A, B-site component superparamagnetic phase perovskite ceramic material, and preparation method and application thereof

Abstract

This invention discloses a superparaelectric perovskite ceramic material with A and B site components, its preparation method, and its application. The chemical formula of the superparaelectric perovskite ceramic material with A and B site components is (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) x Ti 1‑x O3, where 0.1≤x≤0.3, the superparaelectric perovskite ceramic material of the A and B sites of the present invention can be used to prepare relaxor ferroelectric materials with good energy storage performance, which meets the current requirements for lead-free production, is environmentally friendly, has a simple process and stable performance, and is conducive to large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of perovskite oxide material dielectric energy storage technology, and particularly relates to a superparaelectric perovskite ceramic material with A and B site components, its preparation method and application. Background Technology

[0002] Dielectric capacitors are known for their ultra-high power density (10 8 With advantages such as high energy density (W / kg), excellent charge / discharge speed (μs to ns), ultra-long lifespan, high thermal stability (-50℃ to 250℃), and strong mechanical strength, dielectric capacitors have broad application prospects in power electronics, new energy vehicles, and aerospace. However, compared with electrochemical energy storage technologies, dielectric capacitors typically exhibit relatively low energy density, which limits their integration and miniaturization applications. Furthermore, the effective energy density (W / kg) is also limited. rec High energy storage efficiency (η) is an effective parameter for evaluating energy storage performance, and it largely depends on a large polarization difference ΔP (= maximum polarization P) max -Residual polarization P r ) and high breakdown strength (E b Therefore, the development and application of efficient energy storage materials have attracted increasing attention.

[0003] Meanwhile, perovskite oxide (ABO3), as one of the key research structures for energy storage materials, possesses excellent tunability and large structural tolerance, providing abundant possibilities for adjusting the energy storage performance of perovskite-structured ceramic materials. This makes it possible to induce relaxation behavior through composition design, thereby obtaining excellent energy storage performance.

[0004] Relaxor ferroelectrics, as potential candidates for energy storage dielectric materials, possess unique nanodomain structures and dispersed phase transition characteristics. Typical relaxor ferroelectrics exhibit three key characteristic temperatures: the Burns temperature (T0). B ), the temperature corresponding to the maximum dielectric constant (T) m ) and freezing temperature (T f These correspond to different ferroelectric properties and microstructures. Currently, research on relaxor ferroelectrics mainly focuses on T... f ~T m Within a specific temperature range, high polarization capability of the material can be achieved. However, the loss of the domain flipping energy barrier limits further improvement in energy storage performance. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a superparaelectric perovskite ceramic material with A and B site components, its preparation method, and its applications. The chemical formula of the superparaelectric perovskite ceramic material with A and B site components provided by this invention is as follows:

[0006] —(Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) x Ti 1-x O3, where 0.1 ≤ x ≤ 0.3, has a perovskite structure belonging to the cubic crystal system with space group Pm3m. The superparaelectric perovskite ceramic material with A and B site components of this invention can be used to prepare relaxor ferroelectric materials, exhibiting good energy storage performance and thus serving as an energy storage ceramic material. The energy storage ceramic material of this invention meets current lead-free requirements, is environmentally friendly, has a simple process flow and stable performance, and is conducive to large-scale production.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] One of the technical solutions of the present invention:

[0009] A superparaelectric perovskite ceramic material with A and B site components, having the general structural formula ABO3, wherein the A site is composed of three elements: Ba, Sr and Ca, and the B site is composed of two elements: Ti and Sn.

[0010] The three elements at site A occupy site A in an equimolar ratio, and the molar ratio of the two elements Ti and Sn at site B is (1~3)(7~9).

[0011] Preferably, in the superparaelectric perovskite ceramic material with components at the A and B sites, the two metal elements at the B site are respectively represented by Sn. 4+ ∶Ti 4+ =1∶9, Sn 4+ ∶Ti 4+ =1∶4, Sn 4+ ∶Ti 4+ The three molar ratios of 3:7 occupy position B.

