CN108751982A - A kind of unleaded high energy storage density ceramic material and preparation method thereof - Google Patents
A kind of unleaded high energy storage density ceramic material and preparation method thereof Download PDFInfo
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- CN108751982A CN108751982A CN201810609053.1A CN201810609053A CN108751982A CN 108751982 A CN108751982 A CN 108751982A CN 201810609053 A CN201810609053 A CN 201810609053A CN 108751982 A CN108751982 A CN 108751982A
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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Abstract
A kind of unleaded high energy storage density ceramic material and preparation method thereof, first, in accordance with chemical formula (1-x) (0.65BaTiO3‑0.35Bi0.5Na0.5TiO3)‑xSrY0.5Nb0.5O3Dispensing is carried out, wherein x indicates molar fraction, and 0.06≤x≤0.12；Powder is obtained after ball milling, drying；Adhesive is added in the powder of acquisition to be granulated, it is tabletted after aging 24~48 hours, it is sintered at 1100~1200 DEG C after dumping processing, you can obtain unleaded high energy storage density ceramic material.The ceramic material preparation process of the present invention is simple, stablizes, and is suitble to industrialized production, energy storage characteristic excellent.It is calculated based on ferroelectric hysteresis loop, the energy storage density of the ceramic material at room temperature is up to 1.0J/cm3More than；And under the electric field of 152kV/cm, energy storage density is up to 1.36J/cm3。
Description
Technical field
The invention belongs to energy storage ceramic field, specifically a kind of unleaded high energy storage density ceramic material and preparation method thereof.
Background technology
In recent years, with the continuous development of society being constantly progressive with scientific and technological information technology, energy problem is instantly global
The extremely serious problem faced, thus energy utilization rate and energy storage how are improved into concerned weight
Point.The high-speed and high-efficiency development of advanced energy storage material will increase substantially terminal energy sources utilization ratio.Currently, main energy storage device
There are conventional batteries, nickel series and lithium series battery, material fuel battery, ultracapacitor and dielectric capacitor etc..It is modern
Electronic technology requires the devices own wts such as capacitor more and more light, and volume is more and more small, and energy storage density is more and more big.Therefore it reflects
In high energy storage density ceramic dielectric capacitor material have energy storage density is high, charge/discharge rates are fast, anti-cycle aging, mechanical strength
Height is answered extensively suitable for extreme environments and steady performance, the requirements for meeting new energy development and utilizing such as high temperature and pressure
For communicating, the various fields such as computer, automobile, electronic circuit apparatus and military project.
Current existing high energy storage density ceramic dielectric material mainly has four classes.The first kind is antiferroelectric materials, this kind of
Material has higher polarization intensity and breakdown electric field.AgNbO3Wait antiferroelectric materials since high cost is difficult to promote,
His most of antiferroelectric materials contain lead element, the oxide of a large amount of lead and lead exist human body and environment can be caused it is serious
Pollution, for this purpose, at present people in order to environmental protection be just dedicated to it is unleaded.Second class is organic film, such as Kynoar
(PVDF) film, polystyrene film, polyester film etc., with very high disruptive field intensity, but dielectric constant is very small, uses
Temperature range is narrow, leads to its application range critical constraints.Third class is that ceramics are formed with glass or ceramics with polymer
Composite dielectric material, this kind of material has higher breakdown electric field, but mass production technology is still immature.4th class is
The ferroelectric ceramic materials such as barium titanate and bismuth-sodium titanate, this kind of material have higher dielectric constant, lower dielectric loss related
Production technology is highly developed, but energy storage density is less than 1J/cm under normal conditions3, the temperature stability of energy storage density it is bad, and
And the variation of dielectric constant with temperature and frequency is unstable.Therefore, energy storage density and the energy storage of energy storage material are effectively improved
Efficiency becomes hot spot at this stage.
Invention content
It is an object of the invention to overcome defect existing in the prior art, a kind of unleaded high energy storage density ceramics material is provided
Material and preparation method thereof, this ceramic material have good energy-storage property, at room temperature have higher dielectric constant and
Lower dielectric loss, and there are the characteristics such as environmental-friendly, practicability is high.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of unleaded high energy storage density ceramic material, by (1-x) (0.65BaTiO3-
0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3Powder carries out pre-burning, and adhesive is then added after ball milling is granulated, and aging 24
Tabletting after~48 hours, then dumping processing is carried out, it sinters porcelain into, obtains unleaded high energy storage density ceramic material；Wherein x expressions rub
That score, and 0.06≤x≤0.12.
