A barium titanate-based dielectric energy storage ceramic material with low loss and high energy storage efficiency and a preparation method thereof
Patent Information
- Application Number
- CN202610856829.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-15
- Publication Date
- 2026-08-18
AI Technical Summary
然而，其本身具有较高的铁电性，并且具有明显的温度敏感性，使其很难直接应用于储能领域
[0019] The beneficial effects of the technical solution of the present invention include:
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of dielectric electronic functional ceramic materials, specifically relating to a barium titanate-based dielectric energy storage ceramic material with low loss and high energy storage efficiency and its preparation method. Background Technology
[0002] Recent research on energy storage materials has primarily focused on energy storage and conversion, including applications in mobile electronic devices, hybrid electric vehicles, and military fields. In this research, dielectric capacitors have been used in pulsed power applications, which require considerable power densities consisting of moderate energy densities and ultrafast charging / discharging rates on the order of milliseconds. The total energy density (W) of dielectric capacitors is calculated based on integral calculations. total ), energy loss (W) loss ), efficiency (η) and recoverable energy density (W) rec Dielectric energy storage materials are insulating materials that store electrical energy through dielectric polarization, primarily used in high-power pulse power supplies and power electronics. Their core advantages lie in high power density, fast charge / discharge speed, and long cycle life. However, the energy density of ceramic dielectric energy storage materials is generally low, resulting in energy storage components based on them often being bulky and heavy. This problem not only severely limits the application of these materials in high-efficiency energy storage but also directly restricts the development of pulse power systems and other equipment with ceramic capacitors as core components towards high-end, miniaturized, intelligent, and multifunctional directions.
[0003]
[0004] Hu Q et al. studied BT-BMT and found that the maximum energy storage density of 0.88BT-0.12BMT ceramics reached 1.81 J / cm² under an electric field of 287 kV / cm. 3 Furthermore, the efficiency was only 88%. Zhou et al. proposed the feasibility of using 0.7BaTiO3-0.3BiScO3 in high-energy-density capacitors operating at high temperatures. At room temperature, under an electric field of 73 kV / mm, an efficiency of approximately 6.1 J / cm² could be obtained. 3 The energy density is high. However, its application is limited by the large effect of dielectric constant with temperature, significant hysteresis effect, and low breakdown field strength. Pure barium titanate ceramics are a typical dielectric energy storage material with high dielectric constant, low dielectric loss, and ease of preparation. However, it has high ferroelectricity and obvious temperature sensitivity, making it difficult to directly apply in the field of energy storage. Summary of the Invention
[0005] To address the aforementioned problems, this invention provides a method for preparing a barium titanate-based energy storage ceramic material with low loss and high energy storage efficiency, and its energy storage density is 1.50~3.25 J / cm³. 3 With an energy storage efficiency of 89.93%~93.50% and a loss tanδ of 0.0008~0.0033, it can be applied to fields such as electronic power, military industry, and high-energy pulse power technology.
[0006] To achieve the above advantages, the present invention can be implemented through the following technical measures:
[0007] This invention provides a barium titanate-based energy storage ceramic material with low loss and high energy storage efficiency, whose chemical formula is 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+xwt.%MnO2, 0.5≤x≤2, where x is 0.5, 1, 1.5 or 2 respectively.
[0008] The preparation method of barium titanate-based energy storage ceramic materials with low loss, high energy storage efficiency and high energy storage density includes the following steps:
[0009] Preparation and secondary ball milling of BT-BMT-CZ ceramic powder
[0010] The general formula for BT-BMT-CZ ceramics is 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3, the element is added as carbonate or oxide, the raw materials are weighed, mixed and stirred according to the general chemical formula, and mixed according to the mass ratio of raw material: dispersion medium: alcohol 1:6:1 and placed in a polyurethane ball mill jar.
[0011] Furthermore, the ball mill jar is placed on a planetary ball mill and milled for 4-6 hours at a speed of 300-360 r / min, and then dried in a constant temperature drying oven at 80-100℃.
