CN114213122B - Piezoelectric ceramic material and preparation method thereof - Google Patents
Piezoelectric ceramic material and preparation method thereof Download PDFInfo
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- CN114213122B CN114213122B CN202111630276.4A CN202111630276A CN114213122B CN 114213122 B CN114213122 B CN 114213122B CN 202111630276 A CN202111630276 A CN 202111630276A CN 114213122 B CN114213122 B CN 114213122B
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000011267 electrode slurry Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 3
- 239000002003 electrode paste Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000010344 co-firing Methods 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical group [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 4
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The invention relates to the technical field of ceramic materials, in particular to a piezoelectric ceramic material and a preparation method thereof. The piezoelectric ceramic material is a compound with a perovskite structure, and the molecular general formula is ABX 3 (ii) a The A site element comprises Pb and a doping element I, wherein the doping element I is selected from one or more of Cu and La; b site elements comprise Zr, ti and doping elements II, wherein the doping elements II are selected from one or more of Zn and Nb; the X site elements include O and F. The piezoelectric ceramic material can be co-sintered with the pure silver paste at the temperature of less than or equal to 950 ℃ in a multilayer way, the cost is low, and the dielectric property, the piezoelectric constant and the electromechanical coupling coefficient are higher.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a piezoelectric ceramic material and a preparation method thereof.
Background
With the advent of the intelligent era, piezoelectric ceramic elements are increasingly used as high-performance sensing and executing elements, and with the development of applications, miniaturized piezoelectric elements become the main direction of future development. The multi-layer co-fired piezoelectric element is a key component in the miniaturized piezoelectric element.
The application of any device can not be free from the restriction of the cost of the device except the performance and the function of the device; therefore, for the multi-layer co-fired piezoelectric element, in addition to the requirement of high performance, the cost reduction becomes a key.
The multilayer co-fired element is an element prepared by co-sintering a piezoelectric ceramic material and electrode slurry, and the preparation process saves a sintering step, so that the cost is controlled, the cost is further solved and mainly depends on the cost of the co-fired electrode, generally speaking, the cost of the co-fired electrode slurry accounts for about 70% of the cost of the whole piezoelectric element, and for the piezoelectric multilayer element, the co-fired electrode generally has two options: one is silver palladium slurry (Ag/Pd) mainly containing silver, the ratio of silver to palladium is 70/30-100/0, and the other is copper slurry mainly containing copper.
The copper paste is selected as the co-fired electrode of the multilayer piezoelectric element, the material cost is low directly, and the copper paste is a better choice theoretically, but the copper electrode sintering has high requirements on atmosphere control and material design, so that the copper paste is not a mainstream choice at present. The selection of silver or silver palladium electrode as the co-fired electrode of the multilayer piezoelectric element is a main choice at present, but the silver palladium ratio selected by different manufacturers has a large difference, namely (Ag/Pd: 70/30) (70% of silver and 30% of palladium in silver palladium alloy), optionally (Ag/Pd: 85/15), optionally (Ag/Pd: 90/10), and optionally (Ag/Pd: 95/5, and some manufacturers use pure silver electrodes, if the cost of pure silver paste is defined as 1, the cost of the corresponding 95/5 silver palladium paste is 5, the cost of the corresponding 90/10 silver palladium paste is 10, and the cost of the corresponding 70/30 silver palladium paste is 30.
The core of selecting the silver palladium electrode slurry is to select the piezoelectric ceramic material to be co-fired with the silver palladium electrode slurry, the further core is that after the electrode slurry is coated, the piezoelectric ceramic material is suitable for being sintered with the electrode slurry at any temperature, if the co-sintering temperature is not higher than 950 ℃, pure silver slurry can be selected, and the cost can be controlled to be lower; whereas if the sintering temperature of the piezoceramic material is not higher than 990 ℃, a 90/10 silver palladium paste may be selected. Thus, how to prepare high-performance low-temperature co-sintered piezoelectric ceramic materials is critical.
