Ferroelectric-piezoelectric ceramic energy storage material and hybrid process preparation method and application thereof

Abstract

The application discloses a ferroelectric-piezoelectric ceramic energy storage material and a hybrid process preparation method and application thereof, and belongs to the technical field of ferroelectric-piezoelectric ceramic materials. The ferroelectric-piezoelectric ceramic energy storage material comprises polycrystal powder and sol which are mixed uniformly and subjected to heat treatment to form micro-nano composite structure particles, and the micro-nano composite structure particles comprise the polycrystal powder and a PLZS nano component layer distributed around the polycrystal powder. The hybrid process preparation method of the ferroelectric-piezoelectric ceramic energy storage material comprises the following steps: preparing sol and polycrystal powder; subjecting the sol and the polycrystal powder to heat treatment to obtain micro-nano composite structure particles; and obtaining a ferroelectric-piezoelectric ceramic energy storage material sample through flow casting process and sintering of the micro-nano composite structure particles. The ferroelectric-piezoelectric ceramic energy storage material and the hybrid process preparation method and application thereof have the advantages that the specific surface area and the oxygen vacancy content are improved by hybridization with sol components, the sintering temperature of the ceramic material is lowered, and the dielectric energy storage performance of the ceramic material is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ferroelectric-piezoelectric ceramic materials, and particularly relates to a ferroelectric-piezoelectric ceramic energy storage material and a hybrid process preparation method and application thereof. BACKGROUND

[0002] With the development of electronic information technology, ceramic capacitors, as an important electronic component, play an irreplaceable role in the electronic industry. Dielectric energy storage is an important application direction of ceramic capacitors, which puts forward new requirements for the performance of dielectric ceramic materials. Lead zirconate-based ferroelectric-piezoelectric ceramic energy storage materials have the advantages of high power density, fast discharge rate and long service life, and are important candidate materials for pulse power electronic components. However, their application in electronic energy storage components is limited by low energy storage density and high sintering temperature. This is because the co-sintering of dielectric ceramic materials and internal electrodes in multi-layer ceramic capacitors requires the ceramic material to have a low enough sintering temperature. Taking 70 / 30 palladium-silver electrodes as an example, its annealing temperature is 1150℃, but the sintering temperature of lead zirconate-based energy storage ceramics is generally around 1300℃. Therefore, it is necessary to reduce the sintering temperature of lead zirconate-based ceramic materials.

[0003] At present, it is generally believed that adding glass is an effective means to reduce the sintering temperature. In the invention with the patent application number CN202010798450.5, the sintering temperature of lead barium lanthanum zirconium tin ceramic doped with barium boron aluminum silicon glass phase is reduced to 1050℃, and the energy storage density is increased to 6.3J / cm 3 In the invention with the patent application number 202211297267.2, by adding BaCO3-B2O3-SiO2-K2CO3 glass phase, the sintering temperature of Pb 0.95 La 0.02 Sr 0.02 (Zr 0.5 Sn 0.4 Ti 0.1 )O3 ceramic material is reduced from 1300℃ to 960℃, but its energy storage density is only 3.2J / cm 3 In these inventions, the addition of glass is not very effective for the improvement of energy storage characteristics, and even sacrifices the dielectric constant of the material.

[0004] Whether for ferroelectric-piezoelectric ceramic energy storage materials or other functional ceramic materials, reducing the sintering temperature is beneficial to energy saving and cost reduction. How to reduce the sintering temperature while improving the performance of energy storage materials is a technical problem that needs to be solved. SUMMARY

[0005] The application aims to provide a ferroelectric-piezoelectric ceramic energy storage material and a hybrid process preparation method and application thereof.

[0006] To achieve the above-mentioned purpose, the application provides a ferroelectric-piezoelectric ceramic energy storage material, which comprises micro-nano composite structure particles formed by mixing and uniformly mixing polycrystalline powder and sol and then heat treating, and the micro-nano composite structure particles comprise the polycrystalline powder and a PLZS nano component layer distributed around the polycrystalline powder.

