CN103864147A - Potassium niobate powder and preparation method thereof - Google Patents
Potassium niobate powder and preparation method thereof Download PDFInfo
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- CN103864147A CN103864147A CN201210544546.4A CN201210544546A CN103864147A CN 103864147 A CN103864147 A CN 103864147A CN 201210544546 A CN201210544546 A CN 201210544546A CN 103864147 A CN103864147 A CN 103864147A
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- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000843 powder Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 abstract description 22
- 238000009826 distribution Methods 0.000 abstract description 17
- 238000002425 crystallisation Methods 0.000 abstract description 12
- 230000008025 crystallization Effects 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 11
- 239000011259 mixed solution Substances 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 243
- 239000010955 niobium Substances 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000012071 phase Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001778 solid-state sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a potassium niobate powder. The method comprises the steps of: adding Nb2O5 to KOH aqueous solution, conducting hydrothermal synthesis on the mixed solution, carrying out solid-liquid separation on the products of hydrothermal synthesis, and drying to obtain a solid. Compared with the prior art, the method provided by the invention can obtain potassium niobate powder with high purity, narrow distribution of particle size, less particle agglomeration and higher crystallinity (crystallization is more than 95% through the analysis of the XRD results).
Description
Technical field
The present invention relates to a kind of preparation method of potassium niobate powder, and the potassium niobate powder of being prepared by the method.
Background technology
Potassium niobate is possessing special character aspect sense of hearing optics, electron optics, nonlinear optics and piezoelectricity, often as frequency inverted material important in waveguide and holographic storage medium.Aspect the application aspect of nano-machine electronic system and the sensor of unleaded and biocompatibility, all playing very important effect simultaneously.And potassium niobate shows unique and superior performance as heterogeneous catalyst in recent years, especially for the control of environmental pollution and green energy resource aspect.
At present, the preparation method of potassium niobate mainly contains solid phase method, oligometric comples method, sol-gel method, hydrothermal synthesis method etc.Solid state sintering is generally difficult to raw material is mixed, and sintering temperature is high, is difficult to the niobium acid potassium crystal of synthetic homogeneous.Oligometric comples method has been used large amount of organic and has made in roasting process mass loss very large, and the consumption of raw material and pH value formation and the performance to product has considerable influence, so condition is not easy to control.Sol-gel method has been used extremely unsettled alkoxide, expensive, and preparation process conditional is comparatively harsh, and reaction and operation all must be carried out in dry nitrogen atmosphere.And Hydrothermal Synthesis rule is a gentle synthetic method, there is product composition even, particle size distribution is narrow, crystallization degree advantages of higher.And the different crystalline phases of potassium niobate have a great impact for its catalytic performance tool.Therefore seek to utilize the hydrothermal synthesis method of mild condition to synthesize purity high, narrow diameter distribution, particle agglomeration mild degree, the potassium niobate that crystallization degree is high and crystalline phase is controlled becomes the focus in the synthetic field of potassium niobate.
Summary of the invention
The object of this invention is to provide a kind of preparation method of potassium niobate powder, and the purity being prepared by the method is high, narrow diameter distribution, particle agglomeration mild degree, potassium niobate powder that crystallization degree is high.
The present inventor finds by a large amount of experiments, limits feeding sequence, by Nb
2o
5add in KOH solution, the solution mixing is carried out to Hydrothermal Synthesis, contribute to like this KNbO
3the nucleation of crystal and growth.
The invention provides a kind of preparation method of potassium niobate powder, wherein, the method comprises Nb
2o
5join in the KOH aqueous solution, the solution mixing is carried out to Hydrothermal Synthesis, the product of Hydrothermal Synthesis gained is carried out to solid-liquid separation, and the dry solid that obtains.
The present invention also provides the potassium niobate powder being made by aforesaid method.