Disclosure of Invention
Based on the above, the invention provides a piezoelectric ceramic material which can be prepared by multi-layer co-sintering with pure silver slurry at the temperature of less than or equal to 950 ℃, and has low cost and higher dielectric property, piezoelectric constant and electromechanical coupling coefficient.
The technical scheme is as follows:
the piezoelectric ceramic material is a compound with a perovskite structure and has a molecular general formula of ABX 3 ；
The A site element comprises Pb and a doping element I, wherein the doping element I is selected from one or more of Cu and La;
the B site elements comprise Zr, ti and doping elements II, wherein the doping elements II are selected from one or more of Zn and Nb;
the X site elements include O and F.
In one embodiment, the molar ratio of the O element to the F element in the X site elements is (2.985-2.991): (0.009-0.015).
In one embodiment, the molar ratio of the O element to the F element in the X site elements is 2.9905:0.0095.
in one embodiment, the A site is Pb 2+ a Cu + (1-a) ；
B site is (Zn) b Nb 1-b ) 4+ (1-c-d) Zr 4+ c Ti d 4+ ；
X site O e F (3-e) ；
Wherein a, b, c, d and e represent mole fractions;
0.99≤a≤0.998；0.3≤b≤0.45；0.45≤c≤0.495；0.45≤d≤0.495。
the invention also provides a preparation method of the piezoelectric ceramic material.
The technical scheme is as follows:
a preparation method of a piezoelectric ceramic material comprises the following steps:
taking preparation raw materials containing an A site element, a B site element and an X site element, and carrying out grinding, mixing, calcining, crushing, molding, coating electrode slurry, co-sintering and polarization treatment to prepare a piezoelectric ceramic material;
the co-sintering temperature is less than or equal to 950 ℃.
In one embodiment, the preparation raw material containing the a-site element, the B-site element, and the X-site element includes an oxide and a fluoride;
the oxides include oxides of Pb, doping element I, zr, ti, and doping element II;
the fluoride comprises one or more of fluoride of Pb and fluoride of Zn.
In one embodiment, the oxide of Pb is selected from PbO and Pb 3 O 4 One or more of the above;
the oxide of the doping element I is selected from Cu 2 One or more of O and LaO;
the oxide of Zr is ZrO 2 ；
The oxide of Ti is TiO 2 ；
The oxide of the doping element II is selected from Nb 2 O 5 And ZnO;
the fluoride of Pb is PbF 2 ；
The fluoride of Zn is ZnF 2 。
In one embodiment, the sintering time is 4-6 h.
In one embodiment, the method for milling the mixed material is ball milling wet mixing.
In one embodiment, the calcining temperature is 750-850 ℃, and the calcining time is 2-3 h.
In one embodiment, the forming method comprises the following steps: and forming the powder to a preset size by using a binder.
In one embodiment, the electrode paste is a pure silver paste.
In one embodiment, the polarization has an electric field strength of 1.5KV/cm-2.5KV/cm and a temperature of 100-120 ℃.
Compared with the traditional scheme, the invention has the following beneficial effects:
the piezoceramic material is a lead zirconate titanate (PZT) material, the lead of the site A and the zirconium titanium of the site B are doped by introducing a doping element I and a doping element II, and on the basis, the oxygen of the site X is doped with fluorine, so that the sintering temperature is reduced, meanwhile, the volatilization of the oxygen is inhibited, oxygen vacancies cannot be caused, and the high performance of the piezoceramic material is ensured. The piezoelectric ceramic material can be co-sintered with the pure silver paste at the temperature of less than or equal to 950 ℃ in a multi-layer mode, the cost is reduced, and the dielectric property, the piezoelectric constant and the electromechanical coupling coefficient are high.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Term(s) for
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
as used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
In the present invention, "one or more" means any one, any two or more of the listed items. Wherein, the 'several' means any two or more than any two.