The present invention, which further improves, to be, (1-x) (0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3
Powder is made by following procedure：By chemical formula (1-x) (0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3It will
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5It after powder weighs dispensing, is uniformly mixed, then sieving, briquetting, then
Through 800~850 DEG C of pre-burnings 3~5 hours, blocks of solid is obtained, blocks of solid is then smashed it through into 120 mesh sieve, is obtained (1-x)
(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3Powder；Wherein x expression molar fractions, and 0.06≤x≤
0.12。
The present invention, which further improves, to be, uniformly mixed detailed process is：Using absolute ethyl alcohol as medium, pass through ball milling
It carries out, and Ball-milling Time is 20~24 hours, the slurry after ball milling is dried at 100 DEG C.
The present invention, which further improves, to be, the temperature of pre-burning is 800~850 DEG C, and the time is 2~3h.
The present invention, which further improves, to be, 800~850 DEG C are warming up to the heating rate of 3 DEG C/min from room temperature.
The present invention, which further improves, to be, pressure is 220~250MPa when tabletting；PVA adhesives be added quality be
(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3The 8%~15% of powder quality；Adhesive uses
Be mass fraction be 8% PVA aqueous solutions.
The present invention, which further improves, to be, the temperature of dumping is 500~600 DEG C, and the time is 3~5 hours.
The present invention, which further improves, to be, the temperature of sintering is 1100~1200 DEG C, and the time is 2~3 hours.
A kind of unleaded high energy storage density ceramic material, the chemical formula of the unleaded high energy storage density ceramic material are：(1-x)
(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3, wherein x is SrY0.5Nb0.5O3Molar fraction, wherein
0.06≤x≤0.12。
The present invention, which further improves, to be, at room temperature, energy storage density is 0.97~1.36J/cm to the ceramic material3。
Compared with prior art, the device have the advantages that：The present invention is respectively by (1-x) of ball milling
(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3Powder by being made after pre-burning and ball milling process for refining
Grain, then compression moulding in a mold are sintered after dumping processing at 1100~1200 DEG C, you can obtain unleaded high energy storage density
Ceramic material.The present invention is by controlling SrY0.5Nb0.5O3Solid solution capacity, improve ceramics dielectric constant at room temperature, overcome
Most of ceramic medium materials disadvantages that dielectric constant is low in room temperature, dielectric loss is larger.With SrY0.5Nb0.5O3Solid solution
The Curie temperature of the increase of amount, prepared energy storage ceramic dielectric material is moved toward room temperature direction.And (25 DEG C) at room temperature
Larger dielectric constant is obtained, dielectric constant reaches 1500~3000.It is small that elongated, back-shaped area is obtained at room temperature simultaneously
Ferroelectric hysteresis loop, obtain excellent energy storage density, energy storage density reaches 0.97~1.36J/cm3, and the effect of energy storage density
Rate is higher good, and energy storage efficiency reaches 73%~83%.In addition, lead is free of in the raw materials used in the present invention, it is environmentally safe, and
Preparation process is simple, stability is good, consistency is high, can meet the needs of different application, and involved cost of material is cheap, is suitble to
Industrialized production is expected to make the environmental-friendly energy storage ceramic dielectric material of a new generation.
The energy storage characteristic of material of the present invention is excellent, is calculated based on ferroelectric hysteresis loop, and the energy storage of the ceramic material at room temperature is close
Degree is up to 1.3J/cm3More than.