According to technique scheme, by limiting feeding sequence, by Nb
2o
5add in KOH solution, and carry out Hydrothermal Synthesis, by aforesaid method provided by the invention, compared with prior art, purity can be obtained higher, size distribution is narrower (as shown in Figure 5, the size distribution of 500-800nm reaches 67%), particle agglomeration degree is lighter, the potassium niobate powder of crystallization degree higher (by the analysis degree of crystallinity to XRD result more than 95%), in addition, by controlling KOH and Nb
2o
5molar ratio, can obtain different crystalline phases, potassium niobate that crystallization degree is high.
Under preferable case of the present invention, the water content while considering KOH as raw material, and accurately control the concentration of KOH solution, can obtain the better potassium niobate powder of purity and degree of crystallinity.
Under the further preferable case of the present invention, the present inventor finds Nb
2o
5after joining in the KOH aqueous solution, the solution mixing is carried out to Hydrothermal Synthesis under the condition of leaving standstill, than being more conducive to obtain the better potassium niobate powder of degree of crystallinity under the agitation condition of prior art.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the KNbO of the orthogonal phase for preparing of embodiment 1
3the SEM(scanning electronic microscope of powder) photo;
Fig. 2 is the KNbO of the orthogonal phase for preparing of embodiment 1
3the TEM(high resolution transmission electron microscopy of powder) the constituency image of photo;
Fig. 3 is the KNbO of the Emission in Cubic for preparing of embodiment 2
3the SEM(scanning electronic microscope of powder) photo;
Fig. 4 is the KNbO of the Emission in Cubic for preparing of embodiment 2
3the size distribution figure of powder;
Fig. 5 is the KNbO of the Emission in Cubic for preparing of embodiment 2
3the TEM(high resolution transmission electron microscopy of powder) the constituency image of photo;
Fig. 6 is the orthogonal phase for preparing of embodiment 1 and embodiment 2 and the KNbO of Emission in Cubic
3the XRD spectra of powder;
Fig. 7 is the KNbO of the orthogonal phase for preparing of embodiment 6
3the SEM(scanning electronic microscope of powder) photo;
Fig. 8 is the KNbO of the orthogonal phase for preparing of embodiment 6
3the XRD spectra of powder;
Fig. 9 is the KNbO that comparative example 1 prepares
3the SEM(scanning electronic microscope of powdered sample) photo;
Figure 10 is the KNbO that comparative example 1 prepares
3the XRD spectra of powder.
Figure 11 is the KNbO that comparative example 2 prepares
3the SEM(scanning electronic microscope of powdered sample) photo;
Figure 12 is the KNbO that comparative example 2 prepares
3the XRD spectra of powder.
Figure 13 is the KNbO that comparative example 3 prepares
3the SEM(scanning electronic microscope of powdered sample) photo;
Figure 14 is the KNbO that comparative example 3 prepares
3the XRD spectra of powder.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of potassium niobate powder, wherein, the method comprises Nb
2o
5join in the KOH aqueous solution, the solution mixing is carried out to Hydrothermal Synthesis, the product of Hydrothermal Synthesis gained is carried out to solid-liquid separation, and the dry solid that obtains.
According to the present invention, first obtain KOH solution, then by Nb
2o
5add in KOH solution, be conducive to Nb
2o
5in KOH solution, fully dissolve, then carry out Hydrothermal Synthesis, contribute to KNbO by such feeding sequence
3the nucleation of crystal and growth.
In addition, the present inventor finds, the deliquescence because KOH very easily absorbs airborne moisture, so while adopting KOH as raw material, inevitably, containing the water of some, the water content of KOH is 5-10 % by weight conventionally, sometimes up to 30 % by weight.Water contained in KOH becomes the solvent in KOH solution the most at last, and the change of moisture content in KOH raw material is larger, for example can within the scope of 5-30 % by weight, change, the water comprising in KOH will cause the concentration of the KOH solution of the aimed concn of actual preparation to change in a relatively wide scope.Thus, be easy to cause exist difference (between the actual pH of solution and theoretical pH value, the actual pH of solution is less than theoretical pH value), this difference increases with the increase of the water content in KOH raw material, thereby and the pH value of solution can affect by affecting the charging property of particle surface the product types (being pattern and the crystalline phase of resultant) of reaction system.Therefore, further, under preferable case, by the concentration of accurate control potassium hydroxide aqueous solution, thereby can prepare purity and the higher product of degree of crystallinity.
