CN109987629A - A kind of hydrothermal synthesis method for the niobic acid silver preparing perovskite structure using silver nitrate - Google Patents
A kind of hydrothermal synthesis method for the niobic acid silver preparing perovskite structure using silver nitrate Download PDFInfo
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Abstract
The invention discloses a kind of hydrothermal synthesis method of niobic acid silver ceramic powder that perovskite structure is prepared using silver nitrate, specific steps are as follows: accurate weighing ammonium acid fluoride (NH4HF2), silver nitrate (AgNO3) and niobium pentaoxide (Nb2O5), raw material is mixed and is put into polytetrafluoroethylene (PTFE) autoclave liner and is added 50ml deionized water, then obtained mixed liquor is stirred at room temperature 10-30 minutes, sealing is put into 180 DEG C of -220 DEG C of reaction 10-32h in high-temperature water oven heat after mixing evenly；After the reaction was completed by obtained powder suction filtration, washing and the dry 2-5h in 60 DEG C -85 DEG C of baking oven, the niobic acid silver ceramic powder of pure perovskite structure is finally obtained.The present invention can obtain high-purity niobic acid silver ceramic powder at a lower temperature, and simple process is feasible, and the component control for being easy to implement dopant material is designed with structure.
Description
Technical field
The present invention relates to niobic acid ag material preparation technical fields, prepare calcium titanium by raw material of silver nitrate more particularly, to one kind
The hydrothermal synthesis method of the niobic acid silver ceramic powder of mine structure.
Background technique
Dielectric capacitor is known as " blood of modern industry ", is smart grid, electric car, New Energy Industry, elder generation
Into the key components in the fields such as weaponry, suffered from national economy main battle ground and great strategy demand towards the country field important
Effect.Compared with electric chemical super capacitor, dielectric capacitor has structure simple, big without liquid composition, operating voltage
(usually more than several thousand volts), power density high (can be to megawatt magnitude), charge/discharge speed fast (nanosecond order), environmental suitability
Well, the features such as service life is long, safe.These features make it be with a wide range of applications and important strategic position.
By taking national defence high-tech sector as an example: dielectric capacitor is the core energy storage device of high energy pulse power technology.Benefit
It can realize that ultra high power amplifies with its ultra high power density feature, in nuclear blast simulation, high power pulsed laser, electromagnetic path
The national defence high-tech sector such as big gun, electromagnetic launch has irreplaceable key effect.In addition, portable electronic device is sent out in recent years
The with rapid changepl. never-ending changes and improvements of exhibition has driven energy-storage travelling wave tube to develop to high energy storage, miniaturization and environmentally friendly direction, dielectric capacitance
Device is taken as own duty important task of bearing the responsibility.
In order to obtain biggish energy storage density, need to improve dielectric constant and disruptive field intensity simultaneously.Compared to electrostrictive polymer
Medium, inorganic dielectric have high dielectric constant, larger energy storage density, excellent high military service performance, compared with low-dielectric loss and
The features such as big charge-discharge velocity, occupies an important position in stored energy application.According to the feature of ferroelectric hysteresis loop, inorganic dielectric material
Linear dielectric substance, ferroelectricity (containing relaxor ferroelectric) material and antiferroelectric materials three classes can be divided into.Wherein, antiferroelectric materials
There is no intrinsic domain wall drift, and without apparent ysteresis effect before antiferroelectric-ferroelectricity (AFE-FE) phase transformation occurs, thus
Dielectric loss is smaller under existing fringing field；Under high electric field, the dipole of antiparallel arrangements will form the ferroelectricity sequence being collectively aligned, by
This shows energy storage density more higher than linear dielectric and ferroelectric.
Lead base antiferroelectric materials is that a kind of all have wide application prospect in fields in electric flux storage, energy conversion etc.
Material.In recent years, it is contemplated that the cry of the environmental hazard of leaded system, lead-free systems grows to even greater heights.AgNbO3Base ceramics by
It the advantages that high, without volatile alkali metal element in energy storage density, is occupied an important position in lead-free anti-ferroelectric energy storage ceramic field.
