CN111153696A - Low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material - Google Patents
Low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material Download PDFInfo
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Abstract
The invention discloses a low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material with a general formula of 0.5BaZr0.2Ti0.8O3‑0.5Ba0.7Ca0.3TiO3‑xLiCO3Wherein x is more than 0.00 and less than or equal to 0.04. The invention adopts the traditional solid phase method, and realizes the sintering at lower temperature through the process steps of material preparation, pre-sintering, doping and secondary ball milling, granulation and tabletting, binder removal and sintering, electrode coating, silver firing and the like, and the lead-free energy storage ceramic material which has excellent dielectric property, good ferroelectric property, excellent energy storage density and energy storage efficiency, strong practicability, high purity and is easy for industrial production is prepared. The preparation method is simple, good in repeatability and high in yield. The maximum dielectric constant of the ceramic material of the invention can reach 15488 at 75 ℃,meanwhile, the loss is 0.0129, and the energy storage density calculated based on the electric hysteresis loop at room temperature is 142.80mJ/cm3And the energy storage efficiency can reach 69.35 percent.
Description
Technical Field
The invention belongs to a ceramic composition characterized by components, and particularly relates to a low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material and a preparation method thereof.
Background
As is well known, with the increasing prominence of energy crisis and environmental pollution problems, new energy has become one of the most important topics since the 21 st century, and research on development of renewable energy and energy storage technology has received worldwide attention and is becoming one of the most popular research hotspots. Among them, in the development of energy in the world, common energy storage devices such as dielectric capacitors, chemical batteries and super capacitors have been widely studied due to their respective energy storage characteristics and advantages. In summary, dielectric capacitors have been widely used due to their advantages of high dielectric constant, low dielectric loss, high power density, good temperature stability, and long cycle life. Among them, the low energy storage density of the conventional lead-free energy storage ceramic also greatly limits its wider application range because the dielectric ceramic material has low compressive strength and low dielectric strength due to its internal defects and the influence of grain boundaries, thereby causing its energy storage density not to perform well, although it has high dielectric constant and low dielectric loss.
At present, the application of the barium calcium zirconate titanate-based ceramic material as a solid energy storage medium is mainly insufficient in two aspects: firstly, the sintering temperature is too high in the traditional solid phase method preparation process, generally higher than 1400 ℃, which not only easily causes abnormal change of crystal grains to reduce the compression strength of the ceramic, but also causes more energy consumption and is not beneficial to environmental protection; and secondly, the energy storage efficiency is low, and excessive energy is converted into heat to be transferred out, so that the energy is wasted. Therefore, the sintering temperature of the calcium barium zirconate titanate-based ceramic material is reduced, so that the abnormal change of ceramic grains is controlled, the compressive strength of the ceramic grains is improved, the dielectric loss of the ceramic grains is reduced at the common use temperature, the dielectric constant of the ceramic grains is improved, the ceramic temperature interval is regulated, the energy storage efficiency of the ceramic grains is improved, and the energy utilization rate is higher, so that the application range of the calcium barium zirconate titanate-based ceramic material as a solid energy storage ceramic medium under the sintering process and the common use condition is expanded.
Disclosure of Invention
The invention aims to overcome the defects of overhigh sintering temperature and lower energy storage density in the prior art, and provides a low-temperature sintered barium zirconate titanate calcium-based lead-free ceramic material which has low sintering temperature, excellent dielectric property, higher compressive strength and dielectric strength, is environment-friendly, strong in practicability, good in repeatability, high in purity and easy to produce, and a preparation method thereof, so that the energy storage efficiency of a capacitor taking the barium zirconate titanate calcium-based lead-free ceramic material as a medium is improved.
The invention is realized by the following technical scheme.