Therefore, in the time of the KOH aqueous solution of a certain concentration of configuration, the first water content of clear and definite KOH reagent, then weigh the amount in the KOH reagent of KOH butt, calculate the quality of the water in KOH reagent, and the needed water yield the quality of the water of interpolation in KOH reagent, can configure the more accurate KOH aqueous solution of this concentration.
According to the present invention, under preferable case, the described KOH aqueous solution is soluble in water the obtaining of KOH solid by being 5-30 % by weight by water content, water (described water comprises water contained in KOH solid and the water adding as required) with the weight ratio take the KOH solid of butt as 0.95-1.52:1.Adopt the KOH aqueous solution of the concentration of this proportional arrangement, be conducive to obtain the better product of purity and degree of crystallinity.
Owing to considering that KOH can contain the water of 5-30 % by weight conventionally; the KOH solution of its configuration is not only because the minimizing of solute but also the increase because of solvent can reduce the concentration of solution; and the pH value error that conventionally adopts pH value meter or pH value tester to measure is larger, so the pH value of the KOH solution obtaining also out of true conventionally.The present inventor in the time of configuration KOH solution, consider raw material KOH in the contained water yield can become the part of solvent, can the more accurate KOH solution of configuration concentration, thus reach ingredient proportion more accurately, obtain the better product of purity and degree of crystallinity.
According to the present invention, KOH and Nb
2o
5weight ratio those skilled in the art can select according to prior art, still, if KOH is moisture, the existence of water not only can cause KOH strength of solution to reduce, and also can cause the actual KOH molar weight dropping into reduce.So, in order better to realize object of the present invention, at calculating K OH and Nb
2o
5consumption time, KOH need to be in butt, if directly with the weighing scale of the KOH raw material that contains water, the actual KOH obtaining and Nb
2o
5weight ratio will be lower than theoretical KOH and Nb
2o
5weight ratio, for example, adopt water content be KOH raw material and the Nb of 10 % by weight
2o
5when the weight ratio of calculating theoretical input amount is 25:1, in the situation that considering KOH raw material water content, KOH input amount is 111g, Nb
2o
5input amount is that 4g just can reach KOH and Nb
2o
5weight ratio be 25:1; In the situation that not considering KOH raw material water content, KOH input amount is 100g, Nb
2o
5input amount is 4g, its actual KOH and Nb
2o
5weight ratio be 22.5:1.In the situation that raw material KOH water content is higher, actual KOH and Nb
2o
5weight ratio and the gap of theoretical weight ratio will be larger.So, consider in the moisture situation of raw material KOH, preferably in KOH and the Nb of butt
2o
5mol ratio be 25-40:1, in order to obtain the KNbO of orthogonal phase and Emission in Cubic
3crystal, further preferred KOH and Nb
2o
5mol ratio be 25-35:1.
It should be noted that, as the KOH in butt and Nb
2o
5mol ratio while being 25-30:1, can obtain purity high, particle agglomeration mild degree, the potassium niobate of the orthogonal phase that crystallization degree is high; As the KOH in butt and Nb
2o
5mol ratio while being 35:1, can obtain purity high, narrow diameter distribution, particle agglomeration mild degree, the potassium niobate of the Emission in Cubic that crystallization degree is high.And as KOH and Nb in butt
2o
5mol ratio be: be greater than 30 to being less than 35:1, and in being greater than 35 when being less than or equal to 40:1, obtain orthogonal phase phase potassium niobate.
According to the present invention, adopt hydrothermal synthesis method to carry out the preparation of potassium niobate powder, carrying out the condition of Hydrothermal Synthesis can select according to prior art, but in order better to realize object of the present invention, under preferable case, the temperature of carrying out Hydrothermal Synthesis is 160-170 ℃, and the time is 11-12 hour.The temperature of Hydrothermal Synthesis can realize by the type of heating such as oil bath, baking oven.The present invention preferably adopts baking oven for heating, is heated more even, is more conducive to synthetic purity high, the potassium niobate that degree of crystallinity is high.
