CN107459347A - A kind of lead-free ceramicses material with high energy storage density and high energy storage efficiency and preparation method thereof - Google Patents

A kind of lead-free ceramicses material with high energy storage density and high energy storage efficiency and preparation method thereof Download PDF

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CN107459347A
CN107459347A CN201710772039.9A CN201710772039A CN107459347A CN 107459347 A CN107459347 A CN 107459347A CN 201710772039 A CN201710772039 A CN 201710772039A CN 107459347 A CN107459347 A CN 107459347A
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storage density
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杨海波
闫非
林营
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Shaanxi University of Science and Technology
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Abstract

A kind of lead-free ceramicses material with high energy storage density and high energy storage efficiency and preparation method thereof, is first according to chemical formula Ba0.4Sr0.6TiO3‑x(Bi2O3‑B2O3‑SiO2) dispensing is carried out, wherein x is Bi2O3‑B2O3‑SiO2Mass percent, and 3wt%≤x≤12wt%.Material powder is obtained after ball milling, drying；The material powder of acquisition is tabletted, sintered at 1300~1350 DEG C, you can obtain the lead-free ceramicses material of high energy storage density and high energy storage efficiency.The ceramic material preparation technology of the present invention simply, stably, is adapted to industrialized production, and its energy storage characteristic is excellent, and the energy storage density based on ferroelectric hysteresis loop calculating is in 1.73~1.98J/cm3Between, energy storage efficiency is more than 90%.

Description

It is a kind of that there is high energy storage density and the lead-free ceramicses material of high energy storage efficiency and its preparation Method
Technical field
The present invention relates to energy-storage capacitor dielectric material technical field, and in particular to one kind has high energy storage density and height Lead-free ceramicses material of energy storage efficiency and preparation method thereof.
Background technology
At present, advanced energy storage material is played the part of as the important component in new material in various electric power, electronic system Drill more and more important role.Meanwhile with the rapid development of information technology, various electronic equipments just towards miniaturization and collect Develop into the direction of change.Therefore, capacitor is as one of electronic component largely used in electronic equipment, it is necessary to have more Excellent performance.Compared to polymer energy storage material, ceramic energy storage material has dielectric constant height, dielectric loss is low, aging is fast The features such as degree is slow, mechanical performance and temperature stability are good, has relatively broad application prospect.But most of lead-free ceramicses storages Can material breakdown strength is not high enough, remanent polarization is larger, cause energy storage density and energy storage efficiency relatively low, it is difficult to meet new The demand that technology further develops.
Barium strontium titanate ((Ba, Sr) TiO3) it is strontium titanates (SrTiO3) and barium titanate (BaTiO3) unlimited solid solution, both had There is SrTiO3Low-dielectric loss and high stability, there is BaTiO again3High-k, and by adjusting Ba/Sr ratio Example, can obtain different dielectric properties.Ba0.4Sr0.6TiO3It is current relatively one of energy storage ceramic material system of rationality, but It is due to Ba0.4Sr0.6TiO3Grain size distribution it is uneven and crystallite dimension is larger so that breakdown electric field is relatively low, cause its Energy storage density only has 0.3J/cm3.It is modified using various mix with after discharge plasma sintering technique, its energy storage density is still In 1.5J/cm3Hereinafter, and energy storage efficiency is less than 80%, it is difficult to meets the needs of practical application.
The content of the invention
It is an object of the invention to overcome defect present in prior art, there is provided one kind has high energy storage density and high storage Can efficiency lead-free ceramicses material, the energy storage density and energy storage efficiency of ceramic material of the present invention are excellent, energy storage density 1.73~ 1.98J/cm3Between, for energy storage efficiency between 90~92%, electric-field intensity has environment between 241~279kV/cm The characteristics such as friendly, technique is simply ripe, practicality is good.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the lead-free ceramicses material with high energy storage density and high energy storage efficiency, comprises the following steps：
(1) by Ba0.4Sr0.6TiO3Powder and Bi2O3-B2O3-SiO2Glass dust is according to chemical formula Ba0.4Sr0.6TiO3-x (Bi2O3-B2O3-SiO2) carry out dispensing and be well mixed, sieving obtains material powder；Wherein x represents Bi2O3-B2O3-SiO2Matter Measure percentage, and 3%≤x≤12%；
(2) material powder for obtaining step (1) is tabletted under 200~250MPa pressure, obtains lead-free ceramicses Material green compact；
(3) the lead-free ceramicses material green sintering for preparing step (2) is obtained with high energy storage density and high energy storage into porcelain The lead-free ceramicses material of efficiency.