In the present invention, the terms "combination thereof", "any combination thereof", and the like include all suitable combinations of any two or more of the listed items.
In the present invention, "preferred" is only an embodiment or an example for better description, and it should be understood that the scope of the present invention is not limited thereto.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical range is defined to include both end points of the numerical range unless otherwise specified.
In the present invention, the percentage content refers to both mass percentage for solid-liquid mixing and solid-solid phase mixing and volume percentage for liquid-liquid phase mixing, unless otherwise specified.
In the present invention, the percentage concentration is referred to as the final concentration unless otherwise specified. The final concentration refers to the ratio of the added component in the system after the component is added.
In the present invention, the temperature parameter is not particularly limited, and it is permissible to perform a constant temperature treatment or to perform a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The lead zirconate titanate (PZT) ceramic material has a perovskite structure and can be represented by a molecular general formula ABX 3 Wherein a represents the a site of the perovskite lattice; b represents the B site of the perovskite lattice.
Current piezoelectric elements are primarily made using lead zirconate titanate (PZT) ceramic materials. The following three methods are generally used for low-temperature sintering of piezoelectric elements:
1. the low-temperature sintering is realized by adding low-melting-point glass.
2. The low-temperature sintering is realized by a method for improving the appearance or the fineness of the ceramic material.
3. The low-temperature sintering is realized by adding the low-valence oxide.
According to the method 1, low-melting-point glass is added, generally, low-melting-point glass powder such as boron, bismuth, cadmium and boron, bismuth and lead is prepared firstly, then the low-melting-point glass powder is added into a PZT material to be mixed and ground, a piezoelectric ceramic green body is prepared by pre-sintering, and the piezoelectric element is manufactured through the steps of glue removal, sintering, polarization and the like after the green body is finished. The method for adding the low-melting glass is simple, but has the following defects: when the glass amount is less, the cooling effect is not obvious enough (the sintering temperature is not lower than 1000 ℃), and when the glass amount is more, the sintering temperature can be reduced to 900 ℃, but the material performance is far lower than that of a normal PZT material.
For the method 2, there are generally two methods for improving the morphology or fineness of the ceramic material: one is to adopt a chemical method to prepare high-purity nano PZT material; one is to adopt the common solid phase synthesis method to prepare the piezoelectric ceramic material, and high-energy ball milling is carried out after the material preparation to complete the preparation of the superfine material. Although the method for improving the morphology or the fineness has little influence on the performance of the material, the cooling effect is not obvious enough, the sintering temperature is difficult to be reduced to below 1000 ℃, and the molding difficulty is high due to the overlarge specific surface area in the process of preparing the superfine material into the multilayer co-sintered element, so that the method is not a good choice.
For the 3 rd method, a low-valence oxide is added, the low-valence oxide is generally added to replace lead or zirconium titanium in PZT, and the oxides replacing lead in PZT comprise potassium oxide, sodium oxide (generally added in the form of carbonate), silver protoxide and cuprous oxide; oxides replacing zirconium titanium in PZT include zinc oxide, nickel oxide, lithium oxide (typically added in the form of carbonates), iron oxide, cobalt oxide, and the like. The temperature reduction effect is obvious after the addition of the oxide with a low valence state, but the addition of the oxide can result in PZT (ABO) 3 The reduction of the valence state of the A site or the B site in the structure) causes the corresponding oxygen to volatilize to form an oxygen vacancy, thereby causing the reduction of the material performance. To solve this problem, many companies or research structures have used a method of temperature reduction by the combined addition of higher oxides and lower oxides, such as Episcos, which uses a-site addition of trivalent neodymium (Nd) 3+ ) Monovalent potassium that attacks site A: ( 1+ ) And divalent nickel in B position: ( 2+ ) Thereby inhibiting the volatilization of oxygen and ensuring the realization of high performance of PZT. However, the design idea of the method is not universal, and the sintering temperature is difficult to be generally reduced to below 950 ℃.
