CN113603135A - Preparation method of yttrium-doped small-size barium titanate nano powder - Google Patents
Preparation method of yttrium-doped small-size barium titanate nano powder Download PDFInfo
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- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 46
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 159000000009 barium salts Chemical class 0.000 claims abstract description 35
- 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 33
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005642 Oleic acid Substances 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 18
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000011265 semifinished product Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 17
- -1 yttrium ions Chemical class 0.000 abstract description 13
- 229910052788 barium Inorganic materials 0.000 abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a preparation method of yttrium-doped small-size barium titanate nano powder, which comprises the following specific steps: firstly, tetrabutyl titanate is mixed with oleic acid and short-chain alcohols to prepare tetrabutyl titanate solution, barium salt is mixed with inorganic base and deionized water to prepare strong-alkaline barium salt solution, and yttrium nitrate is dissolved in the deionized water to prepare yttrium nitrate solution. The preparation method of the yttrium-doped small-size barium titanate nano powder is based on a hydrothermal method, tetrabutyl titanate is respectively used as a fixed titanium source and barium hydroxide, barium nitrate and the like are used as barium sources, yttrium ions provided by a yttrium nitrate solution are used, and oleic acid is used as a surfactant to prepare the yttrium-doped barium titanate nano particles.
Description
Technical Field
The invention belongs to the technical field of ceramic nanometer split preparation, and particularly relates to a preparation method of yttrium-doped small-size barium titanate nano powder.
Background
Barium titanate is the most common ferroelectric material with the most wide dosage, and ceramics taking barium titanate as a main crystal phase have good dielectric property, and can be widely used for preparing electronic ceramic materials such as ferroelectric multilayer ceramic capacitors (PLCC), multilayer ceramic capacitors (MLCC), semiconductor ceramics and the like. In recent years, with the trend of miniaturization, miniaturization and thinning of electronic components, nano-sized barium titanate powder becomes an inevitable trend of development of barium titanate dielectric ceramics. Barium titanate powders prepared in industry should be as fine and uniformly dispersed as possible so that the fired electronic ceramics can produce smaller, thinner dielectric materials with superior performance.
At present, a plurality of methods for preparing barium titanate powder are available, and the methods mainly comprise a solid phase method and a liquid phase method. The solid phase method comprises high temperature combustion synthesis, low temperature combustion synthesis and high energy ball milling method. The traditional solid phase method can not accurately control the size and the shape of particles, and the performance of the ceramic is seriously influenced. Common liquid phase methods include chemical precipitation, sol-gel, hydrothermal methods, and the like. The chemical precipitation method can be further divided into: coprecipitation method, direct precipitation method and homogeneous precipitation method, wherein the coprecipitation method has been realized in industrial production. The coprecipitation method has the advantages of simple process, low reaction temperature, short preparation time and low cost. But the defects are that the powder material can be obtained only by calcining, impurities are easy to be introduced in the calcining process, and the powder is agglomerated to cause uneven particle size distribution. The sol-gel method has the advantages of uniform doping of various materials, high product purity and small particle size. The method has the disadvantages that metal alkoxide is expensive and high in cost, the sintering property among gel particles is poor, a reaction medium is a toxic organic solvent, the high-temperature calcination treatment easily causes the rapid agglomeration of nano powder, and the requirements on process conditions are harsh. Compared with other liquid phase methods, the hydrothermal method does not need high-temperature calcination, has low cost, small powder agglomeration and uniform components, can regulate and control the morphology and the structure of the powder, and is considered as an ideal synthesis method for promoting the development of electronic components in the directions of chip type, miniaturization and the like.
The dielectric constant of barium titanate is about 1400 at room temperature, which is relatively low, and the requirements of high-performance components are difficult to meet, and the problems greatly limit the application of barium titanate in some high-end electronic industries. Due to the particularity of the chemical properties of the rare earth element ions, the rare earth ions have great potential in doping modification of barium titanate materials. The chemical valence state and the ionic radius of the rare earth ions are between Ba2+ and Ti4+, and can replace Ba2+ or Ti4+, and accordingly lattice defects such as electrons, vacancies and the like can be generated in the barium titanate crystal lattice to compensate the valence state balance. The doping of the rare earth ions can inhibit the grain growth and improve the dielectric constant at room temperature, and has wide application prospect in the field of materials. In patent CN 105254295A, barium titanate powder with good neodymium doping dispersibility is prepared by a sol-hydrothermal method, but the preparation process is complex, and the size of the synthesized barium titanate particles is large. Patent CN106187163A discloses a sol-gel method for preparing neodymium-doped high tetragonal phase barium titanate powder, but the method is complicated to operate and requires high-temperature calcination. .