The present invention, which further improves, to be, Ba0.4Sr0.6TiO3Powder is prepared by procedure below：By chemical formula Ba0.4Sr0.6TiO3, by SrTiO3Nano-powder and BaTiO3Nano-powder carries out dispensing and is well mixed, and then crosses 120 mesh sieves, Obtain Ba0.4Sr0.6TiO3Powder.
The present invention, which further improves, to be, SrTiO3Nano-powder and BaTiO3Particle diameter of nanometer powder is respectively less than 100nm.
The present invention, which further improves, to be, Bi2O3-B2O3-SiO2Glass dust is prepared by procedure below：According to Bi2O3： B2O3：SiO2=13：4：3 mol ratio weighs Bi2O3、B2O3And SiO2, it is warming up to 1200~1300 DEG C after well mixed and is incubated 1~2 hour, high temp glass melt is obtained, then high temp glass melt is poured into deionized water and forms broken small glass blocks, most Broken small glass blocks is ground afterwards, obtains Bi2O3-B2O3-SiO2Glass dust.
Further improve of the invention is that process is well mixed in step (1) to be carried out by ball milling, ball-milling medium For absolute ethyl alcohol, Ball-milling Time is 12~16 hours.
Further improve of the invention is that sieving was specially 200 mesh sieves in step (1).
Further improve of the invention is that the temperature of sintering is 1300~1350 DEG C in step (3), and the time is 2~3 small When.
A kind of lead-free ceramicses material with high energy storage density and high energy storage efficiency, the chemical formula of the lead-free ceramicses material are Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2), wherein, x represents Bi2O3-B2O3-SiO2Glass dust mass percent, and 3%≤ X≤12%.
Further improve of the invention is that the chemical formula of the lead-free ceramicses material is Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2), wherein, x represents Bi2O3-B2O3-SiO2Mass percent, and 6%≤x≤12%.
Of the invention further improve be, the average grain size of the lead-free ceramicses material is 320~360nm, energy storage Density is 1.73~1.98J/cm3, energy storage efficiency is 90~92%, and electric-field intensity is 241~279kV/cm.
Compared with prior art, the device have the advantages that：The present invention is respectively by Ba0.4Sr0.6TiO3Powder and Bi2O3-B2O3-SiO2Glass dust is well mixed according to stoichiometric proportion by ball-milling technology, be then pressed into type and 1300~ 2~3 hours are incubated at 1350 DEG C and sinters porcelain into, you can obtain the lead-free ceramicses material with high energy storage density and high energy storage efficiency Material.Due to adding frit in ceramic material, it can effectively suppress the growth of crystal grain, play a part of crystal grain thinning, and And glass has higher resistance and resistance to breakdown in itself, so the present invention can be improved effectively by adding frit Ba0.4Sr0.6TiO3The breakdown electric field of ceramic material, further improve energy storage density and energy storage efficiency.Ceramics prepared by the present invention The grain size distribution of material is uniformly and average grain size is smaller (≤360nm), breakdown strength height (>240kV/cm), simultaneously With high energy storage density (>1.7J/cm3) and high energy storage efficiency (>=90%), the energy of storage can be effectively avoided with heat Form release, extend the service life of material.Ceramic material preparation technology prepared by the present invention is simple, stability is good, fine and close Degree is high, can meet the needs of different application, is adapted to industrialized production.
Further, due to the SrTiO used in the present invention3Nano-powder (<100nm) and BaTiO3Nano-powder (< 100nm) using the raw material of industry, it is possible to achieve produce in enormous quantities.
