CN112919903B - Strontium bismuth titanate-based lead-free ceramic material for high-efficiency capacitor and preparation method thereof - Google Patents
Strontium bismuth titanate-based lead-free ceramic material for high-efficiency capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 44
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 34
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 83
- 238000004146 energy storage Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 123
- 238000000498 ball milling Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000005245 sintering Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 20
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- 238000005469 granulation Methods 0.000 claims description 17
- 230000003179 granulation Effects 0.000 claims description 17
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- 239000011230 binding agent Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000011232 storage material Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
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- 230000008859 change Effects 0.000 description 7
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 5
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
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Abstract
The invention relates to a strontium bismuth titanate-based lead-free ceramic material for a high-efficiency capacitor and a preparation method thereof, belonging to the field of electric energy storage materials. Adopts a solid-phase synthesis method to relax the ferroelectric material Sr 0.7 Bi 0.2 TiO 3 Based on the method, a certain molar ratio of Nb to Ni aliovalent elements are doped into the B site of the perovskite structure to increase the charge disorder, so as to obtain a novel composite ceramic, the chemical formula of which is (1-x) Sr 0.7 Bi 0.2 TiO 3 ‑xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x is more than or equal to 0 and less than or equal to 0.15. The main performance parameter of the energy storage ceramic material obtained by the invention can restore the energy storage density W rec Reaches 4.19 to 5.98J/cm 3 The energy storage efficiency eta is as high as 92.6-98.6%. The method has simple process flow, is suitable for industrial production, and simultaneously meets the current lead-free environment-friendly requirement.
Description
Technical Field
The invention relates to the technical field of functional materials and devices, in particular to a strontium bismuth titanate-based lead-free ceramic material for a high-efficiency capacitor and a preparation method thereof.
Background
At present, the main electrical energy storage devices are batteries, dielectric capacitors, electrochemical capacitors, and the like. These energy storage devices differ significantly in energy density and power density due to their different energy storage mechanisms and charging and discharging processes. In contrast to other energy storage devices, dielectric capacitors can discharge electric energy in a very short period of time (on the order of nanoseconds to microseconds) and generate a large pulse current or voltage, which also makes the dielectric capacitors have a great potential for use in pulsed power electronic systems. Also, unlike electrochemical capacitors and batteries, dielectric capacitors do not involve chemical reactions during charging and discharging, which makes dielectric capacitors have good thermal and chemical stability and can operate in high voltage environments (hundreds to thousands of volts) for long periods of time.
The dielectric ceramic energy storage material in the dielectric capacitor has the characteristics of high power density, low cost, excellent thermal stability and the like, and is widely applied to high-power systems such as commerce, consumption, medical treatment, military and the like. At present, most of materials used for ceramic capacitors are lead-based ceramics, although the energy storage density is high, the systems contain a large amount of lead elements, which has great harm to human health and environment, and the development of lead-free materials to replace lead-containing system materials is a necessary trend. However, the lead-free dielectric ceramic capacitor has a limitation in that the energy storage density is low and cannot be compared with the energy storage performance of a lead-based ceramic capacitor, which makes it difficult to meet the development requirements of miniaturization, multifunction and integration of devices, thereby limiting its application in portable electronic devices. If the energy storage density of the lead-free dielectric ceramic capacitor can be effectively improved, the lead-free dielectric ceramic capacitor can be more widely applied to the field of energy storage.
The strontium bismuth titanate ceramic inherits the fine hysteresis loop of strontium titanate, and uses Bi element to replace the traditional Pb element to realize the effect of enhancing polarization and reduce the damage to the environment. However, because a small amount of Bi element volatilizes in the sintering process, some oxygen vacancies can be generated to cause lower breakdown strength, and the energy storage density of the strontium bismuth titanate ceramic is influenced, so that the application of the strontium bismuth titanate ceramic in a high-energy-storage-density capacitor is limited. At present, the energy storage density of most strontium titanate bismuth-based ceramics is still lower (<4J/cm 3 ) There is a gap compared with the traditional lead-based ceramic material.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a strontium bismuth titanate-based lead-free ceramic material for a high-efficiency capacitor and a preparation method thereof, wherein a solid-phase synthesis method is adopted to relax a ferroelectric material Sr 0.7 Bi 0.2 TiO 3 Based on the increase of Nb and Ni aliovalent elements with a certain molar ratio doped in the B site of the perovskite structureThe charge disorder of the ceramic material results in a novel composite ceramic with the chemical formula of (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Inducing the B site to form a polar nano micro area to obtain a fine electric hysteresis loop with low remanent polarization; the grain size is further reduced by a two-step sintering method, the compactness is improved, the breakdown strength is further improved, the research direction of doping modification is expanded, the sintering process is optimized, and the lead-free energy storage ceramic with application potential is prepared.
