CN106187189B - A kind of energy storage microwave dielectric ceramic materials and preparation method thereof - Google Patents

A kind of energy storage microwave dielectric ceramic materials and preparation method thereof Download PDF

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CN106187189B
CN106187189B CN201610541177.1A CN201610541177A CN106187189B CN 106187189 B CN106187189 B CN 106187189B CN 201610541177 A CN201610541177 A CN 201610541177A CN 106187189 B CN106187189 B CN 106187189B
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郑兴华
刘洋
肖腾
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Fuzhou University
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Abstract

The invention discloses a kind of energy storage microwave dielectric ceramic materials and preparation method thereof.First pre-burned is for CaTiO3‑NdAlO3Then powder adds different amounts of MgO-Al2O3‑SiO2Glass powder finally prepares energy storage microwave dielectric ceramic materials.Ceramic material of the present invention has perovskite crystal phase structure and good compactness (relative density > 99%), and have excellent microwave dielectric property and energy-storage property: permittivity ε is 30 ~ 100, breakdown field strength Eb is 180 ~ 531kV/cm, and energy storage density E is 0.08 ~ 0.5J/cm3, microwave dielectric property (2 ~ 15GHz range): permittivity ε is 30 ~ 100, Qf 15000-20000GHz, temperature coefficient adjustable.Preparation process of the present invention is simple, and sintering temperature is lower, has great industrial application value.

Description

A kind of energy storage microwave dielectric ceramic materials and preparation method thereof
Technical field
The invention belongs to electronic ceramics preparation and applied technical fields, and in particular to a kind of energy storage microwave dielectric ceramic materials And preparation method thereof.
Background technique
With the continuous consumption of the energy, the non-renewable problem such as petroleum, natural gas, increasingly increasing of the people to energy demand Long, in addition the drawbacks of energy source, the problem of being tapped a new source of energy thus with energy storage, is extremely urgent.Media ceramic is as capacitor Device because it is light, environmentally friendly, efficient the advantages that receive significant attention.Currently, mainly having three classes as the material that energy-accumulating medium is developed: Battery, supercapacitor and energy-accumulating medium capacitor.Wherein battery has as the highest device of energy storage density and meets miniaturization Requirement, but because its utilize material redox reaction, so possessing very low power density (< 500W/kg), while to ring Border is very harmful.Supercapacitor has power density more higher than battery and energy storage density more higher than dielectric capacitor, but Its structure is complicated, operation voltage is low, leakage current is big, cycle period is short.Dielectric capacitor, which has, stores the fast, transmission that releases energy Power is big, combination flexibly, technology maturation, it is cheap the advantages that.Since the essence of pulse device is by pulse energy in the time It is compressed on scale, to obtain the high-peak power output of (20-100ns) in a very short period of time, therefore as pulse power The high function pulse power of technical equipment main part, capacitor energy storage compared to mechanical energy energy storage and electrochemical energy storage have with Upper advantage so that it is widely used in pulse power device, and is the core of Pulse Power Techniques.Pulse power is answered Energy-accumulating medium requires high dielectric constant and high breakdown field strength.
Currently, according to the rule that dielectric polarization property changes with external electric field, energy-accumulating medium material can be divided into three kinds: line Property dielectric, ferroelectric and antiferroelectric material.Linear dielectric Constant is although lower, but it hardly follows outer power-up The variation of field frequencies range and change, can be used under high frequency, and have response quickly, reversible, multiple charge and discharge, energy storage efficiency close 100% the advantages of.Although ferroelectric material has very high dielectric constant, dielectric constant can be reduced with the increase of electric field, and And usually breakdown field strength is not high, thus energy storage density is not high.Antiferroelectric has high dielectric constant and high breakdown potential Field intensity, therefore there is theoretic high energy storage density.With the small integrated of microwave communication industries, multifunction it is quick Development develops the ceramics as low-loss microwave medium material of series, CaTiO in recent years3-NdAlO3Microwave-medium ceramics are exactly it Middle Typical Representative is widely used in microwave satellite with medium dielectric constant microwave medium, high quality factor and good frequency-temperature coefficient The communications field.