Brief description of the drawings
Fig. 1 is the SEM figures of the lead-free ceramicses material prepared by embodiment 1；
Fig. 2 is the SEM figures of the lead-free ceramicses material prepared by embodiment 2；
Fig. 3 is the SEM figures of the lead-free ceramicses material prepared by embodiment 3；
Fig. 4 is the SEM figures of the lead-free ceramicses material prepared by embodiment 4；
Fig. 5 is ferroelectric hysteresis loop figure of the lead-free ceramicses material under 10Hz test frequencies prepared by embodiment 1；
Fig. 6 is ferroelectric hysteresis loop figure of the lead-free ceramicses material under 10Hz test frequencies prepared by embodiment 2；
Fig. 7 is ferroelectric hysteresis loop figure of the lead-free ceramicses material under 10Hz test frequencies prepared by embodiment 3；
Fig. 8 is ferroelectric hysteresis loop figure of the lead-free ceramicses material under 10Hz test frequencies prepared by embodiment 4.
Embodiment
The present invention is described in further details with reference to the accompanying drawings and detailed description.
A kind of lead-free ceramicses material with high energy storage density and high energy storage efficiency, its chemical formula are：Ba0.4Sr0.6TiO3- x(Bi2O3-B2O3-SiO2), wherein x represents Bi2O3-B2O3-SiO2Mass percent, and 3wt%≤x≤12wt%.
The preparation method of the high energy storage density of the present invention and the lead-free ceramicses material of high energy storage efficiency, comprises the following steps：
(1) chemical formula Ba is pressed0.4Sr0.6TiO3By SrTiO3Nano-powder (<100nm) and BaTiO3Nano-powder (< Dispensing and uniform by ball milling mixing 100nm) is carried out, and ball-milling medium be absolute ethyl alcohol, and Ball-milling Time is 12~16 hours, Then 120 mesh sieves are crossed, obtain Ba0.4Sr0.6TiO3Powder.And SrTiO3Nano-powder and BaTiO3Nano-powder buy in Beijing Deco Dao Jin Science and Technology Ltd.s.
(2) according to Bi2O3：B2O3：SiO2=13：4：3 mol ratio weighs Bi successively2O3, B2O3And SiO2, pass through ball milling It is well mixed, and ball-milling medium is absolute ethyl alcohol, and Ball-milling Time is 12~16 hours, then heats to 1200~1300 DEG C simultaneously Insulation 1~2 hour, obtain high-temperature fusant, then obtained high temp glass melt is quickly poured into deionized water formed it is broken small Glass blocks, finally the broken small glass blocks of formation is ground, obtains Bi2O3-B2O3-SiO2Glass dust；
(3) by the Ba of step (1)0.4Sr0.6TiO3Powder and the Bi of step (2)2O3-B2O3-SiO2Glass dust is according to chemistry Formula Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2) dispensing and uniform by ball milling mixing is carried out, and ball-milling medium is anhydrous Ethanol, Ball-milling Time are 12~16 hours, are then dried at 100 DEG C, and material powder is obtained after crossing 200 mesh sieves；Wherein x is represented Mass fraction, and 3wt%≤x≤12wt%；
(4) by step (3) obtain material powder 200~250MPa pressure lower sheeting, prepare high energy storage density and The lead-free ceramicses material green compact of high energy storage efficiency；
(5) lead-free ceramicses material green compact prepared by step (4) are incubated into 2~3 hours at 1300~1350 DEG C to sinter into Porcelain, you can obtain the lead-free ceramicses material of high energy storage density and high energy storage efficiency.
(6) obtained energy-storing dielectric ceramic material is subjected to surface polishing, 25~35 points is incubated at 1250~1300 DEG C Clock carries out heat erosion, then carries out SEM tests.
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room Its ferroelectric properties is tested under temperature under 10Hz frequencies, and carries out energy storage characteristic calculating, energy storage density (W1) and energy loss density (W2) calculation formula be：
Wherein PmaxRepresent maximum polarization, PrRemanent polarization is represented, E represents electric-field intensity, and P represents that polarization is strong Degree.
The embodiment being given by the following, present disclosure can be further apparent from, but it is not to this hair Bright restriction.
Embodiment 1
The chemical formula of the lead-free ceramicses material of high energy storage density and high energy storage efficiency is：Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2), wherein x represents Bi2O3-B2O3-SiO2Mass percent, and x=3wt%.