[0012] Further, the dried powder was placed in a crucible and then placed in a muffle furnace. The temperature was increased to 800-950℃ at a rate of 5℃ / min and held for 2-4 hours. After cooling to room temperature in the furnace, BT-BMT-CZ ceramic powder was obtained. This BT-BMT-CZ ceramic matrix powder was then milled twice with MnO2 of different mass percentages and dried at a constant temperature of 80-100℃ to obtain 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3O3]-0.15CaZrO3+xwt.%MnO2, 0.5≤x≤2, where x is 0.5, 1, 1.5 or 2 respectively.
[0013] Granulation, tableting, and debinding
[0014] Furthermore, the powder dried after secondary milling is mixed with a 5% PVA solution and granulated. The granulated powder is then passed through a 60-mesh 304 stainless steel sieve and pressed under 2-4 MPa into 0.85[0.88BaTiO3-0.12Bi] particles with a diameter of 8 mm and a thickness of 1-1.2 mm. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+xwt.%MnO2 preliminary blank.
[0015] Furthermore, the ceramic blank obtained above is heated to 600℃ at 2℃ / min and held for 3~4h, and then cooled in the furnace to obtain the ceramic body.
[0016] Sintering and silvering
[0017] Furthermore, the ceramic green body obtained after debinding is sintered at 1200~1260℃ and held at that temperature for 2~3 hours, with a heating rate of 10℃ / min for the first 1000℃ and 5℃ / min thereafter. After the holding period, it is cooled in the furnace. The silvering process involves polishing the surface of the sintered and cooled sheet, ultrasonically cleaning it, brushing on high-temperature silver paste, and holding it at 700℃ for 10 minutes, with a heating rate of 5℃ / min.
[0018] 0.85[0.88BaTiO3-0.12Bi] was obtained. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+xwt.%MnO2 ceramic material, 0.5≤x≤2, where x is 0.5, 1, 1.5 or 2 respectively.
[0019] The beneficial effects of the technical solution of the present invention include:
[0020] 1. In terms of sintering temperature, it is lower than that of barium titanate-based dielectric ceramics of the same type, with a sintering temperature of (1200~1260℃), and the grains are uniform, which improves its sintering activity.
[0021] 2. This barium titanate-based energy storage ceramic has excellent energy storage efficiency and density, low loss, and can be used as a dielectric capacitor in fields such as electronic power, military industry, and high-energy pulse power technology. Attached Figure Description
[0022] To better illustrate the technical solution of the present invention in a more detailed manner, please refer to the following accompanying drawings and embodiments.
[0023] Figure 1 The image shows the XRD pattern of the ceramic in an embodiment of the present invention.
[0024] Figure 2 The images shown are electron microscope scans and average grain size diagrams from embodiments of the present invention.
[0025] Figure 3 The dielectric and loss diagrams for embodiments of the present invention are shown in the range of 1kHz to 1000kHz.
[0026] Figure 4 This is a graph showing the loss and dielectric constant at 1 kHz in an embodiment of the present invention.
[0027] Figure 5 The diagram shows the hysteresis loop (PE) curve, energy storage density, and efficiency of an embodiment of the present invention. Detailed Implementation
[0028] The present invention will be described in detail below with reference to examples and embodiments, but this is not intended to limit the invention.
[0029] Example 1
[0030] 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 Preparation and secondary ball milling of O3-0.15CaZrO3 ceramic powder
[0031] Ingredients. Prepare the raw materials according to the general formula 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 Weigh and mix the raw materials, zirconium balls and dispersion medium in a mass ratio of 1:6:1, and place them in a polyurethane ball mill jar.
[0032] Furthermore, the ball mill jar is placed on a planetary ball mill and milled for 4-6 hours at a speed of 300-360 r / min, and then dried in a constant temperature drying oven at 80℃.
