A Pb(Mg 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O 3-y MO-based high-entropy multilayer ceramic material and a method of manufacturing the same

Abstract

The application discloses a Pb(Mg 1 / 2 W 1 / 2 ) (1‑x) (In 1 / 2Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic material and a preparation method thereof. The implementation scheme is as follows: ingredients of Pb(Mg 1 / 2 W 1 / 2 ) (1‑x) (In 1 / 2Nb 1 / 2 ) x O3-yMO are prepared, the raw materials are ball-mixed and pre-sintered to obtain a base ceramic powder; the base ceramic powder is mixed with a solvent, a dispersing agent, a binder and a plasticizer to prepare a ceramic tape-casting slurry, a ceramic film strip is prepared through a tape-casting process, an inner electrode slurry is printed on the surface of the ceramic film strip, and a multilayer ceramic green body is prepared through alternating lamination and pressing; the multilayer ceramic green body is degreased and co-fired to obtain a Pb(Mg 1 / 2 W 1 / 2 ) (1‑x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based multilayer ceramic material. The application can reduce a sintering temperature, improve an electrical card temperature change, has low manufacturing cost, and has a simple preparation process, and can be applied to integration and application of high-performance solid-state electrical card refrigeration devices.

Description

Technical Field

[0001] This invention belongs to the field of ceramic materials technology, and specifically relates to a Pb(Mg)2O3... 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic materials and their preparation methods can be used for solid-state electrocaloric refrigeration. Background Technology

[0002] With the development of high-power-density electronic devices, 5G / 6G communications, power modules, and highly integrated packaging, the demand for chip-level and module-level thermal management continues to increase. Traditional vapor compression refrigeration technology suffers from problems such as complex structure, difficulty in miniaturization, noise and vibration, and the potential greenhouse effect of refrigerants, limiting its application in scenarios such as miniaturization, on-chip integration, and precise local temperature control. Therefore, solid-state refrigeration technology, with its advantages of no moving parts, fast response, easy integration, and environmental friendliness, has attracted attention.

[0003] Electrocaloric refrigeration utilizes the entropy change generated by the dipole-order-disorder transition of ferroelectric / antiferroelectric materials induced by an applied electric field, achieving reversible heat absorption and release, and possessing high energy efficiency and potential for device miniaturization. Lead-based antiferroelectric / ferroelectric materials, due to their ability to undergo field-induced phase transitions accompanied by significant polarization changes, typically exhibit significant electrocaloric responses. Among them, lead scandium tantalate (Pb(Sc)) 1 / 2Ta 1 / 2 Multilayer ceramic devices based on the O3 (PST) system exhibit outstanding performance in terms of electrocardiogram temperature change, but several key bottlenecks remain in engineering and large-scale fabrication: (1) High sintering temperature, usually requiring even higher temperatures to achieve densification, which limits the selection of internal electrode materials and often relies on more expensive precious metal electrodes; (2) Relatively limited effective cooling temperature range, making it difficult to simultaneously cover the application requirements of multiple temperature ranges such as room temperature, refrigeration, and freezing; (3) In order to obtain a higher effective electric field and breakdown strength during device fabrication, further optimization of the synergistic design of the multilayer structure and material system is required, otherwise breakdown failure or performance degradation is likely to occur under high electric field drive; (4) The overall manufacturing cost and process window are relatively demanding, which is not conducive to the low-cost integration of high-performance electrocardiogram cooling devices. In addition, among the existing multilayer ceramic related technologies, thick film dielectrics, multilayer piezoelectric devices, and multilayer energy storage dielectrics have been formed as technical routes. Although the above-mentioned technical solutions have made some progress in terms of high dielectric performance, piezoelectric output performance and energy storage performance, their technical objectives are mainly focused on improving dielectric, piezoelectric or energy storage performance, which are still quite different from the comprehensive requirements of electric card refrigeration devices for wide temperature range phase change control, low temperature co-firing compatibility and high electric field stable operation performance.

