CN106187165B - A kind of high energy storage density medium ceramic material and preparation method thereof - Google Patents

A kind of high energy storage density medium ceramic material and preparation method thereof Download PDF

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CN106187165B
CN106187165B CN201610540311.6A CN201610540311A CN106187165B CN 106187165 B CN106187165 B CN 106187165B CN 201610540311 A CN201610540311 A CN 201610540311A CN 106187165 B CN106187165 B CN 106187165B
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郑兴华
肖腾
刘洋
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Fuzhou University
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Abstract

The invention discloses a kind of high energy storage density medium ceramic materials and preparation method thereof.The ceramic material is combined by BST ceramics mixed powder and MAS glass powder, and the dosage of MAS glass powder is the 0.2% ~ 10% of BST ceramics mixed powder quality；The MAS glass powder is consisting of MgO-Al2O3‑SiO2；The BST ceramics mixed powder is the Ba for being 0.1-0.5 by x value1‑xSrxTiO3In powder a variety of powder equimolars mixing, ball milling and obtain.Compared with prior art, energy-storing dielectric ceramic prepared by the present invention have dielectric constant high (>1600), dielectric loss low (<0.02), breakdown field strength high (>18.0kV/mm), energy storage density it is high (>2.50J/cm3) and -55-125 DEG C within the scope of change in dielectric constant rate -13.0%-5.0% advantage, be with a wide range of applications in pulse power energy-storage system.

Description

A kind of high energy storage density medium ceramic material and preparation method thereof
Technical field
The invention belongs to field of dielectric energy storage material, and in particular to a kind of high energy storage density medium ceramic material and its system Preparation Method.
Technical background
In recent years in electronics industry, high energy storage density device is had been to be concerned by more and more people, and studies new high storage Energy device is extremely urgent.It is compared to traditional energy storage device, dielectric capacitor stores electric energy using polarization charge, fills Discharge rate and discharge energy density several orders of magnitude higher than traditional energy storage device.In addition, it is with better stability, Technical field of pulse power, hybrid vehicle aspect demand is larger, has very high application prospect.But current dielectric The demand of application is also much not achieved in the energy storage density of energy-storage capacitor, thus how to improve the energy storage density of dielectric substance at For research emphasis.
In dielectric energy storage material, energy storage density is usedIt indicates, wherein ε0For permittivity of vacuum, εrFor relative dielectric constant, E is electric field strength.It can be seen that the energy storage density of dielectric energy storage material is determined by two factors: Dielectric constant and breakdown field strength.The dielectric substance of capacitor energy storage device mainly has TiO at present2、BaTiO3、Ba1- xSrxTiO3Deng dielectric constant all with higher, especially Ba1-xSrxTiO3(BST) because it has high dielectric constant and low Dielectric loss has obtained extensive research.But Ba1-xSrxTiO3The dielectric strength of ceramics is generally below 8kV/mm, is unfavorable for Obtain higher energy storage density.In addition, single component Ba1-xSrxTiO3Ceramic dielectric constant varies with temperature larger, is unfavorable for device The stability of part work.
Patent (patent No. 201510243383) by with Ca, Sn to BaTiO3The position A and B simultaneously carry out replace change Property, obtain high dielectric constant and lower dielectric loss.Patent (patent No. 201410606390) epoxy resin modification BaTiO3Ceramic powder is compound with PVDF, substantially increases its breakdown field strength.Patent (patent No. 201210150158.8) By in SrTiO3Middle addition MgO, is increased to 17.4kV/mm for breakdown field strength, obtains 0.36J/cm3Energy storage density.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of with high energy storage density medium ceramic material And preparation method thereof.By the addition MAS glass powder in BST powder, the lower disadvantage of the energy storage density of BST ceramics is improved, Obtained material has high dielectric constant, high breakdown field strength and good temperature stability.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of high energy storage density medium ceramic material is combined by BST ceramics mixed powder and MAS glass powder, The dosage of MAS glass powder is the 0.2% ~ 10% of BST ceramics mixed powder quality；The MAS glass powder is consisting of MgO- Al2O3-SiO2；The BST ceramics mixed powder is the Ba by x value for any value in 0.1-0.51-xSrxTiO3Single-phase powder In body two or more powder equimolars mixing, ball milling and obtain.