Description of the drawings
Fig. 1 is the XRD spectrum of the unleaded energy storage ceramic material prepared by embodiment 1；
Fig. 2 is the XRD spectrum of the unleaded energy storage ceramic material prepared by embodiment 2；
Fig. 3 is the XRD spectrum of the unleaded energy storage ceramic material prepared by embodiment 3；
Fig. 4 is the XRD spectrum of the unleaded energy storage ceramic material prepared by embodiment 4；
Fig. 5 is the SEM figures of the unleaded energy storage ceramic material prepared by embodiment 1；
Fig. 6 is the SEM figures of the unleaded energy storage ceramic material prepared by embodiment 2；
Fig. 7 is the SEM figures of the unleaded energy storage ceramic material prepared by embodiment 3；
Fig. 8 is the SEM figures of the unleaded energy storage ceramic material prepared by embodiment 4；
Fig. 9 is that (test frequency is the ferroelectric hysteresis loop figure of unleaded energy storage ceramic material prepared by embodiment 1 at room temperature
10Hz)；
Figure 10 is that (test frequency is the ferroelectric hysteresis loop figure of unleaded energy storage ceramic material prepared by embodiment 2 at room temperature
10Hz)；
Figure 11 is that (test frequency is the ferroelectric hysteresis loop figure of unleaded energy storage ceramic material prepared by embodiment 3 at room temperature
10Hz)；
Figure 12 is that (test frequency is the ferroelectric hysteresis loop figure of unleaded energy storage ceramic material prepared by embodiment 4 at room temperature
10Hz)；
Figure 13 is Jie temperature collection of illustrative plates of the unleaded energy storage ceramic material under different test frequencies prepared by embodiment 1；
Figure 14 is Jie temperature collection of illustrative plates of the unleaded energy storage ceramic material under different test frequencies prepared by embodiment 2；
Figure 15 is Jie temperature collection of illustrative plates of the unleaded energy storage ceramic material under different test frequencies prepared by embodiment 3；
Figure 16 is Jie temperature collection of illustrative plates of the unleaded energy storage ceramic material under different test frequencies prepared by embodiment 4.
Specific implementation mode
The present invention is described in further details with reference to the accompanying drawings and detailed description.
A kind of unleaded high energy storage density ceramic material, chemical formula are：(1-x)(0.65BaTiO3-
0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3, wherein x expression molar fractions, and 0.06≤x≤0.12.
The preparation method of the unleaded high energy storage density ceramic material of the present invention, includes the following steps：
(1) chemical formula (1-x) (0.65BaTiO is pressed3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5It is small by ball milling 20~24 using absolute ethyl alcohol as medium after dispensing
When be uniformly mixed, then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 800~850 DEG C of pre-burnings 3~5 hours, obtain block
Then blocks of solid is smashed it through 120 mesh sieve, obtains (1-x) (0.65BaTiO by shape solid3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3Powder；
(2) the pre-burning powder of step (1) is subjected to ball milling refinement；Using absolute ethyl alcohol as medium, using planetary ball mill
Ball milling 20~24 hours, is then dried at 100 DEG C, and material powder is obtained after crossing 120 mesh sieve；
(3) PVA adhesives are added in the material powder obtained to step (2) to be granulated, wherein PVA adhesives are added
Quality is that 8%~15%, the PVA adhesives of material powder quality are the polyvinyl alcohol water solution of mass fraction 8%；Aging 24~
After 48 hours, it is unidirectionally pressed into disk under the pressure of 200~250Mpa, then keeps the temperature 3~5 hours at 500~600 DEG C
Exclude PVA adhesives；
(4) sample after step (3) exclusion PVA adhesives 2~3 hours are kept the temperature at 1100~1200 DEG C to sinter into
Porcelain obtains unleaded high energy storage density ceramic material；
(5) unleaded energy storage ceramic material obtained is subjected to X-ray diffraction test；
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, then gold-plated electrode is distinguished
Its ferroelectric properties is tested under frequency of the room temperature in 10Hz, and carries out energy storage characteristic calculating, energy storage density (W1) and energy loss
Density (W2) calculation formula be：
Wherein W1And W2Energy storage density and energy loss density, P are indicated respectivelymaxIndicate maximum polarization, PrIndicate surplus
Remaining polarization intensity, E indicate that electric field strength, P indicate polarization intensity.
Ball-milling Time is 20~24 hours in step (1) and step (2).
The embodiment being given by the following can further be apparent from present disclosure, but it is not to this hair
Bright restriction.