The preparation method of the lead-free ceramicses material of above-mentioned high energy storage density and high energy storage efficiency, comprises the following steps：
(1) chemical formula Ba is pressed0.4Sr0.6TiO3By SrTiO3Nano-powder (<100nm) and BaTiO3Nano-powder (< 100nm) carry out dispensing and be well mixed, then cross 120 mesh sieves, obtain Ba0.4Sr0.6TiO3Powder.
(2) according to Bi2O3：B2O3：SiO2=13：4：3 mol ratio weighs Bi successively2O3, B2O3And SiO2Raw material, pass through 1200 DEG C of insulations are warming up to after ball-milling technology is well mixed and obtain high temp glass melt within 2 hours, the high temp glass that then will be obtained Melt, which is quickly poured into, forms broken small glass blocks in deionized water, be finally ground the broken small glass blocks of formation, obtain Bi2O3-B2O3-SiO2Glass dust；
(3) by the Ba of step (1)0.4Sr0.6TiO3Powder and the Bi of step (2)2O3-B2O3-SiO2Glass dust is according to chemistry Formula Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2) carry out dispensing and be well mixed, wherein x represents mass percent, and x= 3wt%, then dried at 100 DEG C, material powder is obtained after crossing 200 mesh sieves；
(4) the raw material powder that step (3) obtains is suppressed under 250MPa pressure, prepares high energy storage density and high energy storage effect The lead-free ceramicses material green compact of rate；
(5) lead-free ceramicses green material prepared by step (4) is incubated 2 hours at 1350 DEG C and sinters porcelain into, you can To high energy storage density and the lead-free ceramicses material of high energy storage efficiency.
Further, process is well mixed in step (1), step (2), step (3) is carried out by ball milling, and ball milling is situated between Matter is absolute ethyl alcohol, and Ball-milling Time is 12 hours.
(6) obtained energy-storing dielectric ceramic material is subjected to surface polishing, 35 minutes is incubated at 1300 DEG C and carries out heat corruption Erosion, then carry out SEM tests.Fig. 1 show the SEM figures of medium ceramic material obtained by the present embodiment, it can be seen that ceramic structure Densification, for crystallite dimension than more uniform, average grain size is about 340nm.
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room Its ferroelectric properties is tested under temperature under 10Hz frequencies, is illustrated in figure 5 the ferroelectric hysteresis loop of the present embodiment ceramic material, obtained electricity Hysteresis curves are more elongated, and back-shaped area is small, breakdown strength 241kV/cm, can be calculated by energy storage characteristic, the present embodiment without The energy storage density of lead energy-storing dielectric ceramic is 1.73J/cm3, energy storage efficiency 91%.Table 1 is the unleaded energy-accumulating medium of the present embodiment The performance index of ceramic material.
Embodiment 2
The chemical formula of the lead-free ceramicses material of high energy storage density and high energy storage efficiency is：Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2), wherein x represents Bi2O3-B2O3-SiO2Mass percent, and x=6wt%.
The preparation method of the lead-free ceramicses material of above-mentioned high energy storage density and high energy storage efficiency, comprises the following steps：
(1) chemical formula Ba is pressed0.4Sr0.6TiO3By SrTiO3Nano-powder (<100nm) and BaTiO3Nano-powder (< 100nm) carry out dispensing and be well mixed, then cross 120 mesh sieves, obtain Ba0.4Sr0.6TiO3Powder.
(2) according to Bi2O3：B2O3：SiO2=13：4：3 mol ratio weighs Bi successively2O3, B2O3And SiO2Raw material, pass through 1270 DEG C of insulations are warming up to after ball-milling technology is well mixed and obtain high temp glass melt within 1.5 hours, the high temperature glass that then will be obtained Glass melt, which is quickly poured into, forms broken small glass blocks in deionized water, be finally ground the broken small glass blocks of formation, obtain To Bi2O3-B2O3-SiO2Glass dust；
(3) by the Ba of step (1)0.4Sr0.6TiO3Powder and the Bi of step (2)2O3-B2O3-SiO2Glass dust is according to chemistry Formula Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2) carry out dispensing and be well mixed, wherein x represents mass percent, and x= 6wt%, then dried at 100 DEG C, material powder is obtained after crossing 200 mesh sieves；
(4) the raw material powder that step (3) obtains is suppressed under 230MPa pressure, prepares high energy storage density and high energy storage effect The lead-free ceramicses material green compact of rate；
(5) lead-free ceramicses green material prepared by step (4) is incubated 2.5 hours at 1325 DEG C and sinters porcelain into, you can Obtain the lead-free ceramicses material of high energy storage density and high energy storage efficiency.
