CN104725041A - La-doped lead zirconate stannate titanate anti-ferroelectric ceramics with high energy storage efficiency and preparation method thereof - Google Patents

Abstract

The invention relates to La-doped lead zirconate stannate titanate anti-ferroelectric ceramics with high energy storage efficiency and a preparation method thereof. The constitutional chemical formula of the anti-ferroelectric ceramics is (Pb1-1.5xLax)(ZrySn0.9-yTi0.1)O3, wherein x is greater than or equal to 0.02 and smaller than or equal to 0.04, and y is greater than or equal to 0.1 and smaller than or equal to 0.5. According to the preparation method, the anti-ferroelectric ceramics are prepared with a tradional preparation method of electronic ceramics, have the energy storage characteristics of small electric hysteresis and high energy storage efficiency, and have very important significance in developing a high-pressure impulse power capacitor with high energy storage density and high energy storage efficiency.

Description

A kind of high energy storage efficiency La doped zirconium titanium lead stannate antiferroelectric ceramics and preparation method thereof

Technical field

The invention belongs to function ceramics field, relate to a kind of Anti-ferroelectric energy storage ceramic material, particularly relate to a kind of anti-ferroelectric ceramic material and ceramic component of high energy storage efficiency.

Background technology

Since the seventies in last century, along with the development of the technology such as electron beam, laser, Pulse Power Techniques obtain medical widely in new and high technology, the field such as civilian.Energy storage system is the chief component in pulse power device, electrical condenser energy storage fault offset speed is fast, combination flexibly, technology maturation, cheap, become the energy storage device be most widely used at present.In September, 2009, pulse power has answered electricity container item column for its primary study plan by a lot of scientific research institution.

Dielectric material as impulse capacitor mainly contains linear pottery, ferroelectric ceramic(s) and antiferroelectric ceramics three class.Wherein, the key character of antiferroelectric materials has two ferroelectric hysteresis loop, when external electric field is lower, antiferroelectric ceramics is the same with linear pottery, electricdisplacement (D) is linear with electric field (E), after electric field is elevated to certain value, the inner part dipole contrary with direction of an electric field of antiferroelectric structure cell starts to reverse under electric field action, and pottery becomes ferroelectric phase, the electricdisplacement of material and specific inductivity (ε simultaneously _r) increase and the polarizability that reaches capacity suddenly, now pottery is in charging state, the energy density (W stored _st) for forward ferroelectric hysteresis loop is to the integration of polarizability.After removing electric field, the steady ferroelectric phase that is situated between gets back to antiferroelectric phase, and dipole reverses back original state, and ferroelectric-antiferroelectric phase transformation (FE-AFE) occurs, and it is zero that remnant polarization is moved back, the energy density (W discharged _re) for reverse ferroelectric hysteresis loop is to the integration of polarizability.Energy utilization efficiency (η) represents with both ratio, and the energy density of storage, available energy density and energy storage efficiency can be calculated as follows respectively:

$W_{\mathrm{st}}={\∫}_0^{P_{\max }}\mathrm{EdD}$ (during charging)

$W_{\mathrm{re}}={\∫}_{P_r}^{P_{\max }}\mathrm{EdD}$ (during electric discharge)

$\mathrm{\η}=\frac{W_{\mathrm{re}}}{W_{\mathrm{st}}}$

Wherein, the strength of electric field (kV/mm) when E is dielectric medium work, electricdisplacement (μ C/cm when D is applied electric field ²), generally can use polarizability P (μ C/cm ²) replace, P _rand P _maxthe remnant polarization after electric field removes and the maximum polarization when applied electric field respectively.W _rethe main performance perameters of antiferroelectric pulse ceramic condenser in the application two with η, the former determines the available stored energy of capacitance per unit volume device, the miniaturization of paired pulses energy storage device is significant, the latter determines antiferroelectric ceramics electrical condenser available energy proportion in charge and discharge process, has important meaning to improving the heating of impulse capacitor, deformation and cycle charge discharge electric life.In general, the difference of forward and reverse switching electric field and electric hysteresis (Δ E=E _aFE-FE-E _fE-AFE) less, loop line is tiltedly narrower, and η is larger for its energy storage efficiency, and cycle charge discharge electric life is longer (Ferroelectrics, 363:56 – 63,2008) also.

