CN110423111A - A kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof - Google Patents
A kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof Download PDFInfo
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- CN110423111A CN110423111A CN201910697283.2A CN201910697283A CN110423111A CN 110423111 A CN110423111 A CN 110423111A CN 201910697283 A CN201910697283 A CN 201910697283A CN 110423111 A CN110423111 A CN 110423111A
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Abstract
The present invention provides a kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof, the chemical formula of the high energy-storage property lead-free ceramics material of environment-friendly type are as follows: (1-x) BaTiO3‑xK0.73Bi0.09NbO3, wherein 0.02≤x≤0.12.The following steps are included: (1) is by BaCO3、TiO2、K2CO3、Bi2O3And Nb2O5It is uniformly mixed, obtains material powder, briquetting, pre-burning obtain blocks of solid, then blocks of solid is pulverized and sieved, and obtain pre-burning powder；(2) the pre-burning powder that step (1) obtains is obtained into material powder through ball milling；(3) the material powder compression molding for obtaining step (2), reburns and forms porcelain, obtains the high energy-storage property lead-free ceramics material of environment-friendly type.This ceramic material has high dielectric breakdown strength and energy storage density, and has the characteristics such as environmental-friendly, practicability is high.
Description
Technical field
The invention belongs to energy storage ceramic field, the high energy-storage property lead-free ceramics material of specifically a kind of environment-friendly type and its preparation
Method.
Background technique
In recent years, due to non-renewable resources it is continuous consumption and the pollution of environment is got worse, it is renewable environmental protection energy
Source material has been to be concerned by more and more people.Ceramic capacitor is normal with faster charge/discharge speed, biggish dielectric due to it
The advantages that number, temperature limit be wide, long service life, has broad application prospects in pulse power system, and ceramic
Dielectric substance is the critical material for making small-sized, large capacity, high efficiency capacitor, due to high with energy storage density, mechanical
Intensity is high, be widely used in communication suitable for the extreme environments such as high temperature and pressure and steady performance, electronics, automobile and
The various fields such as military project.
Ceramic dielectric material generally comprises linear medium, ferroelectricity medium and anti-ferroelectricity medium.Wherein linear medium
Although having higher dielectric breakdown strength and energy storage efficiency mostly, its minimum polarization intensity causes energy storage density too small, limit
Its practical application is made；Antiferroelectric medium in three kinds of dielectric substances has biggish due to its double ferroelectric hysteresis loop
Energy storage density, but antiferroelectric medium is all containing lead element mostly, the toxicity of lead has very big danger to environment and human health
Many effort have been made to explore lead-free and evade this problem in evil, therefore, people, including study with barium titanate,
Ferroelectric based on bismuth-sodium titanate, but small energy storage density caused by its dielectric breakdown strength is lower limits them in pulse
Practical application in electric system, so improving its energy-storage property as a big heat at this stage by enhancing dielectric breakdown strength
Point.
Summary of the invention
It is an object of the invention to overcome defect existing in the prior art, it is unleaded to provide a kind of high energy-storage property of environment-friendly type
Ceramic material and preparation method thereof, this ceramic material has high dielectric breakdown strength and energy storage density, and has environment
The characteristics such as close friend, practicability height.
The present invention is to be achieved through the following technical solutions:
A kind of high energy-storage property lead-free ceramics material of environment-friendly type, the change of the high energy-storage property lead-free ceramics material of environment-friendly type
Formula are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein 0.02≤x≤0.12.
Preferably, the high energy-storage property lead-free ceramics material of the environment-friendly type is under conditions of room temperature and 10Hz frequency, energy storage
Density is in 1.67~2.51J/cm3Between, energy storage efficiency is between 81.26%~87.15%.
The preparation method of the high energy-storage property lead-free ceramics material of the environment-friendly type, comprising the following steps:
(1) by BaCO3、TiO2、K2CO3、Bi2O3And Nb2O5It is uniformly mixed, obtains material powder, briquetting, pre-burning obtain block
Shape solid, then blocks of solid is pulverized and sieved, obtain pre-burning powder；
(2) the pre-burning powder that step (1) obtains is obtained into material powder through ball milling；
(3) the material powder compression molding for obtaining step (2), reburns and forms porcelain, obtain the high energy-storage property of environment-friendly type without
Lead ceramic material.