Conventionally under the condition stirring, carry out Hydrothermal Synthesis.The present invention preferably carries out Hydrothermal Synthesis under the condition of leaving standstill.Because the present invention defines feeding sequence, be conducive to Nb
2o
5in KOH solution, evenly mix, so by Nb
2o
5join in the KOH aqueous solution, the solution mixing is carried out to Hydrothermal Synthesis under the condition of leaving standstill, be conducive to obtain the better product of purity and degree of crystallinity.
According to the present invention, the product of Hydrothermal Synthesis gained is carried out to the mode of solid-liquid separation and can carry out with reference to prior art, for example filtration, centrifugation etc., the present invention preferably adopts centrifugation mode.
According to the present invention, under preferable case, the method is also included in solid to obtaining and washs before being dried.The object of described washing is to remove foreign ion, and cleaning solvent used can be water and/or ethanol.Preferably adopt water and ethanol respectively the solid obtaining to be washed, and first wash with water, then use washing with alcohol, until the solution of washing is neutrality.
According to the present invention, described dry method is conventionally known to one of skill in the art, for example, seasoning, forced air drying, vacuum-drying etc., the present invention preferably adopts the method for forced air drying to be dried; Dry condition is not particularly limited, and preferably described dry temperature is 60-80 ℃, and the time is 12-18 hour.
In the present invention, KOH butt weight measures by gravitational thermal analysis method.
The present invention also provides a kind of potassium niobate powder of being prepared by aforesaid method.Compared with the potassium niobate powder of preparing according to the conventional method, the grain diameter of described potassium niobate powder of the present invention is 500-1000nm, size distribution is narrower (as shown in Figure 5, the size distribution of 500-800nm reaches 67%), purity is higher, particle agglomeration degree is lighter, crystallization degree higher (by the analysis degree of crystallinity to XRD result more than 95%).
Below will describe the present invention by embodiment, but the present invention is not limited in following embodiment.
In following examples, TEM test adopts the Tecnai G2F20U-TWIN equipment of FEI Co. to carry out; SEM test adopts the Hitachi S-4800 equipment of FEI Co. to carry out; XRD test adopts the XRD-6000 equipment of Shimadzu company to carry out; Degree of crystallinity is analyzed and is obtained by XRD analysis software MDI-jade; Size-grade distribution adopts the methods analyst that SEM photo is carried out to statistical study.
Following reagent is commercial goods unless stated otherwise.
Embodiment 1
Under room temperature (all referring to 25 ℃ in the present invention), in three neck round-bottomed flasks, add 26.92gKOH(water content 30 % by weight) and 20mL deionized water, be stirred to completely and dissolve, by 3.57g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 160 ℃ that autoclave is put into temperature, heats 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
As shown in Figure 1, as shown in Figure 2, XRD spectra as shown in Figure 6 (a) for TEM photo for the SEM photo of gained potassium niobate product.
Potassium niobate particle agglomeration degree is lighter as can be seen from Figure 1; In picture, be (001) and (110) face (by contrasting with PDF card, can find out that the spacing that these two faces are corresponding is consistent mutually with the orthogonal of potassium niobate) of orthogonal phase potassium niobate as can be seen from Figure 2; Can find out that from Fig. 6 (a) potassium niobate obtaining is orthogonal phase, and inclusion-free peak in picture, illustrate that the potassium niobate purity obtaining is higher, and degree of crystallinity reaches 97%.
At room temperature, in three neck round-bottomed flasks, add 37.69g KOH(water content 30 % by weight) and 17mL deionized water, be stirred to completely and dissolve, by 3.57g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 160 ℃ that autoclave is put into temperature, heats 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, XRD spectra as shown in Figure 6 (b) for size distribution for TEM photo for the SEM photo of gained potassium niobate product.
