A gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material, a preparation method and applications thereof

Abstract

The application relates to a gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material and a preparation method and application thereof. 1‑3x Gd x NbO3; wherein 0.04 < x < 0.12, preferably 0.06 <= x <= 0.10, more preferably 0.08.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of functional ceramics, and particularly relates to a gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material and a preparation method and application thereof. BACKGROUND

[0002] With the increasing demand for energy, the continuous consumption of fossil fuels and the escalating environmental problems, improving the utilization efficiency of traditional energy, expanding the use range and application field of new energy has become a hot issue that researchers pay more and more attention to in recent years. Compared with other energy storage materials, ceramic capacitors have high power density, fast charging and discharging speed, good cycle stability and other advantages, and play an extremely important role in modern power and electronic systems.

[0003] Antiferroelectric ceramic capacitors are one of the most promising ceramic capacitors at present, and have the advantages of low remanent polarization, large saturation polarization and high breakdown field strength. However, the mainstream antiferroelectric ceramic capacitors currently contain a large amount of lead, which poses a threat to the ecological environment and human health. Therefore, it is necessary to develop lead-free ceramic capacitors with high energy storage performance and fast discharging performance. NaNbO3(NN) is a typical lead-free antiferroelectric ceramic at room temperature, and is considered to be a potential dielectric energy storage material due to its rich phase structure, large saturation polarization and small density. However, unmodified sodium niobate ceramic has the disadvantages of large remanent polarization and low breakdown field strength. Therefore, how to improve the energy storage characteristics of sodium niobate-based ceramic materials has become a research hotspot in recent years.

[0004] At present, a large number of works focus on improving the comprehensive energy storage characteristics of sodium niobate by solid solution with other strong relaxor components, mainly including two aspects: on the one hand, forming a relaxor antiferroelectric ceramic by solid solution with BiFeO3, (Bi 0.5 Na 0.5 )TiO3 and other components; on the other hand, forming a relaxor ferroelectric ceramic by solid solution with (Bi 0.5 Li 0.5 )TiO3 and other components. Relatively speaking, the modified sodium niobate-based relaxor antiferroelectric ceramic has higher energy storage density.

[0005] However, the sodium niobate-based relaxor antiferroelectric ceramic currently used in practical applications often has the problems of complex components, difficult preparation and serious volatilization of Bi element, which greatly increases the production cost and has a negative impact on the stability and reliability of the capacitor. Therefore, it is of great significance to develop a sodium niobate-based relaxor antiferroelectric ceramic with simple components and without serious volatile elements. SUMMARY

[0006] In order to solve the above technical problems, the application provides a gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material, a preparation method and application thereof. 3+ On the one hand, the tolerance factor is reduced, which is beneficial to enhance the antiferroelectricity, and on the other hand, the local structure disorder degree of sodium niobate is improved, and the relaxor behavior is enhanced, and the introduction of Gd 3+ ions reduces the grain size, and significantly improves the breakdown field strength of the sodium niobate ceramic material.

[0007] In a first aspect, the application provides a gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material, which has a chemical composition of Na 1-3x Gd x NbO3; wherein 0.04 < x < 0.12, preferably 0.06 ≤ x ≤ 0.10, and more preferably 0.08.

[0008] Preferably, the breakdown electric field of the gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material is 371-582 kV / cm, the energy storage density is 2.16-6.77 J / cm 3 , and the energy storage efficiency is 32.8-83.8%.

[0009] Preferably, the breakdown electric field is 534-582 kV / cm, the energy storage density is 5.94-6.77 J / cm 3 , and the energy storage efficiency is 81.0-83.8%.

[0010] In a second aspect, the application provides a preparation method of the above-mentioned gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material, which comprises the following steps:

[0011] (1) Sodium carbonate, niobium pentoxide and gadolinium oxide raw materials are weighed according to the stoichiometric ratio in the chemical composition Na 1-3x Gd x NbO3, mixed and calcined to obtain ceramic raw material mixed powder;

[0012] (2) The ceramic raw material mixed powder is mixed with a binder, granulated, sieved and formed to obtain a ceramic green body;

[0013] (3) The ceramic green body is subjected to plastic arrangement and sintering to obtain the gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate-based ceramic material.