[0007] Preferably, the weight ratio of the sol to the polycrystalline powder is 1-3:5.

[0008] Preferably, the PLZS nano component layer has a chemical formula of (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O3.

[0009] Preferably, the polycrystalline powder has a chemical formula of (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3 (PLZSHT).

[0010] The hybrid process preparation method of the ferroelectric-piezoelectric ceramic energy storage material comprises the following steps:

[0011] S1, preparing a sol and polycrystalline powder respectively;

[0012] S2, mixing the sol and the polycrystalline powder, removing organic matters by heat treatment, and obtaining micro-nano composite structure particles;

[0013] S3, uniformly mixing the micro-nano composite structure particles with a solvent, a binder, a dispersant and a plasticizer to obtain a casting slurry; the solvent is a mixture of ethanol and trichloroethylene, the binder is polyvinyl butyral, the dispersant is triethyl phosphate, and the plasticizer is dibutyl phthalate; the ratio of the micro-nano composite structure particles to the solvent, the binder, the dispersant and the plasticizer is 20:20:2:0.4:0.8;

[0014] S4, removing bubbles and casting the casting slurry to obtain a thick film;

[0015] S5, shearing, laminating and hot pressing the thick film to obtain a ceramic green body;

[0016] S6, degreasing and sintering the ceramic green body to obtain a ferroelectric-piezoelectric ceramic energy storage material sample.

[0017] Preferably, in S1, the preparation method of the sol comprises the following steps:

[0018] S111, lead acetate, lanthanum acetate, zirconium n-propyl alcohol and tin isopropyl alcohol are weighed according to the stoichiometric ratio;

[0019] S112, dissolve the lead acetate and lanthanum acetate in acetic acid, heat to 110°C and stir, and after cooling, mark as A cup; dissolve the zirconium n-propyl alcohol and tin isopropyl alcohol in ethylene glycol methyl ether, introduce acetylacetone after mixing and stirring, and the molar ratio of acetylacetone to the PLZS content in the sol is about 1.1:1. After the sample is stirred uniformly, mark as B cup;

[0020] S113, introduce the B cup solution into the A cup solution, mix and stir uniformly, and then add deionized water, acetic acid and ethylene glycol to adjust the concentration, pH and viscosity, respectively, stir, and then use acetic acid to adjust the volume to obtain a clear sol. The concentration of the sol is 0.027g / ml-0.08g / ml, the pH is 3-5, and the viscosity is 7cP-9cP.

[0021] Preferably, in S1, the preparation method of the polycrystalline powder comprises the following steps:

[0022] S121, mix the lead trioxide, lanthanum trioxide, zirconium dioxide, tin dioxide, hafnium dioxide and titanium dioxide according to the stoichiometric ratio, and perform first ball milling for 20h-30h;

[0023] S122, dry the mixed material obtained after the first ball milling, and perform pre-sintering at a pre-sintering temperature of 900°C for a pre-sintering holding time of 3h, and then cool to room temperature with the furnace to obtain a pre-sintered mixed material;

[0024] S123, perform second ball milling on the pre-sintered mixed material for 20h-30h, dry the mixed material after the second ball milling to obtain a polycrystalline powder.

[0025] Preferably, in S2, the heat treatment temperature is 600°C, the heat treatment holding time is 5h-7h, and the furnace is cooled to room temperature.

[0026] Preferably, in S6, the degreasing temperature is 600°C, the degreasing holding time is 8h, and the furnace is cooled to room temperature; the sintering temperature is 1100°C-1130°C, the sintering holding time is 3h, and the furnace is cooled to room temperature.

[0027] The ferroelectric-piezoelectric ceramic energy storage material prepared by the above-mentioned hybrid process preparation method of the ferroelectric-piezoelectric ceramic energy storage material is applied in electronic functional materials and devices.