[0012] Preferably, the chemical formula of the superparaelectric perovskite ceramic material with components at sites A and B is (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) x Ti 1-x O3, where 0.1≤x≤0.3, more preferably x=0.1, 0.2 or 0.3;

[0013] The perovskite structure of the superparaelectric perovskite ceramic material with components A and B sites belongs to the cubic crystal system, with space group Pm. m.

[0014] The second technical solution of the present invention:

[0015] This invention also provides a method for preparing the superparaelectric perovskite ceramic material with A and B site components, comprising the following steps:

[0016] (1) According to the stoichiometric ratio of the superparaelectric phase perovskite ceramic material of A and B sites, weigh the raw materials BaCO3, SrCO3, CaCO3, TiO2 and SnO2, add them to the ball mill jar, use zirconia balls as grinding balls, add anhydrous ethanol as the ball milling medium, put the ball mill jar into a planetary ball mill, and dry it after ball milling.

[0017] (2) The material dried in step (1) is pre-calcined in air at a temperature of 1000℃~1100℃ for 4~6 hours to obtain pre-calcined powder;

[0018] (3) The pre-calcined powder is added to a ball mill jar, the grinding balls are zirconia balls, anhydrous ethanol is added as the ball milling medium, the ball mill jar is placed in a planetary ball mill, and the powder is dried after ball milling.

[0019] (4) Add polyvinyl alcohol solution to the pre-calcined powder dried in step (3) for granulation, sieve the granules, dry press them into cylindrical green bodies, and then remove the glue from the cylindrical green bodies.

[0020] (5) The cylindrical green body after debinding is sintered in air at a temperature of 1400℃~1500℃ for 4~6 hours to obtain the superparaelectric perovskite ceramic material of the A and B site components.

[0021] Preferably, in the preparation method of the superparaelectric perovskite ceramic material of the A and B sites, in step (1), the mass ratio of the mixture, grinding balls, and grinding media is 1:2:2, where the mass of the mixture refers to the total mass of the raw materials BaCO3, SrCO3, CaCO3, TiO2, and SnO2. Zirconia, as the grinding ball material, can reduce contamination and improve grinding efficiency, while anhydrous ethanol, as the grinding media, can ensure chemical stability. The appropriate mass ratio of the mixture, grinding balls, and grinding media ensures sufficient grinding and uniform mixing, thereby forming a uniform ceramic structure in the subsequent sintering process. The ball milling is performed at a speed of 300–360 r / min for 6 hours, and the milled material is dried at 120°C for 2–3 hours. A reasonable milling time ensures sufficient grinding and mixing of the material, appropriate speed control prevents overheating, and avoids excessive grinding that could affect the particle size of the material and thus the energy storage ceramic performance.

[0022] Preferably, the purity of the raw materials BaCO3, SrCO3, CaCO3, TiO2 and SnO2 is above 99.9%, and the above raw materials are dried at 100-120℃ for 12-24 hours before being mixed.

[0023] Preferably, in the preparation method of the superparaelectric perovskite ceramic material of the A and B sites, in step (2), the heating rate from room temperature to 1000℃~1100℃ is 3~5℃ / min, preferably to 1100℃. A reasonable pre-firing temperature and time help remove organic matter, moisture, and volatile substances from the material. These substances may generate gas during high-temperature sintering, leading to pores or cracks inside the ceramic, affecting the material's mechanical strength and electrical properties. Simultaneously, a suitable heating rate can avoid thermal stress and crack formation, thus facilitating the acquisition of a uniform, crack-free pre-fired sample.

[0024] Preferably, in the preparation method of the superparaelectric perovskite ceramic material of the A and B site components, in step (3), the ball milling is performed at a speed of 300-360 r / min for 6 hours, and the ball-milled material is dried at 120°C for 2-3 hours.

[0025] Preferably, in the preparation method of the superparaelectric perovskite ceramic material of the A and B sites, in step (4), the mass concentration of the polyvinyl alcohol solution is 5%.

[0026] The sieving process is a 60-120 mesh sieve.

