CN107459350B - A kind of dielectric energy storage anti-ferroelectric ceramic material and preparation method thereof - Google Patents
A kind of dielectric energy storage anti-ferroelectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of dielectric energy storage anti-ferroelectric ceramic materials and preparation method thereof, and wherein preparation method includes: by energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material according to mass ratio (30-80): (20-70) is mixed to get mixed-powder；Poly-vinyl alcohol solution is added into mixed-powder, then sintering obtains dielectric energy storage anti-ferroelectric ceramic material.The present invention is by the way that energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material to be dissolved, it obtains within the scope of wide warm area (20 DEG C -150 DEG C), energy storage density stability > 85%, energy storage efficiency are 85% (150 DEG C) and minimum energy storage density is 2.77J/cm3Energy storage material.The present invention solves existing anti-ferroelectric ceramic material, and there are the technical problems of temperature stability difference, this has important value to the practical application of Anti-ferroelectric energy storage ceramic material.
Description
Technical field
The invention belongs to electric energy storage material field, more particularly, to a kind of dielectric energy storage anti-ferroelectric ceramic material and
Preparation method.
Background technique
Classify by working mechanism, electric memory device can be divided into battery, electrochemical capacitor and dielectric capacitor three categories.
Dielectric capacitor carries out energy stores by dielectric polorization, electricdomain steering or transformation behavior, and specific capacity is smaller (to be lower than 30W
H/kg), but specific power is very high (up to 108W/kg), is suitable for high pulse voltage or electric current is supplied, and anti-circulation aging with
Battery and electrochemical capacitor are substantially better than in terms of repid discharge.Currently, dielectric capacitor has become solar energy, wind energy etc. newly
Indispensable component part in energy electricity generation system and hybrid vehicles contravariant equipment energy-storage system；Magnetic artillery,
Also only such capacitor can mention high driving current required for directed energy weapon, comprehensive full electric power push naval vessels etc. to load
For.However, towards working under miniaturization, lightness, adverse circumstances and multifunctional direction development pair in dielectric capacitor practical application
More stringent requirements are proposed for capacitor energy storage density and temperature stability.The key for improving capacitor energy storage characteristic is to develop
Dielectric substance with high energy storage density and high-temperature stability.
Development Level both at home and abroad on high energy storage density antiferroelectric materials is almost the same, and main study subject is lead lanthanum zirconium
Tin titanium (PLZST) material.It is existing the result shows that, the high, ferroelectricity → antiferroelectric phase variable field in conjunction with tetragonal phase PLZST saturated polarization
(EA) small relatively low with orthorhombic phase PLZST ceramics saturated polarization, ferroelectricity-antiferroelectric phase changed electric field is usually above conventional ceramic
The characteristics of disruptive field intensity, design tetragonal phase/orthorhombic phase composite antiferroelectric ceramics are, it can be achieved that improve antiferroelectric ceramics energy storage density
Purpose.Such as Chinese invention patent " a kind of Anti-ferroelectric energy storage ceramic material and its preparation of Patent No. CN201310659224.9
Method " (Authorization Notice No. CN103641477A), for another example entitled " transformation behavior of PLZST based antiferroelectric ceramics and energy storage
Can research " Ph.D. Dissertation.Above-mentioned document, which is mentioned, reaches promotion antiferroelectric ceramics using the method for combining two-phase advantage
The purpose of energy storage density has important application value towards miniaturization, lightness development to electronic product.
However, other than high energy storage density, current power electronic equipment and systems face problem urgently to be resolved: it is good
Temperature stability, especially when material uses at high temperature, when such as 100 DEG C of >.Severe temperature stability prevent material from
Meet application under extreme conditions, such as aerospace power electronics, underground natural gas and oil exploration.In terms of film,
Biaolin Peng etc. studies PBZ, and obtaining temperature, energy storage density reduces by 5% within the scope of DEG C warm area from 25 DEG C to 275
Relaxation film.In terms of thick film, University Of Science and Technology of the Inner Mongol obtains within the scope of 25 DEG C to 200 DEG C warm areas energy storage density by 6.80J/
cm3Drop to 6.40J/cm3PBLZST antiferroelectric thick film material.Ceramic aspect, Zhen Liu et al. have prepared energy storage density W
=1.37J/cm3And the anti-ferroelectric ceramic material of the temperature energy storage density range of decrease≤15% when rising to 100 DEG C by 20 DEG C.Ran Xu etc.