[0028] The ferroelectric-piezoelectric ceramic energy storage material, the hybrid process preparation method and the application have the advantages and positive effects that:

[0029] 1、The sol is mixed with the polycrystal powder and the organic matter is removed to obtain the raw material with micro-nano composite structure, the sol composition effectively reduces the grain size after sintering, and the breakdown strength is improved. The space charge polarization exists in the composite ceramic material, and the introduced orthogonal phase has high polarization strength, so that the dielectric constant is improved. The ceramic material prepared by the hybrid process has greatly improved energy storage density, which is beneficial to solve the problem of volume limitation of energy storage capacitor.

[0030] 2、The sintering temperature of the ferroelectric-piezoelectric ceramic energy storage material prepared by the hybrid process is 1120 DEG C, which is reduced by 180 DEG C than the sintering temperature of the ceramic prepared without the composite sol, which is beneficial to the low-temperature co-sintering of the internal electrode and the ceramic material in the multilayer ceramic capacitor. The sintering temperature of the ferroelectric-piezoelectric ceramic energy storage material is reduced to below 1150 DEG C, which is the co-sintering temperature of Ag-Pd electrode, which has great application significance.

[0031] 3、The hybrid process flow of the ferroelectric-piezoelectric ceramic energy storage material is simple, easy to repeat, does not need to introduce large equipment, has low cost, and can be mass-produced.

[0032] The technical solutions of the present application will be further described in detail below with the help of the drawings and examples. DESCRIPTION OF DRAWINGS

[0033] Figure 1 The hybrid process flow chart of the ferroelectric-piezoelectric ceramic energy storage material of the present application;

[0034] Figure 2 The XRD graphs of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in examples 1-3 and the ceramic material obtained in comparative example 1 of the present application;

[0035] Figure 3 The SEM graphs of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in examples 1-3 and the ceramic material obtained in comparative example 1 of the present application; (a) is the SEM graph of the ceramic material graph of comparative example 1; (b) is the SEM graph of the ferroelectric-piezoelectric ceramic energy storage material sample of example 1; (c) is the SEM graph of the ferroelectric-piezoelectric ceramic energy storage material sample of example 2; (d) is the SEM graph of the ferroelectric-piezoelectric ceramic energy storage material sample of example 3;

[0036] Figure 4 The dielectric constant-temperature curve graphs of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in examples 1-3 and the ceramic material obtained in comparative example 1 of the present application;

[0037] Figure 5Room temperature hysteresis loop of the ferroelectric-piezoelectric ceramic energy storage material sample obtained in Example 1-3 of the present application and the ceramic material obtained in Comparative Example 1;

[0038] Figure 6 Energy storage performance results of the ferroelectric-piezoelectric ceramic energy storage material sample obtained in Example 1-3 of the present application and the ceramic material obtained in Comparative Example 1;

[0039] Figure 7 TEM of the micro-nano composite structure particles obtained in Example 2 of the present application Figure 1 ;

[0040] Figure 8 TEM of the micro-nano composite structure particles obtained in Example 2 of the present application Figure 2 ;

[0041] Figure 9 Undamped discharge condition of the ferroelectric-piezoelectric ceramic energy storage material sample obtained in Example 2 of the present application. DETAILED DESCRIPTION

[0042] In the present application, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. If there is an inconsistency between the commonly used meanings of terms and the meanings expressed in the present specification or derived from the context, the meanings expressed in the present specification or derived from the context prevail. In addition, the terms used herein are only for the purpose of describing the embodiments of the present application and are not intended to limit the present application. In order to accurately describe the technical content in the present application and to accurately understand the present application, the following explanations or definitions of the terms used in the present specification are given before the specific embodiments are described:

[0043] The embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0044] A ferroelectric-piezoelectric ceramic energy storage material, comprising micro-nano composite structure particles formed by heat treatment of a mixture of uniform polycrystalline powder and sol, the micro-nano composite structure particles comprising the polycrystalline powder and a PLZS nano-component layer distributed around the polycrystalline powder.

[0045] The weight ratio of the sol to the polycrystalline powder is 1-3:5.

[0046] The chemical general formula of the PLZS nano-component layer is (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O3. The PLZS nano-component layer is an orthorhombic phase material with higher polarization intensity.

