CN116854464A - 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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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 73
- 238000005245 sintering Methods 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 12
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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 in the invention is (1-x) (Bi) 0.46 Sr 0.06 Na 0.5 )TiO 3 ‑xCa 1‑ y Sr y TiO 3 Wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1, y is more than or equal to 0.9, and subscript numbers represent the molar ratio of elements. The material of the invention has the saturated polarization intensity changing range of 27.58 mu C/cm when the testing frequency changing range is 10Hz-150Hz at the environmental temperature of 25 DEG C 2 ≤P s ≤41.76μC/cm 2 The variation range of breakdown field strength is 300kV/cm less than or equal to E b The effective energy storage density is less than or equal to 440kV/cm, and the change range of the effective energy storage density is 3.34J/cm 3 ≤W rec ≤4.91J/cm 3 The energy storage efficiency is changed within 67.8 percent to 88 percent.
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. The invention is characterized by (Bi) 0.5 Na 0.5 )TiO 3 Introducing CaTiO as a matrix material 3 Phase composite and use Sr 2+ The ion doping modification reduces the residual polarization intensity and simultaneously improves the breakdown resistance field strength, thereby achieving the purpose of optimizing the energy storage performance of the ceramic.
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 0.46 Sr 0.06 Na 0.5 )TiO 3 -xCa 1-y Sr y TiO 3 Wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1, y is more than or equal to 0.9, and subscript numbers represent the molar ratio of elements. The preparation method adopts a traditional solid-phase sintering method and comprises the following steps:
(1) Bi is used as 2 O 3 (99.9％)、SrCO 3 (99.95％)、Na 2 CO 3 (99.5％)、CaCO 3 (99%) and TiO 2 And (99%) is used as a raw material, the raw material is calculated and weighed according to the 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 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.7Ca 0.25 Sr 0.75 TiO 3 When the anti-breakdown 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 reaches 88.0%; 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 the ceramic material has more outstanding performance compared with the similar lead-free energy storage ceramic material.
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 the chemical formula 0.6 (Bi 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.4Ca 0.25 Sr 0.75 TiO 3 Calculating and weighing materials; the weighed raw materials are subjected to canning and ball milling, the ball milling medium is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 8 hours; drying the slurry obtained by ball milling, loading the slurry into a bowl, and performing primary sintering at 800 ℃ for 4 hours; canning and ball-milling the powder after primary sintering again, wherein the ball-milling medium is absolute ethyl alcohol, the ball-milling speed is 400r/min, and the ball-milling time is 8h; drying and granulating the secondary ball milling slurry, wherein the binder adopts 5wt% of polyvinyl alcohol aqueous solution, and the addition amount is 5wt%; dry-pressing the granulated material under the pressure of 250MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm; maintaining the temperature of the formed blank at 500 ℃ for 30min for glue discharging, wherein the heating rate is 5 ℃/min; sintering is carried out after the glue is discharged, the sintering temperature is 980 ℃, the heat preservation time is 3 hours, and the energy storage ceramic sample wafer is obtained after the heat preservation is completed and is cooled to the room temperature along with a hearth.
Example 2
According to the chemical formula 0.5 (Bi 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.5Ca 0.25 Sr 0.75 TiO 3 Weighing after calculation; the weighed raw materials are subjected to canning and ball milling, the ball milling medium is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 8 hours; drying the ball-milled slurry, loading the slurry into a bowl, and performing primary sintering at 800 ℃ for 4 hours; canning and ball-milling the powder after primary sintering again, wherein the ball-milling medium is absolute ethyl alcohol, the ball-milling speed is 400r/min, and the ball-milling time is 8h; drying and granulating the secondary ball milling slurry, wherein the binder adopts 5wt% of polyvinyl alcohol aqueous solution, and the addition amount is 5wt%; dry-pressing the granulated material under the pressure of 250MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm; maintaining the temperature of the formed blank at 500 ℃ for 30min for glue discharging, wherein the heating rate is 5 ℃/min; sintering is carried out after the glue is discharged, the sintering temperature is 1000 ℃, the heat preservation time is 3 hours, and the energy storage ceramic sample wafer is obtained after the heat preservation is completed and is cooled to room temperature along with a hearth.
Example 3
According to chemical formula 0.4 (Bi 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.6Ca 0.25 Sr 0.75 TiO 3 Weighing after calculation; the weighed raw materials are subjected to canning and ball milling, the ball milling medium is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 8 hours; drying the ball-milled slurry, loading the slurry into a bowl, and performing primary sintering at 800 ℃ for 4 hours; canning and ball-milling the powder after primary sintering again, wherein the ball-milling medium is absolute ethyl alcohol, the ball-milling speed is 400r/min, and the ball-milling time is 8h; drying and granulating the secondary ball milling slurry, wherein the binder adopts 5wt% of polyvinyl alcohol aqueous solution, and the addition amount is 5wt%; dry-pressing the granulated material under the pressure of 250MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm; maintaining the temperature of the formed blank at 500 ℃ for 30min for glue discharging, wherein the heating rate is 5 ℃/min; sintering is carried out after the glue is discharged, the sintering temperature is 1010 ℃, the heat preservation time is 3 hours, and the energy storage ceramic sample wafer is obtained after the heat preservation is completed and is cooled to room temperature along with a hearth.
