CN104909744A - Dielectric material and preparation method thereof - Google Patents

Dielectric material and preparation method thereof Download PDF

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CN104909744A
CN104909744A CN201510275559.XA CN201510275559A CN104909744A CN 104909744 A CN104909744 A CN 104909744A CN 201510275559 A CN201510275559 A CN 201510275559A CN 104909744 A CN104909744 A CN 104909744A
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dielectric materials
dielectric
temperature
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CN104909744B (en
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初宝进
陈攀
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

The invention provides a dielectric material with a general formula of Bi<z>(Bi<1/2>Na<1/2>)<(1-x)(1-y)>M<x(1-y)>Ti<1-y/2>Mg<y/2>O3, wherein x is no less than 0 and no more than 1, y is more than 0 and no more than 1, z is more than 0 and no more than 1, and z is no less than y. According to the invention, since magnesium and bismuth are simultaneously doped in a sodium bismuth titanate-based (Na<1/2>Bi<1/2>TiO3) ferroelectric material, the dielectric loss of the prepared dielectric material is substantially reduced and the energy storage density and discharging efficiency of the material are improved and maintain stable in a wide range; and the prepared dielectric material is applicable as an energy storage material in a wide temperature scope, especially at a high temperature.

Description

A kind of dielectric materials and preparation method thereof
Technical field
The invention belongs to field of functional materials, relate generally to a kind of dielectric materials and preparation method thereof.
Background technology
Electrical condenser has important application as energy storage device in power adjusting circuit and pulse power circuit, and utilize dielectric materials to have unique advantage as the electrical condenser of energy storage medium owing to having the high velocity of discharge and power density at capacitor area, and, answer the dielectric materials of electricity container except requiring the velocity of discharge for the preparation of this kind, also need to have high energy density (i.e. the energy stored in the dielectric materials of unit volume or weight) and efficiency for charge-discharge, and then the volume of circuit or system can be reduced, reduce weight and reduce electrical condenser in use procedure energy waste, in addition, electrical condenser is when being applied to some circuit as hybrid power, electromobile and aviation, electrical condenser generally uses at higher temperature (such as 100-200 DEG C), therefore, dielectric materials is also needed still to keep reasonable dielectric and stored energy performance at a relatively high temperature.
At present, used more widely using high molecular polymer as the film capacitor of dielectric materials owing to having the advantages such as higher energy density, high power density and low-dielectric loss, but, as a shortcoming of dielectric materials, high molecular polymer is that the performances such as its dielectric, insulativity and stored energy can produce deterioration at a relatively high temperature, thus, high temperature for electrical condenser is applied, and Inorganic Dielectric Material has certain advantage in the stability of performance.
In Inorganic Dielectric Material, ferroelectric material can produce the polarization response higher than ordinary dielectric material, is conducive to the energy density improving material.But, after spontaneous polarization turns under the effect of electric field when ferroelectric material is in ferroelectric phase, the state after orientation will be kept, make the energy stored in the material to discharge like this, decrease spendable energy, reduce discharging efficiency; And, although ferroelectric material has the dielectric properties higher than ordinary dielectric material, but dielectric properties have very large dependency for temperature, especially occur sharply changing in the dielectric properties of near Curie temperature material, this needs the high temperature application with more stable dielectric properties to be disadvantageous for some.
Bismuth-sodium titanate (Na 1/2bi 1/2tiO 3) ferroelectric material of base is owing to having very strong ferroelectricity, be ferroelectric phase under this kind of ferroelectric material room temperature, dielectric peak temperature is at about 300 DEG C, but, different from a lot of ferroelectric material, far below dielectric peak temperature, this kind of material changes nonpolar phase into by ferroelectric phase; Between phase transition temperature and dielectric peak temperature, its dielectric properties variation with temperature is relatively milder, and thus, it, by the more promising unleaded surrogate of one as lead base piezoelectric, is able to study more widely all the time, as having report at present by Na 1/2bi 1/2tiO 3with Tetragonal BaTiO 3(1-x) Na formed 1/2bi 1/2tiO 3-xBaTiO 3sosoloid, its accurate homotype phase boundary is near the component of x=0.06; Component near accurate homotype phase boundary, except dielectric properties have larger raising, its transformation temperature is relative to pure Na 1/2bi 1/2tiO 3have substantial degradation, such as 0.92Na 1/2bi 1/2tiO 3-0.08BaTiO 3transformation temperature at about about 140 DEG C, far below Na 1/2bi 1/2tiO 3transformation temperature (~ 200 DEG C), but dielectric peak temperature still keeps about about 300 DEG C, make the dielectric properties of sosoloid in wider temperature range, keep stable like this, but, the dielectric loss of this dielectric materials is still larger, and energy storage density and discharging efficiency are also lower.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of dielectric materials and preparation method thereof, and dielectric materials dielectric loss provided by the invention is less, and has high energy storage density and discharging efficiency.