[0004] Patent document CN110642623A discloses "A Lead Magnesium Niobate-Lead Titanate Thick Film Ceramics and Its Preparation Method and Application," which employs a two-step method of powder preparation, secondary ball milling, tape casting, and sintering to prepare PMN-PT thick film ceramics. The resulting material has a high dielectric constant and is suitable for energy storage MLCCs. This approach primarily targets high-dielectric thick film dielectrics and does not address the wide-temperature-range response control, multilayer internal electrode synergistic design, and refrigeration cycle applications required for electrocaloric cooling.

[0005] Patent document CN115321978B discloses "a multilayer lead-based piezoelectric ceramic and its preparation method," which prepares multilayer lead-based piezoelectric ceramics through processes such as tape casting, internal electrode printing, stacking, isostatic pressing, and co-firing, achieving a high piezoelectric displacement output. This method demonstrates that lead-based systems have the foundation for multilayer device fabrication, but its core objective is piezoelectric actuation and drive, without optimization for enhancing electrocardioid effect, wide-temperature range cooling, and low-cost internal electrode compatibility.

[0006] Patent document CN119462080A discloses "A sandwich-structured multilayer high-entropy lead-free dielectric material and its preparation method," which improves the material's density, breakdown field strength, and energy storage density by combining a sandwich heterolayer structure with high-entropy dielectric design and pressure sintering. This approach primarily focuses on improving the performance of the energy storage medium, emphasizing increased breakdown strength and energy storage capacity. It does not address the design of reversible heat absorption / release, wide-temperature range control, or MLCC-type electrode driving structures for electrocaloric refrigeration.

[0007] In summary, existing thick-film dielectrics, multilayer piezoelectric devices, and multilayer energy storage technologies still struggle to simultaneously meet requirements such as low-temperature sintering densification, compatibility with low-cost internal electrodes, and significant electrocaloric effects over a wide temperature range. Therefore, there is an urgent need for a novel multilayer ceramic material system and its preparation method that can achieve densification at lower sintering temperatures, be compatible with low-cost internal electrodes, and maintain significant electrocaloric effects over a wide temperature range to meet the wide-temperature-range cooling needs of solid-state electrocaloric refrigeration devices in applications such as room temperature, refrigeration, and freezing. Summary of the Invention

[0008] The purpose of this invention is to address the shortcomings of the prior art by proposing a Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic materials and their preparation methods are proposed to reduce sintering temperature and preparation cost, while expanding the cooling temperature range and achieving wide-temperature-range caloric cooling capacity.

[0009] The technical approach to achieving the objective of this invention is to reduce the sintering temperature, improve powder stability, and reduce preparation costs by controlling the composition and designing a multilayer structure, and by introducing MO oxide, thereby making it suitable for integrated applications of high-performance solid-state electronic card cooling devices.

[0010] Based on the above ideas, the technical solution of the present invention includes:

[0011] 1. A Pb(Mg) alloy for solid-state capacitor cooling 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic material, characterized in that it comprises a ceramic dielectric layer and an inner electrode layer alternately stacked along the thickness direction;

[0012] The ceramic dielectric layer comprises one or more metallic elements Mg, W, In, Nb and one or more metal oxides MO, with a composition of Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x The chemical formula of O3-yMO is used to jointly occupy B-site lattice sites, form a multi-element disordered high configurational entropy solid solution structure, and regulate the sintering performance of the material, reduce the sintering temperature, and improve the compactness and structural stability of the dielectric layer. Here, x is the amount of In and Nb doping, and y is the amount of MO doping in the metal oxide.

[0013] The inner electrode layer is selected from any one of silver, silver-palladium alloy, platinum, copper, or nickel.

[0014] Furthermore, the metal oxide MO in the chemical formula is selected from one or a combination of several of CaO, Al2O3, MnO, Fe2O3, CuO, Sm2O3, and SiO2.

[0015] Furthermore, the In and Nb doping amount x is taken from 0 to 1. By adjusting the content of x, the antiferroelectric-ferroelectric phase transition point of the material is located in the temperature range of -100 to 60°C. The doping amount y of the metal oxide MO is taken from 0.001 to 0.050. By adjusting the content of y, the stability of the matrix ceramic powder is improved and the sintering temperature is reduced, thereby improving the density and structural stability of the dielectric layer.