A low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material has a chemical general formula as follows:
0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3wherein x is more than 0.00 and less than or equal to 0.04, and x is additionally added LiCO3The mass and percentage content of the components are as follows;
the preparation method of the barium calcium zirconate titanate-based high-energy-storage-efficiency ceramic material comprises the following steps:
(1) ingredients
According to 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3According to the stoichiometric ratio of the raw material BaCO, weighing the raw material BaCO3Powder, ZrO2Powder, TiO2Powder and CaCO3Uniformly mixing the powder to obtain a raw material mixture; ball milling for 12 hours, and drying for 5-7 hours;
(2) pre-firing
Grinding the dried block-shaped mixture obtained in the step (1) by using a grinding body, granulating, sieving by using a 40-mesh sieve, presintering at 1200 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain presintering precursor powder;
(3) doping and secondary ball milling
Pre-sintering precursor powder obtained in the step (2) is subjected to the treatment according to the proportion of 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3X is more than 0.00 and less than or equal to 0.04, and LiCO is additionally added3And then the weight percentage of the added solution is 1 percentThe PVA powder is put into a ball milling tank, ball milled for 12 hours and then dried for 6 to 8 hours;
(4) granulation and tabletting
Grinding and granulating the block mixture subjected to ball milling in the step (3), sieving the mixture by a 80-mesh sieve, and then forming the mixture into a blank by pressure;
(5) binder removal and sintering
And (3) placing the blank in the step (4) on a zirconia substrate, heating to 550 ℃ within 210 minutes, preserving heat for 2 hours, removing glue, heating to 1200-1500 ℃ at a heating rate of 5 ℃/minute, sintering at a constant temperature for 5 hours, cooling to 550 ℃ at a cooling rate of 10 ℃/minute, and naturally cooling to room temperature to prepare the barium calcium zirconate titanate-based high energy storage efficiency ceramic material.
The step (1) and the step (3) are ball-milled by taking zirconium balls as milling balls and deionized water as a ball-milling medium, wherein the mass ratio of the raw materials, the zirconium balls and the deionized water is 1:1: 1.
And (2) pre-sintering at 1200 ℃ at a heating rate of 5 ℃/min.
And (4) performing compression molding in a cold isostatic pressing mode, wherein the pressure is 4MPa, and the time is 1 minute.
The sintering temperature in the step (5) is 1350 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the ceramic material of the invention is prepared by adding a proper amount of Li+Doped to 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3Sintering and compacting at lower temperature to obtain 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3An energy storage ceramic material. Adopting the traditional solid phase sintering method to synthesize 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3The lead-free ceramic material with environmental protection, low loss and high energy storage efficiency is obtained.
(2) The low-temperature sintered barium calcium zirconate titanate based lead-free high energy storage efficiencyThe preparation method of the ceramic material comprises the steps of adding a proper amount of Li+Doped to 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3Sintering and compacting at lower temperature to obtain 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3An energy storage ceramic material. The ceramic powder is synthesized by adopting the traditional solid-phase sintering method, the used materials are easy to obtain, the preparation process is simple, the manufacturing cost is low, the repeatability is good, and the method is suitable for industrial large-scale production.
(3) The low-temperature sintered calcium barium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material is prepared by Li+The doping reduces the crystal grain of the ceramic, regulates and controls the phase transition temperature range of the ceramic, thereby improving the electric breakdown resistance strength of the ceramic, and the ceramic material has high energy storage density, energy storage efficiency and good low-loss and high energy storage efficiency under the conditions of low loss, high dielectric constant and energy storage temperature stability.
(4) The low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material provided by the invention can be used for manufacturing an energy-storage multilayer ceramic capacitor, expands the application field of the barium calcium zirconate titanate-Based (BCZT) lead-free ceramic material in the aspect of energy storage, is beneficial to promoting the application and development of a low-loss ceramic technology, and has good application prospect and heuristic value.
Drawings
FIG. 1: the dielectric constant and dielectric loss of the low-temperature sintered calcium barium zirconate titanate-based lead-free high energy storage efficiency ceramic material prepared in the embodiment 1-5 under 1KHz are in a change relationship with temperature.
FIG. 2: the hysteresis loop diagrams of the low-temperature sintered barium calcium zirconate titanate-based lead-free ceramic material with high energy storage efficiency prepared in the embodiments 1 to 5 under positive bias voltage.
FIG. 3: the energy storage density and the energy storage efficiency of the low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy storage efficiency ceramic material prepared in the embodiments 1 to 5 are plotted in a relation of a value of the energy storage density and the energy storage efficiency with x.
Detailed Description
The invention will be described in more detail hereinafter with reference to the drawings and the detailed description, but the scope of the invention is not limited to these examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Ingredients
According to 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3According to the stoichiometric ratio of the raw material BaCO, weighing the raw material BaCO3Powder of ZrO2Powder of TiO2Powder and CaCO3Uniformly mixing the powder to obtain a raw material mixture; the method comprises the steps of taking zirconium balls as grinding balls and deionized water as a ball milling medium, filling a raw material mixture into a nylon ball milling tank, carrying out ball milling treatment for 12 hours according to the mass ratio of the raw materials, the zirconium balls and the deionized water of 1:1:1, fully and uniformly mixing, discharging, and drying in an infrared drying oven until the materials are dry cracked.