Currently, the most common preparation AgNbO3AgNbO used in base energy storage ceramic3The method of powder is solid reaction process, i.e., with
Silver-colored source (contains Ag2O、AgNO3Deng) and Nb2O5It is raw material in O2AgNbO is synthesized in atmosphere3Powder, then by works such as high-temperature calcinations
Skill obtains potsherd.However, solid reaction process has the following deficiencies: that (1) is easily introduced impurity in ball milling and high-temperature sintering process；
(2)Ag2O and Nb2O5At high temperature during mixed sintering, it is difficult to control Ag2Product caused by the thermodynamic instability of O
Middle Ag2The presence of O；(3) powder size is larger and uncontrollable, is unfavorable for the subsequent AgNbO for obtaining little crystal grain high-compactness3Pottery
Porcelain；(4) the required sintering temperature of gained powder preparation ceramics is high.
And hydro-thermal method is to grow one of simple and appropriate method of complex oxide crystal.Hydro-thermal have synthesis temperature it is low (<
300 DEG C), isobaric, solution condition is conducive to growth has that the crystal grain of balance defect density and rule orientating, product purity be high, grain
The advantages that diameter is uniform, lytic activity is high and the granularity of easily controllable crystalline product.The niobic acid aluminium powder prepared with hydro-thermal method
Activity is higher, can be sintered to obtain fine and close niobic acid silver ceramics at a lower temperature.Simultaneously because sintering temperature is low, by hydro-thermal
AgNbO made from powder3The crystal grain of ceramics is smaller, is conducive to the raising of ceramic disruptive field intensity.
So far, AgNbO is synthesized in hydro-thermal method few in number3Report in, it is Ag that the source Ag, which uses,2O is (such as
Haibo Chang et.al,Hydrothermal Syntheses and Structural Phase Transitions of
AgNbO3,Journal of the American Ceramic Society,2012,95: 3673-3677；He Lijie etc., calcium
Titanium ore type oxygen compound AgNbO3Hydrothermal synthesis and characterization, functional material, 2012,10:1323-1326；Dong Shuchun etc.,
AgNbO3Hydrothermal synthesis and photocatalysis property characterization, molecular science journal, 2012,28:232-236).In these reports,
Some, which are clearly stated, directly uses AgNO3AgNbO can not be obtained as hydrothermal synthesis raw material3Powder (He Lijie etc., Ca-Ti ore type
Oxygen compound AgNbO3Hydrothermal synthesis and characterization, functional material, 2012,10:1323-1326), some used Ag2O is former
Material is to pass through AgNO3It generates heat resolve after AgOH is precipitated in aqueous solution with NaOH and obtains (Dong Shuchun etc., AgNbO3Hydro-thermal
Synthesis and photocatalysis property characterization, molecular science journal, 2012,28:232-236).
Utilize Ag2Although O can synthesize AgNbO as raw material3Powder, but have the following deficiencies: (1) for passing through
AgNO3The Ag that self-control obtains is reacted with metal hydroxides2O, it is necessary first to generate highly unstable silver hydroxide and decompose therewith
Obtain water and silver oxide.After washing precipitating, it is necessary in the fully evenly drying, but lacking in last removing silver oxide less than 85 DEG C
It is extremely difficult to measure water.This method both increases experiment reagent, and increases experimental procedure and accurately weigh Ag2The difficulty of O
(because of the Ag generated2It is relatively difficult that water is completely removed in O)；(2) Ag is directly used2O reagent uses Ag in document as raw material2O
AgNbO of the reagent as Material synthesis3Powder grain larger (~1 μm) (such as: Haibo Chang et.al.,
Hydrothermal Syntheses and Structural Phase Transitions of AgNbO3,Journal of
theAmerican Ceramic Society,2012,95:3673-3677；He Lijie etc., Ca-Ti ore type oxygen compound AgNbO3
Hydrothermal synthesis and characterization, functional material, 2012,10:1323-1326).And the disruptive field intensity of little crystal grain ceramics is generally preferred over greatly
Crystal grain ceramics, thus coarse powder size is unfavorable for obtaining the ceramics of big disruptive field intensity, and then is unfavorable for obtaining high energy storage
Density.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, perovskite structure is prepared using silver nitrate this application provides a kind of
The hydrothermal synthesis method of niobic acid silver.Technical scheme is as follows:
A kind of hydrothermal synthesis method for the niobic acid silver preparing perovskite structure using silver nitrate, comprising the following steps:
(1) the ammonium acid fluoride NH of the corresponding mole specific mass of accurate weighing4HF2, silver nitrate AgNO3With niobium pentaoxide Nb2O5
And it mixes；The corresponding molar ratio is 3NH4HF2: 2AgNO3: xNb2O5, wherein x=0.6-0.85；Or the corresponding molar ratio
For yNH4HF2: 2AgNO3: 1Nb2O5, wherein y=4-5；
(2) 50ml deionized water, packing ratio 50-70% are added in polytetrafluoroethylene (PTFE) autoclave liner；
(3) the resulting raw material of step (1) is mixed to the polytetrafluoroethylene (PTFE) autoclave liner for pouring into step (2) and obtaining
In, obtain mixed liquor；
(4) liner, is put by the mixed liquor magnetic stirrer 10-30min for obtaining step (3) after mixing evenly
High-temperature water oven heat is put into stainless steel autoclave, after sealing, in 180 DEG C of -220 DEG C of reaction 10-32h；
(5) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(6) reactant that washing obtains is put into dry 2-5h in 60 DEG C -85 DEG C of baking oven, finally obtains niobic acid silver ceramics
Powder, i.e., the niobic acid silver of the described perovskite structure.
