CN109650885A - One kind mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material and preparation method thereof - Google Patents
One kind mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind to mix lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material and preparation method thereof, and the lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material of mixing is single perovskite structure, and composition general formula is Ag1‑3xLaxNbO3, wherein 0.01≤x≤0.08, preferably 0.03≤x≤0.04.
Description
Technical field
The invention belongs to ceramic material technical fields, and in particular to a kind of silver niobate-based lead-free anti-ferroelectric energy storage ceramic
Material and preparation method thereof, and the energy storage ceramic material can be used for energy-storage capacitor.
Background technique
High energy storage density ceramics are the critical materials for making high energy-storage capacitor, since it is fast with charge/discharge speed, anti-
Steady performance under the extreme conditions such as the strong, high temperature and high pressure of aging ability is recycled, in electric car, high power electronic device
The basic scientific research such as part, impulse power electrical source, new energy and smart electric grid system and field of engineering technology have wide application.
The main linear ceramics of energy-storing dielectric ceramic material, ferroelectric ceramics and antiferroelectric ceramics three classes.Linear ceramic dielectric
Constant hardly follows electric field change, have many advantages, such as that low field lower linear is reversible, can be repeated several times charge and discharge, breakdown strength it is big, but
Dielectric constant is smaller.Ferroelectric ceramics has spontaneous polarization, has very high dielectric constant in no extra electric field, and makees in electric field
Under, ferroelectric ceramics dielectric constant increases with electric field and is reduced, and its disruptive field intensity is not usually high, causes ceramics under High-Field
Energy storage density is simultaneously little, and anti-ferroelectric ceramic material has double ferroelectric hysteresis loops, and near switching electric field, polarization intensity can dash forward
Increase, continue growing field strength, polarization intensity decline is uprushed using polarization intensity under switching electric field, it can be achieved that high energy storage density is electric
Container.Therefore, antiferroelectric materials has the characteristics that energy storage density is high, charge/discharge speed is fast, is a kind of ideal energy storage material.La
The PZT ceramics of doping are the anti-ferroelectric energy storage ceramics of most study because of its excellent energy storage characteristic.Wherein, (Pb, La, Ba,
Y)(Zr,Ti,Sn)O3Its releasable energy storage density is up to 6.4J/cm3.But contain a large amount of toxic lead in the system material,
During production, use and waste treatment serious harm can be brought to human health and ecological environment.Therefore, research and development property
Lead-free anti-ferroelectric energy storage ceramic material that can be excellent becomes a project urgent and with great Practical significance.
In recent years, it has been found that AgNbO3Ceramics have good energy storage characteristic, but pure AgNbO3Ceramics have at room temperature
Sub- ferroelectric phase (M1), the raising of its energy-storage property is affected, and its turnover electric field and disruptive field intensity be not high.In electric field
Under the conditions of 14kV/mm, pure AgNbO3The releasable energy storage density of ceramics is 1.4J/cm3, energy storage efficiency 40%.The prior art one
As be that AgNbO is realized by doping vario-property3The energy storage characteristic of ceramics is greatly improved, and shows AgNbO3Ceramics are in energy storage
Field has broad application prospects.For example, document 1 (Zhao, Lei, et al.J.Mater.Chem.C 4.36 (2016)) is reported
Road MnO2Doping realizes the raising of the energy-storage property of niobic acid silver, from releasable energy density 1.5J/cm3To 2.5J/cm3；Text
2 (Tian, Ye, et al.J.Mater.Chem.A 5.33 (2017)) are offered to report by adulterating Bi2O3, by AgNbO3Ceramics
Energy storage density has been increased to 2.6J/cm3；Document 3 (Zhao, Lei, et al.Adv.Mater.29.31 (2017)) passes through Ta2O5
Doping, AgNbO3The energy storage density of ceramics is up to 4.2J/cm3, and there is extraordinary temperature stability.This year, document 4
(Zhao, Lei, et al.ACS Appl.Mater.Inter.10.1 (2018)), which is reported, introduces WO3, AgNbO may be implemented3Pottery
The 3.3J/cm of porcelain3Energy storage density.
Summary of the invention
In view of the above-mentioned problems, present invention firstly discovers that realizing AgNbO by La doped3The ferrous electricity of room temperature in ceramic material
The inhibition of phase, has refined crystal grain, improves ceramic dense degree, and improves forward breakover electric field, further enhances
AgNbO3The energy-storage property of lead-free anti-ferroelectric energy storage ceramic.