The energy storage density of the PLZST anti-ferroelectric ceramic material of research is by 0.74J/cm3(20 DEG C) drop to 0.29J/cm3(140℃).It can
Know, the energy storage density temperature stability of existing ceramic material is far from meeting application demand.
It can be seen that there are the technical problems of temperature stability difference for existing anti-ferroelectric ceramic material.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of dielectric energy storage antiferroelectric ceramics materials
Material and preparation method thereof, thus solving existing anti-ferroelectric ceramic material, there are the technical problems of temperature stability difference.
To achieve the above object, according to one aspect of the present invention, a kind of dielectric energy storage anti-ferroelectric ceramic material is provided
Preparation method, comprising:
(1) by energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and the antiferroelectric pottery of energy storage density positive temperature coefficient
Porcelain powder body material is according to mass ratio (30-80): (20-70) is mixed to get mixed-powder；
(2) poly-vinyl alcohol solution is added into mixed-powder, then sintering obtains dielectric energy storage anti-ferroelectric ceramic material.
Further, energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and the anti-iron of energy storage density positive temperature coefficient
The mass ratio of electroceramics powder body material is preferred are as follows: 80: 20,60: 40,50: 50,45: 55 or 30: 70.
Further, the chemical formula of energy storage density negative temperature coefficient antiferroelectric ceramics powder body material is (Pb0.97- xBaxLa0.02)(Zr0.65Sn0.3Ti0.05)O3, x=0~0.08.
Further, energy storage density negative temperature coefficient antiferroelectric ceramics powder body material the preparation method comprises the following steps:
According to molar ratio (0.97-x): x: 0.01: 0.65: 0.3: 0.05, x=0~0.08 weighs raw material PbO, BaCO3、
La2O3、ZrO2、SnO2And TiO2, ball milling, drying are successively carried out after raw material is mixed, 2 hours are kept the temperature in 800 DEG C~850 DEG C~
It obtains powder within 3 hours, powder is successively carried out to ball milling, drying, sieving and precompressed is carried out with the pressure of 20MPa, the powder after precompressed
Material carries out secondary sieving, obtains energy storage density negative temperature coefficient antiferroelectric ceramics powder body material.
Further, the chemical formula of energy storage density positive temperature coefficient antiferroelectric ceramics powder body material is Pb0.97La0.02
(Zr0.93Sn0.05Ti0.02)O3。
Further, energy storage density positive temperature coefficient antiferroelectric ceramics powder body material the preparation method comprises the following steps:
According to molar ratio 0.97: 0.01: 0.93: 0.05: 0.02, raw material PbO, La are weighed2O3、ZrO2、SnO2And TiO2, will
Raw material mixing after successively carry out ball milling, drying, keep the temperature 2 hours~3 hours in 800 DEG C~850 DEG C and obtain powder, by powder according to
Secondary progress ball milling, drying, sieving, obtain energy storage density positive temperature coefficient antiferroelectric ceramics powder body material.
Further, the specific implementation of step (2) are as follows:
By mixed-powder successively after ball milling, drying and crushing, the poly-vinyl alcohol solution of concentration 3%~5% is added, gathers
The mass percent that glycohol solution accounts for mixed-powder is 6~10%, then after being granulated, is dry-pressing formed, 1220 DEG C~1250
It is sintered 2~3 hours at a temperature of DEG C, obtains dielectric energy storage anti-ferroelectric ceramic material.
It is another aspect of this invention to provide that providing a kind of dielectric energy storage anti-ferroelectric ceramic material, the dielectric energy storage is anti-
Ferroelectric ceramic material is prepared by preparation method of the invention.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
The present invention is by by energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and energy storage density positive temperature coefficient
The solid solution of antiferroelectric ceramics powder body material, obtains within the scope of wide warm area (20 DEG C -150 DEG C), energy storage density stability > 85%,
Energy storage efficiency is 85% (150 DEG C) and minimum energy storage density is 2.77J/cm3Energy storage material.The present invention solves existing anti-
There are the technical problems of temperature stability difference for ferroelectric ceramic material, this has weight to the practical application of Anti-ferroelectric energy storage ceramic material
It is worth.