[0027] The uniaxial pressure during dry pressing is 5-8 MPa, and the holding time is 1-2 minutes; the mold used for dry pressing is a cylindrical mold with a diameter of 8-10 mm;

[0028] The debinding process involves removing the binder at 550℃ for 6–8 hours, with a heating rate of 1.5–2℃ / min. During debinding, an excessively rapid heating rate can lead to stress concentration within the green body, causing cracks or deformation and reducing the electrical properties of the energy storage ceramic. Conversely, an excessively slow heating rate may result in uneven material structure and excessive moisture absorption, increasing difficulties in subsequent sintering processes.

[0029] Preferably, in the preparation method of the superparaelectric perovskite ceramic material with components at sites A and B, in step (5), the rate at which the cylindrical green body after debinding is heated to 1400℃~1500℃ in air atmosphere is 3~5℃ / min. The calcination temperature and time affect the grain size, phase purity, and uniformity of the material, thus influencing its electrical properties, thermal stability, and mechanical strength. A suitable heating rate promotes uniform grain growth and the formation of the material's microstructure, effectively increasing the material's density and thereby achieving a higher breakdown field strength.

[0030] The superparaelectric state occurs in T B >T>T m Within a temperature range, the temperature can be adjusted to be close to or lower than the ambient temperature (T). ambThis can significantly improve energy storage performance and dielectric temperature stability. When T <T B In relaxor ferroelectrics, small-sized domains and short-range disordered polar nanodomains (PNRs) enhance local structural disorder. In superparaelectric relaxor ferroelectrics, lower hysteresis loss helps maintain a high polarization state, while the reduction in hysteresis loss and the high dynamics of PNRs jointly promote the formation of a slender PE curve, which is crucial for improving energy storage performance. Based on this, this invention constructs a superparaelectric phase through carefully designed components, providing a new approach to improving the performance of energy storage ceramics. The synergistic effect of multiple elements leads to chemical and structural disorder, thereby reducing the size of nanodomains, which is crucial for enhancing the breakdown field strength (E0). b This invention plays a crucial role in improving energy storage density and efficiency, thereby better meeting the needs of practical applications. It also contributes to enhancing temperature stability.

[0031] The third technical solution of the present invention:

[0032] The present invention also provides a relaxor ferroelectric material based on superparaelectric perovskite ceramic materials with A and B site components, wherein the superparaelectric perovskite ceramic materials with A and B site components are the aforementioned superparaelectric perovskite ceramic materials with A and B site components.

[0033] The relaxor ferroelectric material based on superparaelectric perovskite ceramic material with A and B site components has high energy storage density and high energy storage efficiency, and its energy storage performance is greatly improved compared with existing energy storage materials.

[0034] The fourth technical solution of the present invention:

[0035] The present invention also provides a method for preparing the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components, wherein silver electrodes are plated on the upper and lower surfaces of the superparaelectric perovskite ceramic material with A and B site components, and the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components is obtained after calcination and cooling.

[0036] Preferably, in the method for preparing the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components, the thickness of the superparaelectric perovskite ceramic material with A and B site components is 0.10 to 0.15 mm, and the surface of the superparaelectric perovskite ceramic material with A and B site components is polished smooth before silver plating.

[0037] The calcination temperature is 650℃, and the holding time is 30 minutes.

[0038] The fifth technical solution of the present invention:

[0039] The present invention also provides the application of the superparaelectric perovskite ceramic material with A and B site components or the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components in the field of dielectric energy storage, which is especially suitable for application scenarios that require fast charging and discharging and high energy density.

[0040] The chemical reaction involved in this invention is as follows:

[0041] 3ACO3+xB′O2+(1-x)B″O2→(A′A″A″′)(xB′)[(1-x)B″]O3+3CO2+O2

[0042] Compared with the prior art, the present invention has the following advantages and technical effects:

[0043] 1. This invention employs a traditional solid-state reaction method to prepare perovskite-type ceramic materials. By using three equivalent metals, ACO3, in an equimolar ratio to replace the corresponding A sites, and two types of BO2 in a (9-7):(1-3) molar ratio to replace the B sites, the invention achieves control over multiple components at the A and B sites. By adjusting the temperature to near or below ambient temperature, a superparaelectric phase is successfully constructed for better application in energy storage.

