CN109180178A - A kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and preparation method thereof - Google Patents
A kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of a kind of high energy storage density and preparation method thereof, the chemical composition of the barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material are as follows: (1-x) (Ba0.55Sr0.45)TiO3‑xBi(Mg2/3Nb1/3)O3, wherein 0 x≤0.15 <.
Description
Technical field
The present invention relates to a kind of unleaded energy storage ceramic materials, and in particular to a kind of barium-strontium titanate-based unleaded relaxation of high energy storage density
Henan ferroelectric ceramics and preparation method thereof belongs to function ceramics field.
Background technique
With development in science and technology, the application field of Pulse Power Techniques is more and more wide.Pulse Power Techniques are
Energy stores are got up with more slow speed by means of lower wattage power supply, then pass through pulse power system for these energy pressures
It shortens high power pulse into, (can be to nanosecond) can then be discharged into specific load in a short period of time.Due to pulse function
Rate technology is constantly subjected to the restriction of energy storage technology, therefore electric energy storage material receives more and more attention in recent years.Energy storage material
Covering scope is very extensive, including fuel cell, lithium ion battery, electric chemical super capacitor and electrostatic condenser etc..Although
All kinds of batteries have very high energy storage density, but are constrained to the more slow electric charge carrier of their migration velocities, output work
Rate is all lower；Dielectric capacitor storage energy by the polarization response under external electric field, is able to achieve electric energy in the form of electrostatic charge
It is directly stored in two-plate, which is not related to the diffusion of substance, therefore has high charge/discharge speed, to have very
High output power density.
Currently, the dielectric for energy-storage capacitor can be divided mainly into ceramics and two class of polymer.Polymer Yin Qigao's
Dielectric breakdown strength and there is high energy storage density, but melting point polymer is low, and dielectric properties decline under high temperature；Ceramics have
Unique mechanically and chemically stability can be suitable for the extreme environments such as high temperature and pressure.Ceramic dielectric is not according under the electric field
Same polarization response mechanism, and it is divided into four classes: linear medium, ferroelectric media, relaxor ferroelectric medium and antiferroelectric medium.Linear electricity
The polarization intensity of medium increases with dispatch from foreign news agency vertical linearity, and dielectric constant is held essentially constant, and usually has high dielectric breakdown strength
And low-dielectric loss, but polarization intensity is smaller, is unfavorable for energy storage；Ferroelectric media has biggish spontaneous polarization strength and moderate
Dielectric breakdown strength, but due to excessive remanent polarization, their energy storage density and efficiency is all lower；Antiferroelectric medium
There are biggish spontaneous polarization strength and lesser remanent polarization, so that there is biggish energy storage density, but because it is in electricity
There are phase transition induced with electric field and along with biggish strain under field action, cause that dielectric breakdown easily occurs under turnover electric field.
There is long-range order domain structure and high remanent polarization different from ferroelectric media, relaxor ferroelectric medium is received with polarity
Meter Wei Qu shows lesser remanent polarization, high saturated polarization and lower coercive field.Relaxor ferroelectric medium this
A little characteristics are very beneficial for realizing high energy storage density and energy storage efficiency, but it is all leaded system that this kind of material is most of.From
Since 2002, European Union, the U.S. and Japan have all formulated stringent environmentally friendly law (WEEE/RoHS), limit or forbid including Pb
A variety of noxious materials inside use in electronic device.On the other hand, at present common dielectric capacitor energy storage density all compared with
Low, this results in energy storage device bulky, accounts for about the 40%~60% of whole equipment volume.Therefore energy storage density and reality are improved
Now unleaded is the important trend of dielectric ceramics.
Barium strontium titanate ((BaxSr1-x)TiO3, abbreviation BST) and it is barium titanate (BaTiO3) and strontium titanates (SrTiO3) it is complete
Solid solution has high dielectric constant, and low dielectric loss, changing Ba/Sr ratio can be adjusted within the scope of very wide temperature
The dielectric properties of material.H.B.Yang etc. (J.Eur.Ceram.Soc.38,1367-1373 (2018)) is in Ba0.4Sr0.6TiO3In
Add Bi2O3-B2O3-SiO2Frit, it is 1.98J/cm that maximum energy storage density is obtained at 279kV/cm3, efficiency is
90.57%.J.Y.Wu etc. (Nano Energy, 50,723-732 (2018)) constructs a kind of tool by mixing Sr and Li in BNT
The relaxation ferroelectric ceramic of polarized nanometer microcell (PNRs) structure, obtaining maximum energy storage density is 1.7J/cm3, energy storage efficiency is
87.2%.