The invention can be realized by the following technical scheme:
the chemical composition of the strontium titanate bismuth base lead-free ceramic material for the high-efficiency capacitor is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x is more than or equal to 0 and less than or equal to 0.15.
As a preferred embodiment, x =0.12. This is mainly due to the fact that the component ceramic has a large activation energy and thus a large resistivity, which contributes to the improvement of the breakdown strength. At the same time, the dielectric loss of this component is very small at room temperature, which contributes to the energy storage efficiency of the ceramic.
The strontium bismuth titanate-based lead-free ceramic material for the high-efficiency capacitor is prepared into corresponding energy storage ceramic by using a solid-phase reaction method, and specifically comprises the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder and SrCO 3 Powder, tiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as a raw material and is Sr according to a general formula (1-x) 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, wherein x =0-0.15, adding absolute ethyl alcohol with the same mass as that of the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry;
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 900-1000 ℃ under a closed condition, and keeping the temperature for 2-4h to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained powder, and performing secondary ball milling;
(5) Drying the obtained slurry at 90 ℃, granulating, sieving and carrying out compression molding to obtain a ceramic green body;
(6) Carrying out glue discharging treatment on the ceramic blank at the temperature of 600-650 ℃ for 5-10h, sintering the ceramic blank after glue discharging, wherein the sintering temperature is 1125-1150 ℃, the heating rate is 2-4 ℃/min, the heat preservation time is 2-6h, and cooling to the room temperature to obtain the strontium bismuth titanate lead-free ceramic material for the high-efficiency capacitor.
Further, absolute ethyl alcohol and ZrO are adopted in the primary ball milling and the secondary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 250-330r/min, the running direction is adjusted every half hour, and the ball milling time is 12-24h.
Furthermore, the pre-sintering temperature is preferably 900-1000 ℃, and the heat preservation time is preferably 2-4 hours.
Furthermore, polyvinyl alcohol (PVA) with the concentration of 8% is used as a binder to be mixed into the powder during granulation, the mass of the mixed binder is 5-10% of the mass of the powder, the mass of the mixed distilled water is 2.5-5% of the mass of the powder, the powder is uniformly mixed in a mortar and then placed in a die to be pressed into powder blocks.
Furthermore, sieving with 80 mesh and 140 mesh sieve to obtain powder of the middle layer of 80 mesh and 140 mesh sieve.
Further, the pressure at the time of press molding was controlled to 200MPa.
Furthermore, the heating rate is controlled to be 2-4 ℃/min during ordinary sintering, and the heat preservation time is controlled to be 2-6h.
Further, sintering the ceramic blank after the binder removal in the sixth step is replaced by a two-step sintering method, which specifically comprises the following steps: heating to 950-1000 deg.C at a rate of 3-4 deg.C/min, rapidly heating to 1100-1150 deg.C at a rate of 8-10 deg.C/min, rapidly cooling to 1025-1050 deg.C without heat preservation, and maintaining at 1025-1050 deg.C for 10-40 h.
Compared with the prior art, the (1-x) Sr prepared by the invention 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 The ceramic is doped with Ni and Nb elements in the strontium bismuth titanate ceramic to improve the energy storage characteristic, and the design principle is as follows: the introduction of B-site aliovalent cations greatly improves the resistivity of the ceramic, further enhances the breakdown electric field of the strontium bismuth titanate ceramic, and on the other hand, the B-site cations break the long-range order of dipoles and introduce local random electric fields, so that the residual polarization is reduced and the larger polarization is maintained. And further, by optimizing the two-step sintering process, the grain size is reduced, and the breakdown field strength of the energy storage ceramic is further improved.