Embodiment 1
The chemical formula of this example ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x expression molar fractions, and x=0.06.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, includes the following steps：
(1) 0.94 (0.65BaTiO of chemical formula is pressed3-0.35Bi0.5Na0.5TiO3)-0.06SrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5It is small by ball milling 24 using absolute ethyl alcohol as medium after weighing dispensing
When be uniformly mixed, then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 850 DEG C of pre-burnings 3 hours, obtain blocks of solid,
Then blocks of solid is smashed it through into 120 mesh sieve, obtains unleaded high energy storage ceramic powder；
(2) the pre-burning powder of step (1) is subjected to secondary ball milling refinement；Using absolute ethyl alcohol as medium, ball milling 24 hours, in
It dried at 100 DEG C, obtain powder after the sieve of 120 mesh excessively；
(3) PVA solution that 8% (mass percent) concentration is added in the powder obtained to step (2) is granulated, wherein
After the quality that PVA adhesives are added is the 8%, aging 24 hours of powder quality, disk is unidirectionally pressed under 250MPa,
Then 3 hours are kept the temperature at 600 DEG C excludes PVA adhesives；
(4) disk after step (3) exclusion PVA adhesives is warming up to the heating rate of 3 DEG C/min at 1200 DEG C and is protected
Temperature sinters porcelain into 2.5 hours, obtains unleaded high energy storage density ceramic material；
(5) energy-storing dielectric ceramic obtained is subjected to X-ray diffraction test.Such as Fig. 1, by XRD spectrum it can be seen that this reality
It is pure perovskite structure to apply the obtained ceramic material of example.Fig. 5 show the SEM of medium ceramic material obtained by the present embodiment
Figure, it can be seen that the compact structure of ceramic material；
(6) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room
Temperature tests its ferroelectric properties under 10Hz frequencies, is illustrated in figure 9 the electric hysteresis that the present embodiment ceramic material measures at room temperature and returns
Line carries out energy storage characteristic based on ferroelectric hysteresis loop and can be calculated, and the energy storage density of the unleaded energy-storing dielectric ceramic of the present embodiment is in room temperature
Lower reachable 1.22J/cm3.Jie temperature collection of illustrative plates of the energy storage ceramic material under different test frequencies is as shown in figure 13.At room temperature,
Dielectric constant of the ceramics under four frequencies is between 1500-3000.Within the temperature range of 100~300 DEG C, dielectric constant
Decline as temperature increases, and corresponding dielectric loss is respectively less than 0.05 under four different frequencies.Table 1 is the present embodiment
The dielectric property of unleaded energy-storing dielectric ceramic material at room temperature.The maximum disruptive field intensity of the present embodiment ceramic material at room temperature
Up to 147kV/cm.And at room temperature at 1 khz, the dielectric constant of 1 ceramics of embodiment is up to 2898, compared to other ceramics have compared with
Big advantage.
Embodiment 2
The chemical formula of this example ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x expression molar fractions, and x=0.08.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, includes the following steps：
(1) 0.92 (0.65BaTiO of chemical formula is pressed3-0.35Bi0.5Na0.5TiO3)-0.08SrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5After dispensing, using absolute ethyl alcohol as medium, by ball milling 23.5 hours
It is uniformly mixed, is then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 840 DEG C of pre-burnings 3.5 hours, obtain blocks of solid,
Then blocks of solid is smashed it through into 120 mesh sieve, obtains unleaded high energy storage ceramic powder；
(2) the pre-burning powder of step (1) is subjected to secondary ball milling refinement；Using absolute ethyl alcohol as medium, ball milling 23 hours, in
It dried at 100 DEG C, obtain powder after the sieve of 120 mesh excessively；
(3) PVA solution that 8% (mass percent) concentration is added in the powder obtained to step (2) is granulated, wherein PVA
After the quality that adhesive is added is the 9%, aging 25 hours of powder quality, disk is unidirectionally pressed under 240MPa, so
3.5 hours are kept the temperature at 570 DEG C afterwards and excludes PVA adhesives；
(4) sample after step (3) exclusion PVA adhesives is warming up to the heating rate of 3 DEG C/min at 1175 DEG C and is protected
Temperature sinters porcelain into 2.3 hours, obtains unleaded high energy storage density ceramic material；
