CN116854464B - Ferroelectric composite energy storage ceramic material and preparation method thereof - Google Patents
Ferroelectric composite energy storage ceramic material and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 50
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims description 78
- 238000005245 sintering Methods 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009924 canning Methods 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000012856 weighed raw material Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 210000001161 mammalian embryo Anatomy 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
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- 238000007873 sieving Methods 0.000 claims 1
- 230000010287 polarization Effects 0.000 abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 21
- 239000000919 ceramic Substances 0.000 description 19
- 238000000465 moulding Methods 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
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- 230000009471 action Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a ferroelectric composite energy storage ceramic material and a preparation method thereof. The general formula of the ceramic material is (1-x) (Bi 0.46Sr0.06Na0.5)TiO3-xCa1‑ ySryTiO3, wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1 and y is less than or equal to 0.9, and subscript numbers represent the molar ratio of elements. The material is in a saturated polarization intensity change range of 27.58 mu C/cm 2≤Ps≤41.76μC/cm2, an anti-breakdown field intensity change range of 300kV/cm and less than or equal to E b and less than or equal to 440kV/cm, an effective energy storage density change range of 3.34J/cm 3≤Wrec≤4.91J/cm3 and an energy storage efficiency change range of 67.8 percent and less than or equal to eta and less than or equal to 88 percent under the environment temperature of 25 ℃.
Description
Technical Field
The invention belongs to the technical field of energy storage ceramic materials, and particularly relates to a lead-free relaxation ferroelectric energy storage ceramic material and a preparation method thereof.
Background
Lead-free relaxor ferroelectric energy storage ceramics are widely focused in the technical field of energy storage by virtue of excellent environment-friendly characteristics and excellent relaxor ferroelectricity. Under the excitation of an external electric field, the ceramic has a gentle polarization response, and the electric hysteresis loop is in a long and narrow state and has the characteristic of low residual polarization intensity, so that the ceramic generally has higher energy storage efficiency, but has obvious defects. When the magnetic field is applied under the action of a low external electric field, the saturated polarization intensity is generally lower, and the obtained energy storage density is correspondingly lower. Therefore, to increase the energy storage density of the relaxed ferroelectric ceramic, it is necessary to increase its breakdown strength and saturation polarization under the action of a strong external electric field.
In order to optimize the comprehensive performance of the lead-free relaxation ferroelectric energy storage ceramic, researchers have carried out a great deal of work in terms of process adjustment and formulation improvement. The process adjustment is to optimize the shape, the size and the distribution of ceramic grains by adjusting the parameters of the preparation flow, but the technology is relatively mature and the lifting space is limited; the formula design achieves the aim of optimizing the phase composition and the crystal grain morphology of the ceramic by adjusting the element proportion of the ceramic material, and mainly expands around the two aspects of ion doping modification and multi-component compounding. The ion doping can adjust the defect structure and electrical property of the material, so that the material has better energy storage and release capacity, but the adjustability is obviously limited because of fewer ion types; the multi-component composite is formed by introducing other functional materials, and the diversification of the structure and the diversity of the composite greatly enrich the formula design scheme, so that the multi-component composite is favored by researchers.
Disclosure of Invention
In order to overcome the defects of high remnant polarization and low breakdown field strength of the lead-free relaxor ferroelectric ceramic and improve the energy storage application space, the invention provides a lead-free relaxor ferroelectric composite ceramic material with high energy storage density and a preparation method thereof. According to the invention, (Bi 0.5Na0.5)TiO3 is used as a matrix material, caTiO 3 phase compounding is introduced, sr 2+ ion doping modification is adopted, so that the residual polarization intensity is reduced, the breakdown resistance field intensity is improved, and the purpose of optimizing the energy storage performance of the ceramic is achieved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a ferroelectric composite energy storage ceramic material is characterized in that the general formula of the ceramic material is (1-x) (Bi 0.46Sr0.06Na0.5)TiO3-xCa1-ySryTiO3, wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1 and y is more than or equal to 0.9, and subscript numbers represent the molar ratio of elements:
(1) Bi 2O3(99.9)SrCO3(99.95)Na2CO3(99.5)CaCO3 (99%) and TiO 2 (99%) are used as raw materials, the raw materials are calculated and weighed according to a chemical general formula of the material, and then the technological processes of primary ball milling, primary sintering, secondary ball milling, granulation, molding, glue discharging, sintering and the like are sequentially carried out, so that the ferroelectric composite energy storage ceramic material is obtained.