Compared with the prior art and energy storage materials, the invention has the following beneficial effects:
(1) The energy storage medium ceramic material provided by the invention realizes high energy storage density and high efficiency, and the releasable energy density is 4.19-5.98J/cm 3 The efficiency is 92.6-98.6%;
(2) The energy storage dielectric ceramic material provided by the invention has good temperature and frequency stability, and the releasable energy density exceeds 3J/cm under different temperatures and frequencies 3 Within the temperature range of 25-140 ℃, the change rate of the energy storage density is less than 9 percent, and within the frequency range of 1-200Hz, the change rate of the energy storage density is less than 7 percent;
(3) The energy storage medium ceramic material provided by the invention has excellent charge and discharge behaviors and high discharge power density of 215.94MW/cm 3 And ultra-short discharge time: (<50 ns) and is expected to be applied to high-power pulse dielectric energy storage devices.
(4) The preparation method disclosed by the invention is simple in preparation process, low in preparation cost, good in repeatability, suitable for large-scale industrial production, and expected to be widely applied to pulse power systems such as high-power microwave weapons, laser weapons, electromagnetic emitters and hybrid electric vehicles.
Drawings
FIG. 1 is a scanning electron micrograph of a bismuth strontium titanate-based lead-free ceramic for a high performance capacitor prepared in example 5;
FIG. 2 is a graph showing the dielectric constant and dielectric loss versus temperature curves of the bismuth strontium titanate-based lead-free ceramic for a high performance capacitor prepared in example 3;
FIG. 3 is a hysteresis loop of a bismuth strontium titanate-based lead-free ceramic for a high efficiency capacitor prepared in example 5;
FIG. 4 is a graph showing the change of energy storage characteristics with electric field of the strontium bismuth titanate-based lead-free ceramic for a high efficiency capacitor prepared in example 5;
FIG. 5 is a graph showing the change of energy storage characteristics with temperature of the strontium bismuth titanate-based lead-free ceramic for a high efficiency capacitor prepared in example 5;
FIG. 6 is a graph showing the variation of the energy storage characteristics of the bismuth strontium titanate-based lead-free ceramic for a high performance capacitor prepared in example 5 with frequency;
FIG. 7 shows the peak discharge current (I) of the strontium bismuth titanate-based lead-free ceramic for a high performance capacitor prepared in example 3 max ) Discharge current density (I) max S) and discharge Power Density (P) D ) Curve with field strength.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples will assist the person skilled in the art to further understand the invention, but do not limit it in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The chemical composition of the strontium titanate bismuth-based lead-free ceramic for the high-efficiency capacitor is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x =0, specifically adopting the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder of SrCO 3 Powder, tiO 2 The powder is taken as a raw material and is prepared according to the chemical formula Sr 0.7 Bi 0.2 TiO 3 Weighing raw materials, adding anhydrous ethanol with the same mass as the powder, and uniformly mixing the raw materials and the anhydrous ethanol through a one-time ball milling process to uniformly mix the powderAnd (4) homogenizing to form slurry. Wherein anhydrous ethanol and ZrO are adopted during primary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 250r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Placing the powder in a mould to be pre-pressed into a material block, pre-sintering the material block at 900 ℃ under a closed condition, and keeping the temperature for 2 hours to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained powder, and performing secondary ball milling, wherein the absolute ethyl alcohol and ZrO are still adopted in the process 2 The ball is used as a ball milling medium, the rotating speed is 250r/min, the running direction is adjusted every half hour, and the ball milling time is 12 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8wt% of polyvinyl alcohol (PVA) as a binder to be doped into powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the binder to be mixed is 5% of the mass of the powder, and the mass of the distilled water to be mixed is 2.5% of the mass of the powder.
(6) And placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment for 5 hours at 600 ℃, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering, wherein the sintering temperature is 1125 ℃, the heating rate is 2 ℃/min, the heat preservation time is 2 hours, and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
The ceramic achieves 4.52J/cm charging energy density (total energy density, W) under 350kV/cm electric field through testing 3 Available energy storage density (available energy storage density, W) rec ) Reach 4.43J/cm 3 And the energy storage efficiency (eta) reaches 96.9 percent.
Example 2
Strontium bismuth titanate for high-efficiency capacitorThe chemical composition of the lead-free ceramic is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x =0.05, specifically adopting the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder of SrCO 3 Powder of TiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as raw material and is Sr according to the chemical formula of 0.95 0.7 Bi 0.2 TiO 3 -0.05Bi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, adding absolute ethyl alcohol with the same mass as that of the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 290r/min, the running direction is adjusted every half hour, and the ball milling time is 18h.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 960 ℃ under a closed condition, and keeping the temperature for 3 hours to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained ceramic powder, and performing secondary ball milling, wherein the absolute ethyl alcohol and ZrO are still adopted in the process 2 The ball is used as a ball milling medium, the rotating speed is 280r/min, the running direction is adjusted every half hour, and the ball milling time is 17h.