The energy-accumulating medium reported at present is mostly ferroelectricity antiferroelectric ceramics, glass ceramics and polymer, related linear dielectric Report is very few, and related microwave dielectric material is less as the report of energy storage material.CaTiO3-NdAlO3As the micro- of Ku frequency range Wave media ceramic is widely used in satellite digital TV, while having the potentiality of high-frequency pulse power device applications, at present its There is not been reported for energy-storage property.The present invention is directed to keep CaTiO3-NdAlO3While system's ceramics excellent microwave dielectric property, By add glass, reduce its firing temperature, widen firing range, and improve breakdown field strength, thus obtain compared with High energy storage density, microwave-medium multifunctional ceramic material.
Summary of the invention
Complex process, frequency of use in order to overcome the shortcomings of existing energy-storing dielectric ceramic is relatively low, and the present invention provides one kind Energy storage microwave dielectric ceramic materials and preparation method thereof.There is obtained energy storage microwave dielectric material ceramics excellent microwave to be situated between Electrical property and energy storage characteristic.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of energy storage microwave dielectric ceramic materials, chemical composition expression formula are as follows:
(1-x)CaTiO3-xNdAlO3+a%(mMgO -nAl2O3-kSiO2)；Wherein, x is molar fraction, 0.1≤x≤ 0.6；A is CaTiO3-NdAlO3The percentage of quality, 1≤a≤30；M, n, k be mass percent, 15≤m≤20,20≤n≤ 28,52≤k≤60.
The energy storage microwave dielectric ceramic materials: permittivity ε be 30 ~ 100, breakdown field strength Eb be 180 ~ 531kV/cm, energy storage density E are 0.08 ~ 0.5J/cm3；Microwave dielectric property (2 ~ 15GHz range): permittivity ε be 30 ~ 100, Qf 15000-20000GHz, temperature coefficient adjustable.
The preparation method of energy storage microwave dielectric ceramic materials as described above, specifically includes the following steps:
(1) (1-x) CaTiO3-xNdAlO3The preparation of powder
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein 0.1≤x≤0.6, x are molar fraction, is weighed CaCO3、TiO2、Nd2O3And Al2O3Electron level powder；Load weighted powder mixing and ball milling 8 ~ 24 in deionized water or alcohol Hour, wherein ball-milling medium is one or more kinds of in zirconia ball, corundum ball or agate ball, and 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；Mixed slurry after ball milling dries postposition With 1250 ~ 1350 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO in alumina crucible3-xNdAlO3Powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein 15≤m≤20,20≤n≤28,52≤k≤ 60, m, n, k are mass percent, weigh MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, by uniformly mixed powder It is placed in crucible, keeps the temperature 4 hours at 1450 ~ 1600 DEG C, then 10-50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO made from step (1)3-xNdAlO31% ~ 30% mMgO-made from powder and step (2) nAl2O3-kSiO2Glass powder mixing and ball milling 8 ~ 24 hours in deionized water or alcohol, wherein ball-milling medium is zirconium oxide One or more kinds of in ball, corundum ball or agate ball, 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；After mixed slurry drying after ball milling, powder obtained and binder PVA or The mixing of PVB solution, ratio of binder are 3 ~ 10wt%, are pressed into disk under the pressure of 100MPa；Gained potsherd is arranged After glue in air in prior to 850 ~ 950 DEG C heat preservation 1-2 hours, then 1000 ~ 1300 DEG C heat preservation 1-6 hours be sintered, obtain Dense ceramic material.
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode.
Remarkable advantage of the invention is:
Energy storage microwave dielectric ceramic materials provided by the invention, the raw material of use is without any damage human bodies such as Pb, Bi, Cd The ingredient of health, pollution environment, preparation process is simple, and sintering temperature is lower；With excellent microwave dielectric property and energy storage Can: permittivity ε is 30 ~ 100, and breakdown field strength Eb is 180 ~ 531kV/cm, and energy storage density E is 0.08 ~ 0.5J/cm3, micro- Wave dielectric properties (2 ~ 15GHz range): permittivity ε is 30 ~ 100, Qf 15000-20000GHz, temperature coefficient adjustable.
Detailed description of the invention
Fig. 1 is that the SEM of energy storage microwave dielectric ceramic materials of the invention schemes.
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.