Further, the silver-colored source of the hydrothermal synthesis method is AgNO3, and do not need AgNO before hydro-thermal reaction3Instead
Other raw materials should be generated.
Step (1) described accurate weighing can use high accuracy analysis Libra, and silver source used is AgNO3。
In step (4), when hydrothermal temperature is 180 DEG C, the reaction time is that 10h can synthesize pure phase niobic acid
Silver at least needs to react for 24 hours relative to other hydro-thermals, this experiment reaction time is shorter, and output efficiency is higher.
The present invention is beneficial to be had the technical effect that
Traditional with NH4HF2、Ag2And Nb O,2O5AgNbO is prepared for raw material3During, the reaction of generation are as follows:
①Nb2O5+NH4HF2→(NH4)3NbOF6+H2O(100-130℃)
(NH4)3NbOF6→[NbOF6]3-→[NbO(OH)6]3-→NbO3 -
(hydrolysis) (is dehydrated and polymerize)
②NH4HF2It is dissolved in water and provides acidic environment, in acid condition (i.e. pH < 7), Ag2O dissolution generates Ag+。
To sum up, AgNbO under hydrothermal condition3Ultimately forming for crystal may be expressed as: with growth course
Ag++NbO3 -=AgNbO3
And the present invention is then single step reaction method, i.e., need not first use AgNO3Synthesize Ag2O is reacted again, omits intermediate steps,
Directly use AgNO3In Ag+With NbO3 -Reaction obtains pure phase AgNbO3。
Ca-Ti ore type oxygen compound AgNbO3Hydrothermal synthesis and characterization (He Lijie etc., functional material, 10 phases in 2012
(43) roll up) in, it is general first with NaOH and AgNO3Ag is prepared for raw material2O, then with Nb2O5And NH4HF2In a kettle further into
Row hydro-thermal reaction obtains product AgNbO3.In some documents (He Lijie etc., functional material, 10 phases in 2012 (43) volume) then
It specifically mentions and directlys adopt AgNO3Solution cannot get product as reaction raw materials.And the present invention overcomes above-mentioned technological deficiency and
Technology prejudice directly uses silver nitrate to synthesize niobic acid silver as reaction raw materials.
Particularly, the invention avoids conventional solid-state method, energy consumption is high, low efficiency, and not thin enough the and easy impurity etc. that is mixed into of powder lacks
Point can obtain high-purity niobic acid silver ceramic powder at a lower temperature.And it is different from being closed in other documents with silver oxide hydro-thermal
At or synthesis in solid state niobic acid silver, the method can not only use the direct step hydrothermal synthesis target product of silver nitrate, and can be with
It prevents in solid phase method due to Ag2Ag caused by the thermodynamic phase of O in product2O impurity, simple process is feasible, and
The component control for being easy to implement dopant material is designed with structure.
The size for the niobic acid aluminium powder that the present invention is prepared is adjustable within the scope of 450-1600nm.On the whole partial size with
The corresponding relationship of reaction condition are as follows: (1) under the same reaction time, with the raising of hydrothermal temperature, powder size increases；
(2) the same reaction time and at a temperature of, with NH4HF2The increase of content, powder size increase；(3) in identical NH4HF2Contain
It measures and the same reaction time is at a temperature of, with Nb2O5The reduction of content, powder size increase.