On the one hand, the present invention provides one kind to mix lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material, described to mix lanthanum niobate
Silver-colored lead-free anti-ferroelectric energy storage ceramic material is single perovskite structure, and composition general formula is Ag1-3xLaxNbO3, wherein 0.01≤x
≤ 0.08, preferably 0.03≤x≤0.04.
In the present invention, by AgNbO3Energy storage ceramic material adds La3+Doping vario-property makes M1-M2Phase transition temperature is reduced to
Room temperature enhances anti-ferroelectricity hereinafter, room temperature is made to present antiferroelectric phase.And remanent polarization is reduced, it is improved
Forward breakover electric field obtains the energy storage ceramic material with high energy storage density and energy storage efficiency, has a good application prospect.
Preferably, the energy density for mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material is 3.0~4.6J/cm3,
Energy storage efficiency is 51~75%.
Also, preferably, as x=0.04, the energy density for mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material
For 4.6J/cm3, energy storage efficiency 69%.
On the other hand, lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material is mixed as described above the present invention also provides a kind of
Preparation method, comprising:
Select Ag2O powder, Nb2O5Powder, La2O3Powder is as material powder, according to composition general formula Ag1-3xLaxNbO3Ingredient is simultaneously
Mixing, keeps the temperature 2~3 hours in oxygen-containing atmosphere, at 850 DEG C~900 DEG C, obtains Ag1-3xLaxNbO3Powder；
In gained Ag1-3xLaxNbO3Binder is added in powder and is granulated, then repressed molding, obtains biscuit；
It by gained biscuit after plastic removal, is sintered in oxygen-containing atmosphere, at 1020 DEG C~1200 DEG C, obtains described mixing lanthanum niobium
Sour silver lead-free anti-ferroelectric energy storage ceramic material.
In the present invention, Ag is selected2O powder, Nb2O5Powder, La2O3Powder is as material powder, by adding La3+Doping
It is modified, 2~3 hours are kept the temperature in oxygen-containing atmosphere, at 850 DEG C~900 DEG C, in the process La3+Regulate and control its M1, M2Phase makes
Antiferroelectric phase is presented in it at room temperature, that is, inhibiting ferrous electrically enhances anti-ferroelectricity, and reduce remanent polarization, then
Grinding, drying, obtain the Ag of perovskite structure1-3xLaxNbO3Powder.By gained Ag1-3xLaxNbO3Powder is added binder and makes
Grain and molding, then through plastic removal and sintering processes.Due to adding La3+, refinement crystal grain can also be realized during re-sintering, and improved
Ceramic dense degree.In addition, logical oxygen is Ag to be inhibited2The decomposition of O, so that the niobic acid silver-based with above-mentioned chemical composition is prepared
The powder of lead-free anti-ferroelectric energy storage ceramic.
Preferably, the binder is at least one of polyvinyl alcohol, polyvinyl butyral, additional amount Ag1- 3xLaxNbO3The 3%~8% of powder quality.
Preferably, the pressure of the compression moulding is 150~200MPa.
Preferably, the temperature of the plastic removal is 700 DEG C~900 DEG C, the time is 2~3 hours；Preferably, the plastic removal
Heating rate is 1~3 DEG C/min.
Preferably, the oxygen-containing atmosphere is air atmosphere or oxygen atmosphere.
Preferably, the heating rate of the sintering is 1~3 DEG C/min.
It handles preferably, gained is mixed lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material sanding and polishing to specific thickness
Afterwards, silver electrode is coated on its surface；Preferably, the specific thickness is 0.15~0.20mm.
