CN106995313B - A kind of potassium sodium niobate-based ceramic powder and preparation method thereof - Google Patents
A kind of potassium sodium niobate-based ceramic powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 85
- 239000000919 ceramic Substances 0.000 title claims abstract description 63
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 60
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims abstract description 32
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 15
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 15
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 15
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 15
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 14
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000004939 coking Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 17
- 239000000084 colloidal system Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 239000011858 nanopowder Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000009775 high-speed stirring Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 34
- 229910010252 TiO3 Inorganic materials 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
本发明公开了一种铌酸钾钠基陶瓷粉体，其主要制备原料包括钛酸四丁酯、柠檬酸、乙二醇、乙酸钡、硝酸锶、硝酸钾、硝酸钠、五氧化二铌和酒精。本发明通过聚合物前驱体制备的溶胶，在高速搅拌的情况下将难溶粉体悬浊液包覆，通过焦化、煅烧等工艺得到KNN基陶瓷粉体。解决了液相法和固相法制备纳米‑微米粉体工艺缺陷与性能不足等问题，并能够实现工业化大规模生产。同时，制备的KNN基陶瓷粉体具有组分均一、结晶度高、平均粒径为43~59nm等优异的特征。在提高KNN基陶瓷低温烧结性与电学性能方面具有非常大的潜力；在环保、节能、高效的无铅压电材料的应用中具有巨大的应用价值与商业前景。
The invention discloses a potassium sodium niobate-based ceramic powder. The main preparation raw materials include tetrabutyl titanate, citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate, niobium pentoxide and Alcohol. The sol prepared by the polymer precursor in the present invention coats the insoluble powder suspension under the condition of high-speed stirring, and obtains the KNN-based ceramic powder through coking, calcining and other processes. The problems of process defects and insufficient performance of nano-micron powder prepared by liquid phase method and solid phase method are solved, and industrialized large-scale production can be realized. At the same time, the prepared KNN-based ceramic powder has excellent characteristics such as uniform composition, high crystallinity, and average particle size of 43-59 nm. It has great potential in improving the low-temperature sinterability and electrical properties of KNN-based ceramics; it has great application value and commercial prospects in the application of environmentally friendly, energy-saving and efficient lead-free piezoelectric materials.
Description
Technical Field
The invention relates to the field of piezoelectric ceramic powder and preparation thereof, in particular to potassium sodium niobate-based ceramic powder and a preparation method thereof.
Background
Potassium sodium niobate-based piezoelectric ceramic (referred to as KNN-based ceramic) materials have high curie temperature and excellent dielectric, ferroelectric and piezoelectric properties, etc., are receiving wide attention, and are considered to be the most potential materials for replacing lead-containing solid solutions in electronic ceramic components. However, when preparing KNN-based ceramics, the segregation of potassium and sodium elements in the system due to the over-high sintering temperature generally causes the increase of defects in the structure, the low mechanical quality factor, the weakening of the dielectric property and the like.
In order to improve the sinterability and electrical properties of the KNN-based ceramic, it is generally achieved by adding a sintering aid and a low-temperature solid solution having good sinterability. However, in order to prevent the formation of a foreign phase in the KNN-based ceramic structure and to improve the stability of the electrical properties, a high-quality powder of nano-micron level having a uniform composition, good crystallinity and a narrow particle size distribution is often required.
Aiming at the preparation of high-quality nano-micron powder, a solid phase method is rarely adopted generally, and the powder prepared by the solid phase method has large composition fluctuation, larger particle size, wide particle size distribution and the like; although the liquid phase method can prepare high quality powder with narrow particle size distribution and uniform components, the liquid phase method has the disadvantages of relatively complex process operation, relatively high equipment cost, difficulty in mass production and the like. Therefore, the optimization of the preparation process of the high-quality nano-micron KNN-based ceramic powder is urgently needed, the industrial large-scale production is realized, and the low-temperature large-batch continuous production of the KNN-based ceramic material with excellent electrical properties is finally realized.
In the thirteen-five planning outline in China, the research on materials with environmental protection, energy conservation and high efficiency is further reiterated, and the research on the preparation of the high-quality nano-micron-level KNN-based ceramic powder conforms to the development of the era and can bring great economic and social benefits.