(5) Drying the obtained slurry at 90 ℃, adding 8wt% of polyvinyl alcohol (PVA) as a binder to be doped into powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the mixed binder is 7% of the mass of the powder, and the mass of the mixed distilled water is 4% of the mass of the powder.
(6) And placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment for 7 hours at the temperature of 620 ℃, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering at the sintering temperature of 1130 ℃, at the heating rate of 3 ℃/min for 4 hours, and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
The ceramic achieves 4.83J/cm charging energy density (total energy density, W) under 370kV/cm electric field through testing 3 Available energy storage density (available energy storage density, W) rec ) Reach 4.61J/cm 3 And the energy storage efficiency (eta) reaches 95.3 percent.
Example 3
The chemical composition of the strontium titanate bismuth-based lead-free ceramic for the high-efficiency capacitor is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x =0.12, specifically adopting the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder and SrCO 3 Powder of TiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as raw material and is prepared according to the chemical formula of 0.88Sr 0.7 Bi 0.2 TiO 3 -0.12Bi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, adding absolute ethyl alcohol with the same mass as that of the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 330r/min, the running direction is adjusted every half hour, and the ball milling time is 24 hours.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 1000 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained powder, and performing secondary ball milling, wherein the absolute ethyl alcohol and ZrO are still adopted in the process 2 The ball is used as a ball milling medium and the rotating speed is 330r/min, adjusting the running direction every half hour, and the ball milling time is 24 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8wt% of polyvinyl alcohol (PVA) as a binder to be doped into powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein the mass of the binder incorporated at the time of granulation was 10% of the mass of the powder, and the mass of the distilled water incorporated was 5% of the mass of the powder.
(6) And placing the ceramic blank in a crucible, covering the crucible with a cover and leaving a gap, performing glue discharging treatment at 650 ℃ for 10 hours, then inverting the crucible on the ceramic blank subjected to glue discharging, performing closed sintering at 1150 ℃, at a heating rate of 4 ℃/min and at a heat preservation time of 6 hours, and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
The ceramic achieves 5.24J/cm charging energy density (total energy density, W) under 480kV/cm electric field through testing 3 Available energy storage density (available energy storage density, W) rec ) Reaches 5.09J/cm 3 And the energy storage efficiency (eta) reaches 97.1 percent. The dielectric test of this example is shown in fig. 2, and the dielectric constant does not change significantly with frequency, and the dielectric loss is small. As shown in FIG. 7, which is a graph of the maximum current, current density and power density in the charge and discharge tests of this example, it can be seen that the ceramic material can obtain a higher current density of 1199.68A/cm 2 And simultaneously has higher power density of 215.94MW/cm 3 。
Example 4
The chemical composition of the strontium titanate bismuth-based lead-free ceramic for the high-efficiency capacitor is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x =0.15, specifically adopting the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder and SrCO 3 Powder, tiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as raw material and has a chemical formula of 0.85Sr 0.7 Bi 0.2 TiO 3 -0.15Bi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, adding absolute ethyl alcohol with the same mass as that of the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 330r/min, the running direction is adjusted every half hour, and the ball milling time is 20h.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Placing the powder in a mould to be pre-pressed into a material block, pre-burning the material block at 960 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained ceramic powder, and performing secondary ball milling, wherein the absolute ethyl alcohol and ZrO are still adopted in the process 2 The ball is used as a ball milling medium, the rotating speed is 330r/min, the running direction is adjusted every half hour, and the ball milling time is 24 hours.
(5) Drying the obtained slurry at 90 ℃, adding 8wt% of polyvinyl alcohol (PVA) as a binder to be doped into powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein, in the granulation, the mass of the mixed binder is 5-10% of the mass of the powder, and the mass of the mixed distilled water is 2.5-5% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment at 600 ℃ for 7h, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out closed sintering at the sintering temperature of 1125 ℃, at the heating rate of 3 ℃/min, keeping the temperature for 4h, and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
The ceramic achieves 4.52J/cm charging energy density (total energy density, W) under 400kV/cm electric field through testing 3 Available energy storage density (available energy storage density, W) rec ) Reaching 4.19J/cm 3 And the energy storage efficiency (eta) reaches 92.6 percent.