[0014] Preferably, the sodium carbonate, niobium pentoxide and gadolinium oxide raw materials are weighed by an electronic balance, and the weighing accuracy is 0.001 g; wherein the purity of sodium carbonate is 99.8%, the purity of niobium pentoxide is 99.93%, and the purity of gadolinium oxide is 99.99%.

[0015] Preferably, the mixing method of the raw materials is wet ball milling mixing; the ball milling medium is zirconia ball, zirconia column and anhydrous ethanol, preferably the particle size of the zirconia ball is 6mm, the size of the zirconia column is 10mm in diameter x 10mm in height, and the number of each is half; the ball milling speed is 200-240rpm; the ball milling time is 4-6 hours.

[0016] Preferably, the calcination temperature is 1100-1200℃, and the time is 4-5 hours.

[0017] Preferably, the binder is a polyvinyl alcohol aqueous solution with a concentration of 6-7wt.%; the addition amount of the binder is 5-7wt%, preferably 6-7wt%, of the mass of the ceramic raw material powder;

[0018] The temperature of the plastic removal is 700-800℃, and the time is 1-2 hours; preferably, the plastic removal temperature is 800℃, and the time is 2 hours.

[0019] Preferably, the sintering temperature is 1200-1320℃, preferably 1260-1320℃, the sintering time is 2-4 hours, preferably 2-3 hours, and the sintering heating rate is 1-3℃ / min, preferably 2℃ / min.

[0020] In a third aspect, the application provides a use of the gadolinium-doped high-energy-storage sodium niobate-based ceramic material in the preparation of an energy storage ceramic element.

[0021] In a fourth aspect, the application provides a use of the gadolinium-doped high-energy-storage sodium niobate-based ceramic material in the preparation of a multilayer ceramic capacitor and a high-power pulse capacitor.

[0022] Advantages

[0023] The gadolinium-doped high-energy-storage sodium niobate-based ceramic material prepared in the application has the characteristics of high saturation polarization strength, low remanent polarization strength, high breakdown strength, high energy storage density and efficiency, etc.

[0024] The preparation process provided in the application is simple, can work in extreme environments, and is suitable for the preparation and application of multilayer capacitors. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 X-ray diffraction patterns of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Examples 1-2;

[0026] Figures 2-6The surface micro-morphology diagram of the sodium niobate-based ceramic material prepared in Examples 1-3 and Comparative Example 1-2;

[0027] Figures 7-11 The dielectric temperature spectrum of the sodium niobate-based ceramic material prepared in Examples 1-3 and Comparative Example 1-2;

[0028] Figures 12-14 The monopolar hysteresis loop diagram of the sodium niobate-based ceramic material prepared in Examples 1-3 of the present application;

[0029] Figures 15-16 The monopolar hysteresis loop diagram of the sodium niobate-based ceramic material prepared in Comparative Example 1-2 of the present application;

[0030] Figure 17 The energy storage density and energy storage efficiency change diagram of the sodium niobate-based ceramic material prepared in Examples 1-3 and Comparative Example 1-2. DETAILED DESCRIPTION

[0031] The present application is further illustrated by the following examples, which should not be construed as limiting the present application.

[0032] Firstly, the present application provides a gadolinium-doped high-energy-storage relaxor anti-ferroelectric sodium niobate-based ceramic material. The chemical composition of the gadolinium-doped high-energy-storage relaxor anti-ferroelectric sodium niobate-based ceramic material is Na 1-3x Gd x NbO3; wherein 0.04 < x < 0.12, preferably 0.06 ≤ x ≤ 0.10, and more preferably 0.08.

[0033] The present application introduces small ion radius rare earth ions Gd 3+ into sodium niobate, on the one hand, reduces the material tolerance factor, which is conducive to enhancing its anti-ferroelectricity, and on the other hand, improves the local structure disorder degree of sodium niobate and enhances its relaxor behavior. At the same time, the introduction of Gd 3+ ions reduces the grain size and significantly improves the breakdown field strength of the sodium niobate ceramic material.