Summary of the invention
The purpose of the present invention is to provide a kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density and its preparations
Method, (1-x) (Ba of the invention0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Ferroelectric ceramics effective energy storage density at room temperature
Up to 4.55J/cm3。
Herein, on the one hand, the present invention provides a kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material, the barium strontium titanate
The chemical composition of the unleaded relaxation ferroelectric ceramic material of base are as follows: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3, wherein
0 x≤0.15 <.
It is at room temperature cube para-electric phase structure when Sr content is greater than 0.4 the present invention is based on barium strontium titanate, considers simultaneously
Bi3+With O2-Hybridism can increase spontaneous polarization strength, Mg2+And Nb5+Ferroelectricity long range ordered structure is destroyed, construction polarity is received
Meter Wei Qu designs following component: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3, can be achieved at the same time high energy storage
Density and energy storage efficiency, and realize unleaded.The ceramic material is counterfeit cubic phase at room temperature, and polarity is received under electric field action
Meter Wei Qu, which can be coupled, to be become orientation and tends to the long-range order domain structure of direction of an electric field, is removed after electric field under the action of warm-up movement
It can revert to again and be orientated random polar nano microcell.
Preferably, the energy storage density (effective energy storage density) of the barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material is
3.0J/cm3More than.
The effective energy storage density of the barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material at room temperature is up to 4.55J/cm3,
Energy storage efficiency can be 80% or more.
On the other hand, the present invention also provides a kind of preparation method of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material, packets
It includes:
According to (Ba0.55Sr0.45)TiO3Stoichiometric ratio the source Ba, the source Sr and the source Ti are mixed and dried rear briquetting, in 1100~
1200 DEG C of progress first time synthesis, obtain BST ceramic powder；
By the source Bi, the source Mg, the source Nb and the BST ceramic powder according to (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3
Stoichiometric ratio be mixed and dried rear briquetting, carry out second in 900~1000 DEG C and synthesize, obtain BST-BMN ceramic powder；
Binder is added in the BST-BMN ceramic powder, is granulated, ageing, compression moulding, obtains green compact through plastic removal；And
The green compact are sintered, barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material is obtained.
The present invention prepares BST ceramic powder by solid phase method, and it is mixed with the source Bi, the source Mg, the source Nb, synthesizes BST-
BMN ceramic powder prepares barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material through molding, plastic removal, sintering.Regulated and controled by component
Reduce the volatilization of Bi with optimum synthesis method and keep synthesis more abundant, is prepared for having high energy storage density and high energy storage efficiency
Unleaded BST-BMN ferroelectric ceramics.Ceramics prepared by the present invention have dielectric breakdown strength height, effective energy storage density are big to imitate with energy storage
The high feature of rate, effective energy storage density can reach 4.55J/cm at room temperature3, energy storage efficiency can be 80% or more, with identical item
(the Ba prepared under part0.55Sr0.45)TiO3Ceramic phase ratio, effective energy storage density improve 2.85J/cm3, increase rate is up to
167.6%, energy storage efficiency improves 25.1%.The unleaded relaxation ferroelectric ceramic material is expected to be applied to High pulse power technology neck
Domain.Moreover, method and process of the invention is simple, not high to equipment requirement, production cost is low.
The source Ba can be BaTiO3、BaCO3、Ba(NO3)2、(CH3COO)2At least one of Ba.The source Sr can
Think SrTiO3、SrCO3、Sr(NO3)2、(CH3COO)2At least one of Sr.The source Ti can be BaTiO3、SrTiO3、
TiO2At least one of.
The raw material of the BST ceramic powder can be BaTiO3、SrTiO3Powder or BaCO3、SrCO3And TiO2Powder.
The time of the first time synthesis can be 2~6 hours.
The source Bi can be Bi2O3、Bi(NO3)3、C6H9BiO6At least one of.The source Mg can for MgO,
MgCO3、CH4Mg2O6At least one of.The source Nb can be Nb2O5、Nb(OH)5At least one of.
The time of second of synthesis can be 2~6 hours.
The temperature of the plastic removal can be 600~700 DEG C, and the time can be 2~6 hours.
The temperature of the sintering can be 1250~1350 DEG C, and the time can be 2~6 hours.
Preferably, covering the green compact with the BST-BMN ceramic powder and being sintered.By with same composition
Ceramic powder be covered on above green compact, the volatilization of Bi component can be prevented.
Another aspect, the present invention also provides a kind of ferroelectric ceramics element, the ferroelectric ceramics element is by any of the above-described kind of titanium
The sour unleaded relaxation ferroelectric ceramic material of strontium barium base is made.