Disclosure of Invention
In order to overcome the technical defects and the performance defects of the liquid phase method and the solid phase method for preparing the nano-micron powder in the prior art, the invention provides the potassium sodium niobate-based ceramic powder prepared by using tetrabutyl titanate, citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate and niobium pentoxide as main raw materials and the preparation method thereof.
The purpose of the invention is realized as follows:
potassium sodium niobate-based ceramic powder is mainly prepared from tetrabutyl titanate, citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate, niobium pentoxide and alcohol;
the citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 3-5: 1-2: 14-16: 18 to 21 parts;
the potassium sodium niobate-based ceramic powder is prepared by preparing sol by a modified polymer precursor method, coating an insoluble powder suspension in the sol, and preparing KNN-based ceramic nano powder by coking, calcining and other processes; analyzing the structure and phase characteristics of the powder by a modern test technology;
the components for preparing the potassium-sodium niobate-based ceramic powder can be represented by a chemical formula: (1-x)K0.48Na0.52NbO3–xBa0.90Sr0.10TiO3Whereinx=0.05~0.20；
The preparation method of the potassium sodium niobate-based ceramic powder adopts a sol coating method, and comprises the following specific process steps:
1) according to the weight ratio of citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 3-5: 1-2: 14-16: 18-21, and stirring for 1-2 hours at 40-50 ℃ to obtain a clear solution A;
2) weighing barium acetate and strontium nitrate according to the molar ratio of metal ions in the chemical formula, respectively dissolving the barium acetate and the strontium nitrate in deionized water, adding the barium acetate solution dropwise and the strontium nitrate solution dropwise into the solution A prepared in the step 1), heating to 55-65 ℃, and stirring for 0.5-1 hour to obtain stable sol B;
3) dissolving potassium nitrate and sodium nitrate which are weighed according to the molar ratio of metal ions in the chemical formula in deionized water, dropwise adding the solution into the sol B prepared in the step 2), and stirring for 0.5-1 hour to obtain stable sol C;
4) adding niobium pentoxide powder weighed according to the molar ratio of metal ions in the chemical formula into 40-50 ml of deionized water, carrying out ultrasonic dispersion for 20-30 minutes, and violently stirring to obtain a powder suspension;
5) dropwise adding the suspension prepared in the step 4) into the solution C prepared in the step 3) at a stirring speed of 600-800 r/min, and stirring for 1-2 hours to prepare a sol-coated liquid; drying the sol-coated liquid in an oven at 100-120 ℃ for 1-2 hours to obtain a coated colloid D;
6) coking the coating colloid D prepared in the step 5) in a muffle furnace at 300-400 ℃ for 1.5-2 hours, grinding, and calcining in a high-temperature furnace at 850-950 ℃ for 2-3 hours to obtain the KNN-based ceramic powder.
Has the positive and beneficial effects that: the KNN-based ceramic powder is prepared by coating the suspension of the insoluble powder through the sol prepared from the polymer precursor under the condition of high-speed stirring and through the processes of coking, calcining and the like. Solves the problems of process defects, insufficient performance and the like of the liquid phase method and the solid phase method for preparing the nano-micron powder, and can realize industrialized large-scale production. Meanwhile, the prepared KNN-based ceramic powder has the excellent characteristics of uniform components, high crystallinity, average particle size of 43-59 nm and the like. The low-temperature sintering property and the electrical property of the KNN-based ceramic are improved; has great application value and commercial prospect in the application of the lead-free piezoelectric material with environmental protection, energy saving and high efficiency.
Drawings
FIG. 1 is an X-ray diffraction pattern of KNN-based ceramic nanopowder prepared in the present invention;
FIG. 2 is a scanning electron microscope image of the KNN-based ceramic nanopowder prepared in the present invention.