[0034] It should be noted that: (1) in terms of modification methods, unlike the solid solution of (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Bi 0.2 )(Mg 2 / 3 Nb 1 / 3 )O3 and other high-entropy components without introducing vacancies, the modification method in the present patent is A-site single-element rare earth doping, in which the trivalent Gd 3+ replaces the monovalent Na +In order to maintain charge balance, vacancies will be generated at the A site, which is conducive to stabilizing antiferroelectricity; (2) In terms of mechanism of action, the improvement of energy storage characteristics in conventional technical solutions mainly relies on the high entropy material's natural large lattice disorder, which is conducive to reducing the electric domain size, and the "hysteresis diffusion" effect helps to inhibit grain growth and obtain smaller grain size. However, this patent mainly introduces Gd into the A site. 3+ Radius smaller than Na + , which is beneficial to reduce the overall tolerance factor of ceramics, thereby stabilizing the AFE structure, while Gd 3+ and Na + The difference in ionic radius also causes local structural heterogeneity in ceramics, reducing the size of the electric domain, which is beneficial for inducing relaxation behavior and reducing P r It produces a promoting effect and at the same time introduces a cation vacancy at the A site to stabilize its antiferroelectricity.

[0035] The ceramic material obtained by introducing a specific content of Gd (0.04 < x < 0.12) into NaNbO3 exhibits excellent temperature stability, energy storage characteristics (energy storage density and energy storage efficiency), and electrical properties, and is expected to be used in pulsed power energy storage devices. However, if the value of x is too large, the dielectric constant will be significantly reduced, thereby reducing the maximum polarization intensity and making it difficult to achieve excellent energy storage characteristics. If the value of x is too small, the hysteresis loop will exhibit an antiferroelectric double hysteresis loop morphology, with a large remanent polarization intensity, which will reduce the energy storage density and efficiency.

[0036] In some embodiments, the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material has a breakdown electric field of 371 to 582 kV / cm and an energy storage density of 2.16 to 6.77 J / cm 3 , the energy storage efficiency is 32.8-83.8%; preferably, the breakdown electric field is 534-582 kV / cm, and the energy storage density is 5.94-6.77 J / cm 3 , the energy storage efficiency is 81.0~83.8%.

[0037] The following is an exemplary description of the preparation method of the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material provided by the present invention. The preparation method may include the following steps:

[0038] First, sodium carbonate, niobium pentoxide, and gadolinium oxide are mixed according to the chemical composition of Na 1-3x Gd x The stoichiometric ratio of NbO3 is weighed, and the raw materials are mixed and calcined to obtain a ceramic raw material mixed powder;

[0039] Then, the ceramic raw material mixed powder is mixed with a binder, granulated, sieved, and formed to obtain a ceramic green body;

[0040] Finally, the ceramic green body is plasticized and sintered to obtain the gadolinium-doped high-energy-storage relaxor antiferroelectric sodium niobate ceramic material.

[0041] In some embodiments, the sodium carbonate, niobium pentoxide and gadolinium oxide raw materials are weighed using an electronic balance with an accuracy of 0.001 g; wherein the purity of sodium carbonate is 99.8%, the purity of niobium pentoxide is 99.93%, and the purity of gadolinium oxide is 99.99%.

[0042] In some embodiments, the raw material mixing method can be wet ball milling; the ball milling medium can be zirconia balls, zirconia columns and anhydrous ethanol, preferably the particle size of the zirconia balls is 6 mm, the size of the zirconia columns is 10 mm in diameter x 10 mm in height, and the number of each is half; the ball milling speed can be 200-240 rpm; the ball milling time can be 4-6 hours.

[0043] In some embodiments, the calcination temperature can be 1100-1200°C, and the time can be 4-5 hours.