Preferably, it in step (1), is uniformly mixed specifically；Ball milling, Ball-milling Time 20 are carried out by medium of dehydrated alcohol
~24 hours, dry after ball milling, sieving.
Preferably, in step (1), pre-burning be 900~950 DEG C pre-burning 2~5 hours.
Preferably, in step (2), for the medium that ball milling uses for dehydrated alcohol, Ball-milling Time is 22~24 hours, after ball milling
It is dried.
Preferably, in step (3), compression molding is specifically the method for using cold isostatic compaction.
Preferably, cold isostatic compaction is to form for pressure maintaining 2~4 minutes under the pressure of 190~210MPa.
Preferably, in step (3), sintering porcelain into is specifically to keep the temperature 3~5 hours at 1200~1275 DEG C.
Compared with prior art, the invention has the following beneficial technical effects:
Material (1-x) BaTiO of the present invention3-xK0.73Bi0.09NbO3, K0.73Bi0.09NbO3Introducing significantly reduce BaTiO3
Average grain size, reached minimum submicron order crystallite dimension, and the reduction of crystallite dimension is to improving dielectric breakdown field
It has a significant impact by force.And K0.73Bi0.09NbO3Introducing so that BaTiO3The Relaxivity of ceramics is improved, and makes
BaTiO3Ferroelectric domain be changed into polar nano microcell, the quick overturning of this nano-scale structures electricdomain is conducive to improve energy storage
Performance.When solid solution capacity is greater than 0.12mol, ceramic crystallite dimension starts to increase, and leads to the reduction of dielectric breakdown field strength, in turn
So that energy-storage property declines, therefore, the present invention is by introducing K0.73Bi0.09NbO3And control K0.73Bi0.09NbO3Solid solution capacity, gram
Most of ceramic medium material dielectric breakdown field strength are taken and energy storage density is lower, dielectric loss is larger disadvantage.In addition, this hair
Bright material density is high, and the temperature stability and frequency stability of energy storage density and energy storage efficiency are excellent, can meet different application
Demand, be expected to make the environmental-friendly energy storage ceramic dielectric material of a new generation.
Further, material of the present invention has obtained the small ferroelectric hysteresis loop of elongated, back-shaped area at room temperature (25 DEG C), obtains
Excellent energy storage density and efficiency, energy storage density reach 1.67~2.51J/cm3, energy storage efficiency reaches 81.26%~
87.15%；And the energy storage density of the high energy-storage property lead-free ceramics material of 3 environment-friendly type of embodiment in the present invention and the temperature of efficiency
It spends stability and frequency stability is good, the energy storage density at 10Hz, 20~100 DEG C, under 180kV/cm electric field strength
It is maintained at 1.09~1.14J/cm3Between, energy storage efficiency is maintained between 78.47%~88.77%；In room temperature, 1~100Hz
Under, the energy storage density under 180kV/cm electric field strength is maintained at 1.13~1.19J/cm3Between, energy storage efficiency is maintained at
Between 81.61%~86.87%, the energy storage density of the high energy-storage property lead-free ceramics material of environment-friendly type in the present invention 20~
It is with good stability in 100 DEG C of temperature ranges and in 1~100Hz frequency range, it is suitable for wider operating temperature, frequency
Range and application field；
Sieving is dried in raw material powder by the present invention after mixing, is then pressed into type, rear to be sintered, and ring can be obtained
The high energy-storage property lead-free ceramics material of guarantor's type.Preparation process of the present invention is simple, it is raw materials used in be free of lead, no pollution to the environment,
And it is raw materials used in be free of rare earth element and precious metal element, cost of material is cheap, be suitble to industrialized production.