Maximum antiferroelectric materials mainly lead-containing materials of current research, such as lead zirconates (PbZrO ₃), Pb-based lanthanumdoped zirconate titanates (PZT), zirconium titanium lead stannate (PZST) and doped solid solution thereof, wherein the zirconium titanium lead stannate (PLZST) that adulterates of lanthanum (La) is since D.Berlincourt in 1966 etc. draw its ternary phase diagrams first, be have extensively studied half a century (IEEE Transactions on Sonics and Ultrasonics 13 (1966) 116 – 125), because PLZST has abundant phase structure in the region (Ti<0.15) that Ti content is lower: cubic antiferroelectric phase (AFE _t), orthogonal antiferroelectric phase (AFE _o) and tripartite's ferroelectric phase (FE _r), and abundant external field evoked phase-change characteristic, in stopper, large sstrain driving mechanism, pyroelectric detector, energy storage device etc., there is potential application prospect (Appl.Phys.Lett., Vol.72, No.5,1998).And the antiferroelectric phase region of PLZST is wider, component by regulating Zr:Sn:Ti ratio in wider scope, can obtain different energy storage characteristics.But according to current bibliographical information, energy storage efficiency is low is still one of key issue urgently to be resolved hurrily, energy storage efficiency general all (APPLIEDPHYSICS LETTERS 104,263902 (2014) below 75% of current antiferroelectric ceramics electrical condenser or thin-film memory; JOURNAL OF APPLIED PHYSICS 113,054101 (2013); Ceramics International 39 (2013) 5571-5575; Ceramics International 40 (2014) 5455-5460).

Summary of the invention

The present invention is intended to overcome the performance deficiency of existing anti-ferroelectric ceramic material in energy storage efficiency etc., the invention provides a kind of high energy storage efficiency La doped zirconium titanium lead stannate antiferroelectric ceramics and preparation method thereof.

The invention provides a kind of antiferroelectric ceramics, the constitutional chemistry formula of described antiferroelectric ceramics is (Pb _1-1.5xla _x) (Zr _ysn _{0.9- y}ti _0.1) O ₃, wherein, 0.02≤x≤0.04,0.1≤y≤0.5.

Preferably, under described antiferroelectric ceramics room temperature under intensity is greater than the electric field of 7kV/mm, there is reversible AFE-FE phase transformation in the electric hysteresis≤1kV/mm of described antiferroelectric ceramics.

Preferably, described antiferroelectric ceramics is when room temperature, under saturated electric field, energy storage efficiency is greater than 85%.

Preferably, described antiferroelectric ceramics is when room temperature, under saturated electric field, and available energy storage density is at 0.95J/cm ³above.

Again, present invention also offers a kind of preparation method of above-mentioned antiferroelectric ceramics, comprising:

1) by the constitutional chemistry formula of described antiferroelectric ceramics, Pb is taken ₃o ₄, ZrO ₂, TiO ₂, SnO ₂, La ₂o ₃, after Homogeneous phase mixing, as material powder;

2) by step 1) after described material powder briquetting, first sinter at 820-880 DEG C, then grind, obtain ceramic powder;

3) by step 2) after the ceramic powder prepared and binding agent mixing, for the preparation of ceramic body;

4) by step 3) after the ceramic body plastic removal prepared, sinter at 1260-1360 DEG C, obtain described antiferroelectric ceramics.

Preferably, step 2) in, described sintering comprises, and to rise to 820 ~ 880 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 3 hour.

Preferably, step 2) in, according to ceramic powder: ball: water=1:(1.6 ~ 2.0): the quality of (0.5 ~ 0.7) is than fine grinding, and the fine grinding time is 20 ~ 28 hours.

Preferably, step 3) in, described binding agent comprises PVA, and the add-on of binding agent is 6 ~ 8% of ceramic powder weight, after described ceramic powder and binding agent Homogeneous phase mixing, through ageing 22 ~ 26 hours, sieves, is used further to prepare ceramic body.

Preferably, step 4) in, be incubated 1 ~ 3 hour at plastic removal is included in 750 ~ 800 DEG C.

Preferably, step 4) in, sintering condition is to rise to 1260 ~ 1360 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 2 hour.

Preferably, step 4) in, ceramic body is coated with ceramic powder, sinters in confined conditions.