[0016] 2. A Pb(Mg) alloy for solid-state capacitor cooling 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2) x A method for preparing O3-yMO-based high-entropy multilayer ceramic materials, characterized by comprising the following steps:

[0017] 1) According to Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x The composition of O3-yMO is formulated, where x = 0-1, y = 0.001~0.05, and MO is one or more of CaO, Al2O3, MnO, Fe2O3, CuO, Sm2O3, and SiO2.

[0018] 2) The raw materials obtained in step 1) are ball-milled, mixed, and pre-sintered to obtain matrix ceramic powder;

[0019] 3) The matrix ceramic powder obtained in step 2) is mixed with solvent, dispersant, binder and plasticizer to prepare ceramic casting slurry, and ceramic film tape is obtained by casting process;

[0020] 4) Print the inner electrode paste on the surface of the ceramic film tape, and then alternately stack and press to produce a multi-layer ceramic green body;

[0021] 5) The multi-layer ceramic green body is subjected to debinding and co-firing to obtain Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO based multilayer ceramic materials.

[0022] Further, the solvent used in step 3) is one or more of ethyl acetate, toluene, anhydrous ethanol, tetrabutyl acetate, and methyl ethyl ketone; the dispersant is one or more of tributyl phosphate, polymethacrylic acid, or dodecyl succinic acid; the binder is one or more of polyvinyl butyral, polyvinyl alcohol, or methylcellulose; and the plasticizer is one or more of polyethylene glycol, phthalate, or dibutyl phthalate butyral; the solvent, dispersant, binder, and plasticizer together account for 30-70% of the mass percentage of the basic ceramic powder.

[0023] Furthermore, in step 5), the multi-layer ceramic green body is co-fired at a sintering temperature of 800-1100℃, a cooling rate of 3-10℃ / min, and a holding time of 5-40h.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] Firstly, this invention uses Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x The O3-yMO system, as a ceramic dielectric layer material, can generate a large entropy change by utilizing the antiferroelectric-ferroelectric phase transition that occurs under an applied electric field, thereby obtaining a significant electrocaloric effect. It can achieve an adiabatic temperature change ΔT greater than 5 K under an electric field of 280 kV / cm and above, providing a material basis for solid-state electrocaloric refrigeration.

[0026] Secondly, by constructing a multilayer ceramic structure, the dielectric layer is made thinner, which helps to improve the breakdown field strength and effective working electric field, thereby enhancing the electrical response and improving the reliability of the device operation.

[0027] Thirdly, by adjusting the doping amount x of In and Nb, the phase transition temperature range of the material can be controlled within the range of -100 to 60°C, thereby expanding its application range in different temperature ranges such as freezing, refrigeration and near room temperature, and endowing the material with wide temperature range electrocaloric refrigeration potential.

[0028] Fourth, by introducing metal oxide MO doping, this invention can improve powder stability, sintering performance and dielectric layer density. Furthermore, by controlling the co-firing temperature within the range of 800–1100°C, it can improve co-firing compatibility with internal electrode materials such as silver, silver-palladium alloys, copper, and nickel, thereby reducing preparation costs and facilitating device integration.

[0029] Fifth, the preparation method described in this invention has a clear process flow, is highly operable, and is suitable for the preparation of multilayer ceramic materials. Attached Figure Description

[0030] Figure 1 This invention relates to Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x Schematic diagram of O3-yMO-based high-entropy multilayer ceramic materials;

[0031] Figure 2 This invention is for the preparation of Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x Flowchart for the realization of O3-yMO-based high-entropy multilayer ceramic materials;

[0032] Figure 3 The Pb(Mg) obtained in this invention1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x XRD patterns of O3-yMO-based high-entropy multilayer ceramic materials;

[0033] Figure 4 The Pb(Mg) obtained in this invention 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x Hysteresis loop diagram of O3-yMO-based high-entropy multilayer ceramic material PE;

[0034] Figure 5 The Pb(Mg) obtained in this invention 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x Electrocaloric performance spectrum of O3-yMO-based high-entropy multilayer ceramic materials. Detailed Implementation

[0035] The embodiments of the present invention will be further described in detail below with reference to the accompanying drawings. However, the implementation of the present invention is not limited to the scope shown in the embodiments. These embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Furthermore, after reading the contents of this invention, those skilled in the art can make various modifications to the present invention, and these equivalent changes also fall within the scope defined by the appended claims.