[0044] 2. In this invention, the synergistic effect of component design and superparaelectric relaxor ferroelectricity leads to the formation of small-sized domains and short-range disordered polar nanoregions (PNRs), thereby enhancing the disorder of the local structure. Lower hysteresis loss maintains the material's high polarizability; simultaneously, the reduced hysteresis loss and high-dynamic PNRs also promote the formation of a slender PE curve. These factors contribute to improving the breakdown field strength (E0). b It plays a crucial role in factors such as temperature stability.

[0045] 3. The supercielectric phase energy storage ceramic of this invention exhibits significant performance advantages compared to existing high-entropy energy storage ceramics. The energy storage mechanism of the supercielectric phase energy storage ceramic material is based on the polarization principle of dielectric materials, efficiently storing energy by forming a double electric layer on the electrode surface. This contrasts sharply with high-entropy energy storage ceramics, which rely on a complex solid solution structure composed of multiple elements and the resulting high-entropy effect. The supercielectric phase energy storage ceramic has a simple material composition and a mature and standardized preparation process, which not only ensures its high dielectric properties and low dielectric loss but also significantly reduces production costs. In contrast, the preparation process of high-entropy energy storage ceramics is more complex, involving precise control of multiple elements, which not only increases costs but also makes it difficult to guarantee sample purity. In terms of performance, the supercielectric phase energy storage ceramic excels in energy density, charge / discharge rate, and temperature stability, making it particularly suitable for applications requiring rapid charge / discharge and high energy density. Moreover, in terms of energy storage efficiency and response speed, the supercielectric phase energy storage ceramic is significantly superior to the high-entropy energy storage ceramic.

[0046] 4. The superparaelectric perovskite ceramic material prepared by this invention can be used as an energy storage material, meeting current lead-free requirements, being environmentally friendly, having a simple process, and exhibiting stable performance. Compared with the original material (pure BaTiO3 material without A- and B-site superparaelectric design), its comprehensive energy storage performance is significantly improved, which is conducive to large-scale production and can be widely used in pulse power electronic systems such as radar and communication. Attached Figure Description

[0047] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0048] Figure 1 (Ba) prepared in Example 1 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 XRD pattern of O3 oxide ceramic material.

[0049] Figure 2 (Ba) prepared in Example 1 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 SEM morphology results of O3 oxide ceramic materials.

[0050] Figure 3 (Ba) prepared in Example 1 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 Hysteresis loop (PE curve) of O3 relaxor ferroelectric ceramic material at 10 Hz.

[0051] Figure 4 (Ba) prepared in Example 2 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 XRD pattern of O3 oxide ceramic material.

[0052] Figure 5 (Ba) prepared in Example 2 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 )O3 relaxor ferroelectric ceramic material PE curve at 10Hz frequency.

[0053] Figure 6 (Ba) prepared in Example 3 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 XRD pattern of O3 oxide ceramic material.

[0054] Figure 7 (Ba) prepared in Example 3 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 )O3 relaxor ferroelectric ceramic material PE curve at 10Hz frequency.

[0055] Figure 8 (Ba) prepared for Comparative Example 1 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 XRD pattern of O3 oxide material.

[0056] Figure 9 (Ba) prepared for Comparative Example 2 1 / 3 Sr 1 / 3 Ca 1 / 3 (Zr) 0.2 Ti 0.8 XRD pattern of O3 oxide material.

[0057] Figure 10 (Ba) prepared for Comparative Example 3 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.6 Ti 0.4 XRD pattern of O3 oxide material. Detailed Implementation

[0058] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0059] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0060] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0061] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0062] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0063] Unless otherwise specified, the room temperature in this invention is 25±2℃.

[0064] All raw materials used in the embodiments of the present invention were obtained through commercial purchase.

[0065] In the embodiments of the present invention, the purity of the raw materials BaCO3, SrCO3, CaCO3, TiO2 and SnO2 is all above 99.9%, and the above raw materials are dried at 100-120°C for 12-24 hours before being mixed.

[0066] The technical solution of the present invention will be further illustrated by the following embodiments.