(5) energy-storing dielectric ceramic obtained is subjected to X-ray diffraction test.Such as Fig. 2, by XRD spectrum it can be seen that this reality
It is perovskite structure to apply the obtained ceramic material of example, has the second a small amount of phase to occur.Fig. 6 show obtained Jie of the present embodiment
The SEM of ceramics schemes, it can be seen that the compact structure of ceramic material；
(6) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room
Temperature tests its ferroelectric properties under 10Hz frequencies, is returned as shown in Figure 10 for the electric hysteresis that the present embodiment ceramic material measures at room temperature
Line carries out energy storage characteristic based on ferroelectric hysteresis loop and can be calculated, and the energy storage density of the unleaded energy-storing dielectric ceramic of the present embodiment is in room temperature
Lower reachable 1.36J/cm3.Jie temperature collection of illustrative plates of the energy storage ceramic material under different test frequencies is as shown in figure 14.At room temperature,
Dielectric constant of the ceramics under four frequencies is between 1500-3000.Within the temperature range of 100~350 DEG C, different frequency
Under dielectric constant declines as temperature increases, and corresponding dielectric loss under four different frequencies respectively less than
0.05.Table 1 is the dielectric property of the unleaded energy-storing dielectric ceramic material of the present embodiment at room temperature.The present embodiment ceramics at room temperature
The maximum disruptive field intensity of material reaches 152kV/cm.And at room temperature at 1 khz, the dielectric constant of 1 ceramics of embodiment is up to
2418。
Embodiment 3
The chemical formula of this example ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x expression molar fractions, and x=0.10.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, includes the following steps：
(1) 0.9 (0.65BaTiO of chemical formula is pressed3-0.35Bi0.5Na0.5TiO3)-0.1SrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5After dispensing, using absolute ethyl alcohol as medium, mixed within 22 hours by ball milling
It closes uniform, is then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 820 DEG C of pre-burnings 4 hours, blocks of solid is obtained, then
Blocks of solid is smashed it through into 120 mesh sieve, obtains unleaded high energy storage ceramic powder；
(2) the pre-burning powder of step (1) is subjected to secondary ball milling refinement；Using absolute ethyl alcohol as medium, ball milling 22.5 hours,
It dried at 100 DEG C, obtain powder after the sieve of 120 mesh excessively；
(3) PVA solution that 8% (mass percent) concentration is added in the powder obtained to step (2) is granulated, wherein PVA
After the quality that adhesive is added is the 10%, aging 26 hours of powder quality, disk is unidirectionally pressed under 230MPa, so
3 hours are kept the temperature at 560 DEG C afterwards and excludes PVA adhesives；
(4) sample after step (3) exclusion PVA adhesives is warming up to the heating rate of 3 DEG C/min at 1150 DEG C and is protected
Temperature sinters porcelain into 2 hours, obtains unleaded high energy storage density ceramic material；
(5) energy-storing dielectric ceramic obtained is subjected to X-ray diffraction test.Such as Fig. 3, by XRD spectrum it can be seen that this reality
It is perovskite structure to apply the obtained ceramic material of example, and has the second a small amount of phase to occur.Fig. 7 is shown obtained by the present embodiment
The SEM of medium ceramic material schemes, it can be seen that the compact structure of ceramic material；
(6) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room
Temperature tests its ferroelectric properties under 10Hz frequencies, is returned as shown in figure 11 for the electric hysteresis that the present embodiment ceramic material measures at room temperature
Line carries out energy storage characteristic based on ferroelectric hysteresis loop and can be calculated, and the energy storage density of the unleaded energy-storing dielectric ceramic of the present embodiment is in room temperature
Lower reachable 1.06J/cm3.Jie temperature collection of illustrative plates of the energy storage ceramic material under different test frequencies is as shown in figure 15.At room temperature,
Dielectric constant of the ceramics under four frequencies is between 1250-1800.Within the temperature range of 100~350 DEG C, different frequency
Under dielectric constant declines as temperature increases, and corresponding dielectric loss under four different frequencies respectively less than
0.05.Table 1 is the dielectric property of the unleaded energy-storing dielectric ceramic material of the present embodiment at room temperature.The present embodiment ceramics at room temperature