[0047] The chemical general formula of the polycrystalline powder is (Pb 0.94 La0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3. Polycrystalline powder is a tetragonal phase material with the characteristics of phase change dispersion, but its polarization strength and breakdown strength are low, and the sintering temperature is higher than 1300℃.

[0048] like Figure 1 The hybrid process preparation method of the ferroelectric-piezoelectric ceramic energy storage material comprises the following steps:

[0049] S1. Prepare sol and polycrystalline powder respectively.

[0050] The preparation method of the sol comprises the following steps:

[0051] S111. Weigh lead acetate, lanthanum acetate, zirconium n-propoxide, and tin isopropoxide according to a stoichiometric ratio.

[0052] S112. Dissolve lead acetate and lanthanum acetate in acetic acid, heat to 110°C with stirring, and cool. This is marked as Cup A. Dissolve zirconium n-propoxide and tin isopropoxide in ethylene glycol methyl ether, mix and stir, then introduce the chelating agent acetylacetone. Stir and mix thoroughly until the mixture is uniform. This is marked as Cup B. Acetylacetone can chelate with metal ions such as zirconium ions. By coordinating with zirconium ions, it can control the hydrolysis rate of metal ions, making the hydrolysis process more uniform and slow, avoiding precipitation caused by rapid hydrolysis of metal ions and helping to form a stable sol system. Acetylacetone can also improve the stability of the sol, reduce particle agglomeration, and improve the dispersibility of the prepared sol.

[0053] S113. Introduce the solution in cup B into the solution in cup A, mix and stir evenly, add deionized water, acetic acid and ethylene glycol to the mixture in sequence to adjust the concentration, pH and viscosity, stir and then dilute with acetic acid to obtain a clear sol.

[0054] The concentration of the sol is 0.027g / ml-0.08g / ml, the pH value is 3-5, and the viscosity is 7cP-9cP.

[0055] The method for preparing polycrystalline powder comprises the following steps:

[0056] S121. Mix lead tetroxide, lanthanum trioxide, zirconium dioxide, tin dioxide, hafnium dioxide, and titanium dioxide in a stoichiometric ratio and perform a first ball milling. The first ball milling medium is alcohol, the grinding balls are zirconium oxide, and the first ball milling time is 20 hours to 30 hours.

[0057] S122. Dry the mixture obtained after the first ball milling and pre-calculate it at a temperature of 900° C. for 3 hours. Cool it to room temperature in the furnace to obtain a pre-calcined mixture.

[0058] S123, the pre-sintering mixture is subjected to second ball milling, the medium of the second ball milling is alcohol, the grinding ball is zirconium oxide, the second ball milling time is 20-30h, and the mixture is sieved through a 150 mesh sieve. The mixture after the second ball milling is dried to obtain micron-sized polycrystalline powder.

[0059] S2, the sol and the polycrystalline powder are mixed and ball milled for 24h, and the mixed mixture is dried to obtain a mixture. The mixture is subjected to heat treatment to remove organic matter to obtain micro-nano composite structure particles.

[0060] The heat treatment temperature is 600℃. The heat treatment holding time is 6h. The furnace is cooled to room temperature.

[0061] The lead zirconate-based particles are dispersed in the organic sol, and the organic matter is burned off at a low temperature of 600℃ to prevent the lead zirconate-based particles in the sol from growing.

[0062] S3, the micro-nano composite structure particles are subjected to preliminary crushing to improve the uniformity of the micro-nano composite structure particles. The micro-nano composite structure particles are mixed with ethanol, trichloroethylene and triethyl phosphate and are roller milled for 4h to obtain a uniform and stable slurry. Then, polyvinyl butyral and dibutyl phthalate are added to the slurry, and the slurry is roller milled for 2h to obtain a casting slurry. The weight ratio of the micro-nano composite structure particles to the solvent, the binder, the dispersant and the plasticizer is 20:20:2:0.4:0.8.

[0063] S4, the casting slurry is subjected to vacuum extraction to remove bubbles, and a green sheet is scraped out with a doctor blade to obtain a thick film.