Moreover, the powder active that the present invention obtains is higher, through 1000-1015 DEG C of (powder obtained by conventional solid reaction method
For preparing sintering temperature > 1050 DEG C of ceramics) can reach after sintering 97% or more consistency, and crystallite dimension is in 5 μ
M or less.Its disruptive field intensity can achieve 250kV/cm, for current pure AgNbO3Maximum value (general pure AgNbO in ceramics3Pottery
The disruptive field intensity of porcelain is no more than 180kV/cm).
Detailed description of the invention
Fig. 1 is the XRD spectrum of the niobic acid aluminium powder in embodiment 1；
Fig. 2 is that the SEM of the niobic acid aluminium powder in embodiment 1 schemes (field emission scanning electron microscope figure)；
Fig. 3 is the XRD spectrum of the niobic acid aluminium powder in embodiment 2；
Fig. 4 is that the SEM of the niobic acid aluminium powder in embodiment 2 schemes (field emission scanning electron microscope figure)；
Fig. 5 is the XRD spectrum of the niobic acid aluminium powder in embodiment 3；
Fig. 6 is that the SEM of the niobic acid aluminium powder in embodiment 3 schemes (field emission scanning electron microscope figure)；
Fig. 7 is the XRD spectrum of the niobic acid aluminium powder in embodiment 4；
Fig. 8 is that the SEM of the niobic acid aluminium powder in embodiment 4 schemes (field emission scanning electron microscope figure)；
Fig. 9 is the XRD spectrum of the niobic acid aluminium powder in embodiment 5；
Figure 10 is that the SEM of the niobic acid aluminium powder in embodiment 5 schemes (field emission scanning electron microscope figure)；
Figure 11 is the XRD spectrum of the niobic acid aluminium powder in embodiment 6；
Figure 12 is that the SEM of the niobic acid aluminium powder in embodiment 6 schemes (field emission scanning electron microscope figure)；
Figure 13 is the XRD spectrum of the niobic acid aluminium powder in embodiment 7；
Figure 14 is that the SEM of the niobic acid aluminium powder in embodiment 7 schemes (field emission scanning electron microscope figure)；
Figure 15 is the SEM figure that hydro-thermal niobic acid aluminium powder is sintered gained potsherd after 3h at 1015 DEG C in embodiment 8；
Figure 16 is the D-E loop line of niobic acid silver ceramics in embodiment 8.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.Obviously, described embodiment is only this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 3NH4HF2: 2AgNO3: 0.85Nb2O5Raw material, that is, divide
Also known as take the NH of 0.855g4HF2, the AgNO of 1.7g3With the Nb of 1.1305g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 70%；
(3) the mixed liquor magnetic stirrer 15min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, reacts 10h at 180 DEG C；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figure 1, 2, can see resulting niobic acid silver from XRD diagram
For pure perovskite structure, feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find the presence of other miscellaneous phases；
It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated several
What shape, morphology microstructure is cube, and average grain diameter is about 450nm or so, and purity is higher.
Embodiment 2:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 3NH4HF2: 2AgNO3: 0.85Nb2O5Raw material, that is, divide
Also known as take the NH of 0.855g4HF2, the AgNO of 1.7g3With the Nb of 1.1305g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 70%；
(3) the mixed liquor magnetic stirrer 10min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, reacts 16h at 180 DEG C；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figure 3,4, can see resulting niobic acid silver from XRD diagram
For pure perovskite structure, feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find the presence of other miscellaneous phases；
It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated several
What shape, morphology microstructure is cube, and average grain diameter is about 510nm or so, and purity is higher.
Embodiment 3:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 3NH4HF2: 2AgNO3: 0.85Nb2O5Raw material, that is, divide
Also known as take the NH of 0.855g4HF2, the AgNO of 1.7g3With the Nb of 1.1305g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 70%；
(3) the mixed liquor magnetic stirrer 20min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, reacts 32h at 180 DEG C；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figure 5,6, can see resulting niobic acid silver from XRD diagram
For pure perovskite structure, feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find the presence of other miscellaneous phases；
It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated several
What shape, morphology microstructure is cube, and average grain diameter is about 460nm or so, and purity is higher.