[0033] Further, the dried powder is placed into a crucible, and the crucible is placed in a muffle furnace. The temperature is increased to 900℃ at 5℃ / min and held for 3~5h. After the muffle furnace cools to room temperature, barium titanate-based ceramic powder is obtained, and 0.85[0.88BaTiO3-0.12Bi] is added. 2 / 3 Mg 1 / 3 Ta 2 / 3O3]-0.15CaZrO3 powder was mixed with MnO2 (mass percentage x = 0.5%) and milled twice, then dried at a constant temperature of 80℃ to obtain 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+0.5wt.%MnO2 powder material.
[0034] Granulation, tableting, and debinding
[0035] Furthermore, the powder dried after the second grinding is mixed with 5% PVA solution and granulated. The granulated powder is then passed through a 60-mesh sieve and pressed into BT-BMT-CZ-Mn ceramic blanks with a diameter of 8 mm and a thickness of 1.2-1.4 mm under a pressure of 2.5-4 MPa.
[0036] Furthermore, the ceramic blank obtained above is heated to 600℃ at 2℃ / min and held for 3 hours, and then cooled in the furnace to obtain the ceramic body.
[0037] sintering
[0038] Furthermore, the ceramic blank obtained by debinding is sintered at 1200~1260℃ and held for 2 hours. The heating rate is 10℃ / min for the first 1000℃ and 5℃ / min for the subsequent temperature. After the holding period, the ceramic blank is cooled in the furnace to obtain the BT-BMGT-CZ-Mn dielectric ceramic material.
[0039] The sintered BT-BMT-CZ-Mn ceramic material was ground using an agate mortar and then subjected to X-ray diffraction testing. Figure 1 The XRD pattern shows that the ceramic material in this embodiment has a pure perovskite structure, does not contain a second phase, and has high crystallinity. Figure 2 Image (a) is a scanning electron microscope image of this embodiment, showing uniform grains and an average grain size of 1.03 μm. The sintered sample was processed into a smooth sheet with a thickness of approximately 0.1–0.2 mm. After ultrasonication, a high-temperature silver electrode was prepared (heated to 700 °C at 5 °C / min, held for 10 min, and then cooled with the furnace). Its dielectric properties and losses were then tested at temperatures between -55 and 150 °C and at different frequencies. Figure 3 As shown in (a). Figure 4 The curve at x = 0.5 shows the relationship between the dielectric constant and temperature at 1 kHz in this embodiment. As x increases, the phase transition temperature (T...)... m As the temperature rises, the dielectric property ε gradually decreases, and the loss becomes 0.0008, as shown in Table 1. Figure 5(a) The curve with x=0.5 shows the hysteresis loop of the ceramic material in this embodiment measured at room temperature. The test electric field is 400 kV / cm, and it can be seen that its maximum polarization intensity is 17.05 μC / cm. 2 ,like Figure 5 (b) The bar chart with x = 0.50 shows that the energy storage density of the energy storage ceramic in this embodiment can reach 3.241 J / cm³ at room temperature. 3 The energy storage efficiency can reach 93.51%. The energy storage characteristics of the energy storage ceramic material in this embodiment at room temperature are shown in Table 1.
[0040] Example 2
[0041] 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 Preparation and secondary ball milling of O3-0.15CaZrO3 ceramic powder
[0042] Ingredients. Prepare the raw materials according to the general formula 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3, where x=0.5, is weighed and mixed according to the mass ratio of raw material: zirconium balls: dispersion medium of 1:6:1, and placed in a polyurethane ball mill jar.
[0043] Furthermore, the ball mill jar is placed on a planetary ball mill and milled for 4-6 hours at a speed of 300-360 r / min, and then dried in a constant temperature drying oven at 80℃.