Further, the MAS glass powder is consisting of: MgO 10-18wt%, Al2O325-35wt% and SiO2 50- 58wt%, the sum of mass percent of three kinds of components are 100%.
Further, its dielectric constant of the ceramic material high (>1600), dielectric loss low (<0.02), breakdown electric field Intensity height (> 18.0kV/mm), energy storage density height (> 2.50J/cm3) and -55-125 DEG C within the scope of change in dielectric constant rate - 13.0%-5.0%。
A method of preparing high energy storage density medium ceramic material as described above, comprising the following steps:
(1) preparation of MAS glass powder:
By MgO, Al2O3And SiO2Ball milling 8-24 hours in deionized water or alcohol, ball material mass ratio is not less than powder 1:1, tinning amount be tank volume 1/2-4/5,100-250 revs/min of rotational speed of ball-mill；Then it is kept the temperature at 1475-1550 DEG C 4h melting, then pour into deionized water, grinding obtains 10-50 microns of MAS glass powder after water quenching；
(2) preparation of BST ceramics mixed powder:
It is the Ba of any value in 0.1-0.5 by x value1-xSrxTiO3Two or more powder equimolars in single-phase powder Mixing, ball milling 8-24 hours in deionized water or alcohol；Wherein ball material mass ratio is not less than 1:1, and tinning amount is tank body appearance Long-pending 1/2-4/5,100-250 revs/min of rotational speed of ball-mill；After the mixed slurry drying after ball milling, BST ceramics mixed powder is obtained Body；
(3) preparation of high energy storage density medium ceramic material:
The MAS glass powder of step (1) preparation is added in the BST ceramics mixed powder made from step (2), in deionized water It is uniformly mixed within middle ball milling 24 hours, ball material mass ratio is not less than 1:1, and tinning amount is the 1/2-4/5 of tank volume, rotational speed of ball-mill 100-250 revs/min；Mixed slurry drying after ball milling, obtains the media ceramic powder of high energy storage density；Continue in powder 5 ~ 10wt% poly-vinyl alcohol solution is added, powder is granulated, disk or square piece are then pressed into；By after potsherd dumping Then prior to 850-950 DEG C heat preservation 0-2 hours in air are warming up to 1150 ~ 1300 DEG C of sintering 2-8 hours, it is close to obtain high energy storage Spend medium ceramic material.
More specifically, in step (2) x value be 0.1-0.5 in any value Ba1-xSrxTiO3Single-phase its preparation side of powder Method are as follows: taking purity is 99% or more BaCO3、SrCO3And TiO2As raw material, raw material proportioning is adjusted, deionized water ball milling 8 is added ~ 24 hours, mixed powder kept the temperature pre-burning in 2 ~ 10 hours at 1150-1250 DEG C after drying and screening, and Ba is made1-xSrxTiO3It is single-phase Powder.
Step (1), step (2), ball-milling medium is a kind of in zirconia ball, corundum ball or agate ball in step (3) Or it is a variety of.
Remarkable advantage of the invention is:
1) the dielectric energy storage material prepared by the present invention is mainly Ba1-xSrxTiO3System solid solution and MAS glass, institute Have without ingredients such as environmentally harmful Pb, Bi, Cd in material, it is environmentally friendly；
2) by that will have the Ba of different Curie temperature1-xSrxTiO3Single-phase powder is mixed, and single component dielectric is improved The disadvantage of constant temperature stability difference, to make material that there is lower appearance warm coefficient while keeping high dielectric constant；
3) addition of the MAS glass powder in BST ceramic systems can not only reduce sintering temperature, play energy-efficient effect；And And the Ba of difference x value1-xSrxTiO3Powder keeps original crystal structure as far as possible respectively, preferably reduces dielectric constant pair The dependence of temperature change；
4) addition of MAS glass powder significantly improves dielectric material intensity, to improve energy storage density and the energy storage of material Efficiency；And reduce dielectric loss；
5) the high energy storage density dielectric ceramics obtained by the present invention, permittivity ε are 1600 ~ 4800, dielectric loss Tan δ is less than 0.02, dielectric strength Eb> 18.0kV/mm, energy storage density height (> 2.50J/cm3), dielectric is normal within the scope of -55-125 DEG C Number change rate -13.0%-5.0%.