(2) The primary ball milling in the step 1 means that the weighed raw materials are subjected to canning ball milling, absolute ethyl alcohol is adopted as a ball milling medium, the ball milling rotating speed is 350r/min-450r/min, and the ball milling time is 6h-8h.
(3) The primary sintering in the step 1 is to dry and screen the primary ball milling slurry, fill the slurry into a pot, and keep the temperature at 750-850 for 2-4 h.
(4) And in the step 1, the secondary ball milling is to weigh the powder obtained by primary sintering according to the mole ratio of the general formula, canning and ball milling, absolute ethyl alcohol is adopted as a ball milling medium, the ball milling rotating speed is 350r/min-450r/min, and the ball milling time is 6h-8h.
(5) The granulation in the step 1 means that the secondary ball milling slurry is dried and sieved, 5 to 7 weight percent of polyvinyl alcohol aqueous solution (PVA) is added, and then the mixture is uniformly mixed, wherein the PVA concentration is 5 weight percent.
(6) The molding in the step 1 refers to dry pressing the pelleting material under 200-250 MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm.
(7) The step 1 of glue discharging refers to the steps of filling the formed embryo body into a pot, and preserving the temperature at 450-550 for 30-60 min, wherein the temperature rising rate is 2-8 /min.
(8) The sintering in the step 1 means that the discharged glue blank is insulated for 3 to 5 hours at 980 to 1050 with the heating rate of 2 to 4 /min; and cooling to room temperature along with the furnace to obtain the composite energy storage ceramic sample wafer.
(9) After sintering is completed, the resulting coupon is ground, polished, cleaned, dried, electrode coated, and subjected to a series of performance tests.
Compared with the prior reports, the technical scheme adopted by the invention has the following advantages:
(1) The composite energy storage ceramic material is an environment-friendly material, has no toxicity to human bodies and no heavy metal pollution to the environment.
(2) In the preparation process of the ceramic material, noble metal elements and rare earth elements are not adopted, so that the production cost is low, and the ceramic material is favorable for popularization and application.
(3) The ferroelectric composite ceramic has excellent comprehensive energy storage performance and strong frequency stability, for example, when the chemical formula of the material is 0.3 (Bi 0.46Sr0.06Na0.5)TiO3-0.7Ca0.25Sr0.75TiO3, the breakdown resistance field strength is 420KV/cm under the conditions of 50Hz test frequency and 25 ambient temperature, the energy storage density is up to 4.91J/cm 3, the corresponding energy storage efficiency is 88.0 percent, and when the test frequency is within the range of 10Hz-150Hz, the fluctuation of the energy storage efficiency of the ceramic material is limited to be within 6 percent, and compared with the similar lead-free energy storage ceramic material, the performance is more outstanding.
Drawings
FIG. 1 is an XRD pattern for the energy storage ceramic materials of examples 1-5.
FIG. 2 is a graph of the hysteresis loop of the energy storage ceramic materials of examples 1-5 at a test frequency of 50Hz and an ambient temperature of 25 .
FIG. 3 is a graph showing hysteresis curves of the energy storage ceramic material of example 4 at different test frequencies.
Detailed Description
The invention will now be described in detail with reference to five examples, which are only intended to illustrate a specific embodiment of the invention, the scope of which is not limited to the examples listed.
Example 1
According to a chemical formula of 0.6 (Bi 0.46Sr0.06Na0.5)TiO3-0.4Ca0.25Sr0.75TiO3 is calculated and weighed, the weighed raw materials are subjected to canning and ball milling, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, slurry obtained by ball milling is dried and filled into a bowl, primary sintering is carried out, the sintering temperature is 800 , the heat preservation time is 4 hours, powder obtained by primary sintering is subjected to canning and ball milling again, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, secondary ball milling slurry is dried and granulated, the binder adopts 5wt% of polyvinyl alcohol aqueous solution, the addition amount is 5wt%, the granulated materials are subjected to dry press molding under the pressure of 250MPa, a cylindrical blank body with the thickness of 1.2mm and the diameter of 10mm is prepared, the molded blank body is subjected to heat preservation at the temperature of 500 for 30 minutes, the heating rate is 5 /min, sintering is carried out after glue discharging, the sintering temperature is 980 , the heat preservation time is 3 hours, and the heat preservation is cooled to the room temperature along with a hearth, so that the energy storage ceramic sample sheet is obtained.