Detailed description of the invention
Fig. 1 is that the ferroelectric hysteresis loop for the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention provides is shown
It is intended to；
Fig. 2 be the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention provides energy storage efficiency and
Energy storage density temperature stability schematic diagram；
Fig. 3 is that the ferroelectric hysteresis loop for the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides is shown
It is intended to；
Fig. 4 be the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides energy storage efficiency and
Energy storage density temperature stability schematic diagram；
Fig. 5 is the antiferroelectric ceramics sample XRD schematic diagram that 1-5 of the embodiment of the present invention and comparative example 1-2 is provided；
Fig. 6 (a) is the SEM spectrum for the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention provides；
Fig. 6 (b) is the SEM spectrum for the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides；
Fig. 6 (c) is the SEM spectrum for the dielectric energy storage anti-ferroelectric ceramic material that the embodiment of the present invention 3 provides；
Fig. 7 is the ferroelectric hysteresis loop of the dielectric energy storage anti-ferroelectric ceramic material of the offer of the embodiment of the present invention 3 at different temperatures
Schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of preparation methods of dielectric energy storage anti-ferroelectric ceramic material, comprising:
(1) by energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and the antiferroelectric pottery of energy storage density positive temperature coefficient
Porcelain powder body material is according to mass ratio (30-80): (20-70) is mixed to get mixed-powder；
(2) poly-vinyl alcohol solution is added into mixed-powder, then sintering obtains dielectric energy storage anti-ferroelectric ceramic material.
Embodiment 1
(1) preparation of energy storage density negative temperature coefficient antiferroelectric ceramics powder body material:
Raw material PbO (99.9%), BaCO are weighed according to molar ratio 0.93: 0.04: 0.01: 0.65: 0.3: 0.053
(99.8%), La2O3(99.9%), ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method,
According to raw material: alcohol=1: 0.6 quality rises to 850 DEG C per minute with 5 DEG C after drying, protects in air than 6 hours of ball milling
Temperature 3 hours.Gained powder is subjected to ball milling, drying, sieving, precompressed is carried out with the pressure of 20MPa, the powder after precompressed carries out two
Secondary sieving obtains the pre-burning powder of energy storage density negative temperature coefficient anti-ferroelectric ceramic material.
(2) preparation of energy storage density positive temperature coefficient antiferroelectric ceramics powder body material:
According to molar ratio 0.97: 0.01: 0.93: 0.05: 0.02, raw material PbO (99.9%), La are weighed2O3(99.9%),
ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method, according to raw material: alcohol=1: 0.6
Quality rises to 850 DEG C per minute with 5 DEG C after drying than 6 hours of ball milling, keeps the temperature 3 hours in air.Gained powder is carried out
Ball milling, drying, sieving to get energy storage density positive temperature coefficient anti-ferroelectric ceramic material pre-burning powder.
(3) energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and energy storage density positive temperature coefficient antiferroelectric ceramics
Powder body material solid solution:
By energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and energy storage density positive temperature coefficient antiferroelectric ceramics
Powder body material is mixed according to 30: 70 mass ratio, and ball milling mixing 4 hours, after drying and crushing, the PVA of concentration 5% is added
(polyvinyl alcohol) solution, the mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, at a temperature of 1230 DEG C
Sintering 3 hours, and anneal at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Embodiment 2
(1) pre-burning of energy storage density negative temperature coefficient anti-ferroelectric ceramic material is made with (1) identical method in embodiment 1
Powder；
(2) pre-burning of energy storage density positive temperature coefficient anti-ferroelectric ceramic material is made with (2) identical method in embodiment 1
Powder；
(3) by energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient antiferroelectric ceramics material
Material is mixed according to 50: 50 mass ratio, and ball milling mixing 4 hours, after drying and crushing, the PVA solution of concentration 5% is added,
The mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, is sintered 3 hours at a temperature of 1230 DEG C, and
It anneals at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Embodiment 3
(1) pre-burning of energy storage density negative temperature coefficient anti-ferroelectric ceramic material is made with (1) identical method in embodiment 1
Powder；
(2) pre-burning of energy storage density positive temperature coefficient anti-ferroelectric ceramic material is made with (2) identical method in embodiment 1
Powder；
(3) by energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient antiferroelectric ceramics material
Material is mixed according to 55: 45 mass ratio, and ball milling mixing 4 hours, after drying and crushing, the PVA solution of concentration 5% is added,
The mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, is sintered 3 hours at a temperature of 1230 DEG C, and
It anneals at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Embodiment 4