The invention provides a kind of dielectric materials, there is general formula shown in formula (I),
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
Preferably, described y is 0.01≤y≤0.80.
Preferably, described y is 0.04≤y≤0.60.
Preferably, described x is 0.01≤x≤0.99.
Preferably, described x is 0.02≤x≤0.20.
Preferably, described z is 0.01≤z≤0.80.
Preferably, described M is one or both in Ba and Ca.
Present invention also offers a kind of preparation method of dielectric materials, comprising:
The mixture reaction that bismuth source, sodium source, titanium source, magnesium source, M source and alcohol medium are mixed to get is obtained the dielectric materials shown in formula (I);
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
Preferably, described alcohol medium is one or more in methyl alcohol, ethanol, propyl alcohol and Virahol.
Preferably, the temperature of described reaction is 800 DEG C ~ 900 DEG C.
Compared with prior art, the invention provides a kind of dielectric materials, general formula is Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3, wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z>=y; The present invention passes through at bismuth-sodium titanate (Na 1/2bi 1/2tiO 3) base ferroelectric material in, magnesium-doped and bismuth simultaneously, the dielectric loss of the dielectric materials obtained is reduced greatly, and improve energy storage density and the discharging efficiency of material, and energy storage density and discharging efficiency keep stable in wider scope, are adapted at wide temperature range and especially at high temperature use as energy storage material; Experimental result shows, dielectric materials provided by the invention is at 90 and 150 DEG C, and apply the electric field of 8MV/m, its discharge energy density can reach 1.1J/cm 3, and material has very high discharging efficiency (more than 90%).Even if at 180 DEG C, material still remains higher energy density (about 1J/cm 3) and discharging efficiency (more than 85%), the stored energy dielectric materials used under being suitable as high temperature.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of dielectric materials prepared by the embodiment of the present invention and comparative example;
The temperature variant figure of dielectric properties of the dielectric materials that Fig. 2 provides for the embodiment of the present invention and comparative example;
The ferroelectric hysteresis loop of the dielectric materials that Fig. 3 provides for the embodiment of the present invention and comparative example;
Fig. 4 is typical one pole ferroelectric hysteresis loop;
The dielectric materials discharge energy density at different temperatures that Fig. 5 provides for the embodiment of the present invention and comparative example;
The dielectric materials discharging efficiency at different temperatures that Fig. 6 provides for the embodiment of the present invention and comparative example;
Fig. 7 is the dielectric materials temperature variant figure of dielectric properties at different frequencies of comparative example 1 of the present invention;
Fig. 8 is the dielectric materials temperature variant figure of dielectric properties at different frequencies of comparative example 2 of the present invention.
Embodiment
The invention provides a kind of dielectric materials, there is general formula shown in formula (I),
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
Wherein, described y is preferably 0.01≤y≤0.80, is more preferably 0.04≤y≤0.60, most preferably is 0.06≤y≤0.40, most preferably is 0.08≤y≤0.20, most preferably is 0.10≤y≤0.14, most preferably is 0.10≤y≤0.12; Described z is preferably 0.01≤z≤0.80, is more preferably 0.04≤z≤0.60, most preferably is 0.06≤z≤0.40, most preferably is 0.08≤z≤0.20, most preferably is 0.10≤z≤0.14, most preferably is 0.10≤z≤0.12; Described x is preferably 0.01≤x≤0.99, is more preferably 0.02≤x≤0.70, most preferably is 0.03≤x≤0.50, most preferably is 0.04≤x≤0.30, most preferably is 0.05≤x≤0.10, most preferably is 0.06≤x≤0.08; Described M be preferably in Ba and Ca one or both.
