CN104710171A - High-energy-density strontium bismuth titanate based composite ceramic and preparation method thereof - Google Patents

Abstract

The invention discloses a high-energy-density strontium bismuth titanate based composite ceramic and a preparation method thereof. Constituents of the high-energy-density strontium bismuth titanate based composite ceramic are expressed by a general formula (1-x-y)Sr(1-1.5)z(Bi0.8La0.2)zTiO(3-x)(Bi0.5Na0.5)(1-m)MgmTiO(3-y)Bi0.5Li0.5(Ti0.92Mn0.08)O3, wherein x, y, z and m represent molar fractions; x is greater than or equal to 0.2 and less than or equal to 0.7; y is greater than or equal to 0.01 and less than or equal to 0.2; z is greater than or equal to 0.05 and less than or equal to 0.3; m is greater than or equal to 0.02 and less than or equal to 0.2. The high-energy-density strontium bismuth titanate based composite ceramic is prepared by adjusting the constituents to form a composite composition, and adopting microwave sintering to form a dense structure with uniform and small crystal grains, so as to keep a high dielectric constant and obtain a high withstand voltage. The preparation method disclosed by the invention is simple and stable in preparation process and suitable for industrial popularization and application. The high-energy-density composite ceramic dielectric material is excellent in energy storage characteristic and energy storage efficiency; the stored energy density can be up to 1.9 J/cm<3>; the energy storage efficiency can be up to 65%; the high-energy-density composite ceramic dielectric material is environment-friendly, low in loss and good in practicability.

Description

A kind of high energy storage density strontium bismuth titanate base complex phase ceramic and preparation method thereof

Technical field

The present invention relates to dielectric energy storage ceramic material, specifically a kind of high energy storage density strontium bismuth titanate base complex phase ceramic and preparation method thereof.

Background technology

Economics of underdevelopment increases acceleration along with growing to energy demand, and the problem improving traditional energy utilising efficiency and expansion new forms of energy usage range highlights day by day.Energy storage capacitor has that discharge power is large, utilising efficiency is high, the energy storage density rising space is large, charge/discharge rates is fast, anti-circulation is aging, be applicable to the extreme environments such as High Temperature High Pressure and steady performance, becomes the energy-storage travelling wave tube in pulse-power apparatus just gradually and is widely used in national defence and the modern industry fields such as electromagnetic railgun weapon, all-electric warship, combat vehicle and hybrid vehicle.Meanwhile, the development of new technology is to improving the energy storage characteristic of dielectric materials and then realizing lightweight, the microminiaturization of equipment and meet special purpose and have higher requirement.But existing dielectric energy storage material exists the problems such as energy storage density is low, discharging current is little, discharge life is short, be difficult to meet the demand that new technology further develops.Therefore, develop the dielectric substance with high energy storage density and become the key improving electrical condenser energy storage characteristic.

The specific inductivity of ceramic dielectic energy storage characteristic and medium itself and high workload field intensity square product direct proportionality.General ferroelectric ceramic(s) dielectric material specific inductivity is large, but disruptive strength is low, therefore, finds and a kind ofly has high-k and the High-energy-storage density dielectric material of high breakdown strength can be kept again to be current facing challenges simultaneously.

Summary of the invention

The object of the invention is to provide a kind of high energy storage density strontium bismuth titanate base complex phase ceramic and preparation method thereof, diphase ceramic material is compounded to form by ferroelectric ceramic(s) and aura ferroelectric material, obtain excellent energy storage characteristic and energy storage efficiency, energy storage density can reach 1.9J/cm ³, energy storage efficiency can reach 65%, and environmental friendliness, loss is low, practicality good.

The technical scheme realizing the object of the invention is:

A kind of high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material, its formula is:

(1- x- y)Sr _1-1.5z(Bi _0.8La _0.2) _zTiO ₃- x(Bi _0.5Na _0.5) _{1- m} Mg _m TiO ₃- yBi _0.5Li _0.5(Ti _0.92Mn _0.08)O ₃

Wherein x, y, z, mrepresent molar fraction, 0.2≤ x≤ 0.7; 0.01≤ y≤ 0.2; 0.05≤ z≤ 0.3; 0.002≤ m≤ 0.2.

The preparation method of high energy storage density strontium bismuth titanate base complex phase ceramic of the present invention, comprises the steps:

(1) by raw material according to chemical formula

(1- x- y)Sr _1-1.5z(Bi _0.8La _0.2) _zTiO ₃- x(Bi _0.5Na _0.5) _{1- m} Mg _m TiO ₃- yBi _0.5Li _0.5(Ti _0.92Mn _0.08)O ₃

Wherein x, y, z, mrepresent molar fraction, 0.2≤ x≤ 0.7; 0.01≤ y≤ 0.2; 0.05≤ z≤ 0.3; 0.002≤ m≤ 0.2 prepares burden, and take dehydrated alcohol as vibration of media ball milling 24 hours, is incubated 4 hours synthetic powders after drying in crucible with 800-900 ° of C pre-burning;

(2) powder obtained is dried, and adds the PVA solution granulation of 2% (weight percent) concentration, makes type disk at 50MPa pressure;

(3) disk after shaping is sintered in microwave agglomerating furnace, ramp to the 600 DEG C insulation of 100 DEG C/h 2 hours, then to be rapidly heated 1100 DEG C of insulations 0.1 hour with the speed of 500 DEG C/h, be cooled to room temperature with stove;

(4) sample after sintering is processed into the thin slice that two sides is smooth, thickness is about 0.3mm, drapes over one's shoulders silver electrode.