[0044] Further, the dried powder is placed into a crucible, and the crucible is placed in a muffle furnace. The temperature is increased to 900℃ at 5℃ / min and held for 3~5h. After the muffle furnace cools to room temperature, barium titanate-based ceramic powder is obtained, and 0.85[0.88BaTiO3-0.12Bi] is added. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder was mixed with MnO2 at a mass percentage of x=1%, and then milled twice. The mixture was then dried at a constant temperature of 80℃ to obtain 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+1wt.%MnO2 powder material.
[0045] Granulation, tableting, and debinding
[0046] Furthermore, the powder dried after the second grinding is mixed with 5% PVA solution and granulated. The granulated powder is then passed through a 60-mesh sieve and pressed into BT-BMT-CZ-Mn ceramic blanks with a diameter of 8 mm and a thickness of 1.2-1.4 mm under a pressure of 2.5-4 MPa.
[0047] Furthermore, the ceramic blank obtained above is heated to 600℃ at 2℃ / min and held for 3 hours, and then cooled in the furnace to obtain the ceramic body.
[0048] sintering
[0049] Furthermore, the ceramic blank obtained by debinding is sintered at 1200~1260℃ and held for 2 hours. The heating rate is 10℃ / min for the first 1000℃ and 5℃ / min for the subsequent temperature. After the holding period, the ceramic blank is cooled in the furnace to obtain the BT-BMT-CZ-Mn dielectric ceramic material.
[0050] The sintered BT-BMT-CZ-Mn ceramic material was ground using an agate mortar and then subjected to X-ray diffraction testing. Figure 1 The XRD pattern shows that the ceramic material in this embodiment has a pure perovskite structure, does not contain a second phase, and has high crystallinity. Figure 2 Image (b) is a scanning electron microscope image of this embodiment, showing uniform grains and an average grain size of 1.13 μm. The sintered sample was processed into a smooth sheet with a thickness of approximately 0.1–0.2 mm. After ultrasonication, a high-temperature silver electrode was prepared (heated to 700 °C at 5 °C / min, held for 10 min, and then cooled with the furnace). Its dielectric properties and losses were then tested at temperatures between -55 and 150 °C and at different frequencies. Figure 3 As shown in (b). Figure 4 The curve for x=1 shows the relationship between the dielectric constant and temperature at 1kHz in this embodiment. As x increases, the phase transition temperature (T) increases. m As the temperature rises, the dielectric property ε gradually decreases, and the loss becomes 0.0010, as shown in Table 1. Figure 5 (a) The curve with x=1 shows the hysteresis loop of the ceramic material in this embodiment measured at room temperature. The test electric field is 370 kV / cm, and it can be seen that its maximum polarization intensity is 16.25 μC / cm. 2 ,like Figure 5 (b) The bar chart with x=1 shows that the energy storage density of the energy storage ceramic in this embodiment can reach 2.75 J / cm³ at room temperature. 3 The energy storage efficiency can reach 92.60%. The energy storage characteristics of the energy storage ceramic material in this embodiment at room temperature are shown in Table 1.
[0051] Example 3
[0052] 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 Preparation and secondary ball milling of O3-0.15CaZrO3 ceramic powder
[0053] Ingredients. Prepare the raw materials according to the general formula 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3, where x=0.5, is weighed and mixed according to the mass ratio of raw material: zirconium balls: dispersion medium of 1:6:1, and placed in a polyurethane ball mill jar.
[0054] Furthermore, the ball mill jar is placed on a planetary ball mill and milled for 4-6 hours at a speed of 300-360 r / min, and then dried in a constant temperature drying oven at 80℃.
[0055] Further, the dried powder is placed into a crucible, and the crucible is placed in a muffle furnace. The temperature is increased to 900℃ at 5℃ / min and held for 3~5h. After the muffle furnace cools to room temperature, barium titanate-based ceramic powder is obtained, and 0.85[0.88BaTiO3-0.12Bi] is added. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder was mixed with MnO2 at a mass percentage of x=1.5% and then milled twice. The mixture was then dried at a constant temperature of 80℃ to obtain 0.85[0.88BaTiO3-0.12Bi] 2 / 3 Mg 1 / 3 Ta 2 / [3O3]-0.15CaZrO3+1.5wt.%MnO2 powder material.