Detailed description of the invention
Fig. 1: the XRD spectrum of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 1；
Fig. 2: the XRD spectrum of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 2；
Fig. 3: the XRD spectrum of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3；
Fig. 4: the XRD spectrum of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 4；
Fig. 5: the SEM figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 1；
Fig. 6: the SEM figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 2；
Fig. 7: the SEM figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3；
Fig. 8: the SEM figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 4；
Fig. 9: the ferroelectric hysteresis loop figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 1 at room temperature
(test frequency 10Hz)；
Figure 10: the ferroelectric hysteresis loop figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 2 at room temperature
(test frequency 10Hz)；
Figure 11: the ferroelectric hysteresis loop figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 at room temperature
(test frequency 10Hz)；
Figure 12: the ferroelectric hysteresis loop figure of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 4 at room temperature
(test frequency 10Hz)；
Figure 13: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 25 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 14: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 40 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 15: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 55 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 16: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 70 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 17: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 85 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 18: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is in 100 DEG C and 180kV/cm electric field
Ferroelectric hysteresis loop figure (test frequency 10Hz) under intensity；
Figure 19: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is under room temperature in 1Hz frequency
With the ferroelectric hysteresis loop figure under 180kV/cm electric field strength；
Figure 20: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is under room temperature in 5Hz frequency
With the ferroelectric hysteresis loop figure under 180kV/cm electric field strength；
Figure 21: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is under room temperature in 10Hz frequency
Ferroelectric hysteresis loop figure under rate and 180kV/cm electric field strength；
Figure 22: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is under room temperature in 50Hz frequency
Ferroelectric hysteresis loop figure under rate and 180kV/cm electric field strength；
Figure 23: the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 is under room temperature in 100Hz frequency
Ferroelectric hysteresis loop figure under rate and 180kV/cm electric field strength；
Figure 24: Jie of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 1 under different test frequencies
Warm map；
Figure 25: Jie of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 2 under different test frequencies
Warm map；
Figure 26: Jie of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 3 under different test frequencies
Warm map；
Figure 27: Jie of the high energy-storage property lead-free ceramics material of environment-friendly type prepared by embodiment 4 under different test frequencies
Warm map.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
A kind of high energy-storage property lead-free ceramics material of environment-friendly type, chemical formula are as follows: (1-x) BaTiO3-
xK0.73Bi0.09NbO3, wherein x indicates molar fraction, and 0.02≤x≤0.12.
The ceramic material is under the frequency condition of room temperature and 10Hz, and energy storage density is in 1.67~2.51J/cm3Between, energy storage
Efficiency is between 81.26%~87.15%；At 10Hz, 20~100 DEG C, the high energy-storage property lead-free ceramics of 3 environment-friendly type of embodiment
Energy storage density of the material under 180kV/cm electric field strength is maintained at 1.09~1.14J/cm3Between, energy storage efficiency is maintained at
Between 78.47%~88.77%；At room temperature, 1~100Hz, the high energy-storage property lead-free ceramics material of 3 environment-friendly type of embodiment exists
Energy storage density is maintained at 1.13~1.19J/cm under 180kV/cm electric field strength3Between, energy storage efficiency is maintained at 81.61%~
Between 86.87%.
The preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type of the invention, comprising the following steps:
(1) chemical formula (1-x) BaTiO is pressed3-xK0.73Bi0.09NbO3By analytically pure BaCO3、TiO2、K2CO3、Bi2O3With
Nb2O5Ingredient, wherein x indicates molar fraction, and 0.02≤x≤0.12, small by ball milling 20~24 using dehydrated alcohol as medium
When be uniformly mixed, then at 100 DEG C dry, cross 120 meshes, briquetting, then through 900~950 DEG C pre-burning 3~5 hours, obtain block
Then blocks of solid is smashed it through 120 meshes by shape solid, obtain pre-burning powder；
(2) by the resulting pre-burning powder of step (1) using dehydrated alcohol as medium, ball milling 20~24 hours, then in 100 DEG C
Lower drying obtains material powder after crossing 120 meshes；
(3) by step (2) obtain material powder carry out isostatic cool pressing, wherein the pressure of isostatic cool pressing be 190~
210MPa, dwell time are 2~4 minutes；It is pressed into after disk and sinters porcelain within 3~5 hours in 1200~1275 DEG C of heat preservations,
Obtain the high energy-storage property lead-free ceramics material of the environment-friendly type；
(4) the high energy-storage property lead-free ceramics material of environment-friendly type obtained is subjected to X-ray diffraction test；
(5) 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 different temperatures and frequency, and carries out energy storage characteristic calculating, energy storage density (W1), energy loss density
(W2) and energy storage efficiency (η) calculation formula are as follows:
Wherein W1And W2Respectively indicate energy storage density and energy loss density, PmaxIndicate maximum polarization, PrIndicate surplus
Remaining polarization intensity, E indicate electric field strength, and P indicates polarization intensity, and η indicates energy storage efficiency.