Embodiment 4:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 4NH4HF2: 2AgNO3: 1Nb2O5Raw material, that is, weigh
1.14g NH4HF2, the AgNO of 1.7g3With the Nb of 1.33g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 50%；
(3) the mixed liquor magnetic stirrer 15min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, in 180 DEG C of reaction 16h；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figure 7,8, can see resulting niobic acid silver from XRD diagram
For pure perovskite structure, feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find the presence of other miscellaneous phases；
It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated several
What shape, morphology microstructure is cube, and average grain diameter is about 540nm or so, and purity is higher.
Embodiment 5:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 5NH4HF2: 2AgNO3: 1Nb2O5Raw material, that is, weigh
1.425g NH4HF2, the AgNO of 1.7g3With the Nb of 1.33g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 60%；
(3) the mixed liquor magnetic stirrer 15min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, in 180 DEG C of reaction 16h；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figures 9 and 10, can see resulting niobic acid from XRD diagram
Silver is pure perovskite structure, and feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find depositing for other miscellaneous phases
?；It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated
Geometry, morphology microstructure are cube, and average grain diameter is about 750nm or so, and purity is higher.
Embodiment 6:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 3NH4HF2: 2AgNO3: 0.85Nb2O5Raw material, that is, divide
Also known as take the NH of 0.855g4HF2, the AgNO of 1.7g3With the Nb of 1.1305g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 70%；
(3) the mixed liquor magnetic stirrer 15min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, reacts 16h at 200 DEG C；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 85 DEG C of baking ovens dry 2h, finally obtains niobic acid silver ceramic powder.
XRD and the SEM figure of the present embodiment products obtained therefrom as shown in Figure 11,12, can see resulting niobic acid from XRD diagram
Silver is pure perovskite structure, and feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find depositing for other miscellaneous phases
?；It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated
Geometry, morphology microstructure are cube, and average grain diameter is about 1400nm or so, and purity is higher.
Embodiment 7:
The hydrothermal synthesis method of the niobic acid silver provided in this embodiment that perovskite structure is prepared using silver nitrate includes following
Step:
(1) weighing corresponding molar ratio with high accuracy analysis Libra is 3NH4HF2: 2AgNO3: 0.6Nb2O5Raw material, that is, distinguish
Weigh the NH of 0.855g4HF2, the AgNO of 1.7g3With the Nb of 0.798g2O5；
(2) raw material weighed up is put into polytetrafluoroethylene (PTFE) autoclave liner, and the deionized water of 50ml is added, filled out
It fills than being 70%；
(3) the mixed liquor magnetic stirrer 15min for obtaining step (2) stirs evenly mixed liquor for being equipped with
Liner is put into stainless steel autoclave, and high-temperature water oven heat is put into after sealing, reacts 16h at 180 DEG C；
(4) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed repeatedly with deionized water and dehydrated alcohol
To neutrality；
(5) reactant that washing obtains is put into 60 DEG C of baking ovens dry 3h, finally obtains niobic acid silver ceramic powder.
The XRD and SEM of the present embodiment products obtained therefrom scheme as shown in Figure 13,14, it can be seen that resulting niobic acid from XRD diagram
Silver is pure perovskite structure, and feature peak intensity is high, illustrates that the crystallinity of compound is very high, does not find depositing for other miscellaneous phases
?；It can be seen that AgNO from SEM figure3The AgNbO obtained as starting material3With good crystallinity, and have well-regulated
Geometry, morphology microstructure are cube, and average grain diameter is about 540nm or so, and purity is higher.
Embodiment 8:
It is provided in this embodiment to prepare the niobic acid aluminium powder of perovskite structure using silver nitrate and be sintered to obtain high strike
The step for wearing field strength ceramics includes:
(1) according to 3NH4HF2: 2AgNO3: 0.85Nb2O5Material rate, at 200 DEG C react 20h obtain it is pure
AgNbO3Powder；
(2) 600 DEG C of roasting 2h improve ceramics will wherein hydroxyl, oxygen defect etc. to remove to the powder obtained under oxygen
The disruptive field intensity of piece；
(3) powder after grinding is subjected to granulation tabletting, is pressed into thickness 1mm, the potsherd of diameter 10mm；
(4) potsherd carries out dumping under oxygen, and dump temperature is 600 DEG C, and the dumping time is 5h, cold with furnace after dumping
But to room temperature；
(5) potsherd after dumping is sintered for 1015 DEG C under oxygen atmosphere, sintering time 3h.