[0056] Granulation, tableting, and debinding
[0057] Furthermore, the powder dried after the second grinding is mixed with 5% PVA solution and granulated. The granulated powder is then passed through a 60-mesh sieve and pressed into BT-BMT-CZ-Mn ceramic blanks with a diameter of 8 mm and a thickness of 1.2-1.4 mm under a pressure of 2.5-4 MPa.
[0058] Furthermore, the ceramic blank obtained above is heated to 600℃ at 2℃ / min and held for 3 hours, and then cooled in the furnace to obtain the ceramic body.
[0059] sintering
[0060] Furthermore, the ceramic blank obtained by debinding is sintered at 1200~1260℃ and held for 2 hours. The heating rate is 10℃ / min for the first 1000℃ and 5℃ / min for the subsequent temperature. After the holding period, the ceramic blank is cooled in the furnace to obtain the BT-BMT-CZ-Mn dielectric ceramic material.
[0061] The sintered BT-BMT-CZ-Mn ceramic material was ground using an agate mortar and then subjected to X-ray diffraction testing. Figure 1 The XRD pattern shows that the ceramic material in this embodiment has a pure perovskite structure, does not contain a second phase, and has high crystallinity. Figure 2 Image (c) is a scanning electron microscope image of this embodiment, showing uniform grains and an average grain size of 1.20 μm. The sintered sample was processed into a smooth sheet with a thickness of approximately 0.1–0.2 mm. After ultrasonication, a high-temperature silver electrode was prepared (heated to 700 °C at a rate of 5 °C / min, held for 10 min, and then cooled with the furnace). Its dielectric properties and losses were then tested at temperatures between -55 and 150 °C and at different frequencies. Figure 3 As shown in (c). Figure 4 The curve for x = 1.5 shows the relationship between the dielectric constant and temperature at 1 kHz in this embodiment. As x increases, the phase transition temperature (T...)... m As the temperature rises, the dielectric property ε gradually decreases, and the dielectric loss becomes 0.0013. For example... Figure 5 (a) The curve with x=1.5 shows the hysteresis loop of the ceramic material in this embodiment measured at room temperature. The test electric field is 320 kV / cm, and it can be seen that its maximum polarization intensity is 12.20 μC / cm. 2 ,like Figure 5 (b) The bar chart with x = 1.5 shows that the energy storage density of the energy storage ceramic in this embodiment can reach 1.85 J / cm³ at room temperature. 3 The energy storage efficiency can reach 91.66%. The energy storage characteristics of the energy storage ceramic material in this embodiment at room temperature are shown in Table 1.
[0062] Example 4
[0063] 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 Preparation and secondary ball milling of O3-0.15CaZrO3 ceramic powder
[0064] Ingredients. Prepare the raw materials according to the general formula 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3O3]-0.15CaZrO3, where x=2, is weighed and mixed according to the mass ratio of raw material: zirconium balls: dispersion medium of 1:6:1, and placed in a polyurethane ball mill jar.
[0065] Furthermore, the ball mill jar is placed on a planetary ball mill and milled for 4-6 hours at a speed of 300-360 r / min, and then dried in a constant temperature drying oven at 80℃.
[0066] Further, the dried powder is placed into a crucible, and the crucible is placed in a muffle furnace. The temperature is increased to 900℃ at 5℃ / min and held for 3~5h. After the muffle furnace cools to room temperature, barium titanate-based ceramic powder is obtained, and 0.85[0.88BaTiO3-0.12Bi] is added. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder was mixed with MnO2 at a mass percentage of x=1%, and then milled twice. The mixture was then dried at a constant temperature of 80℃ to obtain 0.85[0.88BaTiO3-0.12Bi 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+2wt.%MnO2 powder material.