The doping element I and the doping element II are introduced to dope lead at the site A and zirconium titanium at the site B, and on the basis, oxygen at the site X is further doped with fluorine, so that the sintering temperature is reduced, meanwhile, multilayer co-sintering with pure silver slurry can be realized, the cost is reduced, oxygen vacancy can not be caused by inhibiting oxygen volatilization, and the high performance of the piezoelectric ceramic material is ensured.
The technical scheme is as follows:
the piezoelectric ceramic material is a compound with a perovskite structure and has a molecular general formula of ABX 3 ；
The A site element comprises Pb and a doping element I, wherein the doping element I is selected from one or more of Cu and La;
b site elements comprise Zr, ti and doping elements II, wherein the doping elements II are selected from one or more of Zn and Nb;
the X site elements include O and F.
Optionally, in the X site element, the molar ratio of the O element to the F element is (2.985-2.991): (0.009-0.015). The F element is a doping element and has a larger atomic diameter than O, and if it exceeds the above range, the performance may be adversely affected.
Preferably, in the X site elements, the molar ratio of O element to F element is 2.9905:0.0095.
optionally, the doping element I is doped in a lower valence state of Cu and La; the doping element II is doped in the form of a composite valence state of Zn and Nb.
In one embodiment, the a site is Pb 2+ a Cu + (1-a) ；
B site is (Zn) b Nb 1-b ) 4+ (1-c-d) Zr 4+ c Ti d 4+ ；
X site O e F (3-e) ；
Wherein a, b, c, d and e represent mole fractions;
0.99≤a≤0.998；0.3≤b≤0.45；0.45≤c≤0.495；0.45≤d≤0.495。
in principle, the amounts of Cu, zn and Nb as doping elements are smaller than those of Pb, zr and Ti.
The invention also provides a preparation method of the piezoelectric ceramic material, which comprises the following steps:
taking preparation raw materials containing an A site element, a B site element and an X site element, and carrying out grinding, mixing, calcining, crushing, molding, coating electrode slurry, co-sintering and polarization treatment to prepare a piezoelectric ceramic material;
the co-sintering temperature is less than or equal to 950 ℃.
Wherein, the oxygen of X site can be doped with fluorine by replacing a part of oxide in the raw material for preparation with fluoride.
Alternatively, the lower oxides may be replaced or partially replaced by fluorides.
In one embodiment, the preparation raw material containing the a site element, the B site element, and the X site element includes an oxide and a fluoride;
the oxides include oxides of Pb, doping element I, zr, ti, and doping element II;
the fluoride comprises one or more of Pb fluoride and Zn fluoride.
In one embodiment, the addition amount of the fluoride can be 0.1-2.0% (mol) of the whole preparation raw material, and the fluoride can be added when grinding and mixing materials or when a green body is formed.
The material mixing method comprises a ball milling wet method. The purpose of this step is to mix the raw materials evenly. Further, the ball-milling medium may be ZrO 2 . It can be understood that after the wet mixing, the step of dehydrating and drying the mixture is also included, the dehydrating and drying may be drying, the drying temperature may be 150 ℃, and the drying time may be 2 hours. And (4) dehydrating, drying and calcining.
In one embodiment, the temperature of the calcination is 750-850 ℃, and the time of the calcination is 2-3 h. Upon calcination, a mixed crystal phase is formed.
And calcining and crushing to obtain powder. The pulverization can be realized by ball milling, and the medium of the ball milling can be ZrO 2 . Optionally, the powder has a particle size of 0.6 μm to 0.8 μm.
And after crushing, forming the powder to a preset size by using a binder.
Optionally, the binder is an organic binder.
Optionally, pressure can be applied during molding, the pressure can be 20-50 tons, and the density after molding is controlled at 4.5-5.1g/cm 3 。
The electrode slurry is pure silver slurry. After the sintering temperature is reduced, the pure silver paste can be used for realizing multilayer co-sintering, and the cost is lower.