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing yttrium-doped small-size barium titanate nano powder, which optimizes the dielectric constant of barium titanate particles by doping modification of yttrium element so as to meet the requirement of manufacturing high-quality micro devices in the current electronic industry.
The technical scheme for solving the technical problems comprises the following steps:
a preparation method of yttrium-doped small-size barium titanate nano powder comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 2-5 ml of oleic acid and 10-20 ml of short-chain alcohol to prepare tetrabutyl titanate solution;
s2, mixing 20-60 mmol of barium salt with 1g of inorganic base and 16-30 ml of deionized water to prepare strong alkaline barium salt solution;
s3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution;
s4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
s5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 15-20 h, wherein the reaction temperature is 150-200 ℃, and after the reaction is finished, cooling air to room temperature;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product;
s7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
Specifically, in the steps S1-S2, the molar ratio of the barium salt to the tetrabutyl titanate is 1:1-3:1, the volume ratio of the deionized water to the short-chain alcohol is 0.8:1-2:1, and the volume ratio of the oleic acid to the short-chain alcohol is 1:2-1: 10.
Specifically, the barium salt is barium hydroxide, barium acetate or barium nitrate, the short-chain alcohol is ethanol, isopropanol or n-butanol, and the inorganic base is potassium hydroxide or sodium hydroxide.
Specifically, in the step S7, the volume fraction of the acetic acid and the ethanol is 1% to 10%, and the drying temperature is 50 to 70 ℃.
Specifically, in step S4, the yttrium nitrate solution is dropped in portions so that the yttrium doping amount is 0.01% mol, 0.05% mol, 0.1% mol, 0.5% mol, 1% mol, and 5% mol.
Preferably, in the steps S1 and S2, the mixing manner is magnetic stirring.
The invention has the following beneficial effects: the method is based on a hydrothermal method, tetrabutyl titanate is respectively adopted as a fixed titanium source, barium hydroxide, barium nitrate and the like are respectively adopted as barium sources, yttrium ions provided by yttrium nitrate solution are utilized, and oleic acid is used as a surfactant to prepare yttrium-doped barium titanate nanoparticles. Compared with other methods, the method has the advantages of simple process, no need of high-temperature calcination, hydrothermal temperature lower than 200 ℃, short hydrothermal time, easy regulation and control of barium-titanium ratio and pH value under hydrothermal conditions, and capability of controlling the appearance and components of the product. The product has particle size less than 50nm, good crystallinity, high purity and concentrated size distribution, and is favorable for application in MLCC and other electronic devices. Meanwhile, the powder is doped with rare earth ions, and the defects generated by the substitution of the rare earth ions are beneficial to obtaining fine-grained ceramics and improving the dielectric constant of the ceramics.
Drawings
FIG. 1 is a step diagram of a process for preparing yttrium-doped small-size barium titanate nanopowder according to an embodiment of the present invention.
FIG. 2 is an X-ray diffraction pattern of the doping levels of yttrium at different concentrations in example 1 of the present invention.
Fig. 3 is an enlarged view of diffraction peaks corresponding to crystal planes at different concentrations of the doping amount of yttrium in example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of doped yttrium at various concentrations in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples.
The general formula of the composition of the yttrium-doped small-size barium titanate nano powder is BYTX, and X represents the doping amount of yttrium.