Detailed description of the invention
1) Fig. 1 is that the XRD of high energy storage density medium ceramic material typical sample of the present invention is composed；
2) Fig. 2 is the typical ferroelectric hysteresis loop of high energy storage density medium ceramic material of the present invention.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
Comparative example 1
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) one-component ceramic powder
Respectively according to Ba1-xSrxTiO3(x=0.1,0.2,0.3,0.4,0.5) weighs BaCO3、SrCO3、TiO2Powder claims Measured powder ball milling 24 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 2:1, tinning Amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry drying after ball milling is placed in alumina crucible Pre-burning 2 hours, obtain Ba respectively at 1150 DEG C0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3、 Ba0.5Sr0.5TiO3This 5 kinds of single-phase powders；
(2) preparation of BST ceramics mixed powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3With Ba0.5Sr0.5TiO3This 5 kinds of crystal phases are that 1:1:1:1:1 is weighed in molar ratio, in deionized water ball milling 12 hours, wherein ball milling Medium is zirconia ball, and ball material mass ratio is 2:1, and tinning amount is the 4/5 of tank volume, 200 revs/min of rotational speed of ball-mill；Ball milling Mixed slurry drying afterwards；
(3) preparation of BST ceramic body
The BST powder that step (2) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 3wt%, Disk is pressed under the pressure of 100MPa；4 hours are kept the temperature at 1300 DEG C, densification BST ceramic material is obtained and is named as BST-0.
The performance of sample made from this comparative example: dielectric constant 8330, dielectric loss 0.055, dielectric strength 13.1kV/ Mm, energy storage density 6.32J/cm3, energy storage efficiency 58%；Change in dielectric constant rate -48.0%-8.8% within the scope of -55-125 DEG C.
Embodiment 1
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
Respectively according to Ba1-xSrxTiO3(x=0.1,0.2,0.3,0.4,0.5) weighs BaCO3、SrCO3And TiO2Powder claims Measured powder ball milling 24 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball/material mass ratio is 2:1, tinning Amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry drying after ball milling is placed in alumina crucible Pre-burning 2 hours at 1150 DEG C obtain Ba0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3With Ba0.5Sr0.5TiO3This 5 kinds of single-phase powders；
(2) preparation of MAS glass powder
According to 15% MgO, 35% Al2O3、50% SiO2Mass ratio weigh MgO, Al2O3And SiO2, load weighted powder Last ball milling 24 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 2:1, and tinning amount is tank body The 1/2 of volume, 250 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1550 DEG C, then is poured into deionized water, is ground after water quenching Obtain 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3With Ba0.5Sr0.5TiO3This 5 kinds of crystal phases are that 1:1:1:1:1 is weighed, and the MAS glass powder prepared in step (2) is added in molar ratio, The additional amount of MAS glass powder is the 1wt% of BST ceramic powder quality, then ball milling 24 hours in deionized water, wherein ball milling Medium is zirconia ball, and ball material mass ratio is 2:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-1 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Disk is pressed under the pressure of 100MPa；It will be sintered 2 hours in 1250 DEG C in air after potsherd dumping, obtain densification BST- 1 ceramics；
The performance of sample made from the present embodiment: dielectric constant 4834, dielectric loss 0.007, dielectric strength 18.5kV/ Mm, energy storage density 7.32J/cm3, energy storage efficiency 89.5%；Change in dielectric constant rate -12.8%- within the scope of -55-125 DEG C 4.8%。
Embodiment 2
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
According to Ba1-xSrxTiO3(x=0.1,0.2,0.3,0.4,0.5) weighs BaCO3、SrCO3And TiO2Powder weighs Powder in alcohol ball milling 24 hours, wherein ball-milling medium be corundum ball, ball material mass ratio be 1:1, tinning amount be tank body hold Long-pending 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry drying after ball milling is placed on 1150 DEG C of pre-burnings 2 in alumina crucible Hour, obtain Ba0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3And Ba0.5Sr0.5TiO3This 5 The single-phase powder of kind；
(2) preparation of MAS glass powder
According to 13wt% MgO, 32wt% Al2O3、55wt% SiO2Ratio weigh MgO, Al2O3And SiO2, load weighted Powder ball milling 8 hours in alcohol, wherein ball-milling medium is corundum ball, and ball material mass ratio is 1:1, and tinning amount is tank volume 1/2,250 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1520 DEG C, then is poured into deionized water, and grinding obtains after water quenching 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3With Ba0.5Sr0.5TiO3This 5 kinds of crystal phases are that 1:1:1:1:1 is weighed, and the MAS glass powder prepared in step (2) is added in molar ratio, The additional amount of MAS glass powder is the 2wt% of BST ceramic powder quality, then ball milling 24 hours in alcohol, wherein ball-milling medium For corundum ball, ball material mass ratio is 1:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-2 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Disk is pressed under the pressure of 100MPa；It will be sintered 2 hours in 1225 DEG C in air after potsherd dumping, obtain densification BST- 2 ceramics.