[0067] Granulation, tableting, and debinding
[0068] Furthermore, the powder dried after the second grinding is mixed with 5% PVA solution and granulated. The granulated powder is then passed through a 60-mesh sieve and pressed into BT-BMT-CZ-Mn ceramic blanks with a diameter of 8 mm and a thickness of 1.2-1.4 mm under a pressure of 2.5-4 MPa.
[0069] Furthermore, the ceramic blank obtained above is heated to 600℃ at 2℃ / min and held for 3 hours, and then cooled in the furnace to obtain the ceramic body.
[0070] sintering
[0071] Furthermore, the ceramic blank obtained by debinding is sintered at 1200~1260℃ and held for 2 hours. The heating rate is 10℃ / min for the first 1000℃ and 5℃ / min for the subsequent temperature. After the holding period, the ceramic blank is cooled in the furnace to obtain the BT-BMT-CZ-Mn dielectric ceramic material.
[0072] The sintered BT-BMT-CZ-Mn ceramic material was ground using an agate mortar and then subjected to X-ray diffraction testing. Figure 1 The XRD pattern shows that the ceramic material in this embodiment has a pure perovskite structure, does not contain a second phase, and has high crystallinity. Figure 2Image (d) is a scanning electron microscope image of this embodiment, showing uniform grains and an average grain size of 1.41 μm. The sintered sample was processed into a smooth sheet with a thickness of approximately 0.1–0.2 mm. After ultrasonication, a high-temperature silver electrode was prepared (heated to 700 °C at a rate of 5 °C / min, held for 10 min, and then cooled with the furnace). Its dielectric properties and losses were then tested at temperatures between -55 and 150 °C and at different frequencies. Figure 3 As shown in (d). Figure 4 The curve for x=2 shows the relationship between the dielectric constant and temperature at 1kHz in this embodiment. As x increases, the phase transition temperature (T) increases. m As the temperature rises, the dielectric property ε gradually decreases, and the loss becomes 0.0010, as shown in Table 1. Figure 5 (a) The curve with x=2 shows the hysteresis loop of the ceramic material in this embodiment measured at room temperature. The test electric field is 290 kV / cm, and it can be seen that its maximum polarization intensity is 11.60 μC / cm. 2 ,like Figure 5 (b) The bar chart with x=2 shows that the energy storage density of the energy storage ceramic in this embodiment can reach 1.55 J / cm³ at room temperature. 3 The energy storage efficiency can reach 89.93%. The energy storage characteristics of the energy storage ceramic material in this embodiment at room temperature are shown in Table 1.
[0073] The above examples demonstrate that doping the BT-BMT matrix with CZ and MnO2 significantly affects the energy storage performance of the ceramic, effectively improving the low dielectric breakdown field strength and energy density, as well as the high dielectric loss, of the calcium barium zirconate titanate-based ceramic dielectric material. The prepared BT-BMT-CZ-MnO2 energy storage ceramic dielectric material exhibits excellent energy storage performance and can achieve high polarization under low electric fields. Therefore, this ceramic can meet the requirements of some low-power applications and is suitable for a wide range of operating temperatures, frequencies, and application fields.
[0074] In one embodiment, the present invention provides a barium titanate-based dielectric ceramic material for electronic power, military, and high-energy pulsed power technologies as described in any of the above embodiments.
[0075] The above embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention.
[0076] Table 1 x=0.5 419.8829 0.0008 3.24 93.51286 x=1 398.4831 0.0010 2.75 92.60632 x=1.5 390.8806 0.0013 1.85 91.66487 x=2 318.9204 0.0033 1.55 89.93561
Claims
1. A barium titanate-based dielectric energy storage ceramic material with low loss and high energy storage efficiency, characterized in that, Its chemical composition is 0.85[0.88BaTiO3-0.12Bi]. 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3+xwt.%MnO2, 0.5≤x≤2.