[0064] S5, after the thick film is subjected to shearing, layering and hot pressing, a ceramic green body is obtained.

[0065] S6, the ceramic green body is subjected to degreasing and sintering to obtain a ferroelectric-piezoelectric ceramic energy storage material sample.

[0066] The degreasing temperature is 600℃. The degreasing holding time is 8h. The furnace is cooled to room temperature; the degreasing process removes the organic matter in the ceramic green body.

[0067] The sintering temperature is 1100-1130℃, the sintering holding time is 3h, and the furnace is cooled to room temperature.

[0068] Example 1

[0069] The chemical formula of the sol and the polycrystalline powder is (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O3 and (Pb 0.94 La 0.04 )(Zr 0.51 Sn0.47 Hf 0.01 Ti 0.01 )O3. The sol concentration is 0.027 g / ml, and the volume is 150 ml. The weight of the polycrystalline powder is 20 g. The weight ratio of the sol to the polycrystalline powder is 1:5.

[0070] A hybrid process preparation method for ferroelectric-piezoelectric ceramic energy storage materials comprises the following steps:

[0071] S1. Pb3O4, La2O3, ZrO2, SnO2, HfO2, and TiO2 powders were weighed according to the stoichiometric ratio and mixed by wet ball milling. After ball milling for 24 hours, the mixture was dried. The mixture was sintered at 900°C and held at this temperature for 2 hours to obtain a pre-calcined mixture. The pre-calcined mixture was ball milled a second time for 24 hours and then dried to obtain a polycrystalline powder.

[0072] Lead acetate, lanthanum acetate, zirconium n-propoxide, and tin isopropoxide were mixed in stoichiometric proportions. The lead acetate and lanthanum acetate were dissolved in acetic acid, heated to 110°C, stirred for 2 hours, and then cooled. This was designated as Cup A. Zirconium n-propoxide and tin isopropoxide were mixed in ethylene glycol methyl ether and stirred for 2 hours. Acetylacetone was then added to the solution in a molar ratio of 1.1:1 to the lead zirconate-based sol, and the mixture was stirred. This was designated as Cup B. The solution in Cup B was introduced into the solution in Cup A, and the mixture was stirred. Deionized water, acetic acid, and ethylene glycol were then added sequentially to adjust the concentration, pH, and viscosity. After stirring for 2 hours, the volume was fixed with acetic acid to obtain a clear sol of 0.027 g / ml, a pH of 4, and a viscosity of 8 cP.

[0073] S2. 20 g of polycrystalline powder was mixed with 150 ml of sol and ball-milled for 24 h. The mixture was dried and kept at 600° C. for 6 h to remove organic matter by heat treatment, thereby obtaining micro-nano composite structure particles.

[0074] S3. The micro-nano composite structure particles are mixed with ethanol, trichloroethylene and tributyl phosphate and roll-milled for 4 hours to obtain a uniform and stable slurry. Then, polyvinyl butyral, dibutyl phthalate and polyethylene glycol are added to the slurry and roll-milled for 2 hours to obtain a casting slurry.

[0075] S4. Vacuum the slurry to remove bubbles and scrape out the blank with a scraper.

[0076] S5. After pressing the green sheet into shape, heat it to 600 min and perform heat treatment for 8 hours to remove organic matter to obtain a ceramic green sheet.

[0077] S6. Sinter the ceramic green body at 1120° C. for 3 h to obtain a ferroelectric-piezoelectric ceramic energy storage material sample.

[0078] Example 2

[0079] The chemical formulas of sol and polycrystalline powder are (Pb 0.97La 0.02 )(Zr 0.6 Sn 0.4 )O3and (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3. The sol concentration is 0.053 g / ml, and the volume is 150 ml. The weight of the polycrystalline powder is 20 g. The weight ratio of the sol to the polycrystalline powder is 2:5.

[0080] The preparation method of the hybrid process of the ferroelectric-piezoelectric ceramic energy storage material is the same as that in Example 1.