In one embodiment, the co-sintering time is 4h to 6h.
In one embodiment, after co-sintering, a polarization process is performed to prepare the piezoelectric ceramic material.
Optionally, the electric field intensity of the polarization is 1.5KV/cm-2.5KV/cm, preferably 2KV/cm, and the temperature is 100-120 ℃.
Optionally, the time for polarization is 30s-10min.
The piezoelectric ceramic material can be sintered in a multi-layer way under the temperature of less than or equal to 950 ℃ in pure silver slurry, the cost is reduced, and the dielectric property, the piezoelectric constant and the electromechanical coupling coefficient are higher.
In the following, the raw materials referred to in the following specific examples are commercially available, unless otherwise specified, the equipment used, and the processes referred to, unless otherwise specified, are all routinely selected by those skilled in the art.
Example 1
This example provides a piezoceramic material with a general molecular formula of ABX 3 In, A site: pb 2 + 0.9905 Cu + 0.0095
B site: (Zn) 1/3 Nb 2/3 ) 4+ 0.05 Zr 4+ 0.48 Ti 4+ 0.47
An O site: o is 2.9905 F 0.0095
The preparation method of the piezoelectric ceramic material comprises the following steps:
weighing 0.3286mol Pb according to the formula 3 O 4 ，0.47mol TiO 2 ，0.48mol ZrO 2 ，0.00475mol Cu 2 O，0.00475mol PbF 2 ，0.033mol Nb 2 O 5 0.0167mol of ZnO is used as a preparation raw material, the preparation raw material is subjected to wet mixing by ball milling, the mixture is dehydrated and dried, calcined at 800 ℃ for 2 hours and crushed to obtain calcined powder, and the powder is molded to a preset size by using an organic binder. Then coating pure silver slurry to carry out multilayer co-sintering, wherein the sintering temperature is 950 DEG CAnd preserving heat for 4 hours, and then applying 2KV/cm direct current voltage to carry out polarization treatment in an environment of 120 ℃ to obtain the ceramic material with piezoelectric property.
The properties of the piezoelectric ceramic material of this example were measured by an impedance analyzer, and the results were as follows:
performance of
Dielectric: 2000, kp =0.67, qm =50, d33=460.
Example 2
This example provides a piezoceramic material with a general molecular formula of ABX 3 In, A site: pb 2 + 0.9905 Cu + 0.0095
B site: (Zn) 1/3 Nb 2/3 ) 4+ 0.05 Zr 4+ 0.48 Ti 4+ 0.47
An O site: o is 2.9905 F 0.0095
The preparation method of the piezoelectric ceramic material comprises the following steps:
weighing 0.3302mol Pb according to the formula 3 O 4 ，0.47mol TiO 2 ，0.48mol ZrO 2 ，0.00475mol Cu 2 O，0.00475mol ZnF 2 ，0.033mol Nb 2 O 5 0.0119mol of ZnO is used as a preparation raw material, the preparation raw materials are mixed by a ball mill in a wet method, the mixture is dehydrated and dried, calcined for 2 hours at 800 ℃, and crushed to obtain calcined powder, and the powder is molded to a preset size by using an organic binder. And then coating pure silver slurry to carry out multilayer co-sintering, wherein the sintering temperature is 950 ℃, the temperature is kept for 4h, and then, a direct current voltage of 2KV/cm is applied to carry out polarization treatment under the environment of 120 ℃ to obtain the ceramic material with piezoelectric property.
The properties of the piezoelectric ceramic material of this example were measured in the same manner as in example 1, and the results were as follows:
dielectric: 2000, kp =0.67, qm =50, d33=460.