Ball-milling Time is 20~24 hours in step (1), step (2).
The embodiment being given by the following can further be apparent from the contents of the present invention, but it is not to this hair
Bright restriction.
Embodiment 1:
The chemical formula of this example ceramic material are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein x indicates molar fraction, and
X=0.02.
The preparation method of the above-mentioned high energy-storage property lead-free ceramics material of environment-friendly type, comprising the following steps:
(1) chemical formula (1-x) BaTiO is pressed3-xK0.73Bi0.09NbO3By analytically pure BaCO3、TiO2、K2CO3、Bi2O3With
Nb2O5Ingredient, wherein x indicates molar fraction, and x=0.02, using dehydrated alcohol as medium, is uniformly mixed by ball milling 20 hours,
Then dried at 100 DEG C, cross 120 meshes, briquetting, then through 950 DEG C pre-burning 2 hours, obtain blocks of solid, then will be blocky solid
Body smashes it through 120 meshes, obtains pre-burning powder；
(2) by the resulting pre-burning powder of step (1) using dehydrated alcohol as medium, ball milling 24 hours,
Then it is dried at 100 DEG C, obtains material powder after crossing 120 meshes；
(3) material powder for obtaining step (2) carries out isostatic cool pressing, and wherein the pressure of isostatic cool pressing is 190MPa, protects
Pressing the time is 2 minutes；It is pressed into after disk and sinters porcelain within 3 hours in 1275 DEG C of heat preservations, obtain the high energy storage of the environment-friendly type
It can lead-free ceramics material；
(4) the high energy-storage property lead-free ceramics material of environment-friendly type obtained is subjected to X-ray diffraction test, such as Fig. 1, by XRD
Map can be seen that the obtained ceramic material of the present embodiment is pure perovskite structure, be free of other second phases；Fig. 5 show this
The SEM of medium ceramic material obtained by embodiment schemes, it can be seen that the compact structure of ceramic material is lacked without apparent stomata etc.
It falls into；
(5) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room
Its ferroelectric properties is tested under mild 10Hz frequency, the electric hysteresis that the present embodiment ceramic material measures at room temperature is illustrated in figure 9 and returns
Line, carrying out energy storage characteristic by ferroelectric hysteresis loop can be calculated, and the energy storage density of the present embodiment energy storage ceramic at room temperature is reachable
1.67J/cm3, energy storage density is reachable
81.26%.The dielectric property of the unleaded energy storage ceramic material of the present embodiment at room temperature is shown in Table 1.The energy storage ceramic material
Expect that Jie's temperature map under different test frequencies is as shown in figure 24, within the temperature range of -190~175 DEG C, dielectric constant is presented
The trend of first increases and then decreases, and corresponding dielectric loss is respectively less than 0.08 under four different frequencies.
Embodiment 2:
The chemical formula of this example ceramic material are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein x indicates molar fraction, and
X=0.04.
The preparation method of the above-mentioned high energy-storage property lead-free ceramics material of environment-friendly type, comprising the following steps:
(1) chemical formula (1-x) BaTiO is pressed3-xK0.73Bi0.09NbO3By analytically pure BaCO3、TiO2、K2CO3、Bi2O3With
Nb2O5Ingredient, wherein x indicates molar fraction, and x=0.04, using dehydrated alcohol as medium, is uniformly mixed by ball milling 22 hours,
Then dried at 100 DEG C, cross 120 meshes, briquetting, then through 920 DEG C pre-burning 4 hours, obtain blocks of solid, then will be blocky solid
Body smashes it through 120 meshes, obtains pre-burning powder；
(2) the resulting pre-burning powder of step (1) ball milling 22 hours, is then dried at 100 DEG C using dehydrated alcohol as medium
It is dry, material powder is obtained after crossing 120 meshes；
(3) material powder for obtaining step (2) carries out isostatic cool pressing, and wherein the pressure of isostatic cool pressing is 200MPa, protects
Pressing the time is 3 minutes；It is pressed into after disk and sinters porcelain within 4 hours in 1275 DEG C of heat preservations, obtain the high energy storage of the environment-friendly type
It can lead-free ceramics material；
(4) the high energy-storage property lead-free ceramics material of environment-friendly type obtained is subjected to X-ray diffraction test, such as Fig. 2, by XRD
Map can be seen that the obtained ceramic material of the present embodiment is pure perovskite structure, be free of other second phases；Fig. 6 show this
The SEM of medium ceramic material obtained by embodiment schemes, it can be seen that the compact structure of ceramic material is lacked without apparent stomata etc.