Example 4
According to chemical formula 0.3 (Bi 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.7Ca 0.25 Sr 0.75 TiO 3 Weighing after calculation; the weighed raw materials are subjected to canning and ball milling, the ball milling medium is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 8 hours; drying the ball-milled slurry, loading the slurry into a bowl, and performing primary sintering at 800 ℃ for 4 hours; canning and ball-milling the powder after primary sintering again, wherein the ball-milling medium is absolute ethyl alcohol, the ball-milling speed is 400r/min, and the ball-milling time is 8h; drying and granulating the secondary ball milling slurry, wherein the binder adopts 5wt% of polyvinyl alcohol aqueous solution, and the addition amount is 5wt%; dry-pressing the granulated material under the pressure of 250MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm; maintaining the temperature of the formed blank at 500 ℃ for 30min for glue discharging, wherein the heating rate is 5 ℃/min; sintering is carried out after the glue is discharged, the sintering temperature is 1020 ℃, the heat preservation time is 3 hours, and the energy storage ceramic sample wafer is obtained after the heat preservation is completed and is cooled to room temperature along with a hearth.
Example 5
According to chemical formula 0.2 (Bi 0.46 Sr 0.06 Na 0.5 )TiO 3 -0.8Ca 0.25 Sr 0.75 TiO 3 Weighing after calculation; the weighed raw materials are canned and ball-milled,the ball milling medium is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 8h; drying the ball-milled slurry, loading the slurry into a bowl, and performing primary sintering at 800 ℃ for 4 hours; canning and ball-milling the powder after primary sintering again, wherein the ball-milling medium is absolute ethyl alcohol, the ball-milling speed is 400r/min, and the ball-milling time is 8h; drying and granulating the secondary ball milling slurry, wherein the binder adopts 5wt% of polyvinyl alcohol aqueous solution, and the addition amount is 5wt%; dry-pressing the granulated material under the pressure of 250MPa to prepare a cylindrical blank body with the thickness of 1.2mm and the diameter of 10 mm; maintaining the temperature of the formed blank at 500 ℃ for 30min for glue discharging, wherein the heating rate is 5 ℃/min; sintering is carried out after the glue is discharged, the sintering temperature is 1050 ℃, the heat preservation time is 3 hours, and the energy storage ceramic sample wafer is obtained after the heat preservation is completed and is cooled to room temperature along with a hearth.
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: breakdown field strength E b At 300kV/cm, saturation polarization P s 41.76. Mu.C/cm 2 Thereby calculating the effective energy storage density W rec 3.465J/cm 3 The energy storage efficiency eta is 67.8 percent.
Example 2: breakdown field strength E b At 320kV/cm, saturation polarization P s 340.6. Mu.C/cm 2 Thereby calculating the effective energy storage density W rec 3.34J/cm 3 The energy storage efficiency eta is 73.2 percent.
Example 3: breakdown field strength E b 360kV/cm, saturation polarization P s Is 32.65 mu C/cm 2 Thereby calculating the effective energy storage density W rec 3.96J/cm 3 The energy storage efficiency eta is 83.5 percent.
Example 4: breakdown field strength E b 420kV/cm, saturation polarization P s 34 μC/cm 2 Thereby calculating the energy storage effective density W rec 4.91J/cm 3 The energy storage efficiency eta is 88 percent.
Example 5: breakdown field strength E b At 440kV/cm, saturation polarization P s 27.58. Mu.C/cm 2 Thereby calculating the effective energy storage density W rec 4.21J/cm 3 The energy storage efficiency eta is 72.2 percent.
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 η 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 0.46 Sr 0.06 Na 0.5 )TiO 3 -xCa 1-y Sr y TiO 3 Wherein x is more than or equal to 0.4 and less than or equal to 0.8,0.1, 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 is used as 2 O 3 (99.9％)、SrCO 3 (99.95％)、Na 2 CO 3 (99.5％)、CaCO 3 (99%) and TiO 2 (99%) is used as a raw material, and the ferroelectric composite energy storage ceramic material is obtained by calculating and weighing according to the general formula of claim 1, and then sequentially carrying out the technological processes of primary ball milling, primary sintering, secondary ball milling, granulation, forming, glue discharging, sintering and the like.
(2) The process flow according to the step 1 is characterized in that one ball milling is to tank ball mill 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) The process flow according to the step 1 is characterized in that the primary sintering is to dry and screen ball-milling slurry, fill the ball-milling slurry into a bowl, and keep the temperature at 750-850 ℃ for 2-4 h.
(4) The process flow according to the step 1 is characterized in that the secondary ball milling is to weigh powder obtained by primary sintering according to the mole ratio of the general formula, canning and ball milling are carried out, 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 process flow according to the step 1 is characterized in that the granulation is to dry and screen the secondary ball milling slurry, add 5wt% -7wt% of polyvinyl alcohol aqueous solution (PVA) and then uniformly mix, wherein the PVA concentration is 5wt%.
(6) The process flow according to the step 1 is characterized in that the forming refers to dry pressing of the granulated material under 200-250 MPa to prepare a cylindrical blank with the thickness of 1.2mm and the diameter of 10 mm.
(7) The process flow according to the step 1 is characterized in that the glue discharging is to fill the formed embryo body into a pot, and the temperature is kept for 30min-60min at 450-550 ℃ with the heating rate of 2 ℃/min-8 ℃/min.
(8) The process flow according to the step 1 is characterized in that the sintering means that the discharged glue blank is kept at 980-1050 ℃ for 3-5 hours, and the heating rate is 2-4 ℃/min.
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