The performance of sample made from the present embodiment: dielectric constant 3340, dielectric loss 0.015, dielectric strength 19.0kV/ Mm, energy storage density 5.34J/cm3, energy storage efficiency 78.0%, change in dielectric constant rate -10.8%- within the scope of -55-125 DEG C 4.2%。
Embodiment 3
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
Respectively according to Ba1-xSrxTiO3(x=0.1,0.2,0.3,0.4,0.5) weighs BaCO3、SrCO3And TiO2Powder claims Measured powder ball milling 24 hours in alcohol, wherein ball-milling medium is agate ball, and ball material mass ratio is 3:1, and tinning amount is tank The 1/2 of body volume, 250 revs/min of rotational speed of ball-mill；Mixed slurry drying after ball milling be placed in alumina crucible 1150 DEG C it is pre- It burns 2 hours, obtains Ba0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3And Ba0.5Sr0.5TiO3This 5 kinds of single-phase powders；
(2) preparation of MAS glass powder
According to 18wt% MgO, 25wt% Al2O3、57wt% SiO2Ratio weigh MgO, Al2O3、SiO2, load weighted powder End ball milling 16 hours in alcohol, wherein ball-milling medium is agate ball, and ball material mass ratio is 3:1, and tinning amount is tank volume 3/5,200 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1480 DEG C, then is poured into deionized water, and grinding obtains after water quenching 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.8Sr0.2TiO3、Ba0.7Sr0.3TiO3、Ba0.6Sr0.4TiO3With Ba0.5Sr0.5TiO3This 5 kinds of crystal phases are that 1:1:1:1:1 is weighed, and the MAS glass powder prepared in step (2) is added in molar ratio, The additional amount of MAS glass powder is the 5wt% of BST ceramic powder quality, then ball milling 24 hours in alcohol, wherein ball-milling medium For corundum ball, ball material mass ratio is 3:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-3 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Disk is pressed under the pressure of 100MPa；It will be sintered 2 hours in 1200 DEG C in air after potsherd dumping, obtain densification BST- 3 ceramics.
The performance of sample made from the present embodiment: dielectric constant 1691, dielectric loss: 0.016, dielectric strength 19.2kV/ Mm, energy storage density 2.76J/cm3, energy storage efficiency: change in dielectric constant rate -10.5%- within the scope of 72.5%, -55-125 DEG C 4.0%。
Embodiment 4
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
Respectively according to Ba1-xSrxTiO3(x=0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5) is weighed BaCO3、SrCO3And TiO2Powder, load weighted powder ball milling 24 hours in alcohol, wherein ball-milling medium is agate ball, ball material Mass ratio is 1:1, and tinning amount is the 1/2 of tank volume, 250 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling dries postposition 1150 DEG C pre-burning 2 hours in alumina crucible obtain Ba0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders；
(2) preparation of MAS glass powder
According to 15wt% MgO, 28wt% Al2O3、57wt% SiO2Ratio weigh MgO, Al2O3And SiO2, load weighted Powder ball milling 8 hours in alcohol, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 1:1, and tinning amount is tank volume 1/2,100 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1500 DEG C, then is poured into deionized water, and grinding obtains after water quenching 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders are weighed according to equimolar, and the MAS glass powder prepared in step (2) is added, The additional amount of MAS glass powder is the 5wt% of BST ceramic powder quality, then ball milling 24 hours in alcohol, wherein ball-milling medium For zirconia ball, ball/material mass ratio is 1:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-4 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Square piece is pressed under the pressure of 100MPa；It will be sintered 2 hours in 1200 DEG C in air after potsherd dumping, obtain densification BST- 4 ceramics.