[0067] Example 1

[0068] A and B site components of superparaelectric perovskite-type ceramic materials (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 Preparation of O3:

[0069] (1) BaCO3, SrCO3, CaCO3, TiO2 and SnO2 raw materials with a purity of 99.9% or higher were dried at 110℃ for 12 hours before batching, and then accurately weighed and mixed according to the stoichiometric ratio (accurate to 0.0001g) to obtain a mixture. The molar ratio of metal elements of BaCO3, SrCO3 and CaCO3 was 1:1:1, and the molar ratio of metal elements of SnO2 and TiO2 was 1:9. The mixture was added to a ball mill jar and wet ball milled. Zirconia balls were used as grinding balls, and anhydrous ethanol was added as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium was 1:2:2. The mixture was fully ball milled at a speed of 320r / min for 6 hours. The ball milled material was then placed in a 120℃ oven and dried for 3 hours.

[0070] (2) The material dried in step (1) is pre-calcined in air at 1050°C for 5 hours at 5°C / min from room temperature to obtain pre-calcined powder.

[0071] (3) Add the pre-burnt powder obtained in step (2) into a ball mill jar and perform wet ball milling. The grinding balls are zirconia balls. Add anhydrous ethanol as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium is 1:2:2. The mixture is fully ball milled at a speed of 320 r / min for 6 hours. The ball-milled material is then placed in a 120℃ oven and dried for 3 hours.

[0072] (4) Add a 5% polyvinyl alcohol solution of binder to the pre-calcined powder dried in step (3) and granulate it. The amount of polyvinyl alcohol added accounts for 3% of the total mass of the pre-calcined powder. Pass it through an 80-mesh sieve and dry press it into a cylindrical green body with a diameter of 8 mm under a pressure of 6 MPa using a powder press. The holding time is 1 minute. Then, the cylindrical green body is debonded at 550℃ for 7 hours with a heating rate of 2℃ / min.

[0073] (5) The cylindrical green body after debinding is heated to 1400℃ in air at a rate of 4℃ / min and sintered at this temperature for 5 hours to obtain (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 O3 oxide ceramic materials.

[0074] The (Ba) prepared in this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 1 It shows that it has been synthesized (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn)0.1 Ti 0.9 O3 phase.

[0075] The (Ba) prepared in this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 The SEM morphology results of the O3 oxide ceramic material are shown in [the image]. Figure 2 This shows that the ceramics have good crystallization properties.

[0076] The (Ba) prepared using this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 Preparation of O3 oxide ceramic materials (Ba 1 / 3Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 O3 relaxor ferroelectric ceramic materials, the specific method is as follows:

[0077] will (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 The top and bottom surfaces of the O3 oxide ceramic material are ground smooth to a thickness of 0.10 mm, then silver electrodes are plated on. After sintering at 650℃ for 30 minutes and cooling, (Ba) is obtained. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 O3 relaxor ferroelectric ceramic materials.

[0078] Figure 3 The (Ba) prepared in this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 The hysteresis loop (PE curve) of O3 relaxor ferroelectric ceramic material at 10 Hz was used to calculate its usable energy storage density (W / cm) under an electric field of 540 kV / cm. rec Reaching 5.05 J / cm 3 The energy storage efficiency (η) reaches 82.56%.

[0079] Example 2

[0080] A and B site components of superparaelectric perovskite-type ceramic materials (Ba 1 / 3 Sr1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 Preparation of O3:

[0081] (1) BaCO3, SrCO3, CaCO3, TiO2 and SnO2 raw materials with a purity of 99.9% or higher were dried at 110℃ for 12 hours before batching, and then accurately weighed and mixed according to the stoichiometric ratio (accurate to 0.0001g) to obtain a mixture. The molar ratio of metal elements of BaCO3, SrCO3 and CaCO3 was 1:1:1, and the molar ratio of metal elements of SnO2 and TiO2 was 1:4. The mixture was added to a ball mill jar and wet ball milled. Zirconia balls were used as grinding balls, and anhydrous ethanol was added as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium was 1:2:2. The mixture was fully ball milled at a speed of 300r / min for 6 hours. The ball milled material was then placed in a 120℃ oven and dried for 2 hours.

[0082] (2) The material dried in step (1) is pre-calcined in air at 1100°C for 4 hours, with the temperature increased from room temperature to 5°C / min at room temperature, to obtain pre-calcined powder.