Further, process is well mixed in step (1), step (2), step (3) is carried out by ball milling, and ball milling is situated between Matter is absolute ethyl alcohol, and Ball-milling Time is 14 hours.
(6) obtained energy-storing dielectric ceramic material is subjected to surface polishing, 30 minutes is incubated at 1275 DEG C and carries out heat corruption Erosion, then carry out SEM tests.Fig. 2 show the SEM figures of medium ceramic material obtained by the present embodiment, it can be seen that ceramic structure Densification, for crystallite dimension than more uniform, average grain size is about 320nm.
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room Its ferroelectric properties is tested under temperature under 10Hz frequencies, is illustrated in figure 6 the ferroelectric hysteresis loop of the present embodiment ceramic material, obtained electricity Hysteresis curves are more elongated, and back-shaped area is small, breakdown strength 260kV/cm, can be calculated by energy storage characteristic, the present embodiment without The energy storage density of lead energy-storing dielectric ceramic is 1.87J/cm3, energy storage efficiency 92%.Table 1 is the unleaded energy-accumulating medium of the present embodiment The performance index of ceramic material.
Embodiment 3
The chemical formula of the lead-free ceramicses material of high energy storage density and high energy storage efficiency is：Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2), wherein x represents Bi2O3-B2O3-SiO2Mass fraction, and x=9wt%.
The preparation method of the lead-free ceramicses material of above-mentioned high energy storage density and high energy storage efficiency, comprises the following steps：
(1) chemical formula Ba is pressed0.4Sr0.6TiO3By SrTiO3Nano-powder (<100nm) and BaTiO3Nano-powder (< 100nm) carry out dispensing and be well mixed, then cross 120 mesh sieves, obtain Ba0.4Sr0.6TiO3Powder.
(2) according to Bi2O3：B2O3：SiO2=13：4：3 mol ratio weighs Bi successively2O3, B2O3And SiO2Raw material, pass through 1300 DEG C of insulations are warming up to after ball-milling technology is well mixed and obtain high temp glass melt within 1 hour, the high temp glass that then will be obtained Melt, which is quickly poured into, forms broken small glass blocks in deionized water, be finally ground the broken small glass blocks of formation, obtain Bi2O3-B2O3-SiO2Glass dust；
(3) by the Ba of step (1)0.4Sr0.6TiO3Powder and the Bi of step (2)2O3-B2O3-SiO2Glass dust is according to chemistry Formula Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2) carry out dispensing and be well mixed, wherein x represents mass percent, and x= 9wt%, then dried at 100 DEG C, material powder is obtained after crossing 200 mesh sieves；
(4) the raw material powder that step (3) obtains is suppressed under 200MPa pressure, prepares high energy storage density and high energy storage effect The lead-free ceramicses material green compact of rate；
(5) lead-free ceramicses green material prepared by step (4) is incubated 3 hours at 1300 DEG C and sinters porcelain into, you can To high energy storage density and the lead-free ceramicses material of high energy storage efficiency.
Further, process is well mixed in step (1), step (2), step (3) is carried out by ball milling, and ball milling is situated between Matter is absolute ethyl alcohol, and Ball-milling Time is 16 hours.
(6) obtained energy-storing dielectric ceramic material is subjected to surface polishing, 30 minutes is incubated at 1250 DEG C and carries out heat corruption Erosion, then carry out SEM tests.Fig. 3 show the SEM figures of medium ceramic material obtained by the present embodiment, it can be seen that ceramic structure Densification, for crystallite dimension than more uniform, average grain size is about 330nm.
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room Its ferroelectric properties is tested under temperature under 10Hz frequencies, is illustrated in figure 7 the ferroelectric hysteresis loop of the present embodiment ceramic material, obtained electricity Hysteresis curves are more elongated, and back-shaped area is small, breakdown strength 279kV/cm, can be calculated by energy storage characteristic, the present embodiment without The energy storage density of lead energy-storing dielectric ceramic is 1.98J/cm3, energy storage efficiency 91%.Table 1 is the unleaded energy-accumulating medium of the present embodiment The performance index of ceramic material.