It can be by the way that any of the above-described kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material be processed into required size, through clear
Clean, Yin Yin is dried, and silver ink firing obtains the ferroelectric ceramics element.
Detailed description of the invention
Fig. 1 shows conventional solid-state method preparation Ba0.55Sr0.45TiO3(1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/ 3Nb1/3)O3The ceramic material of (x=0.05,0.07,0.10) at room temperature put by X ray diffracting spectrum (left figure (a)) and its part
Big figure (right figure (b))；
The dielectric constant and dielectric loss that Fig. 2 (a)-Fig. 2 (d) is barium-strontium titanate-based ceramics sample are at different frequencies with temperature
Change curve；Wherein, Fig. 2 (a) shows Ba0.55Sr0.45TiO3The case where (comparative example 1)；Fig. 2 (b) shows 0.95
(Ba0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3The case where (embodiment 1)；Fig. 2 (c) shows 0.93 (Ba0.55Sr0.45)
TiO3-0.07Bi(Mg2/3Nb1/3)O3The case where (embodiment 2)；Fig. 2 (d) shows 0.90 (Ba0.55Sr0.45)TiO3-0.10Bi
(Mg2/3Nb1/3)O3The case where (embodiment 3)；
Fig. 3 be the barium-strontium titanate-based ceramics sample of each embodiment and comparative example ceramics sample at room temperature 1Hz when maximum electric field intensity
Under ferroelectric hysteresis loop；
Fig. 4 is the energy storage characteristic of embodiment 2 with the change curve of electric field.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention relates to barium-strontium titanate-based unleaded relaxation ferroelectric ceramics of a kind of high energy storage density and preparation method thereof.The present invention
The composition of ceramic material are as follows: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3, wherein 0 < x≤0.15, x is mole
Percentage.The preparation method of the ceramic material includes: by the source Ba, the source Sr and the source Ti (such as BaTiO3And SrTiO3, or
BaCO3、SrCO3And TiO2) press (Ba0.55Sr0.45)TiO3Stoichiometric ratio ingredient, briquetting after drying are closed in 1100~1200 DEG C
At 2~6 hours, BST ceramic powder is obtained；By the source Bi, the source Mg, the source Nb (such as Bi2O3、MgO、Nb2O5) and BST ceramic powder
According to (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3(0 x≤0.15 <) stoichiometric ratio is pressed after being mixed and dried
Block synthesizes 2~6 hours in 900~1000 DEG C, obtains BST-BMN ceramic powder, and binder granulation is added, and molding, plastic removal obtain
Green compact: green compact are sintered in 1250~1350 DEG C, and the barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density is made.System of the present invention
Standby ceramics have the characteristics that breakdown strength is high, effective energy storage density is big and energy storage efficiency is high, and effective energy storage density can at room temperature
Up to 4.55J/cm3, energy storage efficiency can be 80% or more, than (the Ba prepared under the same terms0.55Sr0.45)TiO3Ceramic phase ratio,
Effective energy storage density improves 2.85J/cm3, increase rate is up to 167.6%, and energy storage efficiency improves 25.1%.Here." have
Effect energy storage density " refers to releasable energy density after charging.The unleaded relaxation ferroelectric ceramic material is expected to be applied to high power
Pulse technique field.
It is at room temperature cube para-electric phase structure when Sr content is greater than 0.4 the present invention is based on barium strontium titanate, considers simultaneously
Bi3+With O2-Hybridism can increase spontaneous polarization strength, Mg2+And Nb5+Ferroelectricity long range ordered structure is destroyed, construction polarity is received
Meter Wei Qu designs (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Component, wherein 0 x≤0.15 <, preferably 0.05
≤ x≤0.1 can be achieved at the same time high energy storage density and energy storage efficiency, and realize unleaded.As 0 < x≤0.15, have
Solid solution degree is high, the larger advantage of dielectric constant.
Hereinafter, schematically illustrating the method for preparing barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of the invention.
Firstly, according to (Ba0.55Sr0.45)TiO3Stoichiometric ratio by the source Ba, the source Sr and the source Ti mix, obtain to be synthesized
Powder A.BaTiO can be used in the source Ba3(barium titanate), BaCO3(barium carbonate), Ba (NO3)2(barium nitrate), (CH3COO)2Ba (second
Sour barium) etc..SrTiO can be used in the source Sr3(strontium titanates), SrCO3(strontium carbonate), Sr (NO3)2(strontium nitrate), (CH3COO)2Sr
(strontium acetate) etc..BaTiO can be used in the source Ti3、SrTiO3、TiO2(titanium dioxide) etc..It in one example, can be with
BaTiO3、SrTiO3Powder or BaCO3、SrCO3And TiO2Powder is raw material according to (Ba0.55Sr0.45)TiO3Corresponding element
Stoichiometric ratio ingredient.Mixed method can for example be mixed using wet ball-milling method.In this case, can be according to raw material: ball:
Deionized water=1:(4.5~5.2): the mass ratio of (1.5~1.7), mixing 24~48 hours, wherein ball-milling medium can be zirconium
Ball or agate ball etc..It can be upon mixing by raw mixture drying, sieving (such as crossing 40~120 meshes).
