CN104909744B - A kind of dielectric material and preparation method thereof - Google Patents
A kind of dielectric material and preparation method thereof Download PDFInfo
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- CN104909744B CN104909744B CN201510275559.XA CN201510275559A CN104909744B CN 104909744 B CN104909744 B CN 104909744B CN 201510275559 A CN201510275559 A CN 201510275559A CN 104909744 B CN104909744 B CN 104909744B
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Abstract
The present invention provides a kind of dielectric material, general formula Biz(Bi1/2Na1/2)(1‑x)(1‑y)Mx(1‑y)Ti1‑y/2Mgy/2O3, wherein 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；The present invention passes through in bismuth-sodium titanate (Na1/2Bi1/2TiO3) base ferroelectric material in, magnesium-doped and bismuth simultaneously, so that the dielectric loss of obtained dielectric material greatly reduces, and improve the energy storage density and discharging efficiency of material, and energy storage density and discharging efficiency keep stablizing in wider range, are suitble to especially use as energy storage material at high temperature in wider temperature range.
Description
Technical field
The invention belongs to field of functional materials, a kind of dielectric material and preparation method thereof is related generally to.
Background technology
Capacitor has important application as energy storage device in power adjusting circuit and pulse power circuit, and
Utilize dielectric materials as the capacitor of energy storage medium due to the high velocity of discharge and power density in capacitor area
With unique advantage, moreover, being used to prepare such dielectric material using capacitor other than requiring the velocity of discharge, it is also necessary to
With high energy density (energy stored in the dielectric material of unit volume or weight) and efficiency for charge-discharge, and then can be with
Reduce the volume of circuit or system, reduces weight and reduce capacitor being lost using Process Energy；In addition, capacitor is being answered
When some circuits for such as hybrid power, electric vehicle and aviation, capacitor is generally in relatively high temperature (such as 100-
200 DEG C) under use, deposited therefore, it is also desirable to which dielectric material still maintains relatively good dielectric and energy at a relatively high temperature
Store up performance.
Currently, thin film capacitor using high molecular polymer as dielectric material due to relatively high energy density,
The advantages that high power density and low-dielectric loss and compared and be widely used, still, high molecular polymer is as dielectric material
One disadvantage of material is that the performances such as its dielectric, insulating properties and energy stores will produce deterioration at a relatively high temperature, thus,
High temperature application for capacitor, Inorganic Dielectric Material have certain advantage in terms of the stability of performance.
In Inorganic Dielectric Material, ferroelectric material can generate the polarization response higher than ordinary dielectric material, be conducive to carry
The energy density of high material.However, after since spontaneous polarization turns under the action of electric field when ferroelectric material is in ferroelectric phase, it will
It can keep the state after orientation, so that the energy stored in the material can not release, and reduce workable energy,
Reduce discharging efficiency；Although moreover, ferroelectric material have dielectric properties more higher than ordinary dielectric material, dielectric properties for
Temperature has prodigious dependence, especially change dramatically occurs in the dielectric properties of near Curie temperature material, this needs some
Unfavorable with the high temperature application of more stable dielectric properties.
Bismuth-sodium titanate (Na1/2Bi1/2TiO3) base ferroelectric material due to very strong ferroelectricity, this kind of ferroelectric material room
It is ferroelectric phase that temperature is lower, and dielectric peak temperature is at 300 DEG C or so, however, different from many ferroelectric materials, far below dielectric peak value
Temperature, this kind of material are changed into nonpolar phase by ferroelectric phase；Between phase transition temperature and dielectric peak temperature, dielectric properties
Variation with temperature is than shallower, thus, by a kind of more promising unleaded substitute as lead base piezoelectric material, one
It has been able to more widely study since straight, such as be had been reported that at present by Na1/2Bi1/2TiO3With tetragonal phase BaTiO3(1-x) formed
Na1/2Bi1/2TiO3-xBaTiO3Solid solution, quasi- homotype phase boundary is near the component of x=0.06；Near quasi- homotype phase boundary
Component, in addition to dielectric properties have bigger raising, phase transition temperature is relative to pure Na1/2Bi1/2TiO3There is prodigious drop
It is low, such as 0.92Na1/2Bi1/2TiO3-0.08BaTiO3Phase transition temperature at about 140 DEG C or so, be far below Na1/2Bi1/2TiO3's
Phase transition temperature (~200 DEG C), but dielectric peak temperature still keeps about 300 DEG C or so, so that and the dielectric properties of solid solution exist
It keeps stablizing in broader temperature range, still, the dielectric loss of the dielectric material or bigger, and energy storage density and electric discharge
Efficiency is also relatively low.