Embodiment 4
The chemical formula of the lead-free ceramicses material of high energy storage density and high energy storage efficiency is：Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2), wherein x represents Bi2O3-B2O3-SiO2Mass fraction, and x=12wt%.
The preparation method of the lead-free ceramicses material of above-mentioned high energy storage density and high energy storage efficiency, comprises the following steps：
(1) chemical formula Ba is pressed0.4Sr0.6TiO3By SrTiO3Nano-powder (<100nm) and BaTiO3Nano-powder (< 100nm) carry out dispensing and be well mixed, then cross 120 mesh sieves, obtain Ba0.4Sr0.6TiO3Powder.
(2) according to Bi2O3：B2O3：SiO2=13：4：3 mol ratio weighs Bi successively2O3, B2O3And SiO2Raw material, pass through 1230 DEG C of insulations are warming up to after ball-milling technology is well mixed and obtain high temp glass melt within 1.5 hours, the high temperature glass that then will be obtained Glass melt, which is quickly poured into, forms broken small glass blocks in deionized water, be finally ground the broken small glass blocks of formation, obtain To Bi2O3-B2O3-SiO2Glass dust；
(3) by the Ba of step (1)0.4Sr0.6TiO3Powder and the Bi of step (2)2O3-B2O3-SiO2Glass dust is according to chemistry Formula Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2) carry out dispensing and be well mixed, wherein x represents mass fraction, and x= 12wt%, then dried at 100 DEG C, material powder is obtained after crossing 200 mesh sieves；
(4) the raw material powder that step (3) obtains is suppressed under 200MPa pressure, prepares high energy storage density and high energy storage effect The lead-free ceramicses material green compact of rate；
(5) lead-free ceramicses green material prepared by step (4) is incubated 2.5 hours at 1300 DEG C and sinters porcelain into, you can Obtain the lead-free ceramicses material of high energy storage density and high energy storage efficiency.
Further, process is well mixed in step (1), step (2), step (3) is carried out by ball milling, and ball milling is situated between Matter is absolute ethyl alcohol, and Ball-milling Time is 15 hours.
(6) obtained energy-storing dielectric ceramic material is subjected to surface polishing, 25 minutes is incubated at 1275 DEG C and carries out heat corruption Erosion, then carry out SEM tests.Fig. 4 show the SEM figures of medium ceramic material obtained by the present embodiment, it can be seen that ceramic structure Densification, for crystallite dimension than more uniform, average grain size is about 360nm.
(7) sample sintered is processed into the thin slice that two sides is smooth, thickness is about 0.2mm, gold-plated electrode, then in room Its ferroelectric properties is tested under temperature under 10Hz frequencies, is illustrated in figure 8 the ferroelectric hysteresis loop of the present embodiment ceramic material, obtained electricity Hysteresis curves are more elongated, and back-shaped area is small, breakdown strength 271kV/cm, can be calculated by energy storage characteristic, the present embodiment without The energy storage density of lead energy-storing dielectric ceramic is 1.89J/cm3, energy storage efficiency 90%.Table 1 is the unleaded energy-accumulating medium of the present embodiment The performance index of ceramic material.
The performance indications of 1 each embodiment sample of table
As shown in Table 1, the crystallite dimension of energy storage ceramic material of the present invention is tiny, below 360 nanometers, its breakdown strength 240kV/cm is all higher than, and the energy storage density of the present invention is in 1.7J/cm3More than, energy loss density is smaller so that storage Energy efficiency is more than 90%.In the application of reality, as energy storage ceramic dielectric material, it is close that high energy storage is not needed only to have Degree, should also have high energy storage efficiency.Because if energy storage efficiency is too low to be caused mostly during exergonic The energy of number storage discharges in the form of heat, and the heat discharged can reduce the service life and other property of material Energy.Meanwhile energy storage ceramic dielectric material of the invention has higher breakdown strength, can widen bias in use Scope.
By example given above, present disclosure can be further apparent from, but it is not to this hair Bright restriction.