[0081] Example 3

[0082] The chemical formula of the sol and the polycrystalline powder is (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O3and (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3, respectively. The sol concentration is 0.08 g / ml, and the volume is 150 ml. The weight of the polycrystalline powder is 20 g. The weight ratio of the sol to the polycrystalline powder is 3:5.

[0083] The preparation method of the hybrid process of the ferroelectric-piezoelectric ceramic energy storage material is the same as that in Example 1.

[0084] Comparative Example 1

[0085] In Comparative Example 1, the sol mixing amount is 0, and the ceramic is made of only the single calcined (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3polycrystalline powder.

[0086] The preparation method of the hybrid process of the ferroelectric-piezoelectric ceramic energy storage material comprises the following steps:

[0087] The powders of Pb3O4, La2O3, ZrO2, SnO2, HfO2, and TiO2 are weighed according to the stoichiometric ratio, mixed by wet ball milling, dried after ball milling for 24 h, and sintered at 900°C for 2 h to obtain a pre-sintered mixture. The pre-sintered mixture is subjected to a second ball milling, dried after ball milling for 24 h, to obtain a polycrystalline powder.

[0088] The polycrystalline powder, ethanol, trichloroethylene and tributyl phosphate were mixed and roller milled for 4 h to obtain a uniform and stable slurry, then polyvinyl butyral, dibutyl phthalate, polyethylene glycol were added to the slurry and roller milled for 2 h to obtain a casting slurry.

[0089] The slurry was vacuumed for 5 min to remove bubbles, and the green sheet was scraped out with a doctor blade.

[0090] After the green sheet was pressed and formed, the temperature was raised to 600 min and heat treated for 8 h to remove organic matter to obtain a ceramic green body.

[0091] After the ceramic green body was sintered at 1300 ℃ for 3 h, a ceramic material was obtained.

[0092] The ferroelectric-piezoelectric ceramic energy storage material samples obtained in Examples 1-3 and the ceramic material obtained in Comparative Example 1 were subjected to XRD analysis, and the results are shown in Figure 2 The ceramic material in Comparative Example 1 was a tetragonal perovskite phase. The ferroelectric-piezoelectric ceramic energy storage material in Example 1 was a pure perovskite phase, mainly a tetragonal phase, but contained a small amount of an orthorhombic phase compared to Comparative Example 1. The ferroelectric-piezoelectric ceramic energy storage material in Example 2 was a pure perovskite phase, mainly a tetragonal phase, but the orthorhombic phase content increased compared to the energy storage material in Example 1. The ferroelectric-piezoelectric ceramic energy storage material in Example 3 was a pure perovskite phase, mainly a tetragonal phase, and had the highest orthorhombic phase content.

[0093] The ferroelectric-piezoelectric ceramic energy storage material samples obtained in Examples 1-3 and the ceramic material obtained in Comparative Example 1 were subjected to SEM analysis, and the results are shown in Figure 3 The ceramic material in Comparative Example 1 had relatively large grain size and a small amount of pores. The ferroelectric-piezoelectric ceramic energy storage material in Example 1 had smaller grain size than Comparative Example 1 and no obvious pores. The ferroelectric-piezoelectric ceramic energy storage material in Example 2 had even smaller grain size and no obvious pores. The ferroelectric-piezoelectric ceramic energy storage material in Example 3 had the smallest grain size and a small amount of pores.

[0094] Figure 4The dielectric constant-temperature curves of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in Examples 1-3 of the present application and the ceramic material obtained in Comparative Example 1 are shown in the figure. The results show that the dielectric constant of the ceramic material in Comparative Example 1 is lower than that in Examples 1-3, and a wide dielectric peak is shown in the temperature range of 150-360℃, which is a typical phase transition dispersion behavior. The dielectric constant of the ferroelectric-piezoelectric ceramic energy storage material in Example 1 is higher than that of the ceramic material in Comparative Example 1, and a wide dielectric peak is shown in the temperature range of 150-360℃, but the phase transition dispersion is lower than that in Comparative Example 1. The dielectric constant of the ferroelectric-piezoelectric ceramic energy storage material in Example 2 is higher than that of the ferroelectric-piezoelectric ceramic energy storage material in Example 1, and a wide dielectric peak is shown in the temperature range of 150-360℃, but the phase transition dispersion is lower than that in Example 1. The dielectric constant of the ferroelectric-piezoelectric ceramic energy storage material in Example 3 is the highest, and a wide dielectric peak is shown in the temperature range of 150-360℃, and the phase transition dispersion is the lowest.