[0036] Reference Figure 1 The Pb(Mg) of the present invention 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic materials, including

[0037] A ceramic dielectric layer and an internal electrode layer are alternately stacked along the thickness direction, wherein:

[0038] The ceramic dielectric layer is made of Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) xThe O3-yMO composition system forms a multi-element disordered high configurational entropy solid solution structure through the synergistic occupancy of Mg, W, In, Nb and the metal oxide MO on the B-site lattice, thereby improving material stability, enhancing sintering performance and optimizing the compactness and structural stability of the dielectric layer. The metal oxide MO adopts one or more combinations of CaO, Al2O3, MnO, Fe2O3, CuO, Sm2O3 and SiO2. Where x represents the In and Nb doping amounts, with values ​​ranging from 0 to 1. By adjusting the x content, the antiferroelectric-ferroelectric phase transition point of the material can be located within the temperature range of -100 to 60℃, which is beneficial for expanding the solid-state electro-calorie refrigeration applications of the material in different temperature ranges such as freezing, refrigeration, and near room temperature. y represents the MO metal oxide doping amount, with values ​​ranging from 0.001 to 0.050. By adjusting the y content, the stability of the matrix ceramic powder can be further improved, the sintering temperature can be reduced, and the density and structural stability of the dielectric layer can be improved.

[0039] The inner electrode layer, which is placed between adjacent ceramic dielectric layers, is used to apply a driving electric field to the ceramic dielectric layer under the action of an external electric field. Its material can be selected from any one of silver, silver-palladium alloy, platinum, copper or nickel.

[0040] This multilayer structure, formed by the alternating stacking of ceramic dielectric layers and internal electrode layers, allows for thinning of the dielectric layer, thereby increasing the breakdown field strength and effective operating electric field of the device. This is beneficial for enhancing the electrocaloric response of the material and improving the operational reliability of the device.

[0041] Reference Figure 2 This invention provides a method for preparing Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x Three embodiments of O3-yMO-based high-entropy multilayer ceramic materials.

[0042] Example 1: A substrate with x=0.05, y=0.001, and Mo is CuO, with 5 dielectric layers, and Pb(Mg) is used as the internal electrode with silver-palladium internal electrode. 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy ceramic materials.

[0043] Step 1: Prepare the matrix ceramic powder.

[0044] Based on stoichiometry for Pb(Mg) 1 / 2 W 1 / 2 )0.95 (In 1 / 2 Nb 1 / 2 ) 0.05 The raw materials for O3-0.001CuO ceramics were weighed and added into a ball mill jar. Water was used as the ball milling medium, and zirconia balls were used for wet ball milling for 12 hours to obtain a uniformly mixed slurry.

[0045] After drying and sieving, the slurry was pre-sintered at 700℃ for 2 hours to obtain a perovskite-structured Pb(Mg) matrix. 1 / 2W 1 / 2 ) 0.95 (In 1 / 2 Nb 1 / 2 ) 0.05 O3-0.001CuO ceramic powder.

[0046] Step 2: Prepare ceramic membrane strips.

[0047] 50g of pre-sintered ceramic powder, 8g of ethyl acetate solvent, 2g of tetrabutyl acetate solvent, 1g of dodecyl succinic acid dispersant, 2.5g of methyl cellulose binder, and 1.5g of polyethylene glycol plasticizer were selected. The solvent, dispersant, binder, and plasticizer together accounted for 30% of the mass percentage of the base ceramic powder. After mixing, the mixture was ball-milled again to obtain a ceramic casting slurry with stable and uniform dispersion.