2. The barium titanate-based dielectric energy storage ceramic according to claim 1, characterized in that, The x values are 0.5, 1, 1.5, and 2.
3. A barium titanate-based dielectric energy storage ceramic material with low loss and high energy storage efficiency as described in any one of claims 1-2, characterized in that: The optimal energy storage density is 3.24 J / cm³. 3 The energy storage efficiency is 93.51%.
4. A method for preparing a low-loss, high-energy-storage-efficiency barium titanate-based dielectric energy storage ceramic material as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) Weigh the raw materials of metal carbonate or oxide according to the stoichiometric ratio of the low-loss, high-energy-storage-efficiency barium titanate-based dielectric energy storage ceramic material according to any one of claims 1-3, ball mill the mixture and calcine it to obtain 0.85[0.88BaTiO3-0.12Bi] 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder; (2) The 0.85[0.88BaTiO3-0.12Bi] 2 / 3 Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder was subjected to secondary ball milling, granulation, molding, and debinding with MnO2 of different mass percentages according to the molar mass ratio to obtain 0.85[0.88BaTiO3-0.12Bi 2 / 3Mg 1 / 3 Ta 2 / 3 [O3]-0.15CaZrO3+xwt.%MnO2 Barium titanate-based dielectric energy storage ceramic blank; (3) The 0.85[0.88BaTiO3-0.12Bi] 2 / 3 Mg 1 / 3 Ta 2 / 3 The barium titanate-based dielectric energy storage ceramic blank was sintered and silvered to obtain the barium titanate-based dielectric energy storage ceramic material.
5. The preparation method according to claim 4, characterized in that, The synthesis method involves heating the material in a muffle furnace to 800-950°C at a rate of 5°C / min, holding it at that temperature for 2-4 hours, and then cooling it to room temperature in the furnace to obtain 0.85[0.88BaTiO3-0.12Bi]. 2 / 3Mg 1 / 3 Ta 2 / 3 O3]-0.15CaZrO3 powder was mixed with MnO2 of different mass percentages and then milled twice, and dried at a constant temperature of 80℃.
6. The preparation method according to claim 4, characterized in that, The granulation process involves mixing the dried powder obtained after the second grinding with a 5% PVA solution, granulating the mixture, and then passing the granulated powder through a 60-mesh 304 stainless steel sieve. The granulated powder is then pressed at 2-3 MPa into 0.85[0.88BaTiO3-0.12Bi] particles with a diameter of 8 mm and a thickness of 1-1.2 mm. 2 / 3 Mg 1 / 3 Ta 2 / 3 [O3]-0.15CaZrO3+xwt.%MnO2 Barium titanate-based dielectric energy storage ceramic blank.
7. The preparation method according to claim 4, characterized in that, The process involves heating the material at 2℃ / min to 600℃ and holding it at that temperature for 3-4 hours, followed by cooling it in the furnace to obtain a ceramic blank.
8. The preparation method according to claim 4, characterized in that, The sintering process involves sintering the ceramic green body obtained after debinding at 1200~1260℃ and holding it at that temperature for 2 hours. The heating rate is 10℃ / min to 1000℃, followed by a temperature increase of 5℃ / min. After the holding period, the green body is cooled in the furnace.
9. The preparation method according to claim 4, characterized in that, The silver coating process involves polishing the sintered and cooled sheet, ultrasonically cleaning it, brushing it with high-temperature silver paste, and then heating it to 700°C at a rate of 5°C / min and holding it at that temperature for 10 minutes.
10. A 0.85[0.88BaTiO3-0.12Bi] compound as described in claim 1 for use in fields such as electronic power, military industry, and high-energy pulsed power technology. 2 / 3 Mg 1 / 3 Ta 2 / 3 [O3]-0.15CaZrO3+xwt.%MnO2 barium titanate-based dielectric energy storage ceramic material, where x is 0.5, 1, 1.5 or 2.