Then, by powder A briquetting to be synthesized, first time synthesis is carried out, room temperature is cooled to the furnace, obtains BST ceramic powder.
The pressure of briquetting can be 4~6MPa.The temperature of synthesis can be 1100~1200 DEG C for the first time, and the time can be small for 2~6
When, heating rate can be with≤2 DEG C/min.
Sample can also be crushed to (grinding) again after first time synthesizes, sieving (such as crossing 40~120 meshes), thus
The powder for being 1~5 μm to particle size.
Then, by the source Bi, the source Mg, the source Nb and BST ceramic powder according to (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/ 3Nb1/3)O3The stoichiometric ratio of (0 x≤0.15 <) mixes, and obtains powder material B to be synthesized.Bi can be used in the source Bi2O3(three oxidations
Two bismuths), Bi (NO3)3(bismuth nitrate), C6H9BiO6(bismuth acetate) etc..MgO (magnesia), MgCO can be used in the source Mg3(carbonic acid
Magnesium), CH4Mg2O6(basic magnesium carbonate) etc..Nb can be used in the source Nb2O5(niobium oxide), Nb (OH)5(niobium hydroxide) etc..Mixing
Method can for example be mixed using wet ball-milling method.In this case, can be according to raw material: ball: deionized water=1:(4.5~
5.2): the mass ratio of (1.5~1.7), mixing 24~48 hours, wherein ball-milling medium can be zirconium ball or agate ball etc..It can be with
Upon mixing by raw mixture drying, sieving (such as crossing 40~120 meshes).
Then, it by powder material B briquetting to be synthesized, carries out second and synthesizes, obtain BST-BMN ceramic powder.The pressure of briquetting
It can be 4~6MPa.The condition of second synthesis can be with are as follows: is warming up to 900~1000 with the heating rate not higher than 2 DEG C/min
DEG C, 2~6 hours are kept the temperature, cools to room temperature with the furnace.Powder material B to be synthesized can also be placed in closed environment (such as closed oxidation
In aluminium crucible) it is synthesized, to inhibit the volatilization of Bi.
Sample is crushed to (grinding) again after can also synthesizing at second, sieving (such as crossing 40 meshes).
Then, binder is added in BST-BMN ceramic powder, is granulated, ageing, compression moulding, obtains green compact through plastic removal
(biscuit of ceramics).Binder can be polyvinyl alcohol (PVA), polyvinyl butyral (PVB) etc., concentration 7%, binder
Additional amount can be ceramic powder weight 5~7%.Digestion time can be 21~25 hours.It can also mistake after aging
Sieve (such as crossing 40 meshes).In one example, moulding process for example can be with are as follows: powder obtained is carried out to dry-pressing formed, system
The green compact for being 13mm at diameter, but it is not limited to the size, it can set according to actual needs.The pressure of compression moulding can be
1.3~2.0MPa.
BST-BMN ceramic powder through ball-milling method fine grinding and can also be dried again before binder is added, to obtain grain
Diameter is having a size of 0.5~1.5 μm of powder.In one example, the fine grinding of wet ball-milling method is for example according to ceramic powder: ball: go from
Sub- water=1:(5.0~5.6): the mass ratio of (1.4~1.6), fine grinding 24~48 hours, wherein ball-milling medium can for zirconium ball or
Agate ball.
The condition of plastic removal can be with are as follows: is warming up to 600~700 DEG C with the heating rate not higher than 2 DEG C/min, heat preservation 2~6 is small
When, cool to room temperature with the furnace.Organic binder can be excluded by plastic removal and idiosome is made to have certain mechanical strength.
Then, green compact are sintered.The temperature of sintering (carrying out for example, by using high temperature furnace) can be 1250~1350 DEG C,
Time can be 2~6 hours, and heating rate can be with≤2 DEG C/min.Can cover the green compact with BST-BMN ceramic powder and
It is sintered.By being covered on above green compact with the ceramic powder with same composition, the volatilization of Bi component can be prevented.It can also
Green compact to be sintered under closed environment.