The growth of potassium niobate particle crystalline form is complete as can be seen from Figure 3, size is even, reunion degree is lighter; In picture, be (100) and (001) face (by contrasting with PDF card, can find out that the spacing that these two faces are corresponding is consistent with the Emission in Cubic of potassium niobate) of Emission in Cubic potassium niobate as can be seen from Figure 4; Can obviously find out that from the size distribution figure of Fig. 5 the potassium niobate sample particle size distribution range obtaining is narrower, reach 67% in the size distribution of 500-800nm; Can find out that from Fig. 6 (b) potassium niobate obtaining is Emission in Cubic, and inclusion-free peak in picture, illustrate that the potassium niobate purity obtaining is higher, and degree of crystallinity reaches 98%.
Embodiment 3
At room temperature, in three neck round-bottomed flasks, add 31.04g KOH(water content 15 % by weight) and 23.5mL deionized water, be stirred to completely and dissolve, by 3.57g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 160 ℃ that autoclave is put into temperature, heats 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 80 ℃ dry 15 hours, obtain potassium niobate product.
The SEM photo of gained potassium niobate product is similar to Fig. 3, and TEM photo is similar to Fig. 4, and size distribution and Fig. 5 are close, and XRD spectra is similar to Fig. 6 (b); The growth of particle crystalline form is complete, size is even, crystallization degree is high.
At room temperature, in three neck round-bottomed flasks, add 27.77g KOH(water content 5 % by weight) and 27mL deionized water, be stirred to completely and dissolve, by 3.57g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 160 ℃ that autoclave is put into temperature, heats 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
The SEM photo of gained potassium niobate product is similar to Fig. 3, and TEM photo is similar to Fig. 4, and size distribution and Fig. 5 are close, and XRD spectra is similar to Fig. 6 (b); The growth of particle crystalline form is complete, size is even, crystallization degree is high.
Embodiment 5
At room temperature, in three neck round-bottomed flasks, add 22.689g KOH(water content 30 % by weight) and 14mL deionized water, be stirred to completely and dissolve, by 2.5g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 170 ℃ that autoclave is put into temperature, heats 11 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
The SEM photo of gained potassium niobate product is similar to Fig. 1, and TEM photo is similar to Fig. 2, and XRD spectra is similar to Fig. 6 (a); Crystallization degree is high.
At room temperature, in three neck round-bottomed flasks, add 30.15g KOH(water content 30 % by weight) and 15mL deionized water, be stirred to completely and dissolve, by 2.5g Nb
2o
5join in the above-mentioned KOH aqueous solution, stir half an hour (mixing).Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then leaving standstill under condition, it is in the baking oven of 160 ℃ that autoclave is put into temperature, heats 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
As shown in Figure 7, XRD spectra as shown in Figure 8 for the SEM photo of gained potassium niobate product.
Potassium niobate particle agglomeration degree is lighter as can be seen from Figure 7; The potassium niobate obtaining is as can be seen from Figure 8 orthogonal phase, and inclusion-free peak in picture, illustrate that the potassium niobate purity obtaining is higher, and degree of crystallinity is 95%.
Comparative example 1
At room temperature, in three neck round-bottomed flasks, add 27mL deionized water and 3.57g Nb
2o
5, add 27.77g KOH(water content 5 % by weight), stir half an hour.Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL to sealing.Then autoclave is put into temperature and is in the baking oven of 160 ℃, heat 12 hours.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
As shown in Figure 9, XRD spectra as shown in figure 10 for the SEM photo of gained potassium niobate product.
The growth of gained potassium niobate particle crystalline form is incomplete more as can be seen from Figure 9, and shape size obvious difference, and particle agglomeration degree is serious; The potassium niobate purity obtaining is as can be seen from Figure 10 not high, contains a lot of impurity peaks in figure, and as having impurity peaks the many places such as 12 °, 25 °, 39 °, and degree of crystallinity also reduces, and is 90%.
Comparative example 2
Method according to comparative example 1 is prepared potassium niobate powder, different, while configuring the KOH solution of concentration of comparative example 1, does not consider the water content of KOH, in three neck round-bottomed flasks, adds 27mL deionized water and 3.57g Nb
2o
5, the theoretical concentration that adds 25.1g KOH(KOH solution is 48.2 % by weight), the actual concentrations of KOH solution is 45.8 % by weight.
