CN101935215A - Potassium-sodium lithium niobate-base lead-free piezoelectric ceramic complex with good temperature stability - Google Patents
Potassium-sodium lithium niobate-base lead-free piezoelectric ceramic complex with good temperature stability Download PDFInfo
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- CN101935215A CN101935215A CN201010274117.0A CN201010274117A CN101935215A CN 101935215 A CN101935215 A CN 101935215A CN 201010274117 A CN201010274117 A CN 201010274117A CN 101935215 A CN101935215 A CN 101935215A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- UTBYQPSPFXHANA-UHFFFAOYSA-N [K].[Na].[Li] Chemical compound [K].[Na].[Li] UTBYQPSPFXHANA-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims description 44
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000010287 polarization Effects 0.000 abstract description 5
- 230000005621 ferroelectricity Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 moulding Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a potassium-sodium lithium niobate-base lead-free piezoelectric ceramic complex with good temperature stability, a preparation method and application thereof. The general formula of the complex is as follows: (1-x) (K0.5Na0.5)0.94Li0.06NbO3-xY, wherein, x is equal to 0-0.05 and Y is a perovskite structural component. The complex has the characteristics of good ferroelectricity, relatively higher remanent polarization, relatively higher piezoelectric property, high Curie temperature, low room-temperature dieiectric loss and good temperature stability, thus being applicable to devices such as a piezoelectric actuator, an energy converter, a sensor, a buzzer and the like.
Description
Technical field
The invention belongs to potassium-sodium niobate lithium radical leadless piezo-electric ceramic material field, particularly relate to good lead-free piezoceramic material of a kind of temperature stability and its production and use.
Background technology
Perovskite structure niobate (K, Na) NbO
3(KNN) leadless piezoelectric ceramics, with its superior relatively piezoelectric property be considered to the piezoelectric (H.Birol of a kind of very promising replacement PZT than high-curie temperature, D.Damjanovic, N.Setter, Preparation and characterization of (K
0.5Na
0.5) NbO
3Ceramics[J] .J.Eur.Ceram.Soc.2006,26:861-866.).But since volatile under the basic metal high temperature, thereby adopt conventional solid phase method to be difficult to prepare fine and close KNN pottery, have a strong impact on the performance of material.Though sintering method such as novel preparation technology such as hot pressing, discharge plasma can be prepared fine and close and ceramic body excellent property, to compare with conventional sintering technology, these novel procesies are difficult to realize large-scale industrial production because of cost height, complex process.Therefore, in the last few years, doping vario-property became the main path that improves KNN ceramic post sintering performance and piezoelectric property.Bibliographical information the superior KNN of many piezoelectric properties base pottery, in the KNN of numerous doping vario-properties new system, (K
0.5Na
0.5) NbO
3-LiNbO
3The system pottery has high densification degree, remarkable piezoelectric property and high Curie temperature (Yiping Guo, Ken-ichi Kakimoto, Hitoshi Ohsato.Phase transitionalbehavior and piezoelectric properties of Na
0.5K
0.5NbO
3-LiNbO
3Ceramics[J] .Appl.P hys.Lett.2004,85:4121-4123.), it is the class leadless piezoelectric ceramics that development potentiality is arranged very much, but its temperature stability is relatively poor, (E.Hollenstein, D.Damjanovic, N.Setter, Temperature stability of the piezoelectric properties ofLi-modified KNN ceramics[J] .J.Eur.Ceram.Soc.2007, thus 27:4093-4097) limited (K
0.5Na
0.5) NbO
3-LiNbO
3The system pottery obtains to use comparatively widely in actual production.