(1) pre-burning of energy storage density negative temperature coefficient anti-ferroelectric ceramic material is made with (1) identical method in embodiment 1
Powder；
(2) pre-burning of energy storage density positive temperature coefficient anti-ferroelectric ceramic material is made with (2) identical method in embodiment 1
Powder；
(3) by energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient antiferroelectric ceramics material
Material is mixed according to 60: 40 mass ratio, and ball milling mixing 4 hours, after drying and crushing, the PVA solution of concentration 5% is added,
The mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, is sintered 3 hours at a temperature of 1230 DEG C, and
It anneals at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Embodiment 5
(1) pre-burning of energy storage density negative temperature coefficient anti-ferroelectric ceramic material is made with (1) identical method in embodiment 1
Powder；
(2) pre-burning of energy storage density positive temperature coefficient anti-ferroelectric ceramic material is made with (2) identical method in embodiment 1
Powder；
(3) by energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient antiferroelectric ceramics material
Material is mixed according to 80: 20 mass ratio, and ball milling mixing 4 hours, after drying and crushing, the PVA solution of concentration 5% is added,
The mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, is sintered 3 hours at a temperature of 1230 DEG C, and
It anneals at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Comparative example 1
Raw material PbO (99.9%), BaCO are weighed according to molar ratio 0.93: 0.04: 0.01: 0.65: 0.3: 0.053
(99.8%), La2O3(99.9%), ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method,
According to raw material: alcohol=1: 0.6 quality rises to 850 DEG C per minute with 5 DEG C after drying, protects in air than 6 hours of ball milling
Temperature 3 hours.The PVA solution of concentration 5% is added, the mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed,
It is sintered 3 hours, and anneals at 1000 DEG C 1 hour at a temperature of 1230 DEG C, Anti-ferroelectric energy storage ceramic material is made.
Comparative example 2
According to molar ratio 0.97: 0.01: 0.93: 0.05: 0.02, raw material PbO (99.9%), La are weighed2O3(99.9%),
ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method, according to raw material: alcohol=1: 0.6
Quality rises to 850 DEG C per minute with 5 DEG C after drying than 6 hours of ball milling, keeps the temperature 3 hours in air.Concentration 5% is added
PVA solution, the mass percent that solution accounts for powder is 8%, then after being granulated, is dry-pressing formed, it is small that 3 are sintered at a temperature of 1230 DEG C
When, and anneal at 1000 DEG C 1 hour, Anti-ferroelectric energy storage ceramic material is made.
Electric property will be carried out after the resulting ceramic sample grinding of embodiment 1-5 and comparative example 1-2, cleaning, fired electrodes
Test, the results are shown in Table 1.Wherein, energy storage density stability is on the basis of effective energy storage density at 20 DEG C.
1 sample Specifeca tion speeification of table
According to Specifeca tion speeification and Fig. 1-7 it is found that antiferroelectric energy storage material of the invention mainly has the following characteristics that
(1) electric hysteresis for the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention shown in Fig. 1 provides returns
Line schematic diagram, Fig. 2 be the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention provides energy storage efficiency and
Energy storage density temperature stability schematic diagram；Comprehensive analysis Fig. 1 and Fig. 2 learn energy storage density negative temperature coefficient anti-ferroelectric ceramic material
Energy storage density be substantially reduced with the raising of temperature, when temperature reaches 150 DEG C, the energy storage density temperature stability < of material
50%.Energy storage efficiency varies with temperature smaller.
(2) Fig. 3 is the ferroelectric hysteresis loop for the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides
Schematic diagram；Fig. 4 is energy storage efficiency and the storage for the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides
It can density temperature stability schematic diagram；Comprehensive analysis Fig. 3 and Fig. 4 learn energy storage density positive temperature coefficient anti-ferroelectric ceramic material
Energy storage density first increases the trend reduced afterwards with the raising presentation of temperature, when temperature is lower than 100 DEG C, energy storage density < 1J/cm3
Maximum value is obtained at 150 DEG C.Energy storage efficiency is decreased obviously with temperature increase.
(3) Fig. 5 is the antiferroelectric ceramics sample XRD schematic diagram that 1-5 of the embodiment of the present invention and comparative example 1-2 is provided；Implement
The XRD of example 1-5 and comparative example 1-2 antiferroelectric ceramics sample shows that all ceramic principal crystalline phases are perovskite structure, negative temperature system
Several and positive temperature coefficient solid solution sample shows four diffraction maximums at 44 DEG C or so.The right and left is respectively in (002) and (200) direction
There is splitting peak.The result illustrates that negative temperature coefficient and positive temperature coefficient antiferroelectric materials have obtained good solid solution, this with it is solid
The result that molten material energy storage density temperature stability is adjusted is consistent.