Example 2
According to a chemical formula of 0.5 (Bi 0.46Sr0.06Na0.5)TiO3-0.5Ca0.25Sr0.75TiO3 is calculated and then is weighed, the weighed raw materials are subjected to canning and ball milling, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the slurry after ball milling is dried and filled into a bowl, primary sintering is carried out, the sintering temperature is 800 , the heat preservation time is 4 hours, the powder after primary sintering is subjected to canning and ball milling again, the ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the secondary ball milling slurry is dried and granulated, the binder adopts a polyvinyl alcohol aqueous solution with the weight percent of 5 percent, the addition amount is 5 percent, the granulated materials are subjected to dry press molding under the pressure of 250MPa, a cylindrical blank with the thickness of 1.2mm and the diameter of 10mm is prepared, the molded blank is subjected to heat preservation at the temperature of 500 for 30 minutes, the heating rate is 5 /min, sintering is carried out after glue discharging, the sintering temperature is 1000 , the heat preservation time is 3 hours, and the heat preservation is cooled to the room temperature along with a hearth, so that the energy storage ceramic sample wafer is obtained.
Example 3
According to chemical formula 0.4 (Bi 0.46Sr0.06Na0.5)TiO3-0.6Ca0.25Sr0.75TiO3 is calculated and then is weighed, the weighed raw materials are subjected to canning and ball milling, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the slurry after ball milling is dried and filled into a bowl, primary sintering is carried out, the sintering temperature is 800 , the heat preservation time is 4 hours, the powder after primary sintering is subjected to canning and ball milling again, the ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the secondary ball milling slurry is dried and granulated, the binder adopts 5wt% of polyvinyl alcohol aqueous solution, the addition amount is 5wt%, the granulated materials are subjected to dry press molding under the pressure of 250MPa, a cylindrical blank body with the thickness of 1.2mm and the diameter of 10mm is prepared, the molded blank body is subjected to heat preservation at the temperature of 500 for 30 minutes, the heating rate is 5 /min, sintering is carried out after glue discharging, the sintering temperature is 1010 , the heat preservation time is 3 hours, and the heat preservation is cooled to room temperature along with a hearth, so that the energy storage ceramic sample wafer is obtained.
Example 4
According to a chemical formula of 0.3 (Bi 0.46Sr0.06Na0.5)TiO3-0.7Ca0.25Sr0.75TiO3 is calculated and then is weighed, the weighed raw materials are subjected to canning and ball milling, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the slurry after ball milling is dried and filled into a bowl, primary sintering is carried out, the sintering temperature is 800 , the heat preservation time is 4 hours, the powder after primary sintering is subjected to canning and ball milling again, the ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the secondary ball milling slurry is dried and granulated, the binder adopts a polyvinyl alcohol aqueous solution with the weight percent of 5 percent, the addition amount is 5 percent, the granulated materials are subjected to dry press molding under the pressure of 250MPa, a cylindrical blank with the thickness of 1.2mm and the diameter of 10mm is prepared, the molded blank is subjected to heat preservation at the temperature of 500 for 30 minutes, the heating rate is 5 /min, sintering is carried out after glue discharging, the sintering temperature is 1020 , the heat preservation time is 3 hours, and the heat preservation is cooled to the room temperature along with a hearth, so that the energy storage ceramic sample wafer is obtained.
Example 5
According to a chemical formula of 0.2 (Bi 0.46Sr0.06Na0.5)TiO3-0.8Ca0.25Sr0.75TiO3 is calculated and then is weighed, the weighed raw materials are subjected to canning and ball milling, ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the slurry after ball milling is dried and filled into a bowl, primary sintering is carried out, the sintering temperature is 800 , the heat preservation time is 4 hours, the powder after primary sintering is subjected to canning and ball milling again, the ball milling media are absolute ethyl alcohol, the ball milling speed is 400r/min, the ball milling time is 8 hours, the secondary ball milling slurry is dried and granulated, the binder adopts a polyvinyl alcohol aqueous solution with the weight percent of 5 percent, the addition amount is 5 percent, the granulated materials are subjected to dry press molding under the pressure of 250MPa, a cylindrical blank with the thickness of 1.2mm and the diameter of 10mm is prepared, the molded blank is subjected to heat preservation at the temperature of 500 for 30 minutes, the heating rate is 5 /min, sintering is carried out after glue discharging, the sintering temperature is 1050 , the heat preservation time is 3 hours, and the heat preservation is cooled to the room temperature along with a hearth after the heat preservation is completed, so that the energy storage ceramic sample wafer is obtained.
The ceramic wafers prepared in examples 1 to 5 were ultrasonically cleaned and then dried. The sample pieces of each example were subjected to phase analysis by an X-ray diffractometer (XRD-6100, shimadzu, japan), and the results are shown in FIG. 1. From the graph, each sample has a simple perovskite structure, which indicates that solid solution among the components is complete, and the overall crystallinity is good.