Present invention also offers a kind of preparation method of dielectric materials, comprising:
The mixture reaction that bismuth source, sodium source, titanium source, magnesium source, M source and alcohol are mixed to get is obtained the dielectric materials shown in formula (I);
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
Concrete, the mixture reaction that bismuth source, sodium source, titanium source, magnesium source, M source and alcohol are mixed to get is obtained the dielectric materials shown in formula (I) by the present invention;
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, described y is preferably 0.01≤y≤0.80, is more preferably 0.04≤y≤0.60, most preferably be 0.06≤y≤0.40, most preferably be 0.08≤y≤0.20, most preferably be 0.10≤y≤0.14, most preferably be 0.10≤y≤0.12, most preferably be 0.10≤y≤0.12; Described z is preferably 0.01≤z≤0.80, is more preferably 0.04≤z≤0.60, most preferably is 0.06≤z≤0.40, most preferably is 0.08≤z≤0.20, most preferably is 0.10≤z≤0.14, most preferably is 0.10≤z≤0.12; Described x is preferably 0.01≤x≤0.99, is more preferably 0.02≤x≤0.70, most preferably is 0.03≤x≤0.50, most preferably is 0.04≤x≤0.30, most preferably is 0.05≤x≤0.20, most preferably is 0.06≤x≤0.08; Described M be preferably in Ba and Ca one or both.
Described bismuth source is preferably bismuth oxide or Bismuth carbonate; Described sodium source is preferably sodium carbonate or sodium bicarbonate; Described titanium source is preferably titanium oxide, and described magnesium source is preferably magnesium oxide or magnesiumcarbonate, and described M source is preferably oxide compound or the carbonate of M; Described alcohol is preferably one or more in methyl alcohol, ethanol, propyl alcohol and Virahol.
The temperature of described mixture reaction is preferably 800 ~ 900 DEG C, is more preferably 830 ~ 880 DEG C, most preferably is 850 DEG C; The time of described reaction is preferably 1 ~ 3 hour, is more preferably 2 ~ 2.5 hours.
And in order to make mixture fully mix, preparation method of the present invention is preferably before the reaction by first for mixture ball milling, dry, then reacts under high temperature, obtains dielectric materials; Wherein, the instrument of the present invention to ball milling is not particularly limited, ball milling instrument well known in the art, and the time of described ball milling is preferably 6 ~ 8 hours.
The invention provides a kind of dielectric materials, general formula is Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3, wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z>=y; The present invention passes through bismuth-sodium titanate (Na 1/2bi 1/2tiO 3) ferroelectric material of base is at B position doped with Mg and a certain amount of Bi that simultaneously adulterates in A position, make having the following advantages of the dielectric materials obtained: the transformation temperature between the ferroelectric phase of (1) modified material and nonpolar phase moves to low temperature, and dielectric peak temperature is to high-temperature mobile, the dielectric properties of material between transformation temperature and dielectric peak value change more mild simultaneously, make the dielectric properties of material in wider temperature range keep stable, extend the temperature limit of material; (2) dielectric loss of modified material has larger reduction; (3) because transformation temperature moves to room temperature, make modified material at room temperature under the electric field dielectric depolarization response hysteresis quality greatly reduce, similar ferroelectric material or the relaxation ferroelectric being in paraelectric phase of dielectric properties under its high electric field, improves energy storage density and the discharging efficiency of material; (4) because the dielectric properties of modified material are more stable than maintenance in wide temperature range, its energy density and discharging efficiency are also keeping stable than wide temperature range, and material is adapted at using as energy storage material than (such as 180 DEG C) under wide temperature range and higher temperature.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, and obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
By Bi 2o 3, Na 2cO 3, BaCO 3, TiO 2, MgO weighs by the required stoichiometric ratio of formula (I) as raw material, and ethanol mixing and ball milling 6-8 hour post-drying, within 2 hours, obtains the dielectric materials shown in formula (I) 850 DEG C of insulations, and wherein, x is 0.08, y be 0.04, z is 0.04.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 4 is the dielectric materials described in embodiment 1.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2;
Sawyer-Tower circuit measuring is utilized to treat the ferroelectric hysteresis loop of test sample, the ferroelectric hysteresis loop of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 3, Fig. 3;
And utilize the discharge energy density and discharging efficiency of measuring the ferroelectric hysteresis loop Calculating material obtained, its circular is see Fig. 4, Fig. 4 is typical one pole ferroelectric hysteresis loop, in figure, the area of dash area 1 is the discharge energy density of material, and curve in figure and y-axis comprise the energy density of area for institute's loss in charging and discharging process of part 2, according to the energy density of discharge energy density and loss, the discharging efficiency of material can be calculated further.