The doping of the rare earth ions belongs to non-equivalent doping, and corresponding defects such as electrons, vacancies and the like are generated in the BT crystal lattice to compensate the valence equilibrium. When the rare earth ions replace Ba2+, valence state equilibrium can be compensated by forming electrons, barium vacancies, titanium vacancies, reducing Ti4+, and the like; when rare earth ions replace Ti4+, oxygen vacancies are generally formed to maintain valence neutrality; when rare earth ions occupy both Ba-and Ti-sites, a self-compensating mechanism tends to form. Generally, doping of rare earth ions having a large ionic radius results in a decrease in the tetragonality of BT, and the curie temperature shifts toward a low temperature. This is due to the reduction of oxygen octahedral voids, which results in a corresponding reduction in the distance of Ti4+ ions from the center of the oxygen octahedron, resulting in a reduction in the interaction energy of Ti4+ with O2-, which is shown by the fact that at lower temperatures Ti4+ returns to equilibrium. And secondly, the rare earth ion doping can inhibit the grain growth of the ceramic, is beneficial to obtaining fine-grained ceramic and has great contribution to the dielectric constant of the ceramic. When the doping amount of Y element is less, A-site substitution occurs, mainly by electron compensation mechanism. When the doping amount is increased, barium vacancies are increased, and the electronic compensation is transited to vacancy compensation. The charged defects are unevenly distributed in the barium titanate to generate a potential in the vicinity of the grain boundary, causing the segregation of the dopant ions to the grain boundary. Meanwhile, the vacancy causes lattice distortion, certain energy is consumed for lattice distortion, but the energy is not consumed for solute segregation on the grain boundary with the defects, so that Y3+ is easy to generate grain boundary segregation and is enriched in the grain boundary or the vicinity of the grain boundary to block the movement of the grain boundary and inhibit the growth of the grain. The generated electrons are influenced by the spontaneous polarization field, are far away from the equilibrium position to generate electron displacement polarization, and are superposed with the spontaneous polarization field, so that the ferroelectricity of the material is enhanced, and the dielectric constant is increased. The existence of barium vacancy can cause lattice distortion, which is beneficial to ion polarization, and the dielectric constant of the ceramic is increased. In addition, chemical nonuniformity caused by rare earth doping is beneficial to forming a shell-core structure, and plays an important role in improving the temperature characteristic of the capacitor.
Example 1:
the preparation method of yttrium-doped small-size barium titanate nano powder in embodiment 1 of the invention has a flow as shown in fig. 1, and comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 5ml of oleic acid and 10ml of n-butanol to prepare tetrabutyl titanate solution; the mixing mode adopts magnetic stirring.
S2, mixing 20mmol of barium hydroxide, 1g of sodium hydroxide and 20ml of deionized water to prepare strong alkaline barium salt solution; magnetic stirring was also used for the mixing.
Specifically, in the steps S1 to S2, the molar ratio of the barium salt to the tetrabutyl titanate is 1:1 to 3:1, the volume ratio of the deionized water to the short-chain alcohol is 0.8:1 to 2:1, and the volume ratio of the oleic acid to the short-chain alcohol is 1:2.5 to 1: 10. In this example, the molar ratio of barium salt to tetrabutyl titanate is 1:1, the volume ratio of deionized water to short-chain alcohol is 2:1, and the volume ratio of oleic acid to short-chain alcohol is 1:2.
S3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution; simple mixing is carried out by only completely dissolving yttrium nitrate in deionized water.
S4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
specifically, in the step S4, the yttrium nitrate solution is dropped in portions, and the amounts of the dropping are 1.25ul, 6.25ul, 12.5ul, 62.5ul, 125ul and 625ul, respectively, so that the yttrium doping amount is 0.01% mol (a), 0.05% mol (b), 0.1% mol (c), 0.5% mol (D), 1% mol (e) and 5% mol (f). The corresponding demonstration diagrams and scanning electron microscope diagrams are shown in figures 2-4.
S5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 18 hours at the reaction temperature of 180 ℃, and cooling air to room temperature after the reaction is finished;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product; in this case, the semifinished product contains a large amount of organic matter and needs to be washed.
S7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
In the above step S7, the volume fraction of acetic acid and ethanol used is 5%, and the drying temperature is 60 ℃.
Example 2:
the preparation method of yttrium-doped small-size barium titanate nano powder in embodiment 2 of the invention comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate with 2ml of oleic acid and 20ml of ethanol to prepare tetrabutyl titanate solution; the mixing mode adopts magnetic stirring.
S2, mixing 40mmol of barium hydroxide, 1g of sodium hydroxide and 30ml of deionized water to prepare strong alkaline barium salt solution; magnetic stirring was also used for the mixing.