Detailed Description
The invention will be further described with reference to specific examples:
example 1
Potassium sodium niobate-based ceramic powder is mainly prepared from tetrabutyl titanate, citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate, niobium pentoxide and alcohol; the citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 4: 1: 15: 20; the potassium sodium niobate-based ceramic powder is prepared by preparing sol by a modified polymer precursor method, coating an insoluble powder suspension in the sol, and preparing KNN-based ceramic nano powder by coking, calcining and other processes; analyzing the structure and phase characteristics of the powder by a modern test technology; the components for preparing the potassium-sodium niobate-based ceramic powder can be represented by a chemical formula: (1-x)K0.48Na0.52NbO3–xBa0.90Sr0.10TiO3Whereinx=0.05~0.20；
The preparation method of the potassium sodium niobate-based ceramic powder adopts a sol coating method, and comprises the following specific process steps:
1) according to the weight ratio of citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 4: 1: 15: 20, and stirring the mixture for 1 hour at the temperature of 40 ℃ to obtain a clear solution A;
2) weighing barium acetate and strontium nitrate according to the molar ratio of metal ions in the chemical formula, respectively dissolving the barium acetate and the strontium nitrate in deionized water, adding the barium acetate solution and the strontium nitrate solution into the solution A prepared in the step 1) in the sequence of firstly dripping the barium acetate solution and then dripping the strontium nitrate solution, heating to 55 ℃, and stirring for 0.5 hour to obtain stable sol B;
3) dissolving potassium nitrate and sodium nitrate which are weighed according to the molar ratio of metal ions in the chemical formula in deionized water at the same time, dropwise adding the solution into the sol B prepared in the step 2), and stirring for 0.5 hour to obtain stable sol C;
4) adding niobium pentoxide powder weighed according to the molar ratio of metal ions in the chemical formula into 40ml of deionized water, carrying out ultrasonic dispersion for 20-30 minutes, and violently stirring to obtain a powder suspension;
5) dropwise adding the suspension prepared in the step 4) into the solution C prepared in the step 3) at a stirring speed of 600r/min, and stirring for 1-2 hours to prepare sol-coated liquid; drying the sol-coated liquid in a drying oven at 100 ℃ for 1 hour to obtain a coated colloid D;
6) coking the coating colloid D prepared in the step 5) in a muffle furnace at 300-400 ℃ for 1.5 hours, grinding, and calcining in a high-temperature furnace at 850 ℃ for 2 hours to obtain the KNN-based ceramic powder.
Example 2
Potassium sodium niobate-based ceramic powder is mainly prepared from tetrabutyl titanate, citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate, niobium pentoxide and alcohol; the citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 3: 1: 15: 21; the potassium sodium niobate-based ceramic powder is prepared by preparing sol by a modified polymer precursor method, coating insoluble powder suspension in the sol, coking, calcining and other processesNano powder; analyzing the structure and phase characteristics of the powder by a modern test technology; the components for preparing the potassium-sodium niobate-based ceramic powder can be represented by a chemical formula: (1-x)K0.48Na0.52NbO3–xBa0.90Sr0.10TiO3Whereinx=0.05~0.20；
The preparation method of the potassium sodium niobate-based ceramic powder adopts a sol coating method, and comprises the following specific process steps:
1) according to the weight ratio of citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 3: 1: 15: 21, mixing, and stirring for 1-2 hours at 40-50 ℃ to obtain a clear solution A;
2) weighing barium acetate and strontium nitrate according to the molar ratio of metal ions in the chemical formula, respectively dissolving the barium acetate and the strontium nitrate in deionized water, adding the barium acetate solution and the strontium nitrate solution into the solution A prepared in the step 1) in the sequence of firstly dripping the barium acetate solution and then dripping the strontium nitrate solution, heating to 60 ℃, and stirring for 0.8 hour to obtain stable sol B;
3) dissolving potassium nitrate and sodium nitrate which are weighed according to the molar ratio of metal ions in the chemical formula in deionized water at the same time, dropwise adding the solution into the sol B prepared in the step 2), and stirring for 0.8 hour to obtain stable sol C;
4) adding niobium pentoxide powder weighed according to the molar ratio of metal ions in the chemical formula into 45ml of deionized water, carrying out ultrasonic dispersion for 25 minutes, and violently stirring to obtain powder suspension;
5) dropwise adding the suspension prepared in the step 4) into the solution C prepared in the step 3) with the stirring speed of 700r/min, and stirring for 1.5 hours to prepare sol-coated liquid; drying the sol-coated liquid in a drying oven at 110 ℃ for 1.5 hours to obtain a coating colloid D;
6) the coating colloid D prepared in the step 5) is firstly coked in a muffle furnace at 350 ℃ for 1.8 hours, and is calcined in a high-temperature furnace at 900 ℃ for 2.5 hours after being ground to obtain KNN-based ceramic powder.