Described sees Fig. 5, the dielectric materials discharge energy density at different temperatures that Fig. 5 provides for the embodiment of the present invention and comparative example until the discharge density of test sample when applying electric field is 8MV/m;
Described sees Fig. 6, the dielectric materials discharging efficiency at different temperatures that Fig. 6 provides for the embodiment of the present invention and comparative example until the discharging efficiency of test sample when applying electric field is 8MV/m.
Embodiment 2
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.02, z is 0.02.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 3 is the dielectric materials described in embodiment 2.
Embodiment 3
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.06, z is 0.06.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 5 is the dielectric materials described in embodiment 3.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2;
Sawyer-Tower circuit measuring is utilized to treat the ferroelectric hysteresis loop of test sample, the ferroelectric hysteresis loop of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 3, Fig. 3;
And utilize the discharge energy density and discharging efficiency of measuring the ferroelectric hysteresis loop Calculating material obtained, its circular is see Fig. 4, Fig. 4 is typical one pole ferroelectric hysteresis loop, in figure, the area of dash area 1 is the discharge energy density of material, and curve in figure and y-axis comprise the energy density of area for institute's loss in charging and discharging process of part 2, according to the energy density of discharge energy density and loss, the discharging efficiency of material can be calculated further.
Described sees Fig. 5, the dielectric materials discharge energy density at different temperatures that Fig. 5 provides for the embodiment of the present invention and comparative example until the discharge density of test sample when applying electric field is 8MV/m;
Described sees Fig. 6, the dielectric materials discharging efficiency at different temperatures that Fig. 6 provides for the embodiment of the present invention and comparative example until the discharging efficiency of test sample when applying electric field is 8MV/m.
Embodiment 4
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.10, z is 0.10.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 6 is the dielectric materials described in embodiment 4.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2;
Sawyer-Tower circuit measuring is utilized to treat the ferroelectric hysteresis loop of test sample, the ferroelectric hysteresis loop of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 3, Fig. 3;
And utilize the discharge energy density and discharging efficiency of measuring the ferroelectric hysteresis loop Calculating material obtained, its circular is see Fig. 4, Fig. 4 is typical one pole ferroelectric hysteresis loop, in figure, the area of dash area 1 is the discharge energy density of material, and curve in figure and y-axis comprise the energy density of area for institute's loss in charging and discharging process of part 2, according to the energy density of discharge energy density and loss, the discharging efficiency of material can be calculated further.
Described sees Fig. 5, the dielectric materials discharge energy density at different temperatures that Fig. 5 provides for the embodiment of the present invention and comparative example until the discharge density of test sample when applying electric field is 8MV/m;
Described sees Fig. 6, the dielectric materials discharging efficiency at different temperatures that Fig. 6 provides for the embodiment of the present invention and comparative example until the discharging efficiency of test sample when applying electric field is 8MV/m.
Embodiment 5
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.12, z is 0.12.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 7 is the dielectric materials described in embodiment 5.
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Embodiment 6
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.14, z is 0.14.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 8 is the dielectric materials described in embodiment 6.
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Embodiment 7
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.20, z is 0.20
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 9 is the dielectric materials described in embodiment 7.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Embodiment 8
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.40, z is 0.40.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 10 is the dielectric materials described in embodiment 8.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Embodiment 9
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.60, z is 0.60.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 11 is the dielectric materials described in embodiment 9.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Embodiment 10
Prepare the dielectric materials shown in formula (I) according to the preparation method described in embodiment 1, wherein, x is 0.08, y be 0.80, z is 0.80.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 12 is the dielectric materials described in embodiment 10.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2, Fig. 2.