[0044] In some embodiments, the ceramic raw material powder after calcination can also be finely ground; wherein the fine grinding can use small particle size (such as 1 mm) zirconia balls and anhydrous ethanol as the medium, and the fine grinding time can be 6 hours.

[0045] In some embodiments, the particle size of the ceramic raw material mixed powder can be controlled to be 200 nm-1 μm.

[0046] In some embodiments, the binder can be a polyvinyl alcohol aqueous solution with a concentration of 6-7 wt.%; the amount of the binder added can be 5-7 wt.% of the mass of the ceramic raw material powder, preferably 6-7 wt.%.

[0047] In some embodiments, the screen for sieving can be 20-60 mesh, preferably 40 mesh.

[0048] In some embodiments, the plasticizing temperature can be 700-800°C, and the time can be 1-2 hours; preferably, the plasticizing temperature is 800°C, and the time is 2 hours.

[0049] In some embodiments, the sintering temperature can be 1200-1320°C, preferably 1260-1320°C, the sintering time can be 2-4 hours, preferably 2-3 hours, and the sintering heating rate can be 1-3°C / min, preferably 2°C / min.

[0050] The gadolinium-doped high energy storage relaxor antiferroelectric sodium niobate-based ceramic material prepared by the preparation method provided by the application can be applied to the preparation of an energy storage ceramic element. The energy storage ceramic element comprises the gadolinium-doped high energy storage sodium niobate-based ceramic material and an electrode distributed on the surface of the sodium niobate-based ceramic material.

[0051] Meanwhile, the gadolinium-doped high energy storage relaxor antiferroelectric sodium niobate-based ceramic material provided by the application can also be applied to the preparation of a multi-layer ceramic capacitor (MLCC) and a high-power pulse capacitor.

[0052] The following examples are further provided to illustrate the application in detail. It should also be understood that the following examples are only used to further illustrate the application and cannot be understood as limiting the protection scope of the application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the application all belong to the protection scope of the application. The specific process parameters in the following examples are only one example in the appropriate range, that is, those skilled in the art can select within the appropriate range through the description herein, and are not limited to the specific values in the following examples. If not specifically indicated, the technical means used in the examples are conventional means known to those skilled in the art.

[0053] Example 1

[0054] The preparation method of the gadolinium-doped high energy storage relaxor antiferroelectric sodium niobate-based ceramic material provided in the embodiment comprises the following steps:

[0055] (1) The ingredients are calculated according to the molecular formula Na 1-3x Gd x NbO3(x=0.06); the raw materials used include: sodium carbonate with a purity of 99.8% and a molecular weight of 84.007; niobium pentoxide with a purity of 99.93% and a molecular weight of 265.810; gadolinium oxide with a purity of 99.99% and a molecular weight of 362.5. An electronic balance is used for weighing, and the weighing is accurate to 0.001 g;

[0056] The weighed raw materials are mixed in a nylon tank, and no more than 2 / 3 of the height of the tank of anhydrous ethanol is added to the tank. The nylon tank is placed on a planetary ball mill with zirconia balls and zirconia columns as the medium for mixing for 6 hours (the particle size of the zirconia balls used is 6 mm, and the size of the zirconia columns is 10 mm in diameter x 10 mm in height, with half of each). Then, pour out and dry in an oven, and then sieve with a 40-mesh nylon sieve. The sieved mixed powder is pressed into a cylinder with a size of 65 mm in diameter x 20 mm in height on a press. Synthesis is carried out at 1100-1200℃ for 5 hours under an atmospheric atmosphere, and then crushed through a 40-mesh screen. The obtained powder is placed in a stirring mill with 1 mm diameter zirconia balls and anhydrous ethanol as the medium for fine grinding for 6 hours, dried in an oven, and the ceramic raw material mixed powder is obtained.

[0057] (2) 7wt.% polyvinyl alcohol aqueous solution is added to the obtained ceramic raw material mixed powder, and the amount of the polyvinyl alcohol aqueous solution added is 6.5% of the mass of the ceramic raw material mixed powder. Then, uniform granulation is performed, sieving is performed through a 40-mesh sieve, and molding is performed, to obtain a cylindrical ceramic green body with a size of 13 mm in diameter x 1 mm in height.