Compared with existing material and technology, characteristic of the present invention is embodied in:

1., compared with current material, stupalith of the present invention is diphase ceramic material, namely has the high dielectric property of ferroelectric material, has excellent voltage endurance simultaneously.

2. compared with original technology, the present invention adopts microwave sintering, and sintering temperature is low, soaking time section, and uniform small grains, density is high.

Accompanying drawing explanation

Fig. 1 is stupalith ferroelectric hysteresis loop of the present invention

Fig. 2 stupalith SEM of the present invention schemes.

Embodiment

Embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.7, y=0.1, z=0.1, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.05,

Preparation method comprises the steps:

(1) with analytical pure Bi ₂o ₃, Na ₂cO ₃, SrCO ₃, MgO, TiO ₂, Li ₂cO ₃, MnO ₂and La ₂o ₃for raw material, according to chemical formula (1- x- y) Sr _1-1.5z(Bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08) O ₃( x=0.7, y=0.1, z=0.1, m=0.05), preparing burden, take dehydrated alcohol as vibration of media ball milling 24 hours, is incubated 4 hours synthetic powders after drying in crucible with 850 ° of C pre-burnings;

(2), after powder is dried, add the PVA solution granulation of 2% (weight percent) concentration, make type disk at 50MPa pressure;

(3) disk after shaping sinters in microwave agglomerating furnace, ramp to the 600 DEG C insulation of 100 DEG C/h 2 hours, then to be rapidly heated 1100 DEG C of insulations 0.1 hour with the speed of 500 DEG C/h, is cooled to room temperature with stove;

(4) sample after sintering is processed into the thin slice that two sides is smooth, thickness is about 0.3mm, drapes over one's shoulders silver electrode.

Performance is as shown in table 1.

Embodiment 2:

Composition expression formula is with embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.6, y=0.2, z=0.2, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.1

Preparation method is with embodiment 1, and be incubated 900 ° of C unlike pre-burning, performance is as shown in table 1

Embodiment 3:

Composition expression formula is with embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.4, y=0.15, z=0.08, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.12

Preparation method is with embodiment 1, and be incubated 800 ° of C unlike pre-burning, performance is as shown in table 1

Embodiment 4:

Composition expression formula is with embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.5, y=0.18, z=0.22, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.16

Preparation method is with embodiment 1, and performance is as shown in table 1

Embodiment 5:

Composition expression formula is with embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.3, y=0.18, z=0.26, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.02

Preparation method is with embodiment 1, and performance is as shown in table 1

Embodiment 6:

Composition expression formula is with embodiment 1:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.2, y=0.15, z=0.20, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.15

Preparation method is with embodiment 1, and performance is as shown in table 1

Embodiment 7:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.65, y=0.15, z=0.10, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.10

Preparation method is with embodiment 1, and performance is as shown in table 1

Embodiment 8:

Prepared composition is: (1- x- y) Sr _{1-1.5z (}bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08)

O ₃, wherein x=0.55, y=0.12, z=0.06, mthe high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material of=0.05

Preparation method is with embodiment 1, and performance is as shown in table 1

The electrical property of table 1 embodiment sample

By the embodiment provided, can clearly understand content of the present invention further above, but they not limitation of the invention.

Claims (2)

1. a high energy storage density strontium bismuth titanate base complex phase ceramic dielectric material, is characterized in that: composition general formula is:

(1- x- y)Sr _1-1.5z(Bi _0.8La _0.2) _zTiO ₃- x(Bi _0.5Na _0.5) _{1- m} Mg _m TiO ₃- yBi _0.5Li _0.5(Ti _0.92Mn _0.08)O ₃

Wherein x, y, z, mrepresent molar fraction, 0.2≤ x≤ 0.7; 0.01≤ y≤ 0.2; 0.05≤ z≤ 0.3; 0.02≤ m≤ 0.2.

2. the preparation method of high energy storage density low-loss lead-free ceramics medium as claimed in claim 1, is characterized in that:

(1) according to (1- x- y) Sr _1-1.5z(Bi _0.8la _0.2) _ztiO ₃- x(Bi _0.5na _0.5) _{1- m} mg _m tiO ₃- ybi _0.5li _0.5(Ti _0.92mn _0.08) O ₃

(wherein x, y, z, mrepresent molar fraction, 0.2≤ x≤ 0.7; 0.1≤ y≤ 0.2; 0.05≤ z≤ 0.3; 0.02≤ m≤ 0.2) preparing burden, take dehydrated alcohol as vibration of media ball milling 24 hours, is incubated 4 hours synthetic powders after drying in crucible with 800-900 ° of C pre-burning;

(2) powder obtained is dried, and adds the PVA solution granulation of 2% (weight percent) concentration, makes type disk at 50MPa pressure;

(3) disk after shaping is sintered in microwave agglomerating furnace, ramp to the 600 DEG C insulation of 100 DEG C/h 2 hours, then to be rapidly heated 1100 DEG C of insulations 0.1 hour with the speed of 500 DEG C/h, be cooled to room temperature with stove;

(4) sample after sintering is processed into the thin slice that two sides is smooth, thickness is about 0.3mm, drapes over one's shoulders silver electrode.