The maximum disruptive field intensity of material is 140kV/cm.And at room temperature at 1 khz, the dielectric constant of 1 ceramics of embodiment is up to
1779。
Embodiment 4
The chemical formula of this example ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x expression molar fractions, and x=0.12.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, includes the following steps：
(1) 0.88 (0.65BaTiO of chemical formula is pressed3-0.35Bi0.5Na0.5TiO3)-0.12SrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5After dispensing, using absolute ethyl alcohol as medium, mixed within 21 hours by ball milling
It closes uniform, is then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 800 DEG C of pre-burnings 3.5 hours, blocks of solid is obtained, so
Blocks of solid is smashed it through into 120 mesh sieve afterwards, obtains unleaded high energy storage ceramic powder；
(2) the pre-burning powder of step (1) is subjected to secondary ball milling refinement；Using absolute ethyl alcohol as medium, ball milling 20 hours, in
It dried at 100 DEG C, obtain powder after the sieve of 120 mesh excessively；
(3) PVA solution that 8% (mass percent) concentration is added in the powder obtained to step (2) is granulated, wherein PVA
After the quality that adhesive is added is the 10.5%, aging 27 hours of powder quality, disk is unidirectionally pressed under 220MPa,
Then 3 hours are kept the temperature at 550 DEG C excludes PVA adhesives；
(4) sample after step (3) exclusion PVA adhesives is warming up to the heating rate of 3 DEG C/min at 1125 DEG C and is protected
Temperature sinters porcelain into 2.5 hours, obtains unleaded high energy storage density ceramic material；
(5) energy-storing dielectric ceramic obtained is subjected to X-ray diffraction test.Such as Fig. 4, by XRD spectrum it can be seen that this reality
It is perovskite structure to apply the obtained ceramic material of example, has the second a small amount of phase to occur.Fig. 8 show obtained Jie of the present embodiment
The SEM of ceramics schemes, it can be seen that the compact structure of ceramic material；
(6) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room
Temperature tests its ferroelectric properties under 10Hz frequencies, is returned as shown in figure 12 for the electric hysteresis that the present embodiment ceramic material measures at room temperature
Line carries out energy storage characteristic based on ferroelectric hysteresis loop and can be calculated, and the energy storage density of the unleaded energy-storing dielectric ceramic of the present embodiment is in room temperature
Lower reachable 0.97J/cm3.Jie temperature collection of illustrative plates of the energy storage ceramic material under different test frequencies is as shown in figure 16.At room temperature,
Dielectric constant of the ceramics under four frequencies is between 1250-1800.Within the temperature range of 75~300 DEG C, different frequency
Under dielectric constant declines as temperature increases, and corresponding dielectric loss under four different frequencies respectively less than
0.09.Table 1 is the dielectric property of the unleaded energy-storing dielectric ceramic material of the present embodiment at room temperature.The present embodiment ceramics at room temperature
The maximum disruptive field intensity of material is 141kV/cm.And at room temperature at 1 khz, the dielectric constant of 1 ceramics of embodiment is up to 1628.
The dielectric property of the unleaded energy storage ceramic material of 1 embodiment of table at room temperature
As shown in Table 1, with SrY0.5Nb0.5O3Solid solution capacity is continuously increased, the remaining pole of energy storage ceramic material of the present invention
Change intensity and energy loss density first reduce to be increased afterwards, and electric field shows first increases and then decreases in the ranges of 0.06≤x≤0.12
Trend, higher energy storage density and energy storage efficiency can be obtained under certain proportioning, energy storage density is reachable at room temperature
1.36J/cm3More than；By above example it can be found that control SrY0.5Nb0.5O3Solid solution capacity, effectively overcome mostly
The disadvantage that number ceramic medium material dielectric constant temperature stability is poor, dielectric loss is larger, prepared energy storage ceramic medium
Although the dielectric constant of material is on a declining curve at 60~350 DEG C, and dielectric loss is respectively less than 0.09, is situated between at 60~500 DEG C
Electric constant change rate be less than ± 10%, show excellent temperature stability, be suitable for wider operating temperature, frequency range and
Application field.
Embodiment 5
The chemical formula of this example ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x expression molar fractions, and x=0.07.