The performance of sample made from the present embodiment: dielectric constant 1780, dielectric loss: 0.015, dielectric strength 18.1kV/ Mm, energy storage density 2.58J/cm3, energy storage efficiency: change in dielectric constant rate -8.9%- within the scope of 77.5%, -55-125 DEG C 4.5%。
Embodiment 5
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
According to Ba1-xSrxTiO3(x=0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5) weighs BaCO3、 SrCO3And TiO2Powder, load weighted powder ball milling 24 hours in deionized water, wherein ball-milling medium is corundum ball, ball material matter Amount than be 1:1, tinning amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry drying after ball milling is placed on 1200 DEG C pre-burning 2 hours in alumina crucible obtain Ba0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders；
(2) preparation of MAS glass powder
According to 16% MgO, 32% Al2O3、52% SiO2Ratio weigh MgO, Al2O3And SiO2, load weighted powder exists Ball milling 15 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 1:1, and tinning amount is tank volume 4/5,150 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1525 DEG C, then is poured into deionized water, and grinding obtains after water quenching 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders are weighed according to equimolar, and the MAS glass powder of step (2) preparation, MAS is added The additional amount of glass powder is the 5wt% of BST ceramic powder quality, then ball milling 24 hours in deionized water, wherein ball-milling medium For zirconia ball, ball material mass ratio is 1:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-5 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Disk or square piece are pressed under the pressure of 100MPa；2 hours will be kept the temperature prior to 950 DEG C in air after potsherd dumping, then It is warming up to 1200 DEG C to re-sinter 2 hours, obtains densification BST-5 ceramics.
The performance of sample made from the present embodiment: dielectric constant 1926, dielectric loss 0.008, dielectric strength 25.6kV/ Mm, energy storage density 5.59J/cm3, energy storage efficiency 82.0%, change in dielectric constant rate -8.2%-4.0% within the scope of -55-125 DEG C.
Embodiment 6
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
According to Ba1-xSrxTiO3(x=0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5) weighs BaCO3、 SrCO3And TiO2Powder, load weighted powder ball milling 16 hours in deionized water, wherein ball-milling medium is corundum ball, ball material matter Amount than be 1.5:1, tinning amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling dries postposition 1250 DEG C pre-burning 2 hours in alumina crucible obtain Ba0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders；
(2) preparation of MAS glass powder
According to 15% MgO, 32% Al2O3、53% SiO2Ratio weigh MgO, Al2O3And SiO2, load weighted powder exists Ball milling 15 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 1.5:1, and tinning amount is tank body appearance Long-pending 4/5,150 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1520 DEG C, then is poured into deionized water, is ground after water quenching To 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders are weighed according to equimolar, and the MAS glass powder of step (2) preparation, MAS is added The additional amount of glass powder is the 0.2wt% of BST ceramic powder quality, then ball milling 24 hours in deionized water, and wherein ball milling is situated between Matter is zirconia ball, and ball material mass ratio is 1.5:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-5 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 2.5wt%, Disk or square piece are pressed under the pressure of 100MPa；Then 1260 DEG C are warming up to after potsherd dumping in air and keeps the temperature 8 hours, Obtain densification BST-6 ceramics.