SEM the and D-E curve of the present embodiment products obtained therefrom is as shown in Figure 15,16, although can be seen that burning from SEM figure
Junction temperature compared with solid phase method > 1050 DEG C have at least 35 DEG C of reduction, but due to the high activity of hydro-thermal powder, resulting niobic acid silver
Ceramics are still comparatively dense.Its relative density is tested through Archimedes method and reaches 97%, and crystallite dimension is at 5 μm or less.
As can be seen that its disruptive field intensity can achieve 250kV/cm from D-E curve, for current pure AgNbO3Maximum value in ceramics
(general pure AgNbO3The disruptive field intensity of ceramics is no more than 180kV/cm).
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, for ability
For the those of ordinary skill in domain, these embodiments can be carried out without departing from the principles and spirit of the present invention more
Kind change, modification, replacement and modification, therefore without departing from the general concept defined in the claims and the equivalent scope, this hair
It is bright to be not limited to specific details.
Claims (3)
1. a kind of hydrothermal synthesis method for the niobic acid silver for preparing perovskite structure using silver nitrate, it is characterised in that including following step
It is rapid:
(1) the ammonium acid fluoride NH of the corresponding mole specific mass of accurate weighing4HF2, silver nitrate AgNO3With niobium pentaoxide Nb2O5And it mixes
It closes；The corresponding molar ratio is 3NH4HF2: 2AgNO3: xNb2O5, wherein x=0.6-0.85；Or the corresponding molar ratio is
yNH4HF2: 2AgNO3: 1Nb2O5, wherein y=4-5；
(2) 50ml deionized water, packing ratio 50-70% are added in polytetrafluoroethylene (PTFE) autoclave liner；
(3) the resulting raw material of step (1) is mixed and is poured into the polytetrafluoroethylene (PTFE) autoclave liner that step (2) obtains, obtained
To mixed liquor；
(4) liner, is put into stainless by the mixed liquor magnetic stirrer 10-30min for obtaining step (3) after mixing evenly
High-temperature water oven heat is put into steel autoclave, after sealing, in 180 DEG C of -220 DEG C of reaction 10-32h；
(5) it wait react completion and be cooled to room temperature opening reaction kettle, filtered, washed into repeatedly with deionized water and dehydrated alcohol
Property；
(6) reactant that washing obtains is put into dry 2-5h in 60 DEG C -85 DEG C of baking oven, finally obtains niobic acid silver ceramic powder
Body, i.e., the niobic acid silver of the described perovskite structure.
2. according to the method described in claim 1, it is characterized in that the silver-colored source of the hydrothermal synthesis method is AgNO3, and be not required to
It will be before hydro-thermal reaction by AgNO3Reaction generates other raw materials.
3. according to the method described in claim 1, it is characterized in that generating pure phase AgNbO under step (4) described reaction temperature3
The shortest time of powder is 10h.
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| CN113024248A (en) * | 2021-03-03 | 2021-06-25 | 佛山科学技术学院 | Antiferroelectric ceramic and preparation method thereof |
| CN114914088A (en) * | 2022-05-25 | 2022-08-16 | 南京邮电大学 | High-energy-storage silver niobate ceramic capacitor and preparation method thereof |
| CN115069248A (en) * | 2022-07-12 | 2022-09-20 | 西南交通大学 | Silver niobate nano material and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024248A (en) * | 2021-03-03 | 2021-06-25 | 佛山科学技术学院 | Antiferroelectric ceramic and preparation method thereof |
| CN114914088A (en) * | 2022-05-25 | 2022-08-16 | 南京邮电大学 | High-energy-storage silver niobate ceramic capacitor and preparation method thereof |
| CN114914088B (en) * | 2022-05-25 | 2023-12-19 | 南京邮电大学 | High-energy-storage silver niobate ceramic capacitor and preparation method thereof |
| CN115069248A (en) * | 2022-07-12 | 2022-09-20 | 西南交通大学 | Silver niobate nano material and preparation method and application thereof |
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