Embodiment 1
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.3, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 24 hours in deionized water, wherein ball-milling medium is oxygen Change zirconium ball, ball/material mass ratio 1.5:1, tinning amount be tank volume 1/2,100 revs/min of rotational speed of ball-mill；Mixing after ball milling Slurry drying is placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=15, n=25, k=60, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1500 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO3-xNdAlO3(x=0.3) ceramic powder and 2% mMgO-nAl2O3-kSiO2Glass is in deionization Mixing and ball milling 12 hours in water, wherein ball-milling medium is zirconia ball, and ball/material mass ratio 1.5:1, tinning amount is tank volume 1/2,100 revs/min of rotational speed of ball-mill；It is mixed after mixed slurry drying after ball milling with binder polyvinyl alcohol (PVA) solution, PVA adding proportion is 8wt%, is pressed into disk under the pressure of 100MPa；It will be sintered in air after gained potsherd dumping, 950 DEG C are warming up to furnace and keeps the temperature 1 hour, are then warming up to 1250 DEG C and are kept the temperature 3 hours, then furnace cooling to room temperature, is caused Close ceramic material.
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 2
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.3, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 8 hours in deionized water, wherein ball-milling medium is corundum Ball, ball/material mass ratio 2:1, tinning amount be tank volume 3/5,250 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling dries It is dry to be placed in alumina crucible with 1250 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=20, k=60, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1470 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3Ceramic pre-burning powder and 5% mMgO-nAl2O3-kSiO2Glass Glass ball milling 12 hours in deionized water, wherein ball-milling medium is corundum ball, and ball/material mass ratio 2:1, tinning amount is tank volume 3/5,250 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, powder obtained and binder polyvinyl alcohol (PVA) solution mixes, and PVA adding proportion is 8wt%, is pressed into disk under the pressure of 100MPa；By potsherd dumping obtained It is sintered in air afterwards, is warming up to 850 DEG C with furnace and keeps the temperature 2 hours, be then warming up to 1200 DEG C and keep the temperature 6 hours, it is then cold with furnace But room temperature is arrived, fine and close ceramic material is obtained.
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 3
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.3, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 16 hours in alcohol, wherein ball-milling medium is agate ball, Ball/material mass ratio 2.1:1, tinning amount be tank volume 4/5,200 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling dries It is dry to be placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=18, n=28, k=54, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1550 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3Ceramic pre-burning powder and 10% mMgO-nAl2O3-kSiO2 Glass ball milling 8 hours in alcohol, wherein ball-milling medium is zirconia ball and corundum ball, ball/material mass ratio 2.1:1, tinning amount It is the 1/2 of tank volume, 150 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, powder and binder obtained The mixing of polyvinyl alcohol (PVA) solution, PVA adding proportion are 3wt%, are pressed into disk under the pressure of 100MPa；By gained ceramics It is sintered in air after piece dumping, is warming up to 900 DEG C with furnace and keeps the temperature 1.5 hours, be then warming up to 1150 DEG C and keep the temperature 2 hours, so Furnace cooling obtains fine and close ceramic material to room temperature afterwards.
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 4
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.3, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 12 hours in deionized water, wherein ball-milling medium is rigid Beautiful ball and agate ball, ball/material mass ratio 2.2:1, tinning amount be tank volume 4/5,200 revs/min of rotational speed of ball-mill；After ball milling Mixed slurry drying be placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Pre-burning powder Body；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=28, k=52, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1550 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3(x=0.3) ceramics pre-burning powder and 20% mMgO- nAl2O3-kSiO2Glass ball milling 12 hours in deionized water, wherein ball-milling medium is corundum ball and agate ball, ball/material quality Than 2.2:1, tinning amount is the 4/5 of tank volume, 150 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, it is made Powder mixed with binder polyvinyl alcohol (PVA) solution, PVA adding proportion be 10wt%, be pressed under the pressure of 100MPa Disk；It will be sintered in air after potsherd dumping obtained, be warming up to 850 DEG C with furnace and keep the temperature 2 hours, be then warming up to 1100 DEG C heat preservation 2 hours, then furnace cooling to room temperature, obtain densification ceramic material；
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 5