[0095] Figure 5 The room temperature electric hysteresis loops of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in Examples 1-3 of the present application and the ceramic material obtained in Comparative Example 1 are shown in the figure, Figure 6 The energy storage performance results of the ferroelectric-piezoelectric ceramic energy storage material samples obtained in Examples 1-3 of the present application and the ceramic material obtained in Comparative Example 1 are shown in the table. The results show that the breakdown field strength of the ceramic material in Comparative Example 1 is 517 kV / cm, the maximum polarization strength is 36.4 μC / cm 2 , the effective energy storage density is 9.5 J / cm 3 , and the energy storage efficiency is 95.3%. The breakdown field strength of the ferroelectric-piezoelectric ceramic energy storage material in Example 1 is 664 kV / cm, the maximum polarization strength is 41.7 μC / cm 2 , the effective energy storage density is 12.1 J / cm 3 , and the energy storage efficiency is 94.1%. The breakdown field strength of the ferroelectric-piezoelectric ceramic energy storage material in Example 2 is 664 kV / cm, the maximum polarization strength is 43.6 μC / cm 2 , the effective energy storage density is 12.4 J / cm 3 , and the energy storage efficiency is 92.4%. The breakdown field strength of the ferroelectric-piezoelectric ceramic energy storage material in Example 3 is 595 kV / cm, the maximum polarization strength is 43.0 μC / cm 2 , the effective energy storage density is 6.04 J / cm 3 , and the energy storage efficiency is 86.7%.

[0096] Figure 7 The TEM Figure 1 , Figure 8 of the micro-nano composite structure particles obtained in Example 2 of the present applicationFigure 2 The micro-nano composite structure particles present a two-part composite state with a clear difference, one part is a crystalline state with regularly arranged lattice stripes, and the other part is an amorphous mixed microcrystalline state. The sol composition is included in the outside of the polycrystalline powder. Figure 9 The under-damped discharge condition of the ferroelectric-piezoelectric ceramic energy storage material sample obtained in Embodiment 2 of the present application is as follows: when the electric field intensity is 311 kV / cm, the power density reaches 289 MW / cm 3 , the current density is 1860 A / cm 2 , and the discharge period is 59 ns.

[0097] Therefore, by using the ferroelectric-piezoelectric ceramic energy storage material, the hybrid process preparation method and the application thereof, the micro-nano composite structure particles are formed by mixing and calcining the polycrystalline powder and the sol, the specific surface area and the oxygen vacancy content are improved, the sintering temperature of the ceramic material is reduced, and the dielectric energy storage performance of the ceramic material is improved.

[0098] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application but not to limit it, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that: the technical solutions of the present application can still be modified or replaced by the equivalent, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A ferroelectric-piezoelectric ceramic energy storage material, characterized in that: The method comprises the following steps: uniformly mixing polycrystalline powder and sol and then heat treating to form micro-nano composite structure particles, wherein the micro-nano composite structure particles include polycrystalline powder and a PLZS nano-component layer distributed around the polycrystalline powder; The chemical formula of the polycrystalline powder is (Pb 0.94 La 0.04 )(Zr 0.51 Sn 0.47 Hf 0.01 Ti 0.01 )O3.

2. The ferroelectric-piezoelectric ceramic energy storage material according to claim 1, characterized in that: The weight ratio of the sol to the polycrystalline powder is 1-3:

5.