The preparation method of above-mentioned unleaded high energy storage density ceramic material, includes the following steps：
(1) 0.93 (0.65BaTiO of chemical formula is pressed3-0.35Bi0.5Na0.5TiO3)-0.07SrY0.5Nb0.5O3It will be analytically pure
BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3And Nb2O5After dispensing, using absolute ethyl alcohol as medium, mixed within 24 hours by ball milling
It closes uniform, is then dried at 100 DEG C, cross 120 mesh sieve, briquetting, then through 830 DEG C of pre-burnings 5 hours, blocks of solid is obtained, then
Blocks of solid is smashed it through into 120 mesh sieve, obtains unleaded high energy storage ceramic powder；
(2) the pre-burning powder of step (1) is subjected to secondary ball milling refinement；Using absolute ethyl alcohol as medium, ball milling 21 hours, in
It dried at 100 DEG C, obtain powder after the sieve of 120 mesh excessively；
(3) PVA solution that 8% (mass percent) concentration is added in the powder obtained to step (2) is granulated, wherein PVA
After the quality that adhesive is added is the 15%, aging 48 hours of powder quality, disk is unidirectionally pressed under 250MPa, so
5 hours are kept the temperature at 580 DEG C afterwards and excludes PVA adhesives；
(4) sample after step (3) exclusion PVA adhesives is warming up to the heating rate of 3 DEG C/min at 1200 DEG C and is protected
Temperature sinters porcelain into 2 hours, obtains unleaded high energy storage density ceramic material；
By example given above, it can be further apparent from present disclosure, but it is not to this hair
Bright restriction.
Claims (10)
1. a kind of preparation method of unleaded high energy storage density ceramic material, which is characterized in that by (1-x) (0.65BaTiO3-
0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3Powder carries out pre-burning, and adhesive is then added after ball milling is granulated, and aging 24
Tabletting after~48 hours, then dumping processing is carried out, it sinters porcelain into, obtains unleaded high energy storage density ceramic material；Wherein x expressions rub
That score, and 0.06≤x≤0.12.
2. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 1, which is characterized in that (1-
x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3Powder is made by following procedure：By chemical formula (1-x)
(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-xSrY0.5Nb0.5O3By BaCO3、Na2CO3, SrCO3, Bi2O3, TiO2, Y2O3With
Nb2O5It after powder weighs dispensing, is uniformly mixed, then sieving, briquetting, then through 800~850 DEG C of pre-burnings 3~5 hours, obtains bulk
Then blocks of solid is smashed it through 120 mesh sieve, obtains (1-x) (0.65BaTiO by solid3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3Powder；Wherein x indicates molar fraction, and 0.06≤x≤0.12.
3. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 2, which is characterized in that mixing
Uniformly detailed process is：It using absolute ethyl alcohol as medium, is carried out by ball milling, and Ball-milling Time is 20~24 hours, ball
Slurry after mill is dried at 100 DEG C.
4. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 1, which is characterized in that pre-burning
Temperature be 800~850 DEG C, the time be 2~3h.
5. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 4, which is characterized in that from room
Temperature is warming up to 800~850 DEG C with the heating rate of 3 DEG C/min.
6. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 1, which is characterized in that tabletting
When pressure be 220~250MPa；The quality that PVA adhesives are added is (1-x) (0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3The 8%~15% of powder quality；The PVA aqueous solutions that adhesive is 8% using mass fraction.
7. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 1, which is characterized in that dumping
Temperature be 500~600 DEG C, the time be 3~5 hours.
8. a kind of preparation method of unleaded high energy storage density ceramic material according to claim 1, which is characterized in that sintering
Temperature be 1100~1200 DEG C, the time be 2~3 hours.
9. a kind of unleaded high energy storage density ceramic material prepared according to any one of claim 1-8 the methods, special
Sign is that the chemical formula of the unleaded high energy storage density ceramic material is：(1-x)(0.65BaTiO3-0.35Bi0.5Na0.5TiO3)-
xSrY0.5Nb0.5O3, wherein x is SrY0.5Nb0.5O3Molar fraction, wherein 0.06≤x≤0.12.
10. a kind of unleaded high energy storage density ceramic material according to claim 9, which is characterized in that the ceramic material exists
At room temperature, energy storage density is 0.97~1.36J/cm3。
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