Invention content
In view of this, technical problem to be solved by the present invention lies in a kind of dielectric material of offer and preparation method thereof, this
It is smaller to invent the dielectric material dielectric loss provided, and there is high energy storage density and discharging efficiency.
The present invention provides a kind of dielectric materials, have general formula shown in formula (I),
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；
M is one or more of Ba, Ca and Sr.
Preferably, the y is 0.01≤y≤0.80.
Preferably, the y is 0.04≤y≤0.60.
Preferably, the x is 0.01≤x≤0.99.
Preferably, the x is 0.02≤x≤0.20.
Preferably, the z is 0.01≤z≤0.80.
Preferably, the M is one or both of Ba and Ca.
The present invention also provides a kind of preparation methods of dielectric material, including：
The mixture that bismuth source, sodium source, titanium source, magnesium source, the sources M and alcohol medium are mixed to get is obtained by the reaction shown in formula (I)
Dielectric material；
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；
M is one or more of Ba, Ca and Sr.
Preferably, the alcohol medium is one or more of methanol, ethyl alcohol, propyl alcohol and isopropanol.
Preferably, the temperature of the reaction is 800 DEG C~900 DEG C.
Compared with prior art, the present invention provides a kind of dielectric material, general formula Biz(Bi1/2Na1/2)(1-x)(1-y)
Mx(1-y)Ti1-y/2Mgy/2O3, wherein 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；The present invention passes through in bismuth-sodium titanate (Na1/ 2Bi1/2TiO3) base ferroelectric material in, while magnesium-doped and bismuth so that the dielectric loss of obtained dielectric material greatly drops
It is low, and the energy storage density and discharging efficiency of material are improved, and energy storage density and discharging efficiency keep steady in wider range
It is fixed, it is suitble to especially use as energy storage material at high temperature in wider temperature range；The experimental results showed that the present invention provides
Dielectric material at 90 and 150 DEG C, apply the electric field of 8MV/m, discharge energy density is up to 1.1J/cm3, and material has
There is very high discharging efficiency (more than 90%).Even if at 180 DEG C, material still maintains relatively high energy density (about 1J/
cm3) and discharging efficiency (more than 85%), it is suitable as the energy stores dielectric material used under high temperature.
Description of the drawings
Fig. 1 is the X-ray diffractogram of dielectric material prepared by the embodiment of the present invention and comparative example；
Fig. 2 is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature；
Fig. 3 is the ferroelectric hysteresis loop for the dielectric material that the embodiment of the present invention and comparative example provide；
Fig. 4 is typical monopole ferroelectric hysteresis loop；
Fig. 5 is the discharge energy density of the dielectric material that provides of the embodiment of the present invention and comparative example at different temperatures；
Fig. 6 is the discharging efficiency of the dielectric material that provides of the embodiment of the present invention and comparative example at different temperatures；
Fig. 7 is the dielectric material figure that dielectric properties vary with temperature at different frequencies of comparative example 1 of the present invention；
Fig. 8 is the dielectric material figure that dielectric properties vary with temperature at different frequencies of comparative example 2 of the present invention.
Specific implementation mode
The present invention provides a kind of dielectric materials, have general formula shown in formula (I),
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；
M is one or more of Ba, Ca and Sr.
Wherein, the y is preferably 0.01≤y≤0.80, more preferably 0.04≤y≤0.60, and most preferably 0.06≤y≤
0.40, most preferably 0.08≤y≤0.20, most preferably 0.10≤y≤0.14, most preferably 0.10≤y≤0.12；The z
Preferably 0.01≤z≤0.80, more preferably 0.04≤z≤0.60, most preferably 0.06≤z≤0.40, most preferably 0.08
≤ z≤0.20, most preferably 0.10≤z≤0.14, most preferably 0.10≤z≤0.12；The x be preferably 0.01≤x≤
0.99, more preferably 0.02≤x≤0.70, most preferably 0.03≤x≤0.50, most preferably 0.04≤x≤0.30, most preferably
For 0.05≤x≤0.10, most preferably 0.06≤x≤0.08；The M is preferably one or both of Ba and Ca.