[0058] (3) The obtained cylindrical ceramic green body is subjected to plastic arrangement, and the arranged green body is sintered in an alumina crucible. The sintering temperature is 1300℃, and the sintering time is 2 hours. After natural cooling to room temperature, the sample is taken out, and the gadolinium-doped high-energy storage relaxor antiferroelectric sodium niobate-based ceramic material is obtained.

[0059] Example 2

[0060] The preparation method of the gadolinium-doped high-energy storage relaxor antiferroelectric sodium niobate-based ceramic material provided in this example refers to Example 1, and the main difference is that the molecular formula of Na 1-3x Gd x NbO3, x = 0.08.

[0061] Example 3

[0062] The preparation method of the gadolinium-doped high-energy storage relaxor antiferroelectric sodium niobate-based ceramic material provided in this example refers to Example 1, and the main difference is that the molecular formula of Na 1-3x Gd x NbO3, x = 0.10.

[0063] Comparative Example 1

[0064] The preparation method of the ceramic material provided in this comparative example refers to Example 1, and the main difference is that (1) the molecular formula of Na 1-3x Gd x NbO3, x = 0.04; and (2) the sintering temperature is 1320℃.

[0065] Comparative Example 2

[0066] The preparation method of the ceramic material provided by the present comparative example is similar to that of Example 1, with the main difference being that: (1) the molecular formula of Na 1-3x Gd x NbO3, x = 0.12; (2) the sintering temperature is 1280°C.

[0067] Figure 1 The X-ray diffraction patterns of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 are shown in the figure. As can be seen from the figure, the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 are all free of impurity phases.

[0068] The surface morphology of the ceramic after chromium plating is photographed. Figures 2-6 The surface micro-morphology of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 is shown in the figure. As can be seen from the figure, the surfaces of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 are dense.

[0069] The ceramic is ground and polished on both sides, silver electrodes are plated, and the electrical properties are tested. Figures 7-11 The dielectric temperature spectrum of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 is shown in the figure. As can be seen from the figure, with the addition of gadolinium, the dielectric peak moves to lower temperatures, gradually moving below -100°C, and a frequency dispersion phenomenon appears, representing the appearance of relaxation behavior, and with the increase of gadolinium content, the dielectric constant of the sodium niobate-based ceramic at room temperature gradually decreases.

[0070] Figures 12-14 The monopolar hysteresis loop of the sodium niobate-based ceramic material prepared in Example 1-3 of the present application is shown in the figure. As can be seen from the figure, with the increase of Gd content, the hysteresis loop gradually changes into a narrow relaxation type hysteresis loop, the breakdown electric field of the sodium niobate-based ceramic material prepared in Example 1-3 is 536 kV / cm, 582 kV / cm and 565 kV / cm, respectively, the maximum energy storage density is 5.94 J / cm 3 , 6.77 J / cm 3 and 6.55 J / cm 3 , and the energy storage efficiency is 81.0%, 82.7% and 83.8%, respectively.

[0071] Figures 15-16 The monopolar hysteresis loop of the sodium niobate-based ceramic material prepared in Comparative Example 1-2 of the present application is shown in the figure. As can be seen from the figure, the breakdown electric field of the sodium niobate-based ceramic material prepared in Comparative Example 1-2 is 371 kV / cm and 465 kV / cm, respectively, the maximum energy storage density is 2.16 J / cm 3 and 4.32 J / cm 3 , and the energy storage density of the two comparative examples is less than 5 J / cm 3, the energy storage efficiency is 32.8% and 76.2%, respectively.

[0072] Figure 17 The energy storage density and energy storage efficiency of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 are shown in the following figures. As can be seen from the figures, the energy storage density of the sodium niobate-based ceramics prepared in Comparative Example 1-2 with too low or too high gadolinium content is significantly weaker than that of the sodium niobate-based ceramics prepared in Example 1-3 with moderate gadolinium content. Therefore, the design of gadolinium-doped high energy storage relaxor antiferroelectric sodium niobate-based ceramic material can achieve high energy storage characteristics, and the content of gadolinium has a certain moderate range.