Beneficial effect of the present invention:

The present invention prepares anti-ferroelectric ceramic material by the preparation technology of traditional electronic ceramics, it is little that it has electric hysteresis, the energy storage characteristic that energy storage efficiency is high, has very important significance for the high energy storage density of development cycle discharge and recharge life-span length, the high voltage pulse power electrical condenser of high energy storage efficiency.

Accompanying drawing explanation

Fig. 1 shows the Pb of preparation in embodiment 1 _0.97la _0.02(Zr _0.3sn _0.6ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature, X-coordinate E is strength of electric field, and ordinate zou P is polarizability;

Fig. 2 shows the Pb of preparation in embodiment 2 _0.97la _0.02(Zr _0.22sn _0.68ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature;

Fig. 3 shows the Pb of preparation in embodiment 3 _0.97la _0.02(Zr _0.45sn _0.45ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature;

Fig. 4 shows the comparative data of antiferroelectric ceramics in available energy storage density, stored energy density and energy storage efficiency of embodiment 1, embodiment 2, embodiment 3 preparation.

Embodiment

Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.

The present invention is by adjustment of formula and improving technique, and the PLZST stupalith obtained has narrow ferroelectric hysteresis loop, high energy storage efficiency (η >85%), and energy storage density also higher (>1J/cm ³), the high energy storage density of development cycle discharge and recharge life-span length, the high voltage pulse power electrical condenser of high energy storage efficiency are had very important significance.

The object of this invention is to provide a kind of high energy storage density, the anti-ferroelectric ceramic material of high energy storage efficiency and element, for the field such as high voltage pulse power device preparation in long circulating discharge and recharge life-span provides a kind of antiferroelectric candidate materials.

Consisting of of antiferroelectric ceramics capacitor material of the present invention: (Pb _1-1.5xla _x) (Zr _ysn _0.9-yti _0.1) O ₃, wherein, 0.02≤x≤0.04,0.1≤y≤0.5 is antiferroelectric phase (AFE) during this ceramic room temperature.

This material polarizability-electric field loop line (ferroelectric hysteresis loop) is narrow oblique type, and electric hysteresis little (~ 1kV/mm), have high energy storage efficiency during room temperature, energy storage efficiency is greater than 85%, and available energy storage density is also at 1J/cm ³above, repeatedly cycle charge-discharge work is very beneficial for.Be expected to obtain practical application in high voltage pulse power electrical condenser.

Ceramic component prepared by described anti-ferroelectric ceramic material has excellent performance.

The preparation method of PLZST anti-ferroelectric ceramic material of the present invention, comprises the steps:

A () is with Pb ₃o ₄, ZrO ₂, TiO ₂, SnO ₂, La ₂o ₃powder be raw material, according to (Pb _0.97la _0.02) (Zr _0.58sn _0.42-xti _x) O ₃corresponding element stoichiometric ratio preparation, mix by wet ball-milling method; Briquetting after drying, obtains ceramic block after pre-burning;

In wet ball-milling method mixing described in step (a), according to raw material: ball: water=1:(1.4 ~ 1.8): the mass ratio of (0.7 ~ 1.0), mix 5 ~ 7 hours, wherein ball-milling medium is steel ball or agate ball, and water is deionized water;

Described sintering condition is: to rise to 820 ~ 880 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 3 hour;

B (), by the wet ball-milling method fine grinding of the ceramic block of step (a) gained, adds binding agent granulation, compression moulding after ageing after oven dry, then heat up plastic removal, obtains ceramic body;

In wet ball-milling method described in step (b), according to ceramic powder: ball: water=1:(1.6 ~ 2.0): the quality of (0.5 ~ 0.7) compares fine grinding, to make the particle diameter of ceramic powder comparatively thin and narrowly distributing, wherein ball-milling medium is steel ball, agate ball, and water is deionized water; The described wet ball-milling method fine grinding time is 20 ~ 28 hours, obtains ceramic powder after fine grinding;

Described binding agent is PVA, and the add-on of its binding agent is 6 ~ 8wt.% of ceramic powder weight; Digestion time is 22 ~ 26 hours; Described plastic removal is incubated 1 ~ 3 hour at 750 ~ 800 DEG C to carry out;

C the ceramic body of step (b) gained is put into High Temperature Furnaces Heating Apparatus by (), covering ceramic body, obtaining described stupalith after sintering with having the ceramic powder identical with the moiety of step (a) gained;

Described sintering condition is to rise to 1260 ~ 1360 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 2 hour, furnace cooling.

