anatase and rutile mixed crystal type titanium dioxide powder as raw material A and Ba(OH)2·8H2O powder as raw material B, wherein the ratio of anatase phase to rutile phase in raw material A is 55% - 60%: 40% - 45%; (2) Mix raw material A and raw material B according to the molar ratio of 1: 1.010 - 1.015, and then carry out high-energy ball milling. The ball milling uses binary mixed beads and high-energy ball milling is carried out at a speed of 800 - 1100 rpm for 2 - 3 h. Subsequently, use smaller quaternary mixed beads to carry out high-energy ball milling at a speed of 2500 - 3200 rpm for 3 - 4 h to prepare barium titanate; (3) Incorporate the barium titanate from step (2) with 0.1 wt% - 0.2 wt% of ZnO, 0.2 wt% - 0.6 wt% of Gd2O3, and 0.1 wt% - 0.3 wt% of Pr6O based on the mass of barium titanate, then carry out ball milling to obtain a slurry, dry it, add a binder for granulation, molding, degumming, and sinter at 1100 - 1200 °C for 2 - 4 h to obtain a perovskite structure material that can be used for MLCC; 11 After that, perform ball milling to obtain a slurry, dry it, add a binder for granulation, molding, degumming, and sinter at 1100 - 1200 °C for 2 - 4 h to obtain a perovskite structure material that can be used for MLCC; The mass ratio of the Gd2O3 to Pr6O 11 is 2.0 to 2.3:

1.

2. The preparation method of a perovskite structure material applicable to MLCC according to claim 1, characterized in that, The binary mixed beads described in step (2) are binary mixed beads containing 0.8 mm and 1.2 mm.

3. The preparation method of a perovskite structure material applicable to MLCC according to claim 1, characterized in that, The quaternary mixed beads described in step (2) are quaternary mixed beads containing 0.05 mm, 0.1 mm, 0.3 mm, and 0.6 mm.

4. The preparation method of a perovskite structure material applicable to MLCC according to claim 1, characterized in that, The ball-to-material ratio in step (2) is 4 - 5:

1.

5. The preparation method of a perovskite structure material applicable to MLCC according to claim 1, characterized in that, The binder described in step (3) is a PVA solution.

6. A perovskite-structured material that can be used for MLCC, characterized in that, The perovskite structure material that can be used for MLCC is prepared by the preparation method described in any one of claims 1 - 5.

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