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.2, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 18 hours in alcohol, wherein ball-milling medium is zirconium oxide Ball, ball/material mass ratio 2.3:1, tinning amount be tank volume 1/2,250 revs/min of rotational speed of ball-mill；Mixed slurry after ball milling Drying is placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Pre-burning powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=25, k=55, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1500 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3(x=0.2) ceramics pre-burning powder and 1% mMgO- nAl2O3-kSiO2Glass ball milling 8 hours in deionized water, wherein ball-milling medium is zirconia ball, ball/material mass ratio 2.3:1, Tinning amount be tank volume 3/5,200 revs/min of rotational speed of ball-mill；After ball milling mixed slurry drying after, powder obtained with The mixing of binder polyvinyl alcohol (PVA) solution, PVA adding proportion are 5wt%, are pressed into disk under the pressure of 100MPa；It will system It is sintered in air after the potsherd dumping obtained, is warming up to 950 DEG C with furnace and keeps the temperature 1 hour, it is small to be then warming up to 1300 DEG C of heat preservations 1 When, then furnace cooling to room temperature obtains fine and close ceramic material；
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 6
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.4, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 24 hours in deionized water, wherein ball-milling medium is rigid Beautiful ball, ball/material mass ratio 2.5:1, tinning amount be tank volume 4/5,200 revs/min of rotational speed of ball-mill；Mixing slurry after ball milling Material drying is placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Pre-burning powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=26, k=54, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1570 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3(x=0.4) ceramics pre-burning powder and 30% mMgO- nAl2O3-kSiO2Glass ball milling 8 hours in alcohol, wherein ball-milling medium is corundum ball, ball/material mass ratio 2.5:1, tinning amount It is the 4/5 of tank volume, 200 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, powder and binder obtained The mixing of PVB solution, PVB adding proportion are 8wt%, are pressed into disk under the pressure of 100MPa；By after potsherd dumping in air Middle sintering is warming up to 950 DEG C with furnace and keeps the temperature 1 hour, is then warming up to 1000 DEG C and keeps the temperature 2 hours, then furnace cooling to room temperature, Obtain fine and close ceramic material；
Sample is processed into that two sides is smooth, thin slice with a thickness of 0.7mm, and it is existing to drape over one's shoulders silver electrode, then tests dielectric properties, counts Calculate energy storage density, performance such as table 1.The sheet of another processing 4mm tests microwave dielectric property (table 2).
Embodiment 7
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.1, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 24 hours in deionized water, wherein ball-milling medium is rigid Beautiful ball, ball/material mass ratio 2.5:1, tinning amount be tank volume 4/5,200 revs/min of rotational speed of ball-mill；Mixing slurry after ball milling Material drying is placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Pre-burning powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=26, k=54, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1450 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3(x=0.4) ceramics pre-burning powder and 15% mMgO- nAl2O3-kSiO2Glass ball milling 8 hours in alcohol, wherein ball-milling medium is corundum ball, ball/material mass ratio 2.5:1, tinning amount It is the 4/5 of tank volume, 200 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, powder and binder obtained The mixing of PVB solution, PVB adding proportion are 8wt%, are pressed into disk under the pressure of 100MPa；By after potsherd dumping in air Middle sintering is warming up to 950 DEG C with furnace and keeps the temperature 1 hour, is then warming up to 1150 DEG C and keeps the temperature 2 hours, then furnace cooling to room temperature, Obtain fine and close ceramic material.
Embodiment 8
(1) (1-x) CaTiO3-xNdAlO3The preparation of preburning powdered material
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, wherein x=0.6, x are molar fraction, weigh CaCO3、 TiO2、Nd2O3、Al2O3Electron level powder；Load weighted powder ball milling 24 hours in deionized water, wherein ball-milling medium is rigid Beautiful ball, ball/material mass ratio 2.5:1, tinning amount be tank volume 4/5,200 revs/min of rotational speed of ball-mill；Mixing slurry after ball milling Material drying is placed in alumina crucible with 1300 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Pre-burning powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, wherein m=20, n=26, k=54, m, n, k are quality hundred Divide ratio, weighs MgO, Al2O3And SiO2Electron level powder is simultaneously uniformly mixed, and the powder mixed is placed in crucible, at 1600 DEG C Middle heat preservation 4 hours, then 10 ~ 50 microns of glass powder is made in water quenching；
(3) (1-x) CaTiO3-xNdAlO3+a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO after preheating3-xNdAlO3(x=0.4) ceramics pre-burning powder and 15% mMgO- nAl2O3-kSiO2Glass ball milling 8 hours in alcohol, wherein ball-milling medium is corundum ball, ball/material mass ratio 2.5:1, tinning amount It is the 4/5 of tank volume, 200 revs/min of rotational speed of ball-mill；After mixed slurry drying after ball milling, powder and binder obtained The mixing of PVB solution, PVB adding proportion are 8wt%, are pressed into disk under the pressure of 100MPa；By after potsherd dumping in air Middle sintering is warming up to 950 DEG C with furnace and keeps the temperature 1 hour, is then warming up to 1200 DEG C and keeps the temperature 2 hours, then furnace cooling to room temperature, Obtain fine and close ceramic material.