Specifically, in this example, the molar ratio of barium salt to tetrabutyl titanate is 2:1, the volume ratio of deionized water to short-chain alcohol is 1.5:1, and the volume ratio of oleic acid to short-chain alcohol is 1: 10.
S3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution; simple mixing is carried out by only completely dissolving yttrium nitrate in deionized water.
S4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
specifically, in step S4, the yttrium nitrate solution is dropped in portions, and the amounts of the dropping are 1.5ul, 7.5ul, 15ul, 75ul, 150ul and 750ul, respectively, so that the yttrium doping amount is 0.01% mol, 0.05% mol, 0.1% mol, 0.5% mol, 1% mol and 5% mol.
S5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 20 hours at the reaction temperature of 150 ℃, and cooling air to room temperature after the reaction is finished;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product; in this case, the semifinished product contains a large amount of organic matter and needs to be washed.
S7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
In the above step S7, the volume fraction of acetic acid and ethanol used was 1%, and the drying temperature was 50 ℃.
Example 3:
the preparation method of yttrium-doped small-size barium titanate nano powder in embodiment 3 of the invention comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 5ml of oleic acid and 20ml of isopropanol to prepare tetrabutyl titanate solution; the mixing mode adopts magnetic stirring.
S2, mixing 30mmol of barium nitrate, 1g of sodium hydroxide and 16ml of deionized water to prepare strong alkaline barium salt solution; magnetic stirring was also used for the mixing.
Specifically, in this example, the molar ratio of barium salt to tetrabutyl titanate is 1.5:1, the volume ratio of deionized water to short-chain alcohol is 0.8:1, and the volume ratio of oleic acid to short-chain alcohol is 1: 4.
S3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution; simple mixing is carried out by only completely dissolving yttrium nitrate in deionized water.
S4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
specifically, in step S4, the yttrium nitrate solution is dropped in portions, and the amounts of the dropping are 1.25ul, 6.25ul, 12.5ul, 62.5ul, 125ul and 625ul, respectively, so that the yttrium doping amount is 0.01% mol, 0.05% mol, 0.1% mol, 0.5% mol, 1% mol and 5% mol.
S5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 15 hours at the reaction temperature of 200 ℃, and cooling air to room temperature after the reaction is finished;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product; in this case, the semifinished product contains a large amount of organic matter and needs to be washed.
S7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
In the above step S7, the volume fraction of acetic acid and ethanol used was 5%, and the drying temperature was 70 ℃.
Example 4:
the preparation method of yttrium-doped small-size barium titanate nano powder in embodiment 4 of the invention comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 5ml of oleic acid and 20ml of n-butyl alcohol to prepare tetrabutyl titanate solution; the mixing mode adopts magnetic stirring.
S2, mixing 60mmol of barium acetate, 1g of potassium hydroxide and 20ml of deionized water to prepare strong alkaline barium salt solution; magnetic stirring was also used for the mixing.
Specifically, in this embodiment, the molar ratio of the barium salt to the tetrabutyl titanate is 3:1, the volume ratio of the deionized water to the short-chain alcohol is 1:1, and the volume ratio of the oleic acid to the short-chain alcohol is 1: 4.
S3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution; simple mixing is carried out by only completely dissolving yttrium nitrate in deionized water.
S4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
specifically, in step S4, the yttrium nitrate solution is dropped in portions, and the amounts of the dropping are 1.25ul, 6.25ul, 12.5ul, 62.5ul, 125ul and 625ul, respectively, so that the yttrium doping amount is 0.01% mol, 0.05% mol, 0.1% mol, 0.5% mol, 1% mol and 5% mol.
S5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 15 hours at the reaction temperature of 200 ℃, and cooling air to room temperature after the reaction is finished;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product; in this case, the semifinished product contains a large amount of organic matter and needs to be washed.
S7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
In the above step S7, the volume fraction of acetic acid and ethanol used is 10%, and the drying temperature is 60 ℃.
Example 5:
the preparation method of yttrium-doped small-size barium titanate nano powder in embodiment 5 of the invention comprises the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 4ml of oleic acid and 10ml of n-butanol to prepare tetrabutyl titanate solution; the mixing mode adopts magnetic stirring.