[0073] Table 1 below shows the composition and performance of the sodium niobate-based ceramic materials prepared in Examples 1-3 and Comparative Example 1-2 of the present application:

[0074] x Breakdown field Energy storage density Energy storage efficiency Example 1 0.06 536 kV / cm 5.94 J / cm 3 ]] 81.0％ Example 2 0.08 582 kV / cm 6.77 J / cm 3 ]] 82.7％ Example 3 0.10 565 kV / cm 6.55 J / cm 3 ]] 83.8％ Comparative Example 1 0.04 371 kV / cm 2.16 J / cm 3 ]] 32.8％ Comparative Example 2 0.12 465 kV / cm 4.32 J / cm 3 ]] 76.2％

[0075] Although the content of the present application has been described in detail through the above preferred embodiments, it should be recognized that the above description should not be considered as limiting the present application. After reading the above content, various modifications and alternatives of the present application will be apparent to those skilled in the art. Therefore, the scope of protection of the present application should be defined by the appended claims.

Claims

1. A gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material, characterized in that: The chemical composition of the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material is Na 1-3x Gd x NbO3; wherein, 0.08≤x≤0.

10.

2. The gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material according to claim 1, characterized in that: The gadolinium-doped high-energy storage relaxation antiferroelectric sodium niobate-based ceramic material has a breakdown electric field of 371 to 582 kV / cm and an energy storage density of 2.16 to 6.77 J / cm 3 , the energy storage efficiency is 32.8~83.8%.

3. A method for preparing the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material according to claim 1, characterized in that: The preparation method comprises the following steps: (1) Sodium carbonate, niobium pentoxide and gadolinium oxide are prepared according to the chemical composition of Na 1-3x Gd x The stoichiometric ratio of NbO3 is weighed, and the raw materials are mixed and calcined to obtain a ceramic raw material mixed powder; (2) mixing the ceramic raw material mixed powder with a binder, granulating, screening, and molding to obtain a ceramic green body; (3) The ceramic green body is subjected to plasticizing and sintering to obtain the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material.

4. The preparation method according to claim 3, characterized in that The sodium carbonate, niobium pentoxide, and gadolinium oxide raw materials are weighed using an electronic balance with an accuracy of 0.001 g; wherein the purity of sodium carbonate is 99.8%, the purity of niobium pentoxide is 99.93%, and the purity of gadolinium oxide is 99.99%.

5. The preparation method according to claim 3, characterized in that The raw materials are mixed by wet ball milling; the ball milling media are zirconia balls, zirconia columns and anhydrous ethanol, the zirconia balls have a particle size of 6 mm, the zirconia columns have a size of 10 mm in diameter and 10 mm in height, and the number of each is half; the ball milling speed is 200 to 240 rpm; and the ball milling time is 4 to 6 hours.

6. The preparation method according to claim 3, characterized in that The calcination temperature is 1100-1200° C. and the calcination time is 4-5 hours.

7. The preparation method according to claim 3, characterized in that The binder is a polyvinyl alcohol aqueous solution with a concentration of 6 to 7 wt.%; the amount of the binder added is 5 to 7 wt.% of the mass of the ceramic raw material mixed powder; The temperature of the plastic removal is 700-800° C., and the time is 1-2 hours.

8. The preparation method according to claim 3, characterized in that The sintering temperature is 1200-1320° C., the sintering time is 2-4 hours, and the sintering heating rate is 1-3° C. / min.

9. Use of the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material according to claim 1 in preparing energy storage ceramic components, characterized in that: The energy storage ceramic element comprises: the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material according to claim 1, and electrodes distributed on the surface of the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material.

10. Use of the gadolinium-doped high energy storage relaxation antiferroelectric sodium niobate-based ceramic material according to claim 1 in the preparation of multilayer ceramic capacitors and high power pulse capacitors.

Images