3. The ferroelectric-piezoelectric ceramic energy storage material according to claim 2, characterized in that: The chemical formula of the PLZS nanocomposition layer is (Pb 0.97 La 0.02 )(Zr 0.6 Sn 0.4 )O3.

4. A hybrid process preparation method of a ferroelectric-piezoelectric ceramic energy storage material as claimed in claim 3, characterized in that: The following steps are involved: S1, preparing sol and polycrystalline powder respectively; S2, mixing the sol with the polycrystalline powder, removing organic matter through heat treatment, and obtaining micro-nano composite structure particles; S3, mixing the micro-nano composite structure particles with a solvent, a binder, a dispersant, and a plasticizer to obtain a casting slurry; the solvent is a mixture of ethanol and trichloroethylene, the binder is polyvinyl butyral, the dispersant is triethyl phosphate, and the plasticizer is dibutyl phthalate; the mass ratio of the micro-nano composite structure particles to the solvent, the binder, the dispersant, and the plasticizer is 20:20:2:0.4:0.8; S4, degassing and casting the casting slurry to obtain a thick film; S5, shearing, laminating and hot pressing the thick film to obtain a ceramic green body; S6. Debinding and sintering the ceramic green body to obtain a ferroelectric-piezoelectric ceramic energy storage material sample.

5. The hybrid process preparation method of a ferroelectric-piezoelectric ceramic energy storage material according to claim 4, characterized in that: In S1, the preparation method of the sol comprises the following steps: S111, weighing lead acetate, lanthanum acetate, zirconium n-propoxide, and tin isopropoxide according to a stoichiometric ratio; S112, dissolving lead acetate and lanthanum acetate in acetic acid, heating to 110°C with stirring, and cooling to form cup A; dissolving zirconium n-propoxide and tin isopropoxide in ethylene glycol methyl ether, stirring and mixing, and then introducing acetylacetone, wherein the molar ratio of acetylacetone to the PLZS content in the sol is 1.1:1, and stirring and mixing until uniform, and then forming cup B; S113. Introduce the solution in cup B into the solution in cup A, mix and stir evenly, add deionized water, acetic acid and ethylene glycol to the mixture in sequence to adjust the concentration, pH and viscosity, stir and then adjust the volume with acetic acid to obtain a clear sol; the concentration of the sol is 0.027g / ml-0.08g / ml, the pH is 3-5, and the viscosity is 7cP-9cP.

6. The hybrid process preparation method of a ferroelectric-piezoelectric ceramic energy storage material according to claim 4, characterized in that: In S1, the method for preparing polycrystalline powder comprises the following steps: S121, mixing lead tetroxide, lanthanum trioxide, zirconium dioxide, tin dioxide, hafnium dioxide and titanium dioxide according to a stoichiometric ratio, and performing a first ball milling, wherein the first ball milling time is 20 hours to 30 hours; S122, drying the mixture obtained after the first ball milling, and pre-calcining the mixture at a temperature of 900° C. for a holding time of 1 h to 3 h, and then cooling the mixture to room temperature to obtain a pre-calcined mixture; S123, ball milling the pre-calcined mixture for a second time, the second ball milling time being 20 hours to 30 hours; drying the mixture after the second ball milling to obtain polycrystalline powder.

7. The hybrid process preparation method of a ferroelectric-piezoelectric ceramic energy storage material according to claim 4, characterized in that: In the step S2, the heat treatment temperature is 600° C., the heat treatment holding time is 5 h to 7 h, and the product is cooled to room temperature in the furnace.

8. The hybrid process preparation method of a ferroelectric-piezoelectric ceramic energy storage material according to claim 4, characterized in that: In the above S6, the binder removal temperature is 600°C, the binder removal holding time is 7h-10h, and the furnace is cooled to room temperature; the sintering temperature is 1100°C-1130°C, the sintering holding time is 3h, and the furnace is cooled to room temperature.

9. Application of the ferroelectric-piezoelectric ceramic energy storage material prepared by the hybrid process preparation method of the ferroelectric-piezoelectric ceramic energy storage material according to any one of claims 5 to 8 in electronic functional materials and devices.

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