It falls into；
(5) 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 frequency, returns as shown in Figure 10 for the electric hysteresis that the present embodiment ceramic material measures at room temperature
Line, carrying out energy storage characteristic by ferroelectric hysteresis loop can be calculated, and the energy storage density of the present embodiment energy storage ceramic at room temperature is reachable
1.94J/cm3, energy storage density is up to 85.40%.See for the dielectric property of the unleaded energy storage ceramic material of the present embodiment at room temperature
Table 1.Jie temperature map of the energy storage ceramic material under different test frequencies is as shown in figure 25, in -190~175 DEG C of temperature model
In enclosing, the trend of first increases and then decreases is presented in dielectric constant, and corresponding dielectric loss is respectively less than under four different frequencies
0.06。
Embodiment 3:
The chemical formula of this example ceramic material are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein x indicates molar fraction, and
X=0.08.
The preparation method of the above-mentioned high energy-storage property lead-free ceramics material of environment-friendly type, comprising the following steps:
(1) chemical formula (1-x) BaTiO is pressed3-xK0.73Bi0.09NbO3By analytically pure BaCO3、TiO2、K2CO3、Bi2O3With
Nb2O5Ingredient, wherein x indicates molar fraction, and x=0.08, using dehydrated alcohol as medium, is uniformly mixed by ball milling 24 hours,
Then dried at 100 DEG C, cross 120 meshes, briquetting, then through 950 DEG C pre-burning 5 hours, obtain blocks of solid, then will be blocky solid
Body smashes it through 120 meshes, obtains pre-burning powder；
(2) the resulting pre-burning powder of step (1) ball milling 24 hours, is then dried at 100 DEG C using dehydrated alcohol as medium
It is dry, material powder is obtained after crossing 120 meshes；
(3) material powder for obtaining step (2) carries out isostatic cool pressing, and wherein the pressure of isostatic cool pressing is 210MPa, protects
Pressing the time is 4 minutes；It is pressed into after disk and sinters porcelain within 5 hours in 1250 DEG C of heat preservations, obtain the high energy storage of the environment-friendly type
It can lead-free ceramics material；
(4) the high energy-storage property lead-free ceramics material of environment-friendly type obtained is subjected to X-ray diffraction test, such as Fig. 3, by XRD
Map can be seen that the obtained ceramic material of the present embodiment is pure perovskite structure, be free of other second phases；Fig. 7 show this
The SEM of medium ceramic material obtained by embodiment schemes, it can be seen that the compact structure of ceramic material is lacked without apparent stomata etc.