(4) Fig. 6 (a) is the SEM figure for the energy storage density negative temperature coefficient anti-ferroelectric ceramic material that comparative example 1 of the present invention provides
Spectrum；Fig. 6 (b) is the SEM spectrum for the energy storage density positive temperature coefficient anti-ferroelectric ceramic material that comparative example 2 of the present invention provides；Fig. 6
(c) SEM spectrum of the dielectric energy storage anti-ferroelectric ceramic material provided for the embodiment of the present invention 3；Fig. 6 (a), Fig. 6 (b), Fig. 6 (c)
Shown in the SEM spectrum of antiferroelectric ceramics sample good consistency is presented.Wherein in map shown in Fig. 6 (a), Fig. 6 (b)
Single grain form is presented；Due to clearly visible two different in diversity Fig. 6 (c) figure of grain growth under the same terms
Grain form.The result equally illustrates that negative temperature coefficient and positive temperature coefficient antiferroelectric materials have obtained good solid solution, this with
The result that solid-solution material energy storage density temperature stability is adjusted is consistent.
(5) Fig. 7 is that the electric hysteresis of the dielectric energy storage anti-ferroelectric ceramic material of the offer of the embodiment of the present invention 3 at different temperatures returns
Line schematic diagram.By the ferroelectric hysteresis loop map comparison of Fig. 7 and comparative example 1-2 it is found that 3 sample of embodiment is in 20-150 DEG C of warm area range
More typical double ferroelectric hysteresis loops are inside all had, the polarization intensity of sample maintains higher level, prominent there is no occurring with temperature
Become.In conjunction with table 1 it is found that 3 sample of embodiment has 2.77J/cm at 150 DEG C3Effective energy storage density, 85% energy storage efficiency
And 86.67% energy storage density temperature stability.
Embodiment 6
(1) preparation of energy storage density negative temperature coefficient anti-ferroelectric ceramic material:
Raw material PbO (99.9%), BaCO are weighed according to molar ratio 0.97: 0: 0.01: 0.65: 0.3: 0.053(99.8%),
La2O3(99.9%), ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method, according to raw material:
Alcohol=1: 0.6 quality rises to 800 DEG C per minute with 5 DEG C after drying than 6 hours of ball milling, keeps the temperature 2 hours in air.
Gained powder is subjected to ball milling, drying, sieving, precompressed is carried out with the pressure of 20MPa, the powder after precompressed carries out secondary sieving,
Obtain the pre-burning powder of energy storage density negative temperature coefficient anti-ferroelectric ceramic material.
(2) preparation of energy storage density positive temperature coefficient anti-ferroelectric ceramic material:
According to molar ratio 0.97: 0.01: 0.93: 0.05: 0.02, raw material PbO (99.9%), La are weighed2O3(99.9%),
ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method, according to raw material: alcohol=1: 0.6
Quality rises to 800 DEG C per minute with 5 DEG C after drying than 6 hours of ball milling, keeps the temperature 2 hours in air.Gained powder is carried out
Ball milling, drying, sieving to get energy storage density positive temperature coefficient anti-ferroelectric ceramic material pre-burning powder.
(3) energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material
Solid solution:
By energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material
It is mixed according to 30: 70 mass ratio, ball milling mixing 4 hours, after drying and crushing, the PVA (polyethylene of concentration 3% is added
Alcohol) solution, the mass percent that solution accounts for powder is 10%, then after being granulated, is dry-pressing formed, is sintered at a temperature of 1220 DEG C
2.5 hours, and anneal at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
Embodiment 7
(1) preparation of energy storage density negative temperature coefficient anti-ferroelectric ceramic material:
Raw material PbO (99.9%), BaCO are weighed according to molar ratio 0.89: 0.08: 0.01: 0.65: 0.3: 0.053
(99.8%), La2O3(99.9%), ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method,
According to raw material: alcohol=1: 0.6 quality rises to 820 DEG C per minute with 5 DEG C after drying, protects in air than 6 hours of ball milling
Temperature 2.5 hours.Gained powder is subjected to ball milling, drying, sieving, precompressed is carried out with the pressure of 20MPa, the powder after precompressed carries out
Secondary sieving obtains the pre-burning powder of energy storage density negative temperature coefficient anti-ferroelectric ceramic material.
(2) preparation of energy storage density positive temperature coefficient anti-ferroelectric ceramic material:
According to molar ratio 0.97: 0.01: 0.93: 0.05: 0.02, raw material PbO (99.9%), La are weighed2O3(99.9%),
ZrO2(99.5%), SnO2(99.6%) and TiO2(99.6%), using wet ball-milling method, according to raw material: alcohol=1: 0.6
Quality rises to 820 DEG C per minute with 5 DEG C after drying than 6 hours of ball milling, keeps the temperature 2.5 hours in air.By gained powder into
Row ball milling, drying, sieving to get energy storage density positive temperature coefficient anti-ferroelectric ceramic material pre-burning powder.