Comparative example 1
By Bi 2o 3, Na 2cO 3, BaCO 3, TiO 2after stoichiometrically ratio weighs and ethanol mixing and ball milling 6-8 hour post-drying, within 2 hours, obtain the dielectric materials shown in formula (I) 850 DEG C of insulations, wherein, x is 0.08, y be 0, z is 0.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 1 is the dielectric materials described in comparative example 1.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2 and Fig. 7, Fig. 2; Fig. 7 is the dielectric materials temperature variant figure of dielectric properties at different frequencies of comparative example 1 of the present invention;
Sawyer-Tower circuit measuring is utilized to treat the ferroelectric hysteresis loop of test sample, the ferroelectric hysteresis loop of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 3, Fig. 3;
And utilize the discharge energy density and discharging efficiency of measuring the ferroelectric hysteresis loop Calculating material obtained, its circular is see Fig. 4, Fig. 4 is typical one pole ferroelectric hysteresis loop, in figure, the area of dash area 1 is the discharge energy density of material, and curve in figure and y-axis comprise the energy density of area for institute's loss in charging and discharging process of part 2, according to the energy density of discharge energy density and loss, the discharging efficiency of material can be calculated further.
Described sees Fig. 5, the dielectric materials discharge energy density at different temperatures that Fig. 5 provides for the embodiment of the present invention and comparative example until the discharge density of test sample when applying electric field is 8MV/m;
Described sees Fig. 6, the dielectric materials discharging efficiency at different temperatures that Fig. 6 provides for the embodiment of the present invention and comparative example until the discharging efficiency of test sample when applying electric field is 8MV/m.
Comparative example 2
By Bi 2o 3, Na 2cO 3, BaCO 3, TiO 2, MgO is after stoichiometrically ratio weighs and ethanol mixing and ball milling 6-8 hour post-drying, and within 2 hours, obtain the dielectric materials shown in formula (I) 850 DEG C of insulations, wherein, x is 0.08, y be 0.01, z is 0.
Composition measuring is carried out to the dielectric materials obtained, the results are shown in Figure the X-ray diffractogram that 1, Fig. 1 is dielectric materials prepared by the embodiment of the present invention and comparative example, wherein, in Fig. 1, the X-ray diffractogram that the X-ray diffractogram being labeled as 2 is the dielectric materials described in comparative example 2.
By the dielectric materials ball milling obtained, add suitable binding agent PVA (polyvinyl alcohol), being pressed into diameter is 12.7mm disk, at high temperature thermal treatment is except after no-bonder, put into electric furnace at the temperature of 1000-1200 DEG C, be incubated 1 hour sintering, by two surperficial burning infiltration silver electrodes of the ceramic disks of sintering, obtain treating test sample;
The systematic survey be made up of Agilent E4980 and electric furnace is utilized to treat the dielectric properties variation with temperature of test sample, the temperature variant figure of dielectric properties of the dielectric materials that result provides for the embodiment of the present invention and comparative example see Fig. 2 and Fig. 8, Fig. 2; Fig. 8 is the dielectric materials temperature variant figure of dielectric properties at different frequencies of comparative example 2 of the present invention.
Sum up:
The 0.92Na of the non-modified that Fig. 7 provides for comparative example 1 1/2bi 1/2tiO 3-0.08BaTiO 3dielectric materials dielectric properties variation with temperature curve at different frequencies, as shown in Figure 7, the dielectric peak temperature of material is about 300 DEG C; Dielectric sudden change near about 140 DEG C corresponds to the phase transformation between ferroelectric phase and nonpolar phase.Can see from figure, between transformation temperature and dielectric peak temperature, the dielectric properties of material vary with temperature less relative to other temperature range.
Fig. 8 provides 0.92Na for comparative example 2 1/2bi 1/2tiO 3-0.08BaTiO 3the dielectric materials dielectric properties variation with temperature curve at different frequencies of the magnesium of middle doping 0.5mol%; Can see from figure, the dielectric peak temperature of the material after doping moves to about 200-250 DEG C to low temperature.Although the dielectric loss of material (such as 1MHz) in high frequency decreases relative to unadulterated material after doping, but its dielectric loss under low frequency (such as 100Hz) has very large rising, may be that the dielectric applications of high dielectric loss to material is disadvantageous because the Lacking oxygen of formation after magnesium doping causes.