[0083] (3) Add the pre-burnt powder obtained in step (2) into a ball mill jar and perform wet ball milling. The grinding balls are zirconia balls. Add anhydrous ethanol as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium is 1:2:2. The mixture is fully ball milled at a speed of 300 r / min for 6 hours. The ball-milled material is then placed in a 120℃ oven and dried for 2 hours.

[0084] (4) Add a 5% polyvinyl alcohol solution of binder to the pre-calcined powder dried in step (3) and granulate it. The amount of polyvinyl alcohol added accounts for 3% of the total mass of the pre-calcined powder. Pass it through a 60-mesh sieve and dry press it into a cylindrical green body with a diameter of 8 mm under a pressure of 8 MPa using a powder press. The holding time is 1 minute. Then, the cylindrical green body is debonded at 550℃ for 8 hours with a heating rate of 2℃ / min.

[0085] (5) The cylindrical green body after debinding is heated to 1450℃ in air at a rate of 3℃ / min and sintered at this temperature for 6 hours to obtain (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 O3 oxide ceramic materials.

[0086] The (Ba) prepared in this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti0.8 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 4 It shows that it has been synthesized (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 O3 phase.

[0087] The (Ba) prepared using this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 Preparation of O3 oxide ceramic materials (Ba 1 / 3Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 O3 relaxor ferroelectric ceramic materials, the specific method is as follows:

[0088] will (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 The top and bottom surfaces of the O3 oxide ceramic material are ground smooth to a thickness of 0.10 mm, then silver electrodes are plated on. After sintering at 650℃ for 30 minutes and cooling, (Ba) is obtained. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 O3 relaxor ferroelectric ceramic materials.

[0089] Figure 5 This embodiment (Ba) 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.2 Ti 0.8 The PE curve of O3 relaxor ferroelectric ceramic material at 10 Hz was obtained. Its usable energy storage density (W / cm) at an electric field of 390 kV / cm was calculated. rec ) Reached 4.88 J / cm 3 The energy storage efficiency (η) reaches 92.92%.

[0090] Example 3

[0091] A and B site components of superparaelectric perovskite-type ceramic materials (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 Preparation of O3:

[0092] (1) BaCO3, SrCO3, CaCO3, TiO2 and SnO2 raw materials with a purity of 99.9% or higher were dried at 110℃ for 12 hours before batching, and then accurately weighed and mixed according to the stoichiometric ratio (accurate to 0.0001g) to obtain a mixture. The molar ratio of metal elements of BaCO3, SrCO3 and CaCO3 was 1:1:1, and the molar ratio of metal elements of SnO2 and TiO2 was 3:7. The mixture was added to a ball mill jar and wet ball milled. Zirconia balls were used as grinding balls, and anhydrous ethanol was added as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium was 1:2:2. The mixture was fully ball milled at a speed of 360r / min for 6 hours. The ball milled material was then placed in a 120℃ oven and dried for 2 hours.

[0093] (2) The material dried in step (1) is pre-calcined in air at 3℃ / min from room temperature to 1000℃ for 6 hours to obtain pre-calcined powder.

[0094] (3) Add the pre-burned powder obtained in step (2) into a ball mill jar and perform wet ball milling. The grinding balls are zirconia balls. Add anhydrous ethanol as the ball milling medium. The mass ratio of the mixture, grinding balls and ball milling medium is 1:2:2. The mixture is fully ball milled at a speed of 360 r / min for 6 hours. The ball-milled material is then placed in a 120℃ oven and dried for 3 hours.

[0095] (4) Add a 5% polyvinyl alcohol solution of binder to the pre-calcined powder dried in step (3) and granulate it. The amount of polyvinyl alcohol added accounts for 3% of the total mass of the pre-calcined powder. Pass it through a 120-mesh sieve and dry press it into a cylindrical green body with a diameter of 10 mm under a pressure of 5 MPa using a powder press. The holding time is 2 minutes. Then, the cylindrical green body is debonded at 550℃ for 6 hours with a heating rate of 1.5℃ / min.

[0096] (5) The cylindrical green body after debinding is heated to 1500℃ in air at a rate of 5℃ / min and sintered at this temperature for 4 hours to obtain (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 O3 oxide ceramic materials.