It cools to room temperature with the furnace, obtains barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material.Of the invention is barium-strontium titanate-based
Unleaded relaxation ferroelectric ceramic material is counterfeit cubic phase at room temperature, and polar nano microcell, which can couple, under electric field action becomes orientation
The long-range order domain structure for tending to direction of an electric field, removes that revert to orientation after electric field again under the action of warm-up movement random
Polar nano microcell.
The unleaded relaxation ferroelectric ceramic material is expected to be applied to High pulse power technology field.In one example, it can incite somebody to action
Sintered Ceramic manufacturing obtains the ferroelectric ceramics element at required size, cleaned, Yin Yin, drying, silver ink firing.
The silver ink firing condition can be with are as follows: is warming up to 700~800 DEG C with the heating rate not higher than 2 DEG C/min, heat preservation 10
~30 minutes.There is dielectric using ferroelectric ceramics element made from barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material of the invention
The advantage that breakdown strength is high, effective energy storage density is big and energy storage efficiency is high.
Advantages of the present invention:
Barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material of the invention have that dielectric breakdown strength is high, effective energy storage density is big and
The high feature of energy storage efficiency, effective energy storage density has reached 4.55J/cm at room temperature3, 80% or more energy storage efficiency, with identical item
(the Ba prepared under part0.55Sr0.45)TiO3Ceramic phase ratio, effective energy storage density improve 2.85J/cm3, increase rate is up to
167.6%, energy storage efficiency improves 25.1%.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
The group of material becomes
0.95(Ba0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3
(1) with BaTiO3、SrTiO3Powder is raw material, according to (Ba0.55Sr0.45)TiO3Stoichiometric ratio is prepared, using wet type ball
The mixing of mill method, according to raw material: ball: deionized water=1:4.5:1.7 quality was than ball milling mixing 24 hours, after drying, crossed 40 mesh
Sieve pushes bulk in 5MPa pressure, rises to 1150 DEG C with the heating rate of 2 DEG C/min, keep the temperature 4 hours, synthesize (Ba0.55Sr0.45)
TiO3Powder；
(2) by powder made from step (1) grind, cross 40 meshes, then with Bi2O3、MgO、Nb2O5Equal raw materials are according to 0.95
(Ba0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3Stoichiometric ratio is prepared, according to raw material: ball: deionized water=1:5:
1.55 mass ratio mixes 24 hours, after drying, crosses 40 meshes, depresses to bulk in 5MPa pressure, with the heating speed of 2 DEG C/min
Rate rises to 1000 DEG C, keeps the temperature 2 hours, synthesizes 0.95 (Ba0.55Sr0.45)TiO3-0.05Bi(Mg2/3Nb1/3)O3Powder；
(3) by powder made from step (2) grind, cross 40 meshes, then use the fine grinding of wet ball-milling method, according to raw material: ball: go from
The quality of sub- water=1:5:1.5 dried the powder after fine grinding than fine grinding 24 hours.Then the PVA binder of 5wt.% is added,
It is granulated, briquetting, is aged 24 hours, cross 40 meshes, the green compact that diameter is 13mm are pressed under 1.6MPa pressure, are then warming up to
600 DEG C, 4h plastic removal is kept the temperature, biscuit of ceramics is obtained；
(4) biscuit of ceramics is put into alumina crucible, in order to prevent the volatilization of Bi component, with the ceramic powder with same composition
Material is covered on above biscuit of ceramics, is covered the aluminium oxide cover board through ground, is warming up to 1325 DEG C with the heating rate of 2 DEG C/min,
Heat preservation 2 hours, cools to room temperature with the furnace, obtains ceramic material；
(5) ceramics sample sintered is processed into 0.2mm thickness, cleaned, silver paste is printed in drying, then after drying, with 2 DEG C/
The heating rate of min rises to 750 DEG C, keeps the temperature 30 minutes, obtains ceramic component；
(6) determined using X-ray diffraction analyzer (XRD) powder of synthesis and the ceramics sample of sintering crystal structure and
Phase structure.Dielectric properties are tested with Novocontrol wideband dielectric impedance spectrometer.It is tested and is made pottery using TF-2000 ferroelectricity analyzer
Porcelain ferroelectric hysteresis loop；
(7) ceramic component prepared to the present embodiment 1 has carried out the monopole hysteresis under maximum electric field intensity at room temperature,
As a result see that Fig. 3, maximum effectively energy storage density, dielectric breakdown strength and energy storage efficiency are shown in Table 1.