[0048] The slurry is vacuum degassed and then cast into a ceramic film tape, with the thickness of the ceramic film tape controlled at 60 μm.

[0049] Step 3: Prepare multi-layer ceramic green bodies.

[0050] The ceramic film strip is cut to the specified size, and silver-palladium inner paste electrodes are printed on the surface of the film strip using screen printing.

[0051] The ceramic film strips printed with internal electrodes are alternately stacked and pressed according to the designed number of layers to form a 5-layer ceramic green body.

[0052] Step 4: Debinding and sintering of multilayer ceramic samples.

[0053] The five-layer ceramic green body was subjected to a debinding treatment to remove organic matter, followed by low-temperature co-firing at 1000 °C for 20 h at a heating rate of 10 °C / min to obtain a densified five-layer Pb(Mg)2. 1 / 2 W 1 / 2 ) 0.95 (In 1 / 2 Nb 1 / 2 ) 0.05 O3-0.001CuO ceramics.

[0054] Example 2: Preparation of a Pb(MgO) dielectric layer with x=0.4, y=0.02, MO=MnO, 50 layers, and silver internal electrode. 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy ceramic materials.

[0055] Step 1: Prepare the matrix ceramic powder.

[0056] 1.1) Based on stoichiometry for Pb(Mg) 1 / 2 W 1 / 2 ) 0.6 (In 1 / 2 Nb 1 / 2 ) 0.4 The raw materials for O3-0.02 MnO ceramics were weighed and added into a ball mill jar. Water was used as the ball milling medium, and zirconia balls were used for wet ball milling for 12 hours to obtain a uniformly mixed slurry.

[0057] 1.2) After drying and sieving the slurry, it was pre-sintered at 900℃ for 15 hours to obtain a perovskite-structured matrix Pb(Mg) 1 / 2W 1 / 2 ) 0.6 (In 1 / 2 Nb 1 / 2 ) 0.4 O3-0.002 MnO ceramic powder.

[0058] Step 2: Prepare ceramic membrane strips.

[0059] 2.1) Select 50g of pre-sintered ceramic powder, 14g of butanone solvent, 2.7g of tributyl phosphate dispersant, 1.8g of polyvinyl alcohol binder, and 1.5g of dibutyl phthalate butyral plasticizer respectively;

[0060] 2.2) The solvent, dispersant, binder and plasticizer are mixed and then ball-milled together with the pre-sintered ceramic powder to obtain a ceramic casting slurry with stable and uniform dispersion, wherein the total mass of the solvent, dispersant, binder and plasticizer accounts for 40% of the mass of the pre-sintered ceramic powder;

[0061] 2.3) After vacuum degassing of the slurry, it is cast into a ceramic film tape with a thickness of 5 μm.

[0062] Step 3: Prepare multi-layer ceramic green bodies.

[0063] 3.1) Cut the ceramic film strip to the specified size and print the silver electrode paste on the surface of the film strip using screen printing;

[0064] 3.2) The ceramic film strips printed with internal electrodes are alternately stacked and pressed according to the designed number of layers to form a 50-layer ceramic dielectric green body.

[0065] Step 4: Debinding and sintering the multilayer ceramic sample.

[0066] The 50-layer ceramic green body was subjected to a debinding treatment to remove organic matter, and then co-sintered at 1100 °C for 5 h at a heating rate of 6 °C / min to obtain a densified 50-layer Pb(Mg)2+. 1 / 2 W 1 / 2 ) 0.6 (In 1 / 2 Nb 1 / 2 ) 0.4 O3-0.02 MnO ceramics.

[0067] Example 3: A substrate with x=0.97, y=0.05, and MO is Fe2O3, with 96 dielectric layers, and Pb(Mg) internal electrode using copper internal electrode is prepared. 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy ceramic materials.

[0068] Step A: Prepare the matrix ceramic powder.