Example 3
Potassium sodium niobate based ceramic powder is prepared with tetrabutyl titanate,Citric acid, ethylene glycol, barium acetate, strontium nitrate, potassium nitrate, sodium nitrate, niobium pentoxide and alcohol; the citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 4: 2: 15: 19; the potassium sodium niobate-based ceramic powder is prepared by preparing sol by a modified polymer precursor method, coating an insoluble powder suspension in the sol, and preparing KNN-based ceramic nano powder by coking, calcining and other processes; analyzing the structure and phase characteristics of the powder by a modern test technology; the components for preparing the potassium-sodium niobate-based ceramic powder can be represented by a chemical formula: (1-x)K0.48Na0.52NbO3–xBa0.90Sr0.10TiO3Whereinx=0.05~0.20；
The preparation method of the potassium sodium niobate-based ceramic powder adopts a sol coating method, and comprises the following specific process steps:
1) according to the weight ratio of citric acid: tetrabutyl titanate: ethylene glycol: the molar mass ratio of the alcohol is 4: 2: 15: 19 mixing and stirring at 50 ℃ for 2 hours to obtain a clear solution A;
2) weighing barium acetate and strontium nitrate according to the molar ratio of metal ions in the chemical formula, respectively dissolving the barium acetate and the strontium nitrate in deionized water, adding the barium acetate solution dropwise and the strontium nitrate solution dropwise into the solution A prepared in the step 1), heating to 65 ℃, and stirring for 1 hour to obtain stable sol B;
3) dissolving potassium nitrate and sodium nitrate which are weighed according to the molar ratio of metal ions in the chemical formula in deionized water at the same time, dropwise adding the solution into the sol B prepared in the step 2), and stirring for 1 hour to obtain stable sol C;
4) adding niobium pentoxide powder weighed according to the molar ratio of metal ions in the chemical formula into 50ml of deionized water, carrying out ultrasonic dispersion for 30 minutes, and violently stirring to obtain powder suspension;
5) dropwise adding the suspension prepared in the step 4) into the solution C prepared in the step 3) at the stirring speed of 800r/min, and stirring for 2 hours to prepare sol-coated liquid; drying the sol-coated liquid in a 120 ℃ oven for 2 hours to obtain a coated colloid D;
6) coking the coating colloid D prepared in the step 5) in a muffle furnace at 400 ℃ for 2 hours, grinding and calcining in a high-temperature furnace at 950 ℃ for 3 hours to obtain KNN-based ceramic powder.
Example 4
Preparation of 0.95K0.48Na0.52NbO3–0.05Ba0.90Sr0.10TiO3Ceramic powder: dissolving 0.1702g of tetrabutyl titanate and 0.4203g of citric acid in a mixed solution of 0.4655g of ethylene glycol and 0.6207g of alcohol, and stirring at 45 ℃ for 1 hour to obtain a clear solution A; respectively dissolving 0.1149g of barium acetate and 0.0106g of strontium nitrate in deionized water, dropwise adding the barium acetate and the strontium nitrate into the solution A in the sequence of dropwise adding the barium acetate and the strontium nitrate, heating to 60 ℃, and stirring for 0.5 hour to obtain stable sol B; 0.4610g of potassium nitrate and 0.4199g of sodium nitrate are weighed and dissolved in deionized water, then the mixed solution is dripped into the sol B, and the mixture is stirred for 0.5 hour to prepare stable sol C; 2.5252g of niobium pentoxide powder is added into 45ml of deionized water, and powder suspension is prepared after ultrasonic dispersion for 30 minutes; dropwise adding the suspension into the sol C with the stirring speed of 750r/min, stirring for 1.5 hours to prepare sol-coated liquid, and drying the liquid in a drying oven at the temperature of 110 ℃ for 1.5 hours to obtain a coated colloid D; the colloid D is coked in a muffle furnace at 350 ℃ for 1.5 hours, and is calcined in a high-temperature furnace at 900 ℃ for 2.5 hours after being ground to obtain 0.95K0.48Na0.52NbO3–0.05Ba0.90Sr0.10TiO3Ceramic powder.
0.95K0.48Na0.52NbO3–0.05Ba0.90Sr0.10TiO3The ceramic powder has high crystallinity; the average particle size was 43 nm.