It falls into；
(5) 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 frequency, is as shown in figure 11 the present embodiment ceramic material in room temperature and 10Hz frequency condition
Under the ferroelectric hysteresis loop figure that measures, to carry out energy storage characteristic by ferroelectric hysteresis loop can be calculated, and the present embodiment energy storage ceramic is at room temperature
Energy storage density is up to 2.51J/cm3, energy storage density is up to 86.89%.As Figure 13,14,15,16,17,18 show the present embodiment
Energy storage ceramic material under the conditions of 10Hz frequency and 180kV/cm electric field strength respectively 25 DEG C, 40 DEG C, 55 DEG C, 70 DEG C, 85 DEG C,
Ferroelectric hysteresis loop figure at 100 DEG C, carrying out energy storage characteristic by ferroelectric hysteresis loop can be calculated, and the present embodiment energy storage ceramic is in 10Hz frequency
Under temperature range be 25~100 DEG C when, energy storage density is maintained at 1.09~1.14J/cm3Between, change rate be less than ±
4%；Energy storage efficiency is maintained between 78.47%~88.77%, and change rate is less than ± 14%.Such as Figure 19,20,21,22,23
Show the present embodiment energy storage ceramic material under the conditions of room temperature and 180kV/cm electric field strength respectively 1Hz, 5Hz, 10Hz,
Ferroelectric hysteresis loop figure under 50Hz, 100Hz frequency, carrying out energy storage characteristic by ferroelectric hysteresis loop can be calculated, the present embodiment energy storage ceramic
Energy storage density of the material under the conditions of room temperature and 180kV/cm electric field strength is maintained at 1.13~1.19J/cm3Between, variation
Rate is less than ± 6%；Energy storage efficiency is maintained between 81.61%~86.87%, and change rate is less than ± 7%, this shows this implementation
The energy-storage property of example energy storage ceramic material is higher, and shows preferable temperature stability and frequency stability.The present embodiment without
The dielectric property of lead energy storage ceramic material at room temperature is shown in Table 1.Table 2 be the present embodiment energy storage ceramic material in 10Hz frequency and
Dielectric property at 25 DEG C, 40 DEG C, 55 DEG C, 70 DEG C, 85 DEG C, 100 DEG C respectively under the conditions of 180kV/cm electric field strength.Table 3 is
The present embodiment energy storage ceramic material under the conditions of room temperature and 180kV/cm electric field strength respectively 1Hz, 5Hz, 10Hz, 50Hz,
Dielectric property under 100Hz frequency.Jie temperature map of the energy storage ceramic material under different test frequencies is as shown in figure 26,
Within the temperature range of -190~175 DEG C, the trend of first increases and then decreases is presented in dielectric constant, and corresponding dielectric loss exists
0.13 is respectively less than under four different frequencies.
Embodiment 4:
The chemical formula of this example ceramic material are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein x indicates molar fraction, and
X=0.12.
The preparation method of the above-mentioned high energy-storage property lead-free ceramics material of environment-friendly type, comprising the following steps:
(1) chemical formula (1-x) BaTiO is pressed3-xK0.73Bi0.09NbO3By analytically pure BaCO3、TiO2、K2CO3、Bi2O3With
Nb2O5Ingredient, wherein x indicates molar fraction, and x=0.12, using dehydrated alcohol as medium, is uniformly mixed by ball milling 22 hours,
Then dried at 100 DEG C, cross 120 meshes, briquetting, then through 900 DEG C pre-burning 3 hours, obtain blocks of solid, then will be blocky solid
Body smashes it through 120 meshes, obtains pre-burning powder；
(2) the resulting pre-burning powder of step (1) ball milling 24 hours, is then dried at 100 DEG C using dehydrated alcohol as medium
It is dry, material powder is obtained after crossing 120 meshes；
(3) material powder for obtaining step (2) carries out isostatic cool pressing, and wherein the pressure of isostatic cool pressing is 190MPa, protects
Pressing the time is 2 minutes；It is pressed into after disk and sinters porcelain within 3 hours in 1200 DEG C of heat preservations, obtain the high energy storage of the environment-friendly type
It can lead-free ceramics material；
(4) the high energy-storage property lead-free ceramics material of environment-friendly type obtained is subjected to X-ray diffraction test, such as Fig. 4, by XRD
Map can be seen that the obtained ceramic material of the present embodiment is pure perovskite structure, be free of other second phases；Fig. 8 show this
The SEM of medium ceramic material obtained by embodiment schemes, it can be seen that the compact structure of ceramic material is lacked without apparent stomata etc.
It falls into；
(5) 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 frequency, is as shown in figure 12 the present embodiment ceramic material in room temperature and 10Hz frequency condition
Under the ferroelectric hysteresis loop figure that measures, to carry out energy storage characteristic by ferroelectric hysteresis loop can be calculated, and the present embodiment energy storage ceramic is at room temperature
Energy storage density is up to 2.29J/cm3, energy storage density is up to 87.15%.The present embodiment unleaded energy storage ceramic material is at room temperature
Dielectric property is shown in Table 1.Jie temperature map of the energy storage ceramic material under different test frequencies is as shown in figure 27, -190~175
Within the temperature range of DEG C, the trend of first increases and then decreases is presented in dielectric constant, and corresponding dielectric loss is in four different frequencies
0.15 is respectively less than under rate.