The performance of sample made from the present embodiment: dielectric constant 5780, dielectric loss 0.035, dielectric strength 16.4kV/ Mm, energy storage density 6.88J/cm3, energy storage efficiency 78.5%, change in dielectric constant rate -18.8%- within the scope of -55-125 DEG C 6.5%。
Embodiment 7
A kind of preparation method of high energy storage density medium ceramic material, specific steps are as follows:
(1) Ba1-xSrxTiO3The synthesis of (x=0.1-0.5) ceramic powder
According to Ba1-xSrxTiO3(x=0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5) weighs BaCO3、 SrCO3And TiO2Powder, load weighted powder ball milling 20 hours in deionized water, wherein ball-milling medium is corundum ball, ball material matter Amount than be 2.5:1, tinning amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling dries postposition 1200 DEG C pre-burning 2 hours in alumina crucible obtain Ba0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders；
(2) preparation of MAS glass powder
According to 16% MgO, 30% Al2O3、54% SiO2Ratio weigh MgO, Al2O3And SiO2, load weighted powder exists Ball milling 15 hours in deionized water, wherein ball-milling medium is zirconia ball, and ball material mass ratio is 1.8:1, and tinning amount is tank body appearance Long-pending 4/5,150 revs/min of rotational speed of ball-mill；4h melting is kept the temperature at 1500 DEG C, then is poured into deionized water, is ground after water quenching To 10-50 microns of glass powder；
(3) preparation of BST ceramic powder
The Ba that will be synthesized in step (1)0.9Sr0.1TiO3、Ba0.85Sr0.15TiO3、Ba0.8Sr0.2TiO3、 Ba0.75Sr0.25TiO3、Ba0.7Sr0.3TiO3、Ba0.65Sr0.35TiO3、Ba0.6Sr0.4TiO3、Ba0.55Sr0.55TiO3With Ba0.5Sr0.5TiO3Totally 9 kinds of single-phase BST powders are weighed according to equimolar, and the MAS glass powder of step (2) preparation, MAS is added The additional amount of glass powder is the 10wt% of BST ceramic powder quality, then ball milling 20 hours in deionized water, and wherein ball milling is situated between Matter is zirconia ball, and ball material mass ratio is 1.8:1, and tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；
(4) preparation of BST-5 ceramics
The powder that step (3) obtain is mixed with binder PVAC polyvinylalcohol solution, adding proportion 3.5wt%, Disk or square piece are pressed under the pressure of 100MPa；2 hours will be kept the temperature prior to 850 DEG C in air after potsherd dumping, then It is warming up to 1150 DEG C and keeps the temperature 2 hours again, obtain densification BST-5 ceramics.
The performance of sample made from the present embodiment: dielectric constant 1620, dielectric loss 0.006, dielectric strength 22.8kV/ Mm, energy storage density 3.73J/cm3, energy storage efficiency 84.0%, change in dielectric constant rate -7.9%-4.2% within the scope of -55-125 DEG C.
The energy storage characteristic of 1 embodiment sample of table
Ceramics of the invention have perovskite crystal phase structure (as shown in Figure 1)；Ceramic material of the present invention has thin as shown in Figure 2 Long ferroelectric hysteresis loop, so that it is guaranteed that its energy storage efficiency with higher.And table 1 show ceramics of the invention have high dielectric constant, Low-dielectric loss, good dielectric constant temperature stability and excellent energy storage characteristic.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (5)

1. a kind of high energy storage density medium ceramic material, it is characterised in that: the ceramic material its be by BST ceramics mixed powder Body and MAS glass powder are combined, and the dosage of MAS glass powder is the 0.2% ~ 10% of BST ceramics mixed powder quality；Described MAS glass powder is consisting of MgO-Al2O3-SiO2；The BST ceramics mixed powder is that x value is any value in 0.1-0.5 Ba1-xSrxTiO3In single-phase powder two or more powder equimolars mixing, ball milling and obtain；Described its group of MAS glass powder Become: MgO 10-18wt%, Al2O325-35wt% and SiO2The sum of the mass percent of 50-58wt%, three kinds of components is 100%。
2. high energy storage density medium ceramic material according to claim 1, it is characterised in that: the medium ceramic material Its dielectric constant>1600, dielectric loss<0.02, breakdown field strength>18.0kV/mm, energy storage density>2.50J/cm3。