[0069] A1) Based on stoichiometry for Pb(Mg) 1 / 2 W 1 / 2 ) 0.03 (In 1 / 2 Nb 1 / 2 ) 0.97 The raw materials for O3-0.05Fe2O3 ceramics were weighed and added into a ball mill jar. Water was used as the ball milling medium, and zirconia balls were used for wet ball milling for 12 hours to obtain a uniformly mixed slurry.

[0070] A2) After drying and sieving the slurry, it was placed in a muffle furnace and pre-sintered at 820℃ for 9 hours to obtain a perovskite-structured matrix Pb(Mg) 1 / 2 W 1 / 2 ) 0.03 (In 1 / 2 Nb 1 / 2 ) 0.97 O3-0.05Fe2O3 ceramic powder.

[0071] Step B: Prepare ceramic membrane strips.

[0072] B1) Weigh 50 g of pre-sintered ceramic powder, and weigh solvent, dispersant, binder and plasticizer according to 70% of the mass of the pre-sintered ceramic powder, wherein the solvent includes 28 g of toluene and 8 g of anhydrous ethanol, the dispersant is 3 g of polymethacrylic acid, the binder is 5 g of polyvinyl butyral, and the plasticizer is 1 g of phthalate.

[0073] B2) The weighed solvent, dispersant, binder and plasticizer are mixed and then ball-milled together with the pre-sintered ceramic powder to obtain a ceramic casting slurry with stable and uniform dispersion.

[0074] B2) After vacuum degassing of the slurry, it is cast into a ceramic film with a thickness of 35 μm.

[0075] Step C: Prepare multi-layer ceramic green bodies.

[0076] C1) Cut the ceramic film strip to the specified size and print copper electrode paste on the surface of the film strip using screen printing;

[0077] C2) The ceramic film strips printed with copper internal electrodes are alternately stacked and pressed according to the designed number of layers to form a 96-layer ceramic green body.

[0078] Step D: Debinding and sintering of multilayer ceramic samples.

[0079] The 96-layer ceramic green body was debinded in a muffle furnace to remove organic matter, and then heated to 800 °C at a heating rate of 3 °C / min and held for 40 h to finally obtain a densified 96-layer Pb(Mg)2+. 1 / 2 W 1 / 2 ) 0.03 (In 1 / 2 Nb 1 / 2 ) 0.97 O3-0.05Fe2O3 multilayer ceramics.

[0080] The technical effects of this invention can be further illustrated by test results:

[0081] Test 1: X-ray diffraction testing was performed on the sample obtained in Example 1 of this invention. The results are as follows: Figure 3 As shown. From Figure 3 As can be seen, the sample formed the target perovskite main phase, indicating that the present invention can prepare the high-entropy multilayer ceramic material.

[0082] Test 2: Ferroelectricity tests were performed on the sample obtained in Example 1 of this invention, and the results are as follows. Figure 4 As shown. From Figure 4 It is evident that the sample exhibits a significant polarization response under an applied electric field, indicating that it possesses antiferroelectric to ferroelectric phase transition behavior.

[0083] Test 3: The sample obtained in Example 1 of this invention was subjected to a direct method electronic card performance test, and the results are as follows. Figure 5 As shown. From Figure 5 As can be seen, the sample exhibits a significant electrocaloric effect under a high electric field, indicating that the material described in this invention can be used for solid-state electrocaloric refrigeration.

[0084] The above descriptions are merely a few specific embodiments of the present invention and do not constitute any limitation on the present invention. Obviously, those skilled in the art, after understanding the content and principles of the present invention, may make various modifications and changes in form and detail without departing from the principles and structure of the present invention. For example, in addition to CuO, MnO, and Fe2O3 as described in the above embodiments, one or more of CaO, Al2O3, Sm2O3, and SiO2 can also be used; and in addition to silver, silver-palladium alloy, and copper as described in the above embodiments, platinum or nickel can also be used as the internal electrode material. However, these modifications and changes based on the concept of the present invention are still within the scope of protection of the claims of the present invention.