Beneficial effects of the present invention:
In the present invention, by mixing La3+It can make AgNbO3The M of ceramics1-M2Phase transition temperature be reduced to room temperature hereinafter, make its
Antiferroelectric phase is presented at room temperature, expands antiferroelectric phase region, and crystal grain can be refined, improves consistency, and it can be improved
Forward breakover electric field, to enhance the energy storage density and energy storage efficiency of niobic acid silver based cermets, therefore, Ag of the invention1- 3xLaxNbO3Ceramics have high energy-storage property, low remanent polarization.The releasable storage of energy storage ceramic material of the invention
Energy density may be up to 4.6J/cm3, energy storage efficiency may be up to 69%.Energy storage ceramic of the invention can be used for energy storage ceramic capacitor
Manufacture, and may advantageously facilitate high energy storage density ceramic technology application and development, have a good application prospect.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation；
Fig. 2 is the surface SEM figure of the ceramics sample of comparative example 1 of the present invention preparation；
Fig. 3 is the surface SEM figure of ceramics sample prepared by the embodiment of the present invention 1；
Fig. 4 is the surface SEM figure of ceramics sample prepared by the embodiment of the present invention 2；
Fig. 5 is the surface SEM figure of ceramics sample prepared by the embodiment of the present invention 3；
Fig. 6 is the surface SEM figure of ceramics sample prepared by the embodiment of the present invention 4；
Fig. 7 is the surface SEM figure of ceramics sample prepared by the embodiment of the present invention 5；
Fig. 8 is the average grain size figure of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation；
Fig. 9 is the phase transition temperature figure of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation；
Figure 10 is the ferroelectric hysteresis loop figure of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation；
Figure 11 is the turnover electric field intensity map of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation；
Figure 12 is the energy storage density and efficiency energy-storage property figure of the ceramics sample of comparative example 1 of the present invention and embodiment 1-5 preparation.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the disclosure, have energy storage density high, residual polarization it is low mix lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material
The chemical general formula of material can are as follows: Ag1-3xLaxNbO3, wherein 0.01≤x≤0.08, preferably 0.03≤x≤0.04.The above x is
Mole further increases its energy-storage property with this.
In the disclosure, the doping of La can inhibit AgNbO3Ceramic material Central Asia ferroelectricity enhances anti-ferroelectricity, and mentions
High AgNbO3Forward breakover electric field in ceramic material, so that obtain having high energy storage density and energy storage efficiency mixes lanthanum niobate
Silver-colored lead-free anti-ferroelectric energy storage ceramic material.The present invention can also be by adjusting La doping content 0.01≤x≤0.08, so that mixing lanthanum niobium
The energy density of sour silver lead-free anti-ferroelectric energy storage ceramic material is in 3.0~4.6J/cm3Between, energy storage efficiency 51~75% it
Between.It is antiferroelectric phase that this mixes lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material at room temperature.In alternative embodiments, it mixes
For lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material under the applied electric field of 25kV/mm, releasable energy storage density is up to 4.6J/
cm3, energy storage efficiency is up to 69%.
In an embodiment of the present invention, Ag is synthesized through logical oxygen1-3xLaxNbO3Powder, wherein 0.01≤x≤0.08；It passes through again
After granulation, compression moulding, plastic removal, densified sintering product, obtains Ag at a certain temperature1-3xLaxNbO3Energy storage ceramic material (mixes lanthanum niobium
Sour silver lead-free anti-ferroelectric energy storage ceramic material).Lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material prepared by the present invention of mixing can be used
In energy-storage capacitor, such as the manufacture of energy storage ceramic capacitor, application and the hair of high energy storage density ceramic technology may advantageously facilitate
Exhibition, has a good application prospect.
Hereinafter, illustrating the method that lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material is mixed in preparation of the invention.
Ag is synthesized using logical oxygen1-3xLaxNbO3Powder, wherein 0.01≤x≤0.08；X is molar percentage.Of the invention
Mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material can be used Ag2O powder, Nb2O5Powder, La2O3Powder is starting material, is pressed
It according to stoichiometric ratio ingredient and mixes, keeps the temperature 2~3 hours in oxygen-containing atmosphere, at 850 DEG C~900 DEG C, obtain Ag1- 3xLaxNbO3Powder.As an example, such as Ag of the purity 99.0% or more can be used2O powder, Nb2O5Powder,
La2O3Powder is as material powder, then by raw material A g2O powder, Nb2O5Powder, La2O3Powder according to stoichiometric ratio ingredient,
After ball milling, drying, grinding, 2~3 hours are kept the temperature in lower 850 DEG C~900 DEG C of Oxygen Condition, synthesizes the Ag of perovskite structure1- 3xLaxNbO3Powder.Grinding method of the present invention is not particularly limited, and known grinding method, such as wet ball-milling method can be used
Deng.Using wet ball-milling method, material: ball: the mass ratio (0.8~1.0) of ethyl alcohol: (4.0~4.5): (1.5~
1.7), incorporation time is 12 hours.
In Ag1-3xLaxNbO3Binder is added in powder and is granulated, then repressed molding, obtains biscuit.Specifically, will
Synthetic Ag1-3xLaxNbO3Powder adds binder granulation after sand milling