(2) Pre-firing
Grinding the dried blocky mixture obtained in the step (1) by using a grinding body, granulating, sieving by using a 40-mesh sieve, covering, reserving a seam to promote heat exchange, preserving heat at 1200 ℃ for 3 hours for pre-burning, raising the temperature at a rate of 5 ℃/min, and naturally cooling to room temperature after the pre-burning is finished to obtain pre-burning precursor powder;
(3) doping and secondary ball milling
Pre-sintering precursor powder obtained in the step (2) is subjected to the treatment according to the proportion of 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3Wherein x is 0.01 as LiCO3Adding 1% of polyvinyl alcohol PVA powder to obtain doped mixed powder, putting the mixed powder into a nylon ball milling tank, taking zirconium balls as milling balls and deionized water as a ball milling medium, fully ball milling and mixing for 12 hours according to the mass ratio of the raw materials, the zirconium balls and the deionized water of 1:1:1, discharging, and drying for 5-7 hours in an infrared drying oven until the mixed powder is dry-cracked;
(4) granulation and tabletting
Grinding the dried blocky mixture obtained in the step (3) by using a grinding body, granulating, and sieving by using a 80-mesh sieve to prepare powder particles; the weighed 0.4mg powder particles are subjected to cold static pressure isostatic pressing under the pressure of 4MPa by a tablet machine for 1 minute, and are pressed into a cylindrical body with the diameter of 10.00mm and the thickness of 1.00 mm;
(5) binder removal and sintering
Placing the cylindrical blank prepared in the step (4) on a zirconia substrate, placing the cylindrical blank into a high-temperature muffle furnace, heating to 550 ℃ within 210 minutes, preserving heat for 2 hours, removing glue, then heating to 1350 ℃ at the heating rate of 5 ℃/minute, sintering at constant temperature for 5 hours, then cooling to 550 ℃ at the cooling rate of 10 ℃/minute, and naturally cooling to room temperature to prepare the barium zirconate titanate calcium-based lead-free ceramic material with high energy storage efficiency;
(6) coating electrode and silver firing
And (3) respectively coating a layer of silver paste with the thickness of 0.01-0.03 mm on the upper part and the lower part of the ceramic chip sintered in the step (5), placing the ceramic chip in a medium-temperature resistance furnace, preserving the heat for about 100 minutes at the temperature of 850 ℃, and naturally cooling the ceramic chip to the room temperature to prepare the barium zirconate titanate calcium-based lead-free high-energy storage efficiency ceramic material to be tested and sintered at the low temperature.
(7) Carrying out silver-plated electrode on the ceramic sheet with smooth two surfaces and thickness of 1.0mm sintered in the step (6), then carrying out temperature-holding curve test in the temperature range of-55-115 ℃ to obtain the dielectric constant and dielectric loss in the temperature range of-55-115 ℃, testing the temperature stability of the ceramic sheet, and carrying out energy storage characteristic calculation and energy storage density (W)rec) Energy loss density (W)loss) And the energy storage efficiency (η) is calculated as:
wherein P ismaxTo representMaximum polarization intensity, PrRepresents remanent polarization, E represents electric field intensity, and P represents polarization; wrecRepresents the discharge energy storage density, and W represents the charge energy storage density, which is the sum of the discharge energy storage density and the loss energy storage density.
Example 2
Example 2 step (3) was performed in accordance with 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3Wherein x is 0.02 as additional LiCO3The rest of the process steps and parameters are exactly the same as in example 1.
Example 3
Example 3 step (3) was performed in accordance with 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3Wherein x is 0.03 as additional LiCO3The rest of the process steps and parameters are exactly the same as in example 1.
Example 4
Example 4 step (3) was performed in accordance with 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3Wherein x is 0.04 as additional LiCO3The rest of the process steps and parameters are exactly the same as in example 1.
The low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material prepared in the embodiments 1 to 4 of the invention is subjected to ferroelectric property and electrical property tests, and the results are shown in fig. 1 to 3.
As can be seen from fig. 1, the curie temperature of the ceramic material is firstly reduced and then increased along with the increase of x, the dielectric constant is firstly reduced and then increased along with the increase of x, and then reduced, but the dielectric loss is not much different, when the value of x is 0.03, the dielectric property of the ceramic material is the best, the maximum dielectric constant can reach 15488, the dielectric loss is small, and the curie phase transition temperature is regulated to 75 ℃; fig. 2 shows that the ceramic materials prepared in examples 1 to 5 have a relatively thin hysteresis loop and a small loop area when x is 0.03 in example 3; FIG. 3 shows the energy storage density and energy storage efficiency of example 3, by storing energyThe energy storage density of the lead-free energy storage dielectric ceramic at room temperature is 142.80mJ/cm by characteristic calculation3And the energy storage efficiency reaches 69.35 percent.