Comparative example 1
The present comparative example provides a piezoelectric ceramic material, its compositionHas a sub-formula of ABX 3 In, A site: pb of 2 + 0.9905 Cu + 0.0095
B site: (Zn) 1/3 Nb 2/3 ) 4+ 0.05 Zr 4+ 0.48 Ti 4+ 0.47
An O site: o is 2.99525
The preparation method of the piezoelectric ceramic material comprises the following steps:
weighing 0.3302mol Pb according to the formula 3 O 4 ，0.47mol TiO 2 ，0.48mol ZrO 2 ，0.00475mol Cu 2 O，0.033mol Nb 2 O 5 0.01667mol of ZnO is used as a preparation raw material, the preparation raw material is subjected to wet mixing by ball milling, the mixture is dehydrated and dried, calcined at 800 ℃ for 2 hours, and pulverized to obtain calcined powder, and the powder is molded to a preset size by using an organic binder. And then coating pure silver slurry to carry out multilayer co-sintering, wherein the sintering temperature is 950 ℃, the temperature is kept for 4h, and then, a direct current voltage of 2KV/cm is applied to carry out polarization treatment under the environment of 120 ℃ to obtain the ceramic material with piezoelectric property.
The properties of the piezoelectric ceramic material of this example were measured in the same manner as in example 1, and the results were as follows:
dielectric: 1700, kp =0.60, qm =50, d33=370.
Comparative example 2
The comparative example provides a piezoceramic material having a general molecular formula ABX 3 In, A site: pb 2 + 0.981 Cu + 0.0095 La 3+ 0.0095
B site: (Zn) 1/3 Nb 2/3 ) 4+ 0.05 Zr 4+ 0.48 Ti 4+ 0.47
An O site: o is 3.0
The preparation method of the piezoelectric ceramic material comprises the following steps:
weighing 0.327mol Pb according to the formula 3 O 4 ，0.47mol TiO 2 ，0.48mol ZrO 2 ，0.00475mol Cu 2 O，0.033mol Nb 2 O 5 0.0095mol of LaO and 0.01667mol of ZnO are used as preparation raw materials, the preparation raw materials are subjected to wet mixing by ball milling, the mixture is dehydrated and dried, calcined for 2 hours at 800 ℃, and pulverized to obtain calcined powder, and the powder is molded to a preset size by using an organic binder. And then coating pure silver slurry to perform multilayer co-sintering, wherein the sintering temperature is 950 ℃, and the heat preservation is carried out for 4 hours, and the sintering is not done.
Comparative example 3
This comparative example provides a piezoceramic material having the general molecular formula ABX as a control 3 In (1),
a position: pb 2+
B site: zn 4+ 0.05 Zr 4+ 0.48 Ti 4+ 0.47
An O site: o is 3.0
The preparation method of the piezoelectric ceramic material comprises the following steps:
weighing 0.333mol Pb according to the formula 3 O 4 ，0.47mol TiO 2 ，0.48mol ZrO 2 0.05mol of ZnO is used as a preparation raw material, the preparation raw material is subjected to wet mixing by ball milling, the mixture is dehydrated and dried, calcined at 800 ℃ for 2 hours, and pulverized to obtain calcined powder, and the powder is molded to a preset size by using an organic binder. And then coating 70/30 silver palladium slurry for multi-layer co-sintering, wherein the sintering temperature is 1150 ℃, the heat preservation time is 2 hours, and then applying 2KV/cm direct current voltage for polarization treatment in an environment of 120 ℃ to obtain the ceramic material with piezoelectric property.