S2, mixing 24mmol of barium nitrate, 1g of potassium hydroxide and 20ml of deionized water to prepare strong alkaline barium salt solution; magnetic stirring was also used for the mixing.
Specifically, in this example, the molar ratio of the barium salt to the tetrabutyl titanate is 1.2:1, the volume ratio of the deionized water to the short-chain alcohol is 2:1, and the volume ratio of the oleic acid to the short-chain alcohol is 1: 2.5.
S3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution; simple mixing is carried out by only completely dissolving yttrium nitrate in deionized water.
S4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
specifically, in step S4, the yttrium nitrate solution is dropped in portions, and the amounts of the dropping are 1ul, 5ul, 10ul, 50ul, 100ul and 500ul, respectively, so that the yttrium doping amount is 0.01% mol, 0.05% mol, 0.1% mol, 0.5% mol, 1% mol and 5% mol.
S5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 15 hours at the reaction temperature of 200 ℃, and cooling air to room temperature after the reaction is finished;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product; in this case, the semifinished product contains a large amount of organic matter and needs to be washed.
S7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
In the above step S7, the volume fraction of acetic acid and ethanol used was 8%, and the drying temperature was 65 ℃.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (6)
1. A preparation method of yttrium-doped small-size barium titanate nano powder is characterized by comprising the following steps:
s1, mixing 20mmol of tetrabutyl titanate, 2-5 ml of oleic acid and 10-20 ml of short-chain alcohol to prepare tetrabutyl titanate solution;
s2, mixing 20-60 mmol of barium salt with 1g of inorganic base and 16-30 ml of deionized water to prepare strong alkaline barium salt solution;
s3, dissolving 7.6612g of yttrium nitrate in 5ml of deionized water to prepare 4mol/L yttrium nitrate solution;
s4, slowly adding the strong alkaline barium salt solution into the tetrabutyl titanate solution until the barium salt solution is completely mixed, then dropwise adding the yttrium nitrate solution into the solution to form yttrium doping, and then stirring for 30min by magnetic force to uniformly distribute the yttrium doping to obtain a mixed solution;
s5, transferring the mixed solution into a high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven for hydrothermal reaction for 15-20 h, wherein the reaction temperature is 150-200 ℃, and after the reaction is finished, cooling air to room temperature;
s6, removing the supernatant of the mixed solution after the hydrothermal reaction, and taking out to obtain a semi-finished product;
s7, washing the semi-finished product with acetic acid, deionized water and ethanol respectively, then placing the semi-finished product into a centrifugal machine for centrifugation, and after centrifugation is completed, placing the semi-finished product into a dryer for drying to obtain yttrium-doped small-size barium titanate nano powder, wherein the size of the yttrium-doped small-size barium titanate nano powder is 8-40 nm.
2. The method for preparing yttrium-doped small-size barium titanate nanopowder according to claim 1, wherein the method comprises the following steps: in the steps S1-S2, the molar ratio of barium salt to tetrabutyl titanate is 1:1-3:1, the volume ratio of deionized water to short-chain alcohol is 0.8:1-2:1, and the volume ratio of oleic acid to short-chain alcohol is 1:2-1: 10.
3. The method for preparing yttrium-doped small-size barium titanate nanopowder according to claim 2, wherein the method comprises the following steps: the barium salt is barium hydroxide, barium acetate or barium nitrate, the short-chain alcohol is ethanol, isopropanol or n-butanol, and the inorganic base is potassium hydroxide or sodium hydroxide.
4. The method for preparing yttrium-doped small-size barium titanate nanopowder according to claim 3, wherein the method comprises the following steps: in the step S7, the volume fraction of the acetic acid and the ethanol is 1-10%, and the drying temperature is 50-70 ℃.
5. The method for preparing yttrium-doped small-size barium titanate nanopowder according to any one of claims 1 to 4, wherein the method comprises the following steps: in the step S4, the yttrium nitrate solution is dropped in portions so that the yttrium doping amount is 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.5 mol%, 1 mol%, and 5 mol.
6. The method for preparing yttrium-doped small-size barium titanate nanopowder according to claim 5, wherein the method comprises the following steps: in the steps S1 and S2, the mixing manner is magnetic stirring.
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