Claims (10)

  1. A kind of 1. preparation method of the lead-free ceramicses material with high energy storage density and high energy storage efficiency, it is characterised in that including Following steps：
    (1) by Ba0.4Sr0.6TiO3Powder and Bi2O3-B2O3-SiO2Glass dust is according to chemical formula Ba0.4Sr0.6TiO3-x(Bi2O3- B2O3-SiO2) carry out dispensing and be well mixed, sieving obtains material powder；Wherein x represents Bi2O3-B2O3-SiO2Glass dust quality Percentage, and 3%≤x≤12%；
    (2) material powder for obtaining step (1) is tabletted under 200~250MPa pressure, obtains lead-free ceramicses material Green compact；
    (3) the lead-free ceramicses material green sintering for preparing step (2) is obtained with high energy storage density and high energy storage efficiency into porcelain Lead-free ceramicses material.
  2. A kind of 2. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 1 Method, it is characterised in that Ba0.4Sr0.6TiO3Powder is prepared by procedure below：By chemical formula Ba0.4Sr0.6TiO3, by SrTiO3Receive Ground rice body and BaTiO3Nano-powder carries out dispensing and is well mixed, and then crosses 120 mesh sieves, obtains Ba0.4Sr0.6TiO3Powder.
  3. A kind of 3. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 2 Method, it is characterised in that SrTiO3Nano-powder and BaTiO3Particle diameter of nanometer powder is respectively less than 100nm.
  4. A kind of 4. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 1 Method, it is characterised in that Bi2O3-B2O3-SiO2Glass dust is prepared by procedure below：According to Bi2O3：B2O3：SiO2=13：4：3 Mol ratio weigh Bi2O3、B2O3And SiO2, 1200~1300 DEG C are warming up to after well mixed and is incubated 1~2 hour, obtains height Warm glass melt, then high temp glass melt is poured into deionized water and forms broken small glass blocks, last broken small glass blocks It is ground, obtains Bi2O3-B2O3-SiO2Glass dust.
  5. A kind of 5. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 1 Method, it is characterised in that the process that is well mixed in step (1) is carried out by ball milling, and ball-milling medium is absolute ethyl alcohol, during ball milling Between be 12~16 hours.
  6. A kind of 6. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 1 Method, it is characterised in that sieving was specially 200 mesh sieves in step (1).
  7. A kind of 7. preparation side of lead-free ceramicses material with high energy storage density and high energy storage efficiency according to claim 1 Method, it is characterised in that the temperature of sintering is 1300~1350 DEG C in step (3), and the time is 2~3 hours.
  8. 8. a kind of prepared by method based on described in claim 1-7 any one have high energy storage density and high energy storage efficiency Lead-free ceramicses material, it is characterised in that the chemical formula of the lead-free ceramicses material is Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3- SiO2), wherein, x represents Bi2O3-B2O3-SiO2Mass percent, and 3%≤x≤12%.
  9. 9. a kind of lead-free ceramicses material as claimed in claim 8 with high energy storage density and high energy storage efficiency, its feature exist In the chemical formula of the lead-free ceramicses material is Ba0.4Sr0.6TiO3-x(Bi2O3-B2O3-SiO2), wherein, x represents Bi2O3-B2O3- SiO2Mass percent, and 6%≤x≤12%.
  10. 10. a kind of lead-free ceramicses material as claimed in claim 8 with high energy storage density and high energy storage efficiency, its feature exist In the average grain size of the lead-free ceramicses material is 320~360nm, and energy storage density is 1.73~1.98J/cm3, energy storage effect Rate is 90~92%, and electric-field intensity is 241~279kV/cm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423111A (en) * 2019-07-30 2019-11-08 陕西科技大学 A kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof
CN114671613A (en) * 2022-03-09 2022-06-28 华南理工大学 Glass ceramic material and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423111A (en) * 2019-07-30 2019-11-08 陕西科技大学 A kind of high energy-storage property lead-free ceramics material of environment-friendly type and preparation method thereof
CN110423111B (en) * 2019-07-30 2022-03-25 陕西科技大学 Environment-friendly lead-free ceramic material with high energy storage performance and preparation method thereof
CN114671613A (en) * 2022-03-09 2022-06-28 华南理工大学 Glass ceramic material and preparation method and application thereof

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