[0097] The (Ba) prepared in this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 6 It shows that it has been synthesized (Ba 1 / 3 Sr1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 O3 phase.

[0098] The (Ba) prepared using this embodiment 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 Preparation of O3 oxide ceramic materials (Ba 1 / 3Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 O3 relaxor ferroelectric ceramic materials, the specific method is as follows:

[0099] will (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 The top and bottom surfaces of the O3 oxide ceramic material are ground smooth to a thickness of 0.15 mm, then silver electrodes are plated on. After sintering at 650℃ for 30 minutes and cooling, (Ba) is obtained. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 O3 relaxor ferroelectric ceramic materials.

[0100] Figure 7 This embodiment (Ba) 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.3 Ti 0.7 The PE curve of O3 relaxor ferroelectric ceramic material at 10 Hz was used to calculate its usable energy storage density (W) under an electric field of 250 kV / cm. rec Reaching 2.80 J / cm 3 The energy storage efficiency (η) reaches 93.39%.

[0101] Comparative Example 1

[0102] Compared with Example 1, the only difference is the pre-firing temperature, that is, the pre-firing temperature in step (2) is 900°C.

[0103] The (Ba) prepared in this comparative example 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 8The results show that sintering at 900℃ cannot yield a single-phase (Ba) solution. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.1 Ti 0.9 )O3.

[0104] Comparative Example 2

[0105] The only difference from Example 2 is that SnO2 is replaced with ZrO2.

[0106] The (Ba) prepared in this comparative example 1 / 3 Sr 1 / 3 Ca 1 / 3 (Zr) 0.2 Ti 0.8 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 9 This indicates that sintering at 1450℃ cannot yield a single-phase (Ba) solution. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Zr) 0.2 Ti 0.8 )O3.

[0107] Comparative Example 3

[0108] Compared with Example 3, the only difference is the molar ratio of metal elements in TiO2 and SnO2. Specifically, the molar ratio of metal elements in BaCO3, SrCO3, and CaCO3 is 1:1:1, and the molar ratio of metal elements in SnO2 and TiO2 is 3:2.

[0109] The (Ba) prepared in this comparative example 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.6 Ti 0.4 The XRD pattern of the O3 oxide ceramic material is shown below. Figure 10 The results showed the presence of impurity phases under sintering conditions of 1500℃, making it impossible to obtain a single-phase (Ba) product. 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) 0.6 Ti 0.4 )O3.

[0110] Observation of the data from Comparative Examples 1, 2, and 3 revealed that the presence of the second phase creates a concentrated region of electric field, leading to a decrease in breakdown field strength. Simultaneously, the second phase introduces other dielectric loss mechanisms, increasing dielectric loss and thus reducing the material's energy storage efficiency and density. Therefore, the relaxor ferroelectric ceramic materials prepared in the aforementioned comparative examples significantly reduce overall energy storage performance, limiting their practical application value.

[0111] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A superparaelectric perovskite-type ceramic material with A and B site components, characterized in that, The general structural formula is ABO3, where the A site is composed of three elements: Ba, Sr and Ca, and the B site is composed of two elements: Ti and Sn. The three elements at site A occupy site A in an equimolar ratio, and the molar ratio of the two elements Ti and Sn at site B is (9-7):(1-3). The preparation method of the superparaelectric perovskite ceramic material with components at sites A and B includes the following steps: (1) According to the stoichiometric ratio of the superparaelectric phase perovskite ceramic material of A and B sites, weigh the raw materials BaCO3, SrCO3, CaCO3, TiO2 and SnO2, add them to the ball mill jar, use zirconia balls as grinding balls, add anhydrous ethanol as the ball milling medium, put the ball mill jar into a planetary ball mill, and dry it after ball milling. (2) The material dried in step (1) is pre-calcined in air at a temperature of 1000℃~1100℃ for 4~6 hours to obtain pre-calcined powder; (3) Add the pre-calcined powder into a ball mill jar, the grinding balls are zirconia balls, anhydrous ethanol is added as the ball milling medium, the ball mill jar is placed in a planetary ball mill, and dried after ball milling; (4) Add polyvinyl alcohol solution to the pre-calcined powder after drying in step (3) for granulation, sieve the granules, dry press them into cylindrical green bodies, and then remove the adhesive from the cylindrical green bodies. (5) The cylindrical green body after debinding is sintered in air at a temperature of 1400℃~1500℃ for 4~6 hours to obtain the superparaelectric perovskite ceramic material of the A and B site components.