Example 5
0.90K0.48Na0.52NbO3–0.10Ba0.90Sr0.10TiO3Ceramic powder: dissolving 0.3404g of tetrabutyl titanate and 0.8406g of citric acid in a mixed solution of 0.9310g of ethylene glycol and 1.2414g of alcohol, and stirring at 45 ℃ for 1 hour to obtain a clear solution A; 0.2298g of barium acetate and 0.0 g of barium acetate were mixedRespectively dissolving 212g of strontium nitrate in deionized water, dropwise adding the solution A into barium acetate and then strontium nitrate, heating to 60 ℃, and stirring for 0.5 hour to obtain stable sol B; 0.4367g of potassium nitrate and 0.3978g of sodium nitrate are weighed and dissolved in deionized water, then the mixed solution is dripped into the sol B, and the mixture is stirred for 0.5 hour to prepare stable sol C; 2.3923g of niobium pentoxide powder is added into 42ml of deionized water, and powder suspension is prepared after ultrasonic dispersion for 27 minutes; dropwise adding the suspension into the sol C with the stirring speed of 750r/min, stirring for 1.5 hours to prepare sol-coated liquid, and drying the liquid in a drying oven at the temperature of 110 ℃ for 1.5 hours to obtain a coated colloid D; the colloid D is coked in a muffle furnace at 350 ℃ for 1.5 hours, and is calcined in a high-temperature furnace at 900 ℃ for 2.5 hours after being ground to obtain 0.90K0.48Na0.52NbO3–0.10Ba0.90Sr0.10TiO3Ceramic powder.
0.90K0.48Na0.52NbO3–0.10Ba0.90Sr0.10TiO3The ceramic powder has high crystallinity; the average particle size was 52 nm.
Example 6
0.85K0.48Na0.52NbO3–0.15Ba0.90Sr0.10TiO3Ceramic powder: dissolving 0.5106g of tetrabutyl titanate and 1.2609g of citric acid in a mixed solution of 1.3965g of ethylene glycol and 1.8621g of alcohol, and stirring at 45 ℃ for 1 hour to obtain a clear solution A; respectively dissolving 0.3447g of barium acetate and 0.0318g of strontium nitrate in deionized water, then dropwise adding the barium acetate and the strontium nitrate into the solution A in the sequence of firstly dropwise adding the barium acetate and then dropwise adding the strontium nitrate, heating to 60 ℃, and stirring for 0.5 hour to obtain stable sol B; 0.4125g of potassium nitrate and 0.3757g of sodium nitrate are weighed and dissolved in deionized water, then the mixed solution is dripped into the sol B, and the mixture is stirred for 0.5 hour to prepare stable sol C; 2.2594g of niobium pentoxide powder is added into 40ml of deionized water, and powder suspension is prepared after ultrasonic dispersion is carried out for 25 minutes; dropwise adding the suspension into the above sol C with stirring speed of 750r/min, stirring for 1.5 hr to obtain sol-coated liquidDrying the liquid in a drying oven at 110 ℃ for 1.5 hours to obtain a coating colloid D; the colloid D is coked in a muffle furnace at 350 ℃ for 1.5 hours, and is calcined in a high-temperature furnace at 900 ℃ for 2.5 hours after being ground to obtain 0.85K0.48Na0.52NbO3–0.15Ba0.90Sr0.10TiO3Ceramic powder.
0.85K0.48Na0.52NbO3–0.15Ba0.90Sr0.10TiO3The ceramic powder has high crystallinity; the average particle size was 59 nm.
The KNN-based ceramic powder is prepared by coating the suspension of the insoluble powder through the sol prepared from the polymer precursor under the condition of high-speed stirring and through the processes of coking, calcining and the like. Solves the problems of process defects, insufficient performance and the like of the liquid phase method and the solid phase method for preparing the nano-micron powder, and can realize industrialized large-scale production. Meanwhile, the prepared KNN-based ceramic powder has the excellent characteristics of uniform components, high crystallinity, average particle size of 43-59 nm and the like. The low-temperature sintering property and the electrical property of the KNN-based ceramic are improved; has great application value and commercial prospect in the application of the lead-free piezoelectric material with environmental protection, energy saving and high efficiency.
The above examples are only for illustrating the preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention within the knowledge of those skilled in the art should be covered within the technical scope of the present invention as claimed.
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