Example 5
The chemical composition of the strontium titanate bismuth base lead-free ceramic for the high-efficiency capacitor is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x =0.12, a two-step sintering method is used, specifically employing the following steps:
(1) Selecting Bi with the purity of more than 98 percent 2 O 3 Powder and SrCO 3 Powder, tiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as raw material and has a chemical formula of 0.88Sr 0.7 Bi 0.2 TiO 3 -0.12Bi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, adding absolute ethyl alcohol with the same mass as that of the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry. Wherein, anhydrous ethanol and ZrO are adopted in the primary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 330r/min, the running direction is adjusted every half hour, and the ball milling time is 12h.
(2) Placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
(3) Putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 900 ℃ under a closed condition, and keeping the temperature for 4 hours to obtain pre-synthesized ceramic powder;
(4) Grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained powder, and performing secondary ball milling, wherein the absolute ethyl alcohol and ZrO are still adopted in the process 2 The ball is used as a ball milling medium, the rotating speed is 330r/min, the running direction is adjusted every half hour, and the ball milling time is 12h.
(5) Drying the obtained slurry at 90 ℃, adding 8wt% of polyvinyl alcohol (PVA) as a binder to be doped into powder for granulation, crushing the powder blocks obtained by granulation, sieving the powder blocks by using 80-mesh and 140-mesh sieves, taking the powder blocks in the middle layers of the 80-mesh and 140-mesh sieves, and performing compression molding under the pressure of 200Mpa to obtain the ceramic green bodies. Wherein the mass of the binder incorporated at the time of granulation was 5% of the mass of the powder, and the mass of the distilled water incorporated was 3% of the mass of the powder.
(6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment for 7h at 600 ℃, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out two-step sintering, heating to 950 ℃ at a heating rate of 3 ℃/min during sintering, then rapidly heating to 1100 ℃ at a heating rate of 8 ℃/min, rapidly cooling to 1025 ℃ without heat preservation, and finally carrying out heat preservation for 40h at 1025 ℃. And cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
The test shows that the scanning electron microscope picture of the energy storage dielectric is shown in figure 1, the ceramic material is compact, the grain size is small and uniform, and the average grain size is 0.49 μm at room temperature. The measured unipolar hysteresis loop of the energy storing dielectric is shown in fig. 3, which is relatively long and thin with relatively low loss. As shown in FIG. 4, the effective energy storage density reaches 5.98J/cm under 580kV/cm 3 And the energy storage efficiency reaches 98.6 percent. As shown in FIG. 5, which is a graph of recoverable energy storage density and efficiency of the energy storage dielectric of this embodiment at 420kV/cm and different temperatures, it can be seen that the recoverable energy storage density of the ceramic material varies in a range of 3.12-3.42J/cm 3 The change rate is less than 9%, and the efficiency is kept above 96%. As shown in FIG. 6, which is a graph of recoverable energy storage density and efficiency of the energy storage dielectric medium of this embodiment at 420kV/cm as a function of frequency, it can be seen that the recoverable energy storage density of the ceramic material has a variation range of 3.02-3.20J/cm 3 The change rate is less than 7%, and the efficiency is kept above 95%.
Example 6; wherein the steps (1) to (5) are the same as in example 5; (6) Placing the ceramic blank in a crucible, covering a cover with a gap, carrying out glue discharging treatment for 7h at 600 ℃, then inverting the crucible on the ceramic blank subjected to glue discharging, carrying out two-step sintering, heating to 1000 ℃ at a heating rate of 4 ℃/min during sintering, then rapidly heating to 1150 ℃ at a heating rate of 10 ℃/min, rapidly cooling to 1050 ℃ without heat preservation, and finally carrying out heat preservation for 10h at 1050 ℃; and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
Example 7; wherein the steps (1) to (5) are the same as in example 5; (6) Placing a ceramic blank body in a crucible, covering a cover with a gap, performing glue discharging treatment for 7 hours at 650 ℃, then inverting the crucible on the ceramic blank body subjected to glue discharging to perform two-step sintering, heating to 980 ℃ at a heating rate of 4 ℃/min, then quickly heating to 1130 ℃ at a heating rate of 9 ℃/min, quickly cooling to 1030 ℃ without heat preservation, and finally performing heat preservation for 30 hours at 1030 ℃; and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic for the high-efficiency capacitor.