Become important topic in the research of KNN matrix based material at present for the research of electric property temperature stability, be directed to piezoelectricity excellence, (K that Curie temperature is high
0.5Na
0.5)
0.94Li
0.06NbO
3(abbreviating KNLN6 as) pottery because its polycrystalline transformation temperature PPT (tiltedly side-tetragonal phase converting point) is present near the room temperature, make the KNLN6 pottery that excellent electric property be arranged near room temperature, but when temperature was higher than the PPT temperature, its performance can run down again.[Hollenstein such as E.Hollenstein, E., Damjanovic, D., Setter, N.Temperature stability ofthe piezoelectric properties of Li-modifiedKNN ceramics[J] .J.Eur.Ceram.Soc.2007,27:4093-4097] studied the temperature stability of the piezoelectric property of KNLN6 pottery, the result shows the piezoelectric constant d when temperature pottery when room temperature is raised to 140 ℃
31With planar electromechanical coupling factor k
pDescended 30%.[Higashide, K., Kakimoto, K., Ohsato, H.T emperaturedependence on the piezoelectric property of (1-x) (Na such as K.Higashide
0.5K
0.5) NbO
3-xLiNbO
3Ceramics[J] .J.Eur.Ceram.Soc.2007,27:4107-4110] find KNLN6 at 160 ℃ of remnant polarization P that locate
rP when only being room temperature
r25% of value.The relatively poor temperature stability of KNLN6 has limited the application of this material reality, and therefore the necessary temperature stability of this material that improves is to obtain practical application widely.
The Chinese patent literature of Granted publication CN 100402466C (application number 200510020230.5) discloses a kind of lead-less lithium sodium potassium niobate piezoelectric ceramic with high curie point and preparation technology thereof, and this pottery is by general formula (1-u) (LixNayK
1-x-yNbO
3+ uMnO
2Going up of expression wants component to form 0.01≤x in the formula≤0.2,0.2≤y≤0.7,0≤u≤0.05.The Chinese patent literature of publication number CN101062864A (application number 200710099675.6) discloses a kind of niobic acid sodium potassium lithium radical leadless piezo-electric ceramic and preparation method thereof.This pottery non-stoichiometric general formula (Na
aK
bLi
c) (Nb
xTa
ySb
Z) O
3Expression, a wherein, b, c represents A position composition element, x, and y, z represent the molar fraction of B position composition element, the range of choice of numerical value is: 0≤a≤1.5,0≤b≤1.5,0≤c≤1.5,1＜a+b+c≤3,0＜x≤1.5,0≤y≤1.5,0≤z≤1.5,1＜(a+b+c)/(x+y+z)≤3 or 0.2＜(a+b+c)/(x+y+z)＜1.The Chinese patent literature of publication number CN 101289318A (application number 200810114773.7) discloses a kind of low temperature synthetic sodion compensating potassium and sodium niobate based leadless piezoelectric ceramics, and material constitutional chemistry formula general formula is (Na
A+x+ K
bLi
c) NbO
3, a wherein, b, c represent Na respectively, K, the molar fraction of Li component, a+b+c=1; X represents to compensate Na
+Molar fraction; Its span is: 0.20＜a＜0.80,0.20＜b＜0.80,0.00＜c＜p, 30,0.00＜x＜0.20; The Na of compensation
+With Na
2O, NaCO
3Or any form adds in the sodium bicarbonate.
But the disclosed technology of above-mentioned patent documentation, only be Curie temperature (CN100402466C), the piezoelectric constant (CN 101062864A) and reduction sintering temperature (CN 101289318A) that improves potassium sodium niobate piezoelectric ceramics, and do not relate to the temperature stability of potassium sodium niobate piezoelectric ceramics.The temperature stability of material property plays crucial effects in actual applications, and temperature stability is relatively poor, makes it unstable at work, and can not be used widely.Therefore, for further improving (K
0.5Na
0.5) NbO
3-LiNbO
3The performance of system pottery to be to obtain the potassium-sodium niobate lithium radical leadless piezo-electric ceramic that over-all properties reaches application standard, all dropped into great amount of manpower both at home and abroad and material resources are carried out the research and development of practicability piezoelectric ceramics, and obtained progress.But can practical application still seldom, it is imperative therefore to develop new potassium-sodium niobate lithium radical leadless piezo-electric ceramic.