Dielectric property of the high energy-storage property lead-free ceramics material of 1 embodiment environment-friendly type of table under the conditions of room temperature and 10Hz
Dielectric of the high energy-storage property lead-free ceramics material of 2 embodiment of table, 3 environment-friendly type under 10Hz frequency and different temperatures is special
Property
The high energy-storage property lead-free ceramics material of 3 embodiment of table, 3 environment-friendly type is special in the dielectric of room temperature condition at different frequencies
Property
By table 1, table 2 and table 3 it is found that with K0.73Bi0.09NbO3Solid solution capacity is continuously increased, energy storage ceramic material of the present invention
The remanent polarization of material constantly reduces, and electric field strength shows the trend constantly increased in the range of 0.02≤x≤0.08,
Higher energy storage density and energy storage efficiency can be obtained under certain proportion, energy storage density and efficiency are reachable respectively at room temperature
2.51J/cm3With 86.89%；3 energy storage ceramic material of embodiment is 10Hz in frequency in the present invention and electric field strength is 180kV/
Under conditions of cm, energy storage density at a temperature of 25~100 DEG C is positively retained at 1.09~1.14J/cm3, and energy storage efficiency with
Temperature raising without biggish reduction occurs, show preferable temperature stability；In addition in room temperature and electric field strength
Under conditions of 180kV/cm, the energy storage density under 1~100Hz frequency is positively retained at 1.13~1.19J/cm3, energy storage efficiency can
It is maintained at 81.61%~86.87%, energy storage density and efficiency show preferable frequency stability without larger fluctuation.It is logical
Above embodiments are crossed it can be found that control K0.73Bi0.09NbO3Solid solution capacity, effectively overcome most of ceramic medium materials
Temperature and the disadvantage that frequency stability is poor, dielectric loss is larger, prepared energy storage ceramic dielectric material show excellent
Temperature and frequency stability are suitable for wider operating temperature, frequency range and application field.
By example given above, the contents of the present invention can be further apparent from, but it is not to this hair
Bright restriction.
Claims (9)
1. a kind of high energy-storage property lead-free ceramics material of environment-friendly type, which is characterized in that the unleaded pottery of the high energy-storage property of environment-friendly type
The chemical formula of ceramic material are as follows: (1-x) BaTiO3-xK0.73Bi0.09NbO3, wherein 0.02≤x≤0.12.
2. the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 1, which is characterized in that the environment-friendly type is high
For energy-storage property lead-free ceramics material under conditions of room temperature and 10Hz frequency, energy storage density is in 1.67~2.51J/cm3Between, storage
Energy efficiency is between 81.26%~87.15%.
3. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type of any of claims 1 or 2, which is characterized in that packet
Include following steps:
(1) by BaCO3、TiO2、K2CO3、Bi2O3And Nb2O5It is uniformly mixed, obtains material powder, briquetting, pre-burning obtain blocky solid
Body, then blocks of solid is pulverized and sieved, obtain pre-burning powder；
(2) the pre-burning powder that step (1) obtains is obtained into material powder through ball milling；
(3) the material powder compression molding for obtaining step (2), reburns and forms porcelain, obtains the unleaded pottery of the high energy-storage property of environment-friendly type
Ceramic material.
4. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that step
Suddenly it in (1), is uniformly mixed specifically；Ball milling is carried out by medium of dehydrated alcohol, Ball-milling Time is 20~24 hours, is done after ball milling
Dry, sieving.
5. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that step
Suddenly in (1), pre-burning be 900~950 DEG C pre-burning 2~5 hours.
6. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that step
Suddenly in (2), for the medium that ball milling uses for dehydrated alcohol, Ball-milling Time is 22~24 hours, is dried after ball milling.
7. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that step
Suddenly in (3), compression molding is specifically the method for using cold isostatic compaction.
8. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that cold
Isostatic pressing is to form for pressure maintaining 2~4 minutes under the pressure of 190~210MPa.
9. the preparation method of the high energy-storage property lead-free ceramics material of environment-friendly type according to claim 3, which is characterized in that step
Suddenly in (3), sintering porcelain into is specifically to keep the temperature 3~5 hours at 1200~1275 DEG C.
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