Claims (7)
1. The preparation method of the strontium bismuth titanate-based lead-free ceramic material for the high-efficiency capacitor is characterized in that the chemical composition of the ceramic is (1-x) Sr 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Wherein x is more than 0 and less than or equal to 0.15, and the preparation method is prepared by a solid-phase reaction method and specifically comprises the following steps:
the method comprises the following steps: selecting Bi with the purity of more than 98 percent 2 O 3 Powder of SrCO 3 Powder of TiO 2 Powder, niO powder and Nb 2 O 5 The powder is used as a raw material and is Sr according to a general formula (1-x) 0.7 Bi 0.2 TiO 3 -xBi(Ni 2/3 Nb 1/3 )O 3 Weighing raw materials, wherein x is more than 0 and less than or equal to 0.15, adding absolute ethyl alcohol with the same mass as the powder, and uniformly mixing the raw materials and the absolute ethyl alcohol through a primary ball milling process to uniformly mix the powder to form slurry;
step two: placing the slurry in a constant-temperature oven at 90 ℃ for baking, removing absolute ethyl alcohol, and grinding in a mortar to obtain powder;
step three: putting the powder into a die to be pre-pressed into a material block, pre-sintering the material block at 900-1000 ℃ under a closed condition, and keeping the temperature for 2-4h to obtain pre-synthesized ceramic powder;
step four: grinding the pre-synthesized ceramic material block in a mortar to obtain ceramic powder, adding absolute ethyl alcohol with equal mass into the obtained powder, and performing secondary ball milling;
step five: drying the obtained slurry at 90 ℃, granulating, sieving and carrying out compression molding to obtain a ceramic green body;
step six: carrying out glue discharging treatment on the ceramic green body at the temperature of 600-650 ℃ for 5-10h, sintering the ceramic green body after glue discharging, heating to 950-1000 ℃ at the heating rate of 3-4 ℃/min, then rapidly heating to 1100-1150 ℃ at the heating rate of 8-10 ℃/min, rapidly cooling to 1025-1050 ℃ without heat preservation, finally carrying out heat preservation at 1025-1050 ℃ for 10-40h, and cooling to room temperature to obtain the strontium bismuth titanate-based lead-free ceramic material for the high-efficiency capacitor.
2. The method for preparing a bismuth strontium titanate-based lead-free ceramic material for a high efficiency capacitor as claimed in claim 1, wherein x =0.12.
3. The method for preparing the strontium bismuth titanate-based lead-free ceramic material for the high-efficiency capacitor according to claim 1, wherein when x is more than 0 and less than or equal to 0.15, the released energy density of the strontium bismuth titanate-based lead-free ceramic material for the high-efficiency capacitor is 4.19 to 5.98J/cm under the condition that the released energy density is more than 350kV/cm 3 The high energy storage efficiency is more than 92%, and the high energy storage efficiency has good temperature and frequency stability and ultrashort discharge time of 40ns.
4. The method for preparing the strontium bismuth titanate-based lead-free ceramic material for the high efficiency capacitor as claimed in claim 1, wherein absolute ethyl alcohol and ZrO are adopted during the primary ball milling and the secondary ball milling 2 The ball is used as a ball milling medium, the rotating speed is 250-330r/min, the running direction is adjusted every half hour, and the ball milling time is 12-24h.
5. The method for preparing a strontium bismuth titanate-based lead-free ceramic material for a high-efficiency capacitor according to claim 1, wherein polyvinyl alcohol with a mass concentration of 8% is used as a binder to be mixed into the powder during granulation, the mass of the mixed binder is 5-10% of the mass of the powder, the mass of the mixed distilled water is 2.5-5% of the mass of the powder, and the powder is uniformly mixed in a mortar, placed in a mold and pressed into a powder block.
6. The method for preparing the strontium bismuth titanate-based lead-free ceramic material for the high efficiency capacitor as claimed in claim 1, wherein the powder of the intermediate layer of 80 mesh and 140 mesh is obtained by sieving with 80 mesh and 140 mesh sieves.
7. The method for preparing a bismuth strontium titanate-based lead-free ceramic material for a high efficiency capacitor as claimed in claim 1, wherein the pressure during compression molding is controlled to 200MPa.
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