Embodiment 2:
The group of material becomes
0.93(Ba0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3
(1) with BaTiO3、SrTiO3Powder is raw material, according to (Ba0.55Sr0.45)TiO3Stoichiometric ratio is prepared, using wet type ball
The mixing of mill method, according to raw material: ball: deionized water=1:4.5:1.7 quality was than ball milling mixing 24 hours, after drying, crossed 40 mesh
Sieve pushes bulk in 5MPa pressure, rises to 1150 DEG C with the heating rate of 2 DEG C/min, keep the temperature 4 hours, synthesize (Ba0.55Sr0.45)
TiO3Powder；
(2) by powder made from step (1) grind, cross 40 meshes, then with Bi2O3、MgO、Nb2O5Equal raw materials are according to 0.93
(Ba0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3Stoichiometric ratio is prepared, according to raw material: ball: deionized water=1:5:
1.55 mass ratio mixes 24 hours, after drying, crosses 40 meshes, depresses to bulk in 5MPa pressure, with the heating speed of 2 DEG C/min
Rate rises to 1000 DEG C, keeps the temperature 2 hours, synthesizes 0.93 (Ba0.55Sr0.45)TiO3-0.07Bi(Mg2/3Nb1/3)O3Powder；
(3) by powder made from step (2) grind, cross 40 meshes, then use the fine grinding of wet ball-milling method, according to raw material: ball: go from
The quality of sub- water=1:5:1.5 dried the powder after fine grinding than fine grinding 24 hours.Then the PVA binder of 5wt.% is added,
It is granulated, briquetting, is aged 24 hours, cross 40 meshes, the green compact that diameter is 13mm are pressed under 1.6MPa pressure, are then warming up to
600 DEG C, 4h plastic removal is kept the temperature, biscuit of ceramics is obtained；
(4) biscuit of ceramics is put into alumina crucible, in order to prevent the volatilization of Bi component, with the ceramic powder with same composition
Material is covered on above biscuit of ceramics, is covered the aluminium oxide cover board through ground, is warming up to 1300 DEG C with the heating rate of 2 DEG C/min,
Heat preservation 2 hours, cools to room temperature with the furnace, obtains ceramic material；
(5) ceramics sample sintered is processed into 0.2mm thickness, cleaned, silver paste is printed in drying, then after drying, with 2 DEG C/
The heating rate of min rises to 750 DEG C, keeps the temperature 30 minutes, obtains ceramic component；
(6) determined using X-ray diffraction analyzer (XRD) powder of synthesis and the ceramics sample of sintering crystal structure and
Phase structure.Dielectric properties are tested with Novocontrol wideband dielectric impedance spectrometer.It is tested and is made pottery using TF-2000 ferroelectricity analyzer
Porcelain ferroelectric hysteresis loop；
(7) ceramic component prepared to the present embodiment 2 has carried out the monopole hysteresis under maximum electric field intensity at room temperature,
As a result see that Fig. 3, maximum effectively energy storage density, dielectric breakdown strength and energy storage efficiency are shown in Table 1.
Embodiment 3:
The group of material becomes
0.90(Ba0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3
(1) with BaTiO3、SrTiO3Powder is raw material, according to (Ba0.55Sr0.45)TiO3Stoichiometric ratio is prepared, using wet type ball
The mixing of mill method, according to raw material: ball: deionized water=1:4.5:1.7 quality was than ball milling mixing 24 hours, after drying, crossed 40 mesh
Sieve pushes bulk in 5MPa pressure, rises to 1150 DEG C with the heating rate of 2 DEG C/min, keep the temperature 4 hours, synthesize (Ba0.55Sr0.45)
TiO3Powder；
(2) by powder made from step (1) grind, cross 40 meshes, then with Bi2O3、MgO、Nb2O5Equal raw materials are according to 0.90
(Ba0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3Stoichiometric ratio is prepared, according to raw material: ball: deionized water=1:5:
1.55 mass ratio mixes 24 hours, after drying, crosses 40 meshes, depresses to bulk in 5MPa pressure, with the heating speed of 2 DEG C/min
Rate rises to 1000 DEG C, keeps the temperature 2 hours, synthesizes 0.90 (Ba0.55Sr0.45)TiO3-0.10Bi(Mg2/3Nb1/3)O3Powder；
(3) by powder made from step (2) grind, cross 40 meshes, then use the fine grinding of wet ball-milling method, according to raw material: ball: go from
The quality of sub- water=1:5:1.5 dried the powder after fine grinding than fine grinding 24 hours.Then the PVA binder of 5wt.% is added,
It is granulated, briquetting, is aged 24 hours, cross 40 meshes, the green compact that diameter is 13mm are pressed under 1.6MPa pressure, are then warming up to
600 DEG C, 4h plastic removal is kept the temperature, biscuit of ceramics is obtained；
(4) biscuit of ceramics is put into alumina crucible, in order to prevent the volatilization of Bi component, with the ceramic powder with same composition
Material is covered on above biscuit of ceramics, is covered the aluminium oxide cover board through ground, is warming up to 1275 DEG C with the heating rate of 2 DEG C/min,
Heat preservation 2 hours, cools to room temperature with the furnace, obtains ceramic material；
(5) ceramics sample sintered is processed into 0.2mm thickness, cleaned, silver paste is printed in drying, then after drying, with 2 DEG C/
The heating rate of min rises to 750 DEG C, keeps the temperature 30 minutes, obtains ceramic component；
(6) determined using X-ray diffraction analyzer (XRD) powder of synthesis and the ceramics sample of sintering crystal structure and
Phase structure.Dielectric properties are tested with Novocontrol wideband dielectric impedance spectrometer.It is tested and is made pottery using TF-2000 ferroelectricity analyzer
Porcelain ferroelectric hysteresis loop；
(7) ceramic component prepared to the present embodiment 3 has carried out the monopole hysteresis under maximum electric field intensity at room temperature,
As a result see that Fig. 3, maximum effectively energy storage density, dielectric breakdown strength and energy storage efficiency are shown in Table 1.