The present invention also provides a kind of preparation methods of dielectric material, including：
Dielectric shown in formula (I) is obtained by the reaction in the mixture that bismuth source, sodium source, titanium source, magnesium source, the sources M and alcohol are mixed to get
Material；
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；
M is one or more of Ba, Ca and Sr.
Specifically, formula is obtained by the reaction in the mixture that bismuth source, sodium source, titanium source, magnesium source, the sources M and alcohol are mixed to get by the present invention
(I) dielectric material shown in；
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, the y is preferably 0.01≤y≤0.80, more preferably 0.04≤y≤0.60, and most preferably 0.06≤y≤
0.40, most preferably 0.08≤y≤0.20, most preferably 0.10≤y≤0.14, most preferably 0.10≤y≤0.12, most preferably
For 0.10≤y≤0.12；The z is preferably 0.01≤z≤0.80, more preferably 0.04≤z≤0.60, most preferably 0.06≤
Z≤0.40, most preferably 0.08≤z≤0.20, most preferably 0.10≤z≤0.14, most preferably 0.10≤z≤0.12；Institute
It is preferably 0.01≤x≤0.99 to state x, more preferably 0.02≤x≤0.70, most preferably 0.03≤x≤0.50, most preferably
0.04≤x≤0.30, most preferably 0.05≤x≤0.20, most preferably 0.06≤x≤0.08；The M is preferably in Ba and Ca
One or two.
The bismuth source is preferably bismuth oxide or waltherite；The sodium source is preferably sodium carbonate or sodium bicarbonate；The titanium source
Preferably titanium oxide, the magnesium source are preferably magnesia or magnesium carbonate, and the sources M are preferably the oxide or carbonate of M；It is described
Alcohol is preferably one or more of methanol, ethyl alcohol, propyl alcohol and isopropanol.
The temperature of the mixture reaction is preferably 800~900 DEG C, more preferably 830~880 DEG C, most preferably 850
℃；The time of the reaction is preferably 1~3 hour, more preferably 2~2.5 hours.
And in order to make mixture be sufficiently mixed, preparation method of the present invention preferably before the reaction by mixture elder generation ball milling,
It is dry, it is then reacted under high temperature, obtains dielectric material；Wherein, the present invention is not particularly limited the instrument of ball milling, this field
The time of well known ball milling instrument, the ball milling is preferably 6~8 hours.
The present invention provides a kind of dielectric material, general formula Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3,
In, 0≤x≤1,0 ＜ y≤1,0 ＜ z≤1, z >=y；The present invention passes through to bismuth-sodium titanate (Na1/2Bi1/2TiO3) base ferroelectricity material
Material adulterates Mg at B and adulterates a certain amount of Bi at A simultaneously so that obtained dielectric material has the following advantages：(1) change
Property after material ferroelectric phase and nonpolar phase between phase transition temperature moved to low temperature, and dielectric peak temperature is to high-temperature mobile,
Dielectric properties variation of the material between phase transition temperature and dielectric peak value simultaneously is more gentle so that material is in broader temperature range
Interior dielectric properties keep stablizing, and extend the temperature limit of material；(2) dielectric loss of modified material has bigger
Reduction；(3) it is moved to room temperature due to phase transition temperature so that the dielectric polarization response of modified material at room temperature under the electric field
Hysteresis quality substantially reduce, the similar ferroelectric material or relaxation ferroelectric for being in paraelectric phase of the dielectric properties under high electric field carries
The high energy storage density and discharging efficiency of material；(4) since the dielectric properties of modified material are in wider temperature range
Interior holding is stablized, and energy density and discharging efficiency also keep stablizing in wider temperature range, and material is suitble to wider
Temperature range and relatively high temperature under (such as 180 DEG C) used as energy storage material.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
By Bi2O3, Na2CO3, BaCO3, TiO2, MgO is weighed by stoichiometric ratio needed for formula (I) as raw material and ethyl alcohol
Mixing and ball milling is dried after 6-8 hours, and keeping the temperature 2 hours at 850 DEG C obtains dielectric material shown in formula (I), wherein x 0.08, y
For 0.04, z 0.04.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 4 is dielectric described in embodiment 1
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2；
The ferroelectric hysteresis loop of test sample is waited for using Sawyer-Tower circuit measurings, is as a result that the present invention is implemented referring to Fig. 3, Fig. 3
The ferroelectric hysteresis loop for the dielectric material that example and comparative example provide；
And utilize the discharge energy density and discharging efficiency for measuring obtained ferroelectric hysteresis loop calculating material, specific calculating side
For method referring to Fig. 4, Fig. 4 is typical monopole ferroelectric hysteresis loop, and the area of dash area 1 is the discharge energy density of material in figure, and
The area of the included part of curve in figure and y-axis 2 is by the energy density that is lost during charging and discharging, according to discharge energy
The energy density of density and loss can further calculate out the discharging efficiency of material.