2. The superparaelectric perovskite ceramic material with A and B site components according to claim 1, characterized in that, The chemical formula of the superparaelectric perovskite ceramic material with components at positions A and B is (Ba 1 / 3 Sr 1 / 3 Ca 1 / 3 (Sn) x Ti 1-x O3, where 0.1 ≤ x ≤ 0.3; The perovskite structure of the superparaelectric perovskite ceramic material with components A and B sites belongs to the cubic crystal system, with space group Pm. m.

3. A method for preparing a superparaelectric perovskite ceramic material with A and B site components as described in any one of claims 1 to 2, characterized in that, Includes the following steps: (1) According to the stoichiometric ratio of the superparaelectric phase perovskite ceramic material of A and B sites, weigh the raw materials BaCO3, SrCO3, CaCO3, TiO2 and SnO2, add them to the ball mill jar, use zirconia balls as grinding balls, add anhydrous ethanol as the ball milling medium, put the ball mill jar into a planetary ball mill, and dry it after ball milling. (2) The material dried in step (1) is pre-calcined in air at a temperature of 1000℃~1100℃ for 4~6 hours to obtain pre-calcined powder; (3) Add the pre-calcined powder into a ball mill jar, the grinding balls are zirconia balls, anhydrous ethanol is added as the ball milling medium, the ball mill jar is placed in a planetary ball mill, and dried after ball milling; (4) Add polyvinyl alcohol solution to the pre-calcined powder after drying in step (3) for granulation, sieve the granules, dry press them into cylindrical green bodies, and then remove the adhesive from the cylindrical green bodies. (5) The cylindrical green body after debinding is sintered in air at a temperature of 1400℃~1500℃ for 4~6 hours to obtain the superparaelectric perovskite ceramic material of the A and B site components.

4. The method for preparing the superparaelectric perovskite ceramic material with components at sites A and B according to claim 3, characterized in that, In step (1), the mass ratio of the mixture, grinding balls, and grinding media is 1:2:2; The ball milling was performed at a speed of 300~360 r / min for 6 hours, and the milled material was dried at 120 ℃ for 2~3 hours.

5. The method for preparing the superparaelectric perovskite ceramic material with A and B site components according to claim 3, characterized in that, In step (3), the ball milling is performed at a speed of 300~360 r / min for 6 hours, and the milled material is dried at 120 ℃ for 2~3 hours.

6. The method for preparing the superparaelectric perovskite ceramic material with A and B site components according to claim 3, characterized in that, In step (4), the mass concentration of the polyvinyl alcohol solution is 5%; The sieving process is a 60-120 mesh sieve. The uniaxial pressure during dry pressing is 5~8MPa, and the holding time is 1~2 minutes; The glue removal process involves removing glue at 550℃ for 6-8 hours, with a heating rate of 1.5-2℃ / min.

7. A method for preparing relaxor ferroelectric materials based on superparaelectric perovskite ceramic materials with A and B site components, characterized in that, Silver electrodes are plated on the upper and lower surfaces of the superparaelectric perovskite ceramic material with A and B site components as described in any one of claims 1 to 2, and the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components is obtained after calcination and cooling.

8. The method for preparing relaxor ferroelectric materials based on superparaelectric perovskite ceramic materials with A and B site components according to claim 7, characterized in that, The thickness of the superparaelectric perovskite ceramic material with A and B site components is 0.10~0.15mm. Before silver plating the electrode, the surface of the superparaelectric perovskite ceramic material with A and B site components is polished smooth. The calcination temperature is 650℃, and the holding time is 30 minutes.

9. The application of the superparaelectric perovskite ceramic material with A and B site components as described in any one of claims 1 to 2, or the relaxor ferroelectric material based on the superparaelectric perovskite ceramic material with A and B site components prepared by the method according to any one of claims 7 to 8, in the field of dielectric energy storage.

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