Comparative example 1:
The group of material becomes
(Ba0.55Sr0.45)TiO3
(1) with BaTiO3、SrTiO3Powder is raw material, according to (Ba0.55Sr0.45)TiO3Stoichiometric ratio is prepared, using wet type ball
The mixing of mill method, according to raw material: ball: alcohol=1:4.5:1.7 quality was than ball milling mixing 24 hours, after drying, crossed 40 meshes,
5MPa pressure pushes bulk, rises to 1150 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 4 hours, synthesizes (Ba0.55Sr0.45)TiO3
Powder；
(2) powder made from step (1) is ground, 40 meshes is crossed, using wet ball-milling method fine grinding, according to raw material: ball: deionization
Water=1:5:1.6 quality dried the powder after fine grinding than fine grinding 24 hours.Then the PVA binder of 5 wt.% is added,
It is granulated, briquetting, is aged 24 hours, cross 40 meshes, the green compact that diameter is 13mm are pressed under 1.5MPa pressure, obtain ceramic green
Base；
(3) green sheet rises to 600 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 2 hours；It is risen to again with 2 DEG C/min heating rate
1200 DEG C, keep the temperature 2 hours；1350 DEG C of heat preservation 4h are finally risen to 3 DEG C/min heating rate；
(4) ceramics sample sintered is processed into 0.2mm thickness, it is cleaned, silver paste is printed after drying, then dry, then with 2 DEG C
Heating rate rise to 750 DEG C, keep the temperature 30 minutes, obtain ceramic component；
(5) ceramic component prepared to this comparative example 1 has carried out the monopole hysteresis under maximum electric field intensity at room temperature,
As a result see that Fig. 3, maximum effectively energy storage density, dielectric breakdown strength and energy storage efficiency are shown in Table 1.
Table 1: the dielectric breakdown strength of each embodiment and comparative example, effective energy storage density and energy storage efficiency
| Sample | Dielectric breakdown strength (kV/cm) | Effective energy storage density (J/cm3) | Energy storage efficiency (%) |
| Embodiment 1 | 420 | 3.92 | 72.5 |
| Embodiment 2 | 450 | 4.55 | 81.8 |
| Embodiment 3 | 380 | 3.56 | 86.2 |
| Comparative example 1 | 240 | 1.70 | 56.7 |
Table 1 is the (Ba that in the invention patent prepared by Examples 1 to 3 and comparative example 10.55Sr0.45)TiO3(1-x)
(Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3Dielectric breakdown strength of the ceramics in room temperature under 1Hz, maximum effectively energy storage are close
Degree and energy storage efficiency.As shown in Table 1, the barium-strontium titanate-based unleaded relaxation ferroelectric ceramic of high energy storage density produced by the present invention is in room temperature
Lower energy storage density is 3.56~4.55J/cm3, energy storage efficiency is 72.5~86.2%, and is prepared under the same terms pure
(Ba0.55Sr0.45)TiO3Energy storage density is 1.7J/cm to ceramics at room temperature3, energy storage efficiency only has 56.7%.
Fig. 1 is that conventional solid-state method prepares Ba0.55Sr0.45TiO3(1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)
O3The ceramic material of (x=0.05,0.07,0.10) X ray diffracting spectrum at room temperature.By (a) in Fig. 1 it is found that introducing Bi
(Mg2/3Nb1/3)O3Afterwards, ceramics are still single Perovskite Phase, occur without the second phase, illustrate Bi (Mg2/3Nb1/3)O3It is complete
It is dissolved into host's lattice entirely；(b) in Fig. 1 is (200) peak partial enlarged view, it can be seen that ceramics are counterfeit cubic structure,
And with Bi (Mg2/3Nb1/3)O3The increase diffraction maximum of content is deviated toward low angle, shows that lattice constant increases.