It is described when power-discharging density of the test sample when applying electric field and being 8MV/m see Fig. 5, Fig. 5 be the embodiment of the present invention and
The discharge energy density of the dielectric material that comparative example provides at different temperatures；
It is described when discharging efficiency of the test sample when applying electric field and being 8MV/m see Fig. 6, Fig. 6 be the embodiment of the present invention and
The discharging efficiency of the dielectric material that comparative example provides at different temperatures.
Embodiment 2
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.02, z 0.02.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 3 is the dielectric described in embodiment 2
The X-ray diffractogram of material.
Embodiment 3
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.06, z 0.06.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 5 is dielectric described in embodiment 3
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2；
The ferroelectric hysteresis loop of test sample is waited for using Sawyer-Tower circuit measurings, is as a result that the present invention is implemented referring to Fig. 3, Fig. 3
The ferroelectric hysteresis loop for the dielectric material that example and comparative example provide；
And utilize the discharge energy density and discharging efficiency for measuring obtained ferroelectric hysteresis loop calculating material, specific calculating side
For method referring to Fig. 4, Fig. 4 is typical monopole ferroelectric hysteresis loop, and the area of dash area 1 is the discharge energy density of material in figure, and
The area of the included part of curve in figure and y-axis 2 is by the energy density that is lost during charging and discharging, according to discharge energy
The energy density of density and loss can further calculate out the discharging efficiency of material.
It is described when power-discharging density of the test sample when applying electric field and being 8MV/m see Fig. 5, Fig. 5 be the embodiment of the present invention and
The discharge energy density of the dielectric material that comparative example provides at different temperatures；
It is described when discharging efficiency of the test sample when applying electric field and being 8MV/m see Fig. 6, Fig. 6 be the embodiment of the present invention and
The discharging efficiency of the dielectric material that comparative example provides at different temperatures.
Embodiment 4
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.10, z 0.10.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 6 is the dielectric described in embodiment 4
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2；
The ferroelectric hysteresis loop of test sample is waited for using Sawyer-Tower circuit measurings, is as a result that the present invention is implemented referring to Fig. 3, Fig. 3
The ferroelectric hysteresis loop for the dielectric material that example and comparative example provide；
And utilize the discharge energy density and discharging efficiency for measuring obtained ferroelectric hysteresis loop calculating material, specific calculating side
For method referring to Fig. 4, Fig. 4 is typical monopole ferroelectric hysteresis loop, and the area of dash area 1 is the discharge energy density of material in figure, and
The area of the included part of curve in figure and y-axis 2 is by the energy density that is lost during charging and discharging, according to discharge energy
The energy density of density and loss can further calculate out the discharging efficiency of material.
It is described when power-discharging density of the test sample when applying electric field and being 8MV/m see Fig. 5, Fig. 5 be the embodiment of the present invention and
The discharge energy density of the dielectric material that comparative example provides at different temperatures；
It is described when discharging efficiency of the test sample when applying electric field and being 8MV/m see Fig. 6, Fig. 6 be the embodiment of the present invention and
The discharging efficiency of the dielectric material that comparative example provides at different temperatures.
Embodiment 5
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.12, z 0.12.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 7 is the dielectric described in embodiment 5
The X-ray diffractogram of material.
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Embodiment 6
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.14, z 0.14.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 8 is the dielectric described in embodiment 6
The X-ray diffractogram of material.