The properties of the piezoelectric ceramic material of this example were measured in the same manner as in example 1, and the results were as follows:
dielectric: 2000,kp =0.66, qm =50, d33=450
From the above results, it can be seen that:
example 1 and example 2 were each formulated with PbF 2 And ZnF 2 Replacing a part of ZnO, and carrying out fluorine doping on oxygen at X site of the piezoelectric ceramic materialCompared with the comparative example 1, only the doping of the A site and the B site in a low valence state and a complex valence state is carried out, so that the sintering temperature is reduced, oxygen vacancy is not caused by inhibiting the volatilization of oxygen, and the dielectric property, the piezoelectric constant and the electromechanical coupling coefficient are higher. With the formulation of comparative example 2, the pure silver paste could not be co-sintered with the piezoelectric ceramic material at 950 ℃. In comparative example 4, the A site and the B site are not doped with a low valence state and a complex valence state, and the X site is not doped with oxygen with fluorine, 70/30 silver palladium slurry is adopted to be co-sintered with the piezoelectric ceramic material of the formula at high temperature, and the properties of the prepared ceramic material are basically similar to those of the ceramic material of example 1 and example 2, which shows that the ceramic material of example 1 and example 2 can be co-sintered with pure silver slurry in a multi-layer manner while the sintering temperature is reduced, and the high performance of the piezoelectric ceramic material is kept.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. The piezoelectric ceramic material is characterized in that the piezoelectric ceramic material is a compound with a perovskite structure, and the molecular general formula is ABX 3 ；
Wherein the A site elements comprise Pb and a doping element I, and the doping element I is selected from Cu;
the B site elements comprise Zr, ti and a doping element II, wherein the doping element II is selected from Zn and Nb;
the X site elements comprise O and F;
the A site is Pb 2+ a Cu + (1-a) ；
B site is (Zn) b Nb 1-b ) 4+ （1-c-d） Zr 4+ c Ti 4+ d ；
X site O e F （3-e） ；
Wherein a, b, c, d and e represent mole fractions;
a is more than or equal to 0.99 and less than or equal to 0.998; b is 1/3; c is more than or equal to 0.45 and less than or equal to 0.495; d is more than or equal to 0.45 and less than or equal to 0.495.
2. The piezoceramic material according to claim 1, wherein the molar ratio of the O element to the F element in the X site element is (2.985-2.991): (0.009-0.015).
3. A method for preparing a piezoceramic material according to claim 1, comprising the steps of:
taking preparation raw materials containing an A site element, a B site element and an X site element, grinding and mixing, calcining, crushing, molding, coating electrode slurry, co-sintering and polarizing to prepare a piezoelectric ceramic material, wherein the powder is obtained by crushing after calcining;
the co-sintering temperature is less than or equal to 950 ℃.
4. The method of producing a piezoelectric ceramic material according to claim 3, wherein the production raw material containing the a site element, the B site element, and the X site element includes an oxide and a fluoride;
the oxides include oxides of Pb, doping element I, zr, ti, and doping element II;
the fluoride comprises one or more of fluoride of Pb and fluoride of Zn.
5. The method for preparing a piezoelectric ceramic material according to claim 4, wherein the oxide of Pb is selected from PbO;
the oxide of the doping element I is selected from Cu 2 O；
The oxide of Zr is ZrO 2 ；
The oxide of Ti is TiO 2 ；
The oxide of the doping element II is selected from Nb 2 O 5 And ZnO;
the fluoride of Pb is PbF 2 ；
The fluoride of Zn is ZnF 2 。
6. The method for producing a piezoelectric ceramic material according to claim 3, wherein the co-firing time is 4 to 6 hours.
7. The method for preparing a piezoelectric ceramic material according to any one of claims 3 to 6, wherein the method for grinding and mixing materials is ball milling wet mixing.
8. The method for preparing a piezoelectric ceramic material according to any one of claims 3 to 6, wherein the calcining temperature is 750 to 850 ℃, and the calcining time is 2h to 3h.
9. The method for preparing a piezoelectric ceramic material according to any one of claims 3 to 6, wherein the molding method comprises the following steps: and forming the powder to a preset size by using a binder.
10. The method for preparing a piezoelectric ceramic material according to any one of claims 3 to 6, wherein the electrode paste is a pure silver paste.
11. The method for preparing a piezoceramic material according to any one of claims 3 to 6, wherein the polarized electric field strength is 1.5KV/cm to 2.5KV/cm, and the temperature is 100 to 120 ℃.
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