Fig. 2 (a)-Fig. 2 (d) is the dielectric constant and dielectric damage of the barium-strontium titanate-based ceramics sample of each embodiment and comparative example
Consume variation with temperature curve at different frequencies.By Fig. 2 (a)-Fig. 2 (d) it is found that with BMN incorporation, sharp Curie peak
Gradually become flat, and the characteristic feature of relaxation ferroelectric occur, is i.e. frequency dispersion phenomenon.Fig. 3 is each embodiment and comparison
Example barium-strontium titanate-based ceramics sample at room temperature 1Hz when maximum electric field intensity under ferroelectric hysteresis loop.From the figure 3, it may be seen that with BMN's
Incorporation, the maximum electric field intensity that ceramics sample is resistant to first are increased and are reduced afterwards, and ferroelectric hysteresis loop is more and more elongated, but maximum polarization
Intensity is gradually reduced.Fig. 4 is the energy storage characteristic of embodiment 2 with the change curve of electric field.As shown in Figure 4, it is gradually increased electric-field strength
Degree, effective energy storage density are gradually increased, and energy storage efficiency has slight decline.
Claims (10)
1. a kind of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material, which is characterized in that the barium-strontium titanate-based unleaded relaxation iron
The chemical composition of electroceramics material are as follows: (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3, wherein 0 < x≤
0.15。
2. barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material according to claim 1, which is characterized in that the strontium titanates
The energy storage density of the unleaded relaxation ferroelectric ceramic material of barium base is 3.0 J/cm3More than.
3. a kind of preparation method of barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material of any of claims 1 or 2, feature exist
In, comprising:
According to (Ba0.55Sr0.45)TiO3Stoichiometric ratio the source Ba, the source Sr and the source Ti are mixed and dried rear briquetting, in 1100~
1200 DEG C of progress first time synthesis, obtain BST ceramic powder；
By the source Bi, the source Mg, the source Nb and the BST ceramic powder according to (1-x) (Ba0.55Sr0.45)TiO3-xBi(Mg2/3Nb1/3)O3
Stoichiometric ratio be mixed and dried rear briquetting, carry out second in 900~1000 DEG C and synthesize, obtain BST-BMN ceramic powder；
Binder is added in the BST-BMN ceramic powder, is granulated, ageing, compression moulding, obtains green compact through plastic removal；And
The green compact are sintered, barium-strontium titanate-based unleaded relaxation ferroelectric ceramic material is obtained.
4. preparation method according to claim 3, which is characterized in that the source Ba is BaTiO3、BaCO3、Ba(NO3)2、
(CH3COO)2At least one of Ba；The source Sr is SrTiO3、SrCO3、Sr(NO3)2、(CH3COO)2At least one of Sr；
The source Ti is BaTiO3、SrTiO3、TiO2At least one of.
5. preparation method according to claim 3 or 4, which is characterized in that the source Bi is Bi2O3、Bi(NO3)3、
C6H9BiO6At least one of；The source Mg is MgO, MgCO3、CH4Mg2O6At least one of；The source Nb is Nb2O5、Nb
(OH)5At least one of.
6. preparation method according to any one of claim 3 to 5, which is characterized in that the time of the first time synthesis
It is 2~6 hours；
The time of second of synthesis is 2~6 hours.
7. preparation method according to any one of claim 3 to 6, which is characterized in that the temperature of the plastic removal be 600~
700 DEG C, the time is 2~6 hours.
8. the preparation method according to any one of claim 3 to 7, which is characterized in that the temperature of the sintering is 1250
~1350 DEG C, the time is 2~6 hours.
9. the preparation method according to any one of claim 3 to 8, which is characterized in that with the BST-BMN ceramic powder
It covers the green compact and is sintered.
10. a kind of ferroelectric ceramics element, which is characterized in that by barium-strontium titanate-based unleaded relaxor ferroelectric of any of claims 1 or 2
Ceramic material is made.
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| CN116425527B (en) * | 2023-02-02 | 2024-02-02 | 福建火炬电子科技股份有限公司 | Pulse power type ceramic dielectric material, pulse power type ceramic capacitor and preparation method thereof |
| CN117153562A (en) * | 2023-09-19 | 2023-12-01 | 江苏飞特尔通信有限公司 | Bismuth-based adjustable MLCC capacitor for LTCC and preparation method |
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