3. a kind of prepare the method such as the described in any item high energy storage density medium ceramic materials of claim 1-2, feature exists In: the following steps are included:
(1) preparation of MAS glass powder:
By MgO, Al2O3And SiO2For powder ball milling 8-24 hours in deionized water or alcohol, ball material mass ratio is not less than 1:1, Tinning amount be tank volume 1/2-4/5,100-250 revs/min of rotational speed of ball-mill；Then it is molten that 4h is kept the temperature at 1475-1550 DEG C Melt, then pour into deionized water, grinding obtains 10-50 microns of MAS glass powder after water quenching；
(2) preparation of BST ceramics mixed powder:
It is the Ba of any value in 0.1-0.5 by x value1-xSrxTiO3Two or more powder equimolars mixing in single-phase powder, Ball milling 8-24 hours in deionized water or alcohol；Wherein ball material mass ratio is not less than 1:1, and tinning amount is the 1/ of tank volume , 100-250 revs/min of rotational speed of ball-mill；After the mixed slurry drying after ball milling, BST ceramics mixed powder is obtained；
(3) preparation of high energy storage density medium ceramic material:
The MAS glass powder of step (1) preparation, the ball in deionized water are added in the BST ceramics mixed powder made from step (2) Mill 24 hours is uniformly mixed it, and ball material mass ratio is not less than 1:1, and tinning amount is the 1/2-4/5 of tank volume, rotational speed of ball-mill 100-250 revs/min；Mixed slurry drying after ball milling, obtains the media ceramic powder of high energy storage density；Continue in powder 5 ~ 10wt% poly-vinyl alcohol solution is added, powder is granulated, disk or square piece are then pressed into；By after potsherd dumping Then prior to 850-950 DEG C heat preservation 0-2 hours in air are warming up to 1150 ~ 1300 DEG C of sintering 2-8 hours, it is close to obtain high energy storage Spend medium ceramic material.
4. the method for high energy storage density medium ceramic material according to claim 3, it is characterised in that: x takes in step (2) Value is the Ba of any value in 0.1-0.51-xSrxTiO3Single-phase powder preparation method are as follows: taking purity is 99% or more BaCO3、 SrCO3And TiO2As raw material, raw material proportioning is adjusted, is added deionized water ball milling 8 ~ 24 hours, mixed powder exists after drying and screening Pre-burning in 2 ~ 10 hours is kept the temperature at 1150-1250 DEG C, synthesizes Ba1-xSrxTiO3Single-phase powder.
5. the method for high energy storage density medium ceramic material according to claim 3, it is characterised in that: step (1), step (2), ball-milling medium is one or more of zirconia ball, corundum ball or agate ball in step (3).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199036A (en) * 2011-02-25 2011-09-28 武汉理工大学 Method for preparing energy storage ceramic with high breakdown strength
CN102775069A (en) * 2012-07-20 2012-11-14 同济大学 Preparation method of barium strontium titanate based glass ceramic energy storage material
CN105198409A (en) * 2015-10-21 2015-12-30 浙江大学 Preparation method of barium-strontium-titanate-based glass composite ceramic with high energy storage density

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199036A (en) * 2011-02-25 2011-09-28 武汉理工大学 Method for preparing energy storage ceramic with high breakdown strength
CN102775069A (en) * 2012-07-20 2012-11-14 同济大学 Preparation method of barium strontium titanate based glass ceramic energy storage material
CN105198409A (en) * 2015-10-21 2015-12-30 浙江大学 Preparation method of barium-strontium-titanate-based glass composite ceramic with high energy storage density

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Ba0.4Sr0.6TiO3/MgO Composites with Enhanced Energy Storage Density and Low Dielectric Loss for Solid-State Pulse-Forming Line;Qingmeng Zhang et al.;《Int. J. Appl. Ceram. Technol.》;20101231;第7卷;第124-128页
Effect of borosilicate glass on the fabrication and;Hua Hao et al.;《IEEE》;20121231;第1-3页
Effect of MgO–CaO–Al2O3–SiO2 glass additive on dielectric properties;Qing Xu et al.;《Journal of Alloys and Compounds》;20130122;第77-83页

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