Summary of the invention
The object of the present invention is to provide a kind of piezoelectric property excellence, potassium-sodium niobate potassium based leadless piezoelectric ceramics mixture that temperature stability is good and preparation method thereof, and can design different material prescriptions, be made into different components, can satisfy the application in electro-optical devices such as piezoelectric actuator, transverter, transmitter and hummer.
The present invention obtains national natural science fund subsidy project (50602021); The subsidy of country's 863 subsidy projects (2006AA03Z437).
Technical scheme of the present invention is: a class has the potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture of good temperature stability, and general formula is: (1-x) (K
0.5Na
0.5)
0.94Li
0.06NbO
3-xY, x=0-0.05 in the formula, Y are the perovskite structure constituent element.
Aforesaid potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture, preferred scheme is that described perovskite structure constituent element is (Na
0.5Bi
0.5) TiO
3, (K
0.5Bi
0.5) TiO
3, BaTiO
3, PbTiO
3In a kind of or its combination.
Aforesaid potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture, preferred scheme is x=0.01-0.05.Be more preferably, x=0.02-0.04, titanium ore structure constituent element is selected (Na for use
0.5Bi
0.5) TiO
3When x=0.03, resulting mixture 0.97 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.03 (Na
0.5Bi
0.5) TiO
3Also has good performance.
The solid-phase synthesis of aforementioned potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture, step is as follows:
A, prepare burden according to the stoichiometric ratio of general formula;
B, ball milling mix, drying, and 800-900 ℃ of insulation 1-5h is synthetic in advance;
C, fine grinding, oven dry, granulation;
D, moulding, plastic removal;
E, 1060-1130 ℃ sintering, insulation 1-3h.
Aforesaid preparation method, preferred scheme is that step B ball milling mixing time is 2-8h, 850 ℃ of insulation 2h are synthetic in advance.
Aforesaid preparation method, preferred scheme is, step e 1060-1120 ℃ of sintering, insulation 2h.
The present invention also provides the purposes of aforesaid potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture in the preparation piezo ceramic element.
The chemical general formula that the invention provides the potassium-sodium niobate lithium radical leadless piezo-electric ceramic is: (1-x) (K
0.5Na
0.5)
0.94Li
0.06NbO
3-xY[x=0-0.05, Y=(Na
0.5Bi
0.5) TiO
3, (K
0.5Bi
0.5) TiO
3, BaTiO
3And PbTiO
3In a kind of or its combination etc.].The crystalline structure of this material is typical single cubic phase perovskite structure.The preparation technology of this leadless piezoelectric ceramics mixture adopts solid-phase synthesis, and process is as follows: the stoichiometric ratio according to chemical general formula is prepared burden; Ball milling mixes, drying, and pre-synthesizing (800-900 ℃, 4h); Fine grinding, oven dry, granulation; Moulding, plastic removal (550-800 ℃, 2h); Sintering (1060-1130 ℃).The leadless piezoelectric ceramics mixture is prepared into piezoelectric element through top electrode, polarization (room temperature, 40kV/cm, 30 minutes time).
The characteristic of this piezo ceramic element by the preparation of above-mentioned technological process is:
1, such potassium-sodium niobate lithium base piezoelectric ceramic mixture has good ferroelectric, higher relatively remnant polarization, 7.6 μ C/cm
2≤ P
r≤ 20.7 μ C/cm
2
2, such potassium-sodium niobate lithium base piezoelectric ceramic mixture has higher relatively piezoelectric property: d
33=108-212pC/N; k
p=33-41.6%;
3, such potassium-sodium niobate lithium based piezoelectric ceramic materials has high Curie temperature: T
c=388-452 ℃, low room temperature dielectric loss tan δ=0.018-0.037.
4, the piezoelectric property of such potassium-sodium niobate lithium base piezoelectric ceramic mixture has good temperature stability.
Potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture provided by the invention can have excellent temperature stability and good piezoelectric property (d because of the material of other perovskite structure constituent element modifications
33〉=108pC/N; k
p〉=0.33), can satisfy application in devices such as piezoelectric actuator, transverter, transmitter and hummer.
Description of drawings
Fig. 1: embodiment gained piezoelectric ceramic complexes 0.96 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.04 (Na
0.5Bi
0.5) TiO
3XRD figure spectrum.
Fig. 2: embodiment gained piezoelectric ceramic complexes 0.97 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.03 (Na
0.5Bi
0.5) TiO
3Ferroelectric hysteresis loop and coercive field strength.
Fig. 3: embodiment gained piezoelectric ceramic complexes 0.98 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.02 (Na
0.5Bi
0.5) TiO
3Specific inductivity-temperature curve collection of illustrative plates.
Fig. 4: embodiment gained piezoelectric ceramic complexes 0.96 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.04 (Na
0.5Bi
0.5) TiO
3Planar electromechanical coupling factor k
pWith the variation of temperature collection of illustrative plates.
Embodiment
Further illustrate characteristics of the present invention below by embodiment, apparent, embodiment only for the explanation goal of the invention, limits the present invention absolutely not.
Embodiment: with Na
2CO
3, K
2CO
3, Li
2CO
3, Nb
2O
5, Bi
2O
3, TiO
2Be raw material, the purity of all raw materials all is analytically pure.By (1-x) (K
0.5Na
0.5)
0.94Li
0.06NbO
3-x (Na
0.5Bi
0.5) TiO
3(x=0-0.05) stoichiometry weighing, by solid-phase synthesis prepare burden, ball milling mixes pre-synthetic, the fine grinding in 4 hours, dry, 850 ℃ of insulations 2 hours, drying, adding additives, moulding, plastic removal (850 ℃/2 hours), 1060-1130 ℃ sintered heat insulating 2 hours, promptly forms the as above perovskite structure ceramic composite article of prescription.Correlated performance is listed in table 1.Fig. 1 is gained piezoelectric ceramic complexes 0.96 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.04 (Na
0.5Bi
0.5) TiO
3XRD figure spectrum, as seen it is typical single cubic phase perovskite structure.Fig. 2 is gained piezoelectric ceramic complexes 0.97 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.03 (Na
0.5Bi
0.5) TiO
3Ferroelectric hysteresis loop and coercive field strength with the variation of temperature collection of illustrative plates, as seen such potassium-sodium niobate lithium base piezoelectric ceramic mixture has good ferroelectric, higher relatively remnant polarization, very significantly descending does not appear in the ferroelectricity of sample under the high temperature, and shows as P
rAnd E
cAll the rising along with probe temperature slowly descends, and illustrates that the temperature stability of the sample ferroelectric properties after BNT mixes is significantly improved.Fig. 3 is gained piezoelectric ceramic complexes 0.9S (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.02 (Na
0.5Bi
0.5) TiO
3Specific inductivity-temperature curve, as can be seen, such potassium-sodium niobate lithium based piezoelectric ceramic materials has high Curie temperature, low room temperature dielectric loss.Fig. 4 is gained piezoelectric ceramic complexes 0.96 (K
0.5Na
0.5)
0.94Li
0.06NbO
3-0.04 (Na
0.5Bi
0.5) TiO
3Radially electromechanical coupling factor k
pWith the variation of temperature collection of illustrative plates, in the time of 185 ℃, its k
pStill keep more than 85%, as seen it has good temperature stability.
Table 1:(1-x) (K
0.5Na
0.5)
0.94Li
0.06NbO
3-x (Na
0.5Bi
0.5) TiO
3The typical electrical performance of sample
Claims (9)
1. have the potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture of good temperature stability, it is characterized in that general formula is: (1-x) (K
0.5Na
0.5)
0.94Li
0.06NbO
3-xY, x=0-0.05 in the formula, Y are the perovskite structure constituent element.