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Embodiment 7
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.20, z 0.20
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 9 is the dielectric described in embodiment 7
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Embodiment 8
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.40, z 0.40.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 10 is the dielectric described in embodiment 8
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Embodiment 9
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.60, z 0.60.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 11 is the dielectric described in embodiment 9
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Embodiment 10
Dielectric material shown in formula (I) is prepared according to preparation method described in embodiment 1, wherein x 0.08, y are
0.80, z 0.80.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 12 is Jie described in embodiment 10
The X-ray diffractogram of electric material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2, Fig. 2.
Comparative example 1
By Bi2O3, Na2CO3, BaCO3, TiO2It is dried after 6-8 hours with ethyl alcohol mixing and ball milling after stoichiometrically ratio weighs
It is dry, it keeps the temperature 2 hours at 850 DEG C and obtains dielectric material shown in formula (I), wherein x 0.08, y 0, z 0.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 1 is the dielectric described in comparative example 1
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2 and Fig. 7, Fig. 2
Figure；Fig. 7 is the dielectric material figure that dielectric properties vary with temperature at different frequencies of comparative example 1 of the present invention；
The ferroelectric hysteresis loop of test sample is waited for using Sawyer-Tower circuit measurings, is as a result that the present invention is implemented referring to Fig. 3, Fig. 3
The ferroelectric hysteresis loop for the dielectric material that example and comparative example provide；
And utilize the discharge energy density and discharging efficiency for measuring obtained ferroelectric hysteresis loop calculating material, specific calculating side
For method referring to Fig. 4, Fig. 4 is typical monopole ferroelectric hysteresis loop, and the area of dash area 1 is the discharge energy density of material in figure, and
The area of the included part of curve in figure and y-axis 2 is by the energy density that is lost during charging and discharging, according to discharge energy
The energy density of density and loss can further calculate out the discharging efficiency of material.
It is described when power-discharging density of the test sample when applying electric field and being 8MV/m see Fig. 5, Fig. 5 be the embodiment of the present invention and
The discharge energy density of the dielectric material that comparative example provides at different temperatures；
It is described when discharging efficiency of the test sample when applying electric field and being 8MV/m see Fig. 6, Fig. 6 be the embodiment of the present invention and
The discharging efficiency of the dielectric material that comparative example provides at different temperatures.
Comparative example 2
By Bi2O3, Na2CO3, BaCO3, TiO2, MgO is after stoichiometrically ratio weighs and ethyl alcohol mixing and ball milling 6-8 hours
After dry, keeping the temperature 2 hours at 850 DEG C obtains dielectric material shown in formula (I), wherein x 0.08, y 0.01, z 0.
Composition measuring, the result is shown in Figure 1 are carried out to obtained dielectric material, Fig. 1 is the embodiment of the present invention and comparative example system
The X-ray diffractogram of standby dielectric material, wherein in Fig. 1, the X-ray diffractogram labeled as 2 is the dielectric described in comparative example 2
The X-ray diffractogram of material.
Binder PVA (polyvinyl alcohol) appropriate is added in the dielectric material ball milling that will be obtained, and is pressed into a diameter of 12.7mm circles
Piece after heat treatment removes no-bonder at high temperature, is put into electric furnace at a temperature of 1000-1200 DEG C and keeps the temperature sintering in 1 hour, will
Two surface burning infiltration silver electrodes of the ceramic disks of sintering, obtain waiting for test sample；
The dielectric properties variation with temperature of test sample is waited for using the systematic survey being made of Agilent E4980 and electric furnace, is tied
Fruit is that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature referring to Fig. 2 and Fig. 8, Fig. 2
Figure；Fig. 8 is the dielectric material figure that dielectric properties vary with temperature at different frequencies of comparative example 2 of the present invention.
It summarizes：
Fig. 7 is the non-modified 0.92Na that comparative example 1 provides1/2Bi1/2TiO3-0.08BaTiO3Dielectric material is in difference
Dielectric properties variation with temperature curve under frequency, as shown in Figure 7, the dielectric peak temperature of material is about 300 DEG C；About 140
Dielectric mutation near DEG C corresponds to the phase transformation between ferroelectric phase and nonpolar phase.From the figure it may be seen that in phase transition temperature and Jie
Between electric peak temperature, the dielectric properties of material vary with temperature smaller relative to other temperature ranges.