As shown in figure 11, XRD spectra as shown in figure 12 for the SEM photo of gained potassium niobate product.
The growth of gained potassium niobate particle crystalline form is incomplete more as can be seen from Figure 11, and shape size obvious difference, and particle agglomeration degree is serious; The potassium niobate degree of crystallinity obtaining as can be seen from Figure 12 reduces, and is 87%.
Comparative example 3
At room temperature, in three neck round-bottomed flasks, add 27mL deionized water and 3.57g Nb
2o
5, add 25.1gKOH(not consider water content), stir half an hour.Mixed solution in three neck round-bottomed flasks is transferred in the autoclave that volume is 50mL, sealed after putting into magnetic stir bar.Then autoclave is put in the middle of the oil bath pan that fills silicone oil, temperature control is 160 ℃, heats 12 hours under agitation condition.Naturally cool to after room temperature, it is 7 left and right that the white product obtaining successively water and ethanol (deionized water wash three times, washing with alcohol one time) are carried out to eccentric cleaning to pH value of solution, then in the baking oven of 60 ℃ dry 12 hours, obtain potassium niobate product.
As shown in figure 13, XRD spectra as shown in figure 14 for the SEM photo of gained potassium niobate product.
The growth of gained particle crystalline form is incomplete more as can be seen from Figure 13, and shape size obvious difference, and should be unreacted Niobium Pentxoxide from the known most of particle of XRD analysis; The XRD peak of the potassium niobate obtaining as can be seen from Figure 14 do not occur substantially, and the XRD peak in figure and the peak of commercial Niobium Pentxoxide are more identical, illustrates that reaction not exclusively.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (7)
1. a preparation method for potassium niobate powder, is characterized in that, the method comprises Nb
2o
5join in the KOH aqueous solution, the solution mixing is carried out to Hydrothermal Synthesis, the product of Hydrothermal Synthesis gained is carried out to solid-liquid separation, and the dry solid that obtains.
2. method according to claim 1, wherein, the described KOH aqueous solution is soluble in water the obtaining of KOH solid by being 5-30 % by weight by water content, water with the weight ratio take the KOH solid of butt as 0.95-1.52:1.
3. method according to claim 1, wherein, in KOH and the Nb of butt
2o
5mol ratio be 25-40:1, be preferably 25-35:1.
4. method according to claim 1, wherein, the condition of carrying out Hydrothermal Synthesis comprises: temperature is 160-170 ℃, the time is 11-12 hour.
5. according to the method described in claim 1 or 4, wherein, the solution mixing is carried out to Hydrothermal Synthesis under the condition of leaving standstill.
6. method according to claim 1, wherein, dry condition comprises: temperature is 60-80 ℃, the time is 12-18 hour.
7. the potassium niobate powder being prepared by the method described in any one in claim 1-6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186339A (en) * | 2007-12-04 | 2008-05-28 | 北京科技大学 | Microwave hydro-thermal synthesis method for sodium niobate potassium niobate leadless piezoelectric ceramic powder |
| CN101249985A (en) * | 2008-03-25 | 2008-08-27 | 大连理工大学 | Controllable preparation method of orthorhombic-phase rhombohedral-phase sodium niobate having high Curie point |
| CN101575215A (en) * | 2009-06-10 | 2009-11-11 | 桂林理工大学 | Hydro-thermal synthesis method of potassium niobate powder |
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| CN101186339A (en) * | 2007-12-04 | 2008-05-28 | 北京科技大学 | Microwave hydro-thermal synthesis method for sodium niobate potassium niobate leadless piezoelectric ceramic powder |
| CN101249985A (en) * | 2008-03-25 | 2008-08-27 | 大连理工大学 | Controllable preparation method of orthorhombic-phase rhombohedral-phase sodium niobate having high Curie point |
| CN101575215A (en) * | 2009-06-10 | 2009-11-11 | 桂林理工大学 | Hydro-thermal synthesis method of potassium niobate powder |
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