The preparation method of ferroelectric ceramic(s) element of the present invention, comprises the steps:

The Machining of Ceramics sintered is become desired size, the screen printing of silver paste, dry, after silver ink firing, obtain described ferroelectric ceramic(s) element; Described silver ink firing condition is be incubated 20 ~ 40 minutes at 650 ~ 750 DEG C.

Fig. 1 is Pb _0.97la _0.02(Zr _0.3sn _0.6ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature, X-coordinate E is strength of electric field, and ordinate zou P is polarizability.Can find out, this pottery is AFE phase, and ferroelectric hysteresis loop is " narrow oblique type ".Switching electric field high (>7.5kV/mm), when electric field is 10kV/mm, its room temperature available energy density is 1.28J/cm ³, energy storage efficiency is 90.4%;

Fig. 2 is Pb _0.97la _0.02(Zr _0.22sn _0.68ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature.This pottery is AFE phase, and ferroelectric hysteresis loop is " narrow oblique type ".Switching electric field high (>7.5kV/mm), breaking down field strength high (>11kV/mm), can work under the electric field being greater than 10kV/mm.When electric field is 10kV/mm, its room temperature available energy density is 0.99J/cm ³, energy storage efficiency is 89.5%;

Fig. 3 is Pb _0.97la _0.02(Zr _0.45sn _0.45ti _0.1) O ₃ferroelectric hysteresis loop under pottery room temperature.This pottery is AFE phase, and ferroelectric hysteresis loop is " narrow oblique type ".When electric field is 9kV/mm, its room temperature available energy density is 1.40J/cm ³, energy storage efficiency is 85.1%; Fig. 4 is the comparison of embodiment 1, embodiment 2, the available energy storage density of embodiment 3, stored energy density and energy storage efficiency.3 scope of embodiments spans are larger, and visible the present invention has the higher (>1J/cm of available energy density in very wide compositional range ³), the feature of energy storage efficiency high (>85%).

The present invention prepares anti-ferroelectric ceramic material by the preparation technology of traditional electronic ceramics, it is little that it has electric hysteresis, the energy storage characteristic that energy storage efficiency is high, has very important significance for the high energy storage density of development cycle discharge and recharge life-span length, the high voltage pulse power electrical condenser of high energy storage efficiency.

Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The processing parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.

Embodiment 1:

Anti-ferroelectric ceramic material consists of: Pb _0.97la _0.02(Zr _0.3sn _0.6ti _0.1) O ₃

(1) each constituent Pb in powder raw material is calculated by above-mentioned chemical formula composition ₃o ₄, La ₂o ₃, ZrO ₂, TiO ₂and SnO ₂quality also presses proportion of composing preparation, adopts the mixing of wet ball-milling method, according to raw material: ball: the mass ratio of water=1:1.6:0.9 mixes 7 hours, each component is mixed.After oven dry, cross 40 mesh sieves, in air atmosphere briquetting, rise to 850 DEG C with the heat-up rate of 2 DEG C/min, be incubated synthesis in 2 hours and consist of Pb _0.97la _0.02(Zr _0.58sn _0.33ti _0.09) O ₃ceramic block;

(2) ceramic block of step (1) gained is smashed to pieces, cross 30 mesh sieves, then refine 24 hours by wet ball-milling method, dry the ceramic powder after fine grinding, then the 7wt.%PVA binding agent of powder weight is added, granulation, ageing 24 hours, crosses 30 mesh sieves, be pressed into diameter 15mm, the circular piece of thickness 2.5mm, then heat up plastic removal at 800 DEG C, obtains ceramic body;

(3) in order to prevent plumbous component from volatilizing in the process of sintering, ceramic body is put into alumina crucible, with the ceramic powder with same composition, base substrate is covered, cover ground lid, 1320 DEG C are risen to the heat-up rate of 2 DEG C/min, be incubated 2 hours, after furnace cooling, obtain ceramic material sample;

(4) ceramic material sample sintered is worn into the slice, thin piece of diameter 8mm thickness 0.5mm, cleaning, dry, silk screen printing silver slurry, then dry, rise to 700 DEG C with the heat-up rate of 2 DEG C/min, be incubated 0.5 hour silver ink firing and obtain ceramic component;

(5) ceramic component of the present embodiment has been carried out to the measurement of the ferroelectric hysteresis loop under room temperature, and energy storage density, energy storage efficiency calculate, and the results are shown in Table 1, Fig. 1 and Fig. 4.