2. by the described potassium-sodium niobate lithium radical leadless piezo-electric ceramic of claim 1 mixture, it is characterized in that described perovskite structure constituent element is (Na
0.5Bi
0.5) TiO
3, (K
0.5Bi
0.5) TiO
3, BaTiO
3, PbTiO
3In a kind of or its combination.
3. by the described potassium-sodium niobate lithium radical leadless piezo-electric ceramic of claim 1 mixture, it is characterized in that x=0.01-0.05.
4. by the described potassium-sodium niobate lithium radical leadless piezo-electric ceramic of claim 3 mixture, it is characterized in that, x=0.02-0.04, titanium ore structure constituent element is selected (Na for use
0.5Bi
0.5) TiO
3
5. by the described potassium-sodium niobate lithium radical leadless piezo-electric ceramic of claim 3 mixture, it is characterized in that x=0.03.
6. the solid-phase synthesis of the arbitrary described potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture of claim 1-5 is characterized in that step is as follows:
A, prepare burden according to the stoichiometric ratio of general formula;
B, ball milling mix, drying, and 800-900 ℃ of insulation 1-5h is synthetic in advance;
C, fine grinding, oven dry, granulation;
D, moulding, plastic removal;
E, 1060-1130 ℃ sintering, insulation 1-3h.
7. by the described preparation method of claim 6, it is characterized in that step B ball milling mixing time is 2-8h, 850 ℃ of insulation 2h are synthetic in advance.
8. by the described preparation method of claim 6, it is characterized in that step e 1060-1120 ℃ of sintering, insulation 2h.
9. the arbitrary described potassium-sodium niobate lithium radical leadless piezo-electric ceramic mixture of claim 1-5 is in the purposes of preparation in the piezo ceramic element.
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Cited By (6)
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|---|---|---|---|---|
| CN102491752A (en) * | 2011-11-18 | 2012-06-13 | 河南科技大学 | Preparation method of lithium and antimony doped potassium sodium niobate leadless piezoelectric ceramic |
| CN108484167A (en) * | 2018-03-23 | 2018-09-04 | 桂林理工大学 | A kind of the high-temp leadless ceramic capacitor material and preparation method of width temperature range |
| CN112313808A (en) * | 2018-06-21 | 2021-02-02 | 爱奥尼克斯先进科技有限公司 | Method for annealing polarized ceramics |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN114907122A (en) * | 2022-04-01 | 2022-08-16 | 贵州理工学院 | Calcium zirconate-sodium bismuth titanate-sodium lithium sodium potassium antimonate lead-free piezoelectric ceramic and preparation method thereof |
| CN114988871A (en) * | 2022-05-16 | 2022-09-02 | 清华大学 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491752A (en) * | 2011-11-18 | 2012-06-13 | 河南科技大学 | Preparation method of lithium and antimony doped potassium sodium niobate leadless piezoelectric ceramic |
| CN102491752B (en) * | 2011-11-18 | 2013-04-24 | 河南科技大学 | Preparation method of lithium and antimony doped potassium sodium niobate leadless piezoelectric ceramic |
| CN108484167A (en) * | 2018-03-23 | 2018-09-04 | 桂林理工大学 | A kind of the high-temp leadless ceramic capacitor material and preparation method of width temperature range |
| CN112469682A (en) * | 2018-04-21 | 2021-03-09 | 西安交通大学 | Method for obtaining lead-free piezoelectric material and corresponding lead-free piezoelectric material |
| CN112313808A (en) * | 2018-06-21 | 2021-02-02 | 爱奥尼克斯先进科技有限公司 | Method for annealing polarized ceramics |
| CN114907122A (en) * | 2022-04-01 | 2022-08-16 | 贵州理工学院 | Calcium zirconate-sodium bismuth titanate-sodium lithium sodium potassium antimonate lead-free piezoelectric ceramic and preparation method thereof |
| CN114988871A (en) * | 2022-05-16 | 2022-09-02 | 清华大学 | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method and application thereof |
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