The ceramic sample plates prepared in examples 1 to 5 above were polished to 0.1mm with 1500 mesh silicon carbide, ultrasonically cleaned and then dried, coated with high temperature conductive silver paste on both sides, dried and then cured with silver electrodes at 500 c, and then left to cool naturally for 30 minutes, and the hysteresis loops of each sample were measured using a ferroelectric tester (LCII-100 v, radio, usa) at a test frequency of 50Hz and an ambient temperature of 25 c, with the result shown in fig. 2. The energy storage performance of each composite ceramic material is as follows:
Example 1: the anti-breakdown field strength E b is 300kV/cm, the saturation polarization intensity P s is 41.76 mu C/cm 2, and the effective energy storage density W rec is 3.465J/cm 3 and the energy storage efficiency eta is 67.8%.
Example 2: the anti-breakdown field strength E b is 320kV/cm, the saturation polarization intensity P s is 340.6 mu C/cm 2, and the effective energy storage density W rec is 3.34J/cm 3 and the energy storage efficiency eta is 73.2%.
Example 3: the anti-breakdown field strength E b is 360kV/cm, the saturation polarization intensity P s is 32.65 mu C/cm 2, and the effective energy storage density W rec is 3.96J/cm 3 and the energy storage efficiency eta is 83.5%.
Example 4: the anti-breakdown field strength E b is 420kV/cm, the saturation polarization intensity P s is 34 mu C/cm 2, and therefore the energy storage effective density W rec is 4.91J/cm 3 and the energy storage efficiency eta is 88%.
Example 5: the anti-breakdown field strength E b is 440kV/cm, the saturation polarization intensity P s is 27.58 mu C/cm 2, and the effective energy storage density W rec is 4.21J/cm 3 and the energy storage efficiency eta is 72.2%.
It is also an important object of the present invention to improve the stability of the lead-free relaxor ferroelectric ceramic, and FIG. 3 shows that the lead-free energy storage ceramic material of example 3 has excellent energy storage efficiency fluctuation of less than 6% in the hysteresis loop within the frequency range of 10Hz-150Hz under the conditions of 320kV/cm external electric field and 25 ambient temperature.
Claims (2)
1. A ferroelectric composite energy storage ceramic material is characterized in that the chemical general formula of the material is (1-x) (Bi 0.46Sr0.06Na0.5)TiO3-xCa1-ySryTiO3, wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1 and y is more than or equal to 0.9, and subscript numbers represent the molar ratio of elements.
2. The preparation method of the ferroelectric composite energy storage ceramic material is characterized by comprising the following steps of:
(1) Bi 2O3SrCO3Na2CO3CaCO3 and TiO 2 are used as raw materials, the materials are calculated and weighed according to the general formula of claim 1, and then the technological processes of primary ball milling, primary sintering, secondary ball milling, granulating, forming, glue discharging and sintering are sequentially carried out, so that the ferroelectric composite energy storage ceramic material is obtained;
(2) According to the process flow in the step 1, one-time ball milling refers to canning and ball milling of the weighed raw materials, absolute ethyl alcohol is adopted as a ball milling medium, the ball milling rotating speed is 350r/min-450r/min, and the ball milling time is 6h-8h;
(3) According to the process flow in the step 1, the primary sintering is to dry and screen the ball milling slurry, fill the bowl, and keep the temperature at 750-850 for 2-4 h;
(4) According to the process flow in the step 1, the secondary ball milling is to weigh the powder obtained by primary sintering according to the mole ratio of the general formula, canning and ball milling, absolute ethyl alcohol is adopted as a ball milling medium, the ball milling rotating speed is 350r/min-450r/min, and the ball milling time is 6h-8h;
(5) According to the process flow in the step 1, granulating refers to drying and sieving the secondary ball milling slurry, adding 5-7wt% of polyvinyl alcohol aqueous solution (PVA), and then uniformly mixing, wherein the concentration of the PVA is 5wt%;
(6) According to the process flow in the step 1, the forming refers to dry pressing the granular material under 200MPa-250 MPa to prepare a cylindrical blank with the thickness of 1.2mm and the diameter of 10 mm;
(7) According to the process flow in the step 1, glue discharging means that the formed embryo body is filled into a pot, and is kept at the temperature of 450-550 for 30-60 min, and the heating rate is 2-8 /min;
(8) According to the process flow in the step 1, sintering refers to the step of preserving the heat of the discharged glue blank for 3-5 hours at 980-1050 with the heating rate of 2-4 /min.
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