Fig. 8 is that comparative example 2 provides 0.92Na1/2Bi1/2TiO3-0.08BaTiO3The dielectric material of the magnesium of middle doping 0.5mol%
Expect dielectric properties variation with temperature curve at different frequencies；From the figure it may be seen that the dielectric peak value of the material after doping
Temperature is moved to about 200-250 DEG C to low temperature.Although doping after material in high frequency (such as 1MHz) dielectric loss relative to
Undoped material decreases, but its dielectric loss under low frequency (such as 100Hz) has prodigious raising, it may be possible to by
Caused by the Lacking oxygen formed after magnesium doping, high dielectric loss is unfavorable to the dielectric applications of material.
Fig. 2 is the figure that the dielectric properties for the dielectric material that the embodiment of the present invention and comparative example provide vary with temperature, from
It is as follows that Fig. 2 can be seen that dielectric properties variation with temperature of the material of the additive amount of different magnesium and bismuth at 100Hz, with
The dielectric loss of the increase of the additive amount of magnesium and bismuth, material reduces (at 300 DEG C or less), and phase transition temperature is moved to low temperature, simultaneously
Dielectric peak temperature expands the temperature range between phase transition temperature and dielectric peak temperature to high-temperature mobile, and material is from room
Temperature is to dielectric properties variation within the temperature range of nearly 300 DEG C than shallower, it is seen then that at A while B cation doping magnesium
A certain amount of bismuth is added to compensate the lower valency of magnesium, reduces the formation of Lacking oxygen, can make the high dielectric of material at low frequency
Loss is greatly improved；And it is doped with the material of magnesium and bismuth simultaneously due to features above, so, compare and is suitable as
For the dielectric material used under from room temperature to relatively high temperature.
Fig. 3 is the ferroelectric hysteresis loop for the dielectric material that the embodiment of the present invention and comparative example provide, from figure 3, it can be seen that adding
After adding magnesium and bismuth, the hysteresis quality of the polarization response of material under the electric field has substantial degradation, with the increase of the amount of magnesium and bismuth, electricity
Hysteresis curves are become to compare " thin " thin curve by rectangular, since the area that ferroelectric hysteresis loop is surrounded was being used equal to dielectric material
The energy loss of journey, thus with the increase of additive, the energy loss of material reduces.
In pulse power application, dielectric material can be from the list for measuring material as the energy density of energy storage material
Pole ferroelectric hysteresis loop obtains, that is, the electric field applied on the dielectric material from zero linear increases to maximum value, then linearly reduces
To zero, the polarization response of material under the electric field is measured；Fig. 5 and Fig. 6 is the dielectric material that the embodiment of the present invention and comparative example provide
Material discharge energy density and discharging efficiency at different temperatures, from figs. 5 and 6, it can be seen that with magnesium and bismuth additive amount
Increase, the energy density and discharging efficiency of material also improve a lot, and these performance variation with temperature ease up, example
Such as：For Biz(Bi1/2Na1/2)(1-x)(1-y)Bax(1-y)Ti1-y/2Mgy/2O3(x=0.08, y=0.10, z=0.10) ceramics, 90
At 150 DEG C, apply the electric field of 8MV/m, discharge energy density is up to 1.1J/cm3, and there is material very high electric discharge to imitate
Rate (more than 90%).Even if at 180 DEG C, material still maintains relatively high energy density (about 1J/cm3) and discharging efficiency
(more than 85%) is suitble to the energy stores dielectric material under as high temperature.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (4)
1. a kind of dielectric material suitable for as energy storage material under high temperature has general formula shown in formula (I),
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0.08 x, y 0.02,0.04,0.06,0.10,0.12,0.14,0.20,0.40,0.60 or 0.80, z=y；
M is Ba.
2. a kind of preparation method of dielectric material, including：
Dielectric shown in formula (I) is obtained by the reaction in the mixture that bismuth source, sodium source, titanium source, magnesium source, the sources M and alcohol medium are mixed to get
Material；
Biz(Bi1/2Na1/2)(1-x)(1-y)Mx(1-y)Ti1-y/2Mgy/2O3Formula (I)；
Wherein, 0.08 x, y 0.02,0.04,0.06,0.10,0.12,0.14,0.20,0.40,0.60 or 0.80, z=y；
M is Ba.
3. preparation method according to claim 2, which is characterized in that the alcohol medium is methanol, ethyl alcohol, propyl alcohol and isopropyl
One or more of alcohol.
4. preparation method according to claim 2, which is characterized in that the temperature of the reaction is 800 DEG C~900 DEG C.
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