Claims

1. A Pb(Mg) alloy for solid-state capacitor cooling 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO-based high-entropy multilayer ceramic material, characterized in that... It includes ceramic dielectric layers and internal electrode layers that are alternately stacked along the thickness direction; The ceramic dielectric layer comprises one or more metallic elements Mg, W, In, Nb and one or more metal oxides MO, with a composition of Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x The chemical formula of O3-yMO is used to jointly occupy B-site lattice sites, form a multi-element disordered high configurational entropy solid solution structure, and regulate the sintering performance of the material, reduce the sintering temperature, and improve the compactness and structural stability of the dielectric layer. Here, x is the amount of In and Nb doping, and y is the amount of MO doping in the metal oxide. The inner electrode layer is selected from any one of silver, silver-palladium alloy, platinum, copper, or nickel.

2. The material according to claim 1, characterized in that, The metal oxide MO in the chemical formula is selected from one or a combination of several of CaO, Al2O3, MnO, Fe2O3, CuO, Sm2O3, and SiO2.

3. The material according to claim 1, characterized in that: The In and Nb doping amount x is between 0 and 1. By adjusting the content of x, the antiferroelectric-ferroelectric phase transition point of the material is located in the temperature range of -100 ~ 60°C. The doping amount y of the metal oxide MO is between 0.001 and 0.

050. By adjusting the content of y, the stability of the matrix ceramic powder is improved and the sintering temperature is reduced, thereby improving the density and structural stability of the dielectric layer.

4. A Pb(Mg) alloy for solid-state capacitor cooling 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x A method for preparing O3-yMO-based high-entropy multilayer ceramic materials, characterized in that... Including the following: 1) According to Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x The composition of O3-yMO is formulated, where x = 0-1, y = 0.001~0.05, and MO is one or more of CaO, Al2O3, MnO, Fe2O3, CuO, Sm2O3, and SiO2. 2) The raw materials obtained in step 1) are ball-milled, mixed, and pre-sintered to obtain matrix ceramic powder; 3) The matrix ceramic powder obtained in step 2) is mixed with solvent, dispersant, binder and plasticizer to prepare ceramic casting slurry, and ceramic film tape is obtained by casting process; 4) Print the inner electrode paste on the surface of the ceramic film tape, and then alternately stack and press to produce a multi-layer ceramic green body; 5) The multi-layer ceramic green body is subjected to debinding and co-firing to obtain Pb(Mg) 1 / 2 W 1 / 2 ) (1-x) (In 1 / 2 Nb 1 / 2 ) x O3-yMO based multilayer ceramic materials.

5. The preparation method according to claim 4, characterized in that, In step 2), the raw materials are pre-sintered at a temperature of 700-900℃ for 2-15 hours.

6. The preparation method according to claim 4, characterized in that, The solvents, dispersants, binders, and plasticizers used in step 3) are as follows: The solvent is one or more selected from ethyl acetate, toluene, anhydrous ethanol, tetrabutyl acetate, and methyl ethyl ketone. The dispersant is one or more of tributyl phosphate, polymethacrylic acid, or dodecyl succinic acid; The adhesive is one or more of polyvinyl butyral, polyvinyl alcohol, or methylcellulose. The plasticizer is one or more of polyethylene glycol, phthalate, or dibutyl phthalate butyral; The solvent, dispersant, binder, and plasticizer together account for 30-70% of the mass of the base ceramic powder.

7. The preparation method according to claim 4, characterized in that, The ceramic film strip produced in step 3) has a thickness of 5-60 μm.

8. The preparation method according to claim 4, characterized in that, In step 4), an internal electrode paste is printed on the surface of the ceramic film tape, which is one of silver, silver-palladium alloy, platinum, copper or nickel.

9. The preparation method according to claim 4, characterized in that, Step 4) The number of ceramic media layers in the multi-layer ceramic green body obtained is 5-100.

10. The preparation method according to claim 4, characterized in that, In step 5), the multi-layer ceramic green body is co-fired at a sintering temperature of 800-1100℃, a heating rate of 3-10℃ / min, and a holding time of 5-40h.

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