Embodiment 2:

Material consists of: Pb _0.97la _0.02(Zr _0.22sn _0.68ti _0.1) O ₃

Repeat the preparation method of embodiment 1 by above-mentioned formula, prepare ceramic component;

The ceramic component of the present embodiment has been carried out to the measurement of the ferroelectric hysteresis loop under room temperature, and energy storage density, energy storage efficiency calculate, and the results are shown in Table 1, Fig. 2 and Fig. 4.

Embodiment 3:

Material consists of: Pb _0.97la _0.02(Zr _0.45sn _0.45ti _0.1) O ₃

Repeat the preparation method of embodiment 1 by above-mentioned formula, prepare ceramic component;

The ceramic component of the present embodiment has been carried out to the measurement of the ferroelectric hysteresis loop under room temperature, and energy storage density, energy storage efficiency calculate, and the results are shown in Table 1, Fig. 3 and Fig. 4.

The main antiferroelectric performance perameter of stupalith when room temperature in table 1 embodiment 1-3

Claims (9)

1. an antiferroelectric ceramics, is characterized in that, the constitutional chemistry formula of described antiferroelectric ceramics is (Pb _1-1.5xla _x) (Zr _ysn _0.9-yti _0.1) O ₃, wherein, 0.02≤x≤0.04,0.1≤y≤0.5.

2. antiferroelectric ceramics according to claim 1, is characterized in that, the electric hysteresis≤1kV/mm of described antiferroelectric ceramics, under described antiferroelectric ceramics room temperature under intensity is greater than the electric field of 7kV/mm, reversible AFE-FE phase transformation occurs.

3. antiferroelectric ceramics according to claim 1 and 2, is characterized in that, described antiferroelectric ceramics is when room temperature, under saturated electric field, energy storage efficiency is greater than 85%.

4., according to described antiferroelectric ceramics arbitrary in claim 1-3, it is characterized in that, described antiferroelectric ceramics is when room temperature, under saturated electric field, and available energy storage density is at 0.95J/cm ³above.

5. the preparation method of arbitrary described antiferroelectric ceramics in claim 1-4, is characterized in that, comprising:

1) by the constitutional chemistry formula of described antiferroelectric ceramics, Pb is taken ₃o ₄, ZrO ₂, TiO ₂, SnO ₂, La ₂o ₃, after Homogeneous phase mixing, as material powder;

2) by after material powder briquetting described in step 1), first sinter at 820-880 DEG C, then grind, obtain ceramic powder;

3) by step 2) after the ceramic powder prepared and binding agent mixing, for the preparation of ceramic body;

4), after the ceramic body plastic removal prepared by step 3), sinter at 1260-1360 DEG C, obtain described antiferroelectric ceramics.

6. preparation method according to claim 5, is characterized in that, step 2) in, described sintering comprises, and to rise to 820 ~ 880 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 3 hour.

7. the preparation method according to claim 5 or 6, is characterized in that, step 2) in, according to ceramic powder: ball: water=1:(1.6 ~ 2.0): the quality of (0.5 ~ 0.7) is than fine grinding, and the fine grinding time is 20 ~ 28 hours.

8. according to described preparation method arbitrary in claim 5-7, it is characterized in that, in step 3), described binding agent comprises PVA, the add-on of binding agent is 6 ~ 8 % of ceramic powder weight, after described ceramic powder and binding agent Homogeneous phase mixing, through ageing 22 ~ 26 hours, sieve, be used further to prepare ceramic body.

9. according to described preparation method arbitrary in claim 5-8, it is characterized in that, in step 4), at plastic removal is included in 750 ~ 800 DEG C, be incubated 1 ~ 3 hour;

Sintering condition is to rise to 1260 ~ 1360 DEG C lower than the heat-up rate of 2 DEG C/min, is incubated 1 ~ 2 hour;

Ceramic body is coated with ceramic powder, sinters in confined conditions.