Table 1 shows the value ranges and performance test results of examples 1 to 4.
TABLE 1
As can be seen from table 1, in example 3, when x is 0.03, the maximum dielectric constant, the remanent polarization and the energy storage efficiency of the energy storage ceramic material of the present invention are maximized, and a high energy storage density and an energy storage efficiency are obtained, wherein the energy storage efficiency can reach 69.35% at room temperature. By controlling Li+The doping amount of the ceramic dielectric material effectively overcomes the defects of low energy storage density and large dielectric loss of most ceramic dielectric materials, reduces the sintering temperature of barium calcium zirconate titanate-based ceramics, ensures that the dielectric property of the prepared energy storage ceramic dielectric material has excellent performance in a test range, shows excellent temperature stability, and is suitable for wider temperature range and application field.
In practical applications, as an energy storage ceramic dielectric material, not only a high energy storage density but also a high energy storage efficiency should be achieved. Since if the energy storage efficiency is too low, most of the stored energy will be released as heat during the energy release process, the released heat will reduce the life and other properties of the material. In actual industrial production, it is very important to reduce the sintering temperature and improve the energy utilization rate, so the invention reduces the sintering temperature of the barium calcium zirconate titanate base and improves the energy storage efficiency of the barium calcium zirconate titanate base.
Claims (5)
1. A low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material has a chemical general formula as follows:
0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3wherein x is more than 0.00 and less than or equal to 0.04, and x is additionally added LiCO3The mass percentage content of (A);
the preparation method of the barium calcium zirconate titanate-based high-energy-storage-efficiency ceramic material comprises the following steps:
(1) ingredients
According to 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3According to the stoichiometric ratio of the raw material BaCO, weighing the raw material BaCO3Powder, ZrO2Powder, TiO2Powder and CaCO3Uniformly mixing the powder to obtain a raw material mixture; ball milling for 12 hours, and drying for 5-7 hours;
(2) pre-firing
Grinding the dried block-shaped mixture obtained in the step (1) by using a grinding body, granulating, sieving by using a 40-mesh sieve, presintering at 1200 ℃, preserving heat for 3 hours, and naturally cooling to room temperature to obtain presintering precursor powder;
(3) doping and secondary ball milling
Pre-sintering precursor powder obtained in the step (2) is subjected to the treatment according to the proportion of 0.5BaZr0.2Ti0.8O3-0.5Ba0.7Ca0.3TiO3-xLiCO3X is more than 0.00 and less than or equal to 0.04, and LiCO is additionally added3Then adding 1% polyvinyl alcohol PVA powder by mass percent, putting the mixture into a ball milling tank, carrying out ball milling for 12 hours, and then drying for 6-8 hours;
(4) granulation and tabletting
Grinding and granulating the block mixture subjected to ball milling in the step (3), sieving the mixture by a 80-mesh sieve, and then forming the mixture into a blank by pressure;
(5) binder removal and sintering
And (3) placing the blank in the step (4) on a zirconia substrate, heating to 550 ℃ within 210 minutes, preserving heat for 2 hours, removing glue, heating to 1200-1500 ℃ at a heating rate of 5 ℃/minute, sintering at a constant temperature for 5 hours, cooling to 550 ℃ at a cooling rate of 10 ℃/minute, and naturally cooling to room temperature to prepare the barium calcium zirconate titanate-based high energy storage efficiency ceramic material.
2. The low-temperature sintered barium calcium zirconate titanate-based lead-free high-energy-storage-efficiency ceramic material as claimed in claim 1, wherein zirconium balls are used as grinding balls in the step (1) and the step (3) and deionized water is used as a ball milling medium for ball milling, and the mass ratio of the raw materials, the zirconium balls and the deionized water is 1:1: 1.
3. The low-temperature sintered barium calcium zirconate titanate-based lead-free high energy storage efficiency ceramic material as claimed in claim 1, wherein the step (2) is pre-sintering at 1200 ℃ at a heating rate of 5 ℃/min.
4. The low-temperature sintered barium calcium zirconate titanate-based lead-free high energy storage efficiency ceramic material as claimed in claim 1, wherein the compression molding in the step (4) is performed by cold isostatic pressing at a pressure of 4MPa for 1 minute.
5. The low-temperature sintered barium calcium zirconate titanate-based lead-free high energy storage efficiency ceramic material as claimed in claim 1, wherein the sintering temperature in the step (5) is 1350 ℃.
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