The energy storage characteristic of 1 embodiment sample of table
The microwave dielectric property of 2 embodiment sample of table
Present invention ceramics have perovskite crystal phase structure, and are scanned by it known to Electronic Speculum SEM figure (Fig. 1) with good Compactness (relative density > 99%).Present invention ceramics are with normal with high dielectric under Ku frequency range microwave frequency known to table 1 and 2 Number, high quality factor and nearly zero-temperature coefficient, while there is good 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 (3)

1. a kind of energy storage microwave dielectric ceramic materials, it is characterised in that: the chemical composition expression formula of the ceramic material are as follows: (1- x)CaTiO3-xNdAlO3+a%(mMgO -nAl2O3-kSiO2)；Wherein, x is molar fraction, 0.1≤x≤0.6；A is CaTiO3- NdAlO3The percentage of quality, 1≤a≤30；M, n, k are mass percent, 15≤m≤20,20≤n≤28,52≤k≤60； The dielectric constant of the energy storage microwave dielectric ceramic materialsFor 30 ~ 100, Qf 15000-20000GHz, breakdown field strength Eb is 180 ~ 531kV/cm, and energy storage density E is 0.08 ~ 0.5J/cm3。
2. a kind of preparation method of energy storage microwave dielectric ceramic materials as described in claim 1, it is characterised in that: specifically include Following steps:
(1) (1-x) CaTiO3-xNdAlO3The preparation of powder
According to chemical formula (1-x) CaTiO3-xNdAlO3Ingredient is carried out, CaCO is weighed3、TiO2、Nd2O3And Al2O3Electron level powder； Load weighted powder mixing and ball milling 8 ~ 24 hours in deionized water or alcohol；Mixed slurry drying after ball milling is placed on oxygen Change in aluminium crucible with 1250 ~ 1350 DEG C of heat preservations, 3 hours synthesis (1-x) CaTiO3-xNdAlO3Powder；
(2) mMgO-nAl2O3-kSiO2The preparation of glass powder
According to chemical formula mMgO-nAl2O3-kSiO2Ingredient is carried out, MgO, Al are weighed2O3And SiO2Electron level powder simultaneously mixes equal It is even, uniformly mixed powder is placed in crucible, keeps the temperature 4 hours in 1450 ~ 1600 DEG C, then water quenching is made 10-50 microns Glass powder；
(3) (1-x) CaTiO3-xNdAlO3 +a(mMgO -nAl2O3-kSiO2) ceramic system is standby
By (1-x) CaTiO made from step (1)3-xNdAlO3MMgO-nAl made from powder and step (2)2O3-kSiO2Glass Powder is mixing and ball milling 8-24 hours in deionized water or alcohol；After ball milling mixed slurry drying after, powder obtained with The mixing of binder PVA or PVB solution, ratio of binder are 3 ~ 10wt%, are pressed into disk under the pressure of 100MPa； , in air in keeping the temperature 1 ~ 2 hour prior to 850 ~ 950 DEG C, 1 ~ 6 then will be kept the temperature at 1000 ~ 1300 DEG C after gained potsherd dumping Hour sintering, obtains dense ceramic material.
3. a kind of preparation method of energy storage microwave dielectric ceramic materials according to claim 2, it is characterised in that: step (1) technological parameter of ball milling and in step (3) are as follows: ball-milling medium be it is a kind of in zirconia ball, corundum ball or agate ball or It is a variety of, ball/material mass ratio be not less than 1:1, tinning amount be tank volume 1/2 ~ 4/5,100 ~ 250 revs/min of rotational speed of ball-mill.
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