(3) energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material
Solid solution:
By energy storage density negative temperature coefficient anti-ferroelectric ceramic material and energy storage density positive temperature coefficient anti-ferroelectric ceramic material
It is mixed according to 30: 70 mass ratio, ball milling mixing 4 hours, after drying and crushing, the PVA (polyethylene of concentration 4% is added
Alcohol) solution, the mass percent that solution accounts for powder is 6%, then after being granulated, is dry-pressing formed, it is small that 2 are sintered at a temperature of 1250 DEG C
When, and anneal at 1000 DEG C 1 hour, dielectric energy storage anti-ferroelectric ceramic material is made.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of dielectric energy storage anti-ferroelectric ceramic material characterized by comprising
(1) by energy storage density negative temperature coefficient antiferroelectric ceramics powder body material and energy storage density positive temperature coefficient antiferroelectric ceramics powder
Body material is according to mass ratio (30-80): (20-70) is mixed to get mixed-powder；
(2) poly-vinyl alcohol solution is added into mixed-powder, then sintering obtains dielectric energy storage anti-ferroelectric ceramic material；
The chemical formula of the energy storage density negative temperature coefficient antiferroelectric ceramics powder body material is (Pb0.97-xBaxLa0.02)
(Zr0.65Sn0.3Ti0.05)O3, x=0~0.08；The chemical formula of the energy storage density positive temperature coefficient antiferroelectric ceramics powder body material
For Pb0.97La0.02(Zr0.93Sn0.05Ti0.02)O3。
2. a kind of preparation method of dielectric energy storage anti-ferroelectric ceramic material as described in claim 1, which is characterized in that the storage
The matter of energy density negative temperature coefficient antiferroelectric ceramics powder body material and energy storage density positive temperature coefficient antiferroelectric ceramics powder body material
Amount is than preferred are as follows: 80:20,60:40,50:50,45:55 or 30:70.
3. a kind of preparation method of dielectric energy storage anti-ferroelectric ceramic material as described in claim 1, which is characterized in that the storage
Can density negative temperature coefficient antiferroelectric ceramics powder body material the preparation method comprises the following steps:
According to molar ratio (0.97-x): x:0.01:0.65:0.3:0.05, x=0~0.08 weigh raw material PbO, BaCO3、
La2O3、ZrO2、SnO2And TiO2, ball milling, drying are successively carried out after raw material is mixed, 2 hours are kept the temperature in 800 DEG C~850 DEG C~
It obtains powder within 3 hours, powder is successively carried out to ball milling, drying, sieving and precompressed is carried out with the pressure of 20MPa, the powder after precompressed
Material carries out secondary sieving, obtains energy storage density negative temperature coefficient antiferroelectric ceramics powder body material.
4. a kind of preparation method of dielectric energy storage anti-ferroelectric ceramic material as described in claim 1, which is characterized in that the storage
Can density positive temperature coefficient antiferroelectric ceramics powder body material the preparation method comprises the following steps:
According to molar ratio 0.97:0.01:0.93:0.05:0.02, raw material PbO, La are weighed2O3、ZrO2、SnO2And TiO2, by raw material
Successively carried out after mixing ball milling, drying, keep the temperature 2 hours~3 hours in 800 DEG C~850 DEG C and obtain powder, by powder successively into
Row ball milling, drying, sieving obtain energy storage density positive temperature coefficient antiferroelectric ceramics powder body material.
5. a kind of preparation method of dielectric energy storage anti-ferroelectric ceramic material as described in claim 1, which is characterized in that the step
Suddenly the specific implementation of (2) are as follows:
By mixed-powder successively after ball milling, drying and crushing, the poly-vinyl alcohol solution of concentration 3%~5%, polyethylene is added
The mass percent that alcoholic solution accounts for mixed-powder is 6~10%, then after being granulated, is dry-pressing formed, in 1220 DEG C~1250 DEG C temperature
Degree lower sintering 2~3 hours, obtain dielectric energy storage anti-ferroelectric ceramic material.
6. a kind of dielectric energy storage anti-ferroelectric ceramic material, which is characterized in that the dielectric energy storage anti-ferroelectric ceramic material is by right
It is required that preparation method described in 1-5 any one is prepared.
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