The temperature variant figure of dielectric properties of the dielectric materials that Fig. 2 provides for the embodiment of the present invention and comparative example, as can be seen from Figure 2, the dielectric properties variation with temperature of material under 100Hz of the addition of different magnesium and bismuth is as follows, along with the increase of the addition of magnesium and bismuth, the dielectric loss of material reduces (below 300 DEG C), transformation temperature moves to low temperature, dielectric peak temperature is to high-temperature mobile simultaneously, expand the temperature range between transformation temperature and dielectric peak temperature, and material is milder to dielectric properties change in the temperature range of nearly 300 DEG C from room temperature, visible, a certain amount of bismuth is added in A position to compensate the lower valency of magnesium while the cation doping magnesium of B position, reduce the formation of Lacking oxygen, material high dielectric loss at low frequency can be made to be improved greatly, and the material being doped with magnesium and bismuth is owing to having above feature simultaneously, so, compare the dielectric materials being suitable as and using from room temperature to higher temperature.
The ferroelectric hysteresis loop of the dielectric materials that Fig. 3 provides for the embodiment of the present invention and comparative example, as can be seen from Figure 3, after adding magnesium and bismuth, the hysteresis quality of material polarization response under the electric field has substantial degradation, along with the increase of the amount of magnesium and bismuth, ferroelectric hysteresis loop compares " thin " thin curve by square becoming, and the area surrounded due to ferroelectric hysteresis loop equals the energy waste of dielectric materials in use procedure, thus along with the increase of additive, the energy waste of material reduces.
In pulse power application, dielectric materials can obtain from the one pole ferroelectric hysteresis loop measuring material as the energy density of energy storage material, namely apply electric field on the dielectric material and be increased to maximum value from zero linear, be then reduced to zero linearly, measure material polarization response under the electric field; The dielectric materials that Fig. 5 and Fig. 6 provides for the embodiment of the present invention and comparative example discharge energy density at different temperatures and discharging efficiency, as can be seen from Fig. 5 and Fig. 6, along with the increase of magnesium and bismuth addition, energy density and the discharging efficiency of material also improve a lot, and these performance variation with temperature ease up, such as: for Bi z(Bi 1/2na 1/2) (1-x) (1-y)ba x (1-y)ti 1-y/2mg y/2o 3(x=0.08, y=0.10, z=0.10) pottery, at 90 and 150 DEG C, apply the electric field of 8MV/m, its discharge energy density can reach 1.1J/cm 3, and material has very high discharging efficiency (more than 90%).Even if at 180 DEG C, material still remains higher energy density (about 1J/cm 3) and discharging efficiency (more than 85%), be adapted at as the stored energy dielectric materials under high temperature.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (10)

1. a dielectric materials, has general formula shown in formula (I),
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
2. material according to claim 1, is characterized in that, described y is 0.01≤y≤0.80.
3. material according to claim 1, is characterized in that, described y is 0.04≤y≤0.60.
4. material according to claim 1, is characterized in that, described x is 0.01≤x≤0.99.
5. material according to claim 1, is characterized in that, described x is 0.02≤x≤0.20.
6. material according to claim 1, is characterized in that, described z is 0.01≤z≤0.80.
7. material according to claim 1, is characterized in that, described M is one or both in Ba and Ca.
8. a preparation method for dielectric materials, comprising:
The mixture reaction that bismuth source, sodium source, titanium source, magnesium source, M source and alcohol medium are mixed to get is obtained the dielectric materials shown in formula (I);
Bi z(Bi 1/2na 1/2) (1-x) (1-y)m x (1-y)ti 1-y/2mg y/2o 3formula (I);
Wherein, 0≤x≤1,0 < y≤1,0 < z≤1, z >=y;
M is one or more in Ba, Ca and Sr.
9. preparation method according to claim 8, is characterized in that, described alcohol medium is one or more in methyl alcohol, ethanol, propyl alcohol and Virahol.
10. preparation method according to claim 8, is characterized in that, the temperature of described reaction is 800 DEG C ~ 900 DEG C.
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CN109180181A (en) * 2018-09-28 2019-01-11 西安交通大学 A kind of unleaded relaxation antiferroelectric ceramics energy storage material and preparation method thereof
CN109180181B (en) * 2018-09-28 2020-10-27 西安交通大学 Lead-free relaxation antiferroelectric ceramic energy storage material and preparation method thereof
CN109320236A (en) * 2018-11-09 2019-02-12 同济大学 A kind of composite material and preparation method of high energy storage density and charge-discharge performance
CN109320236B (en) * 2018-11-09 2021-09-03 同济大学 Composite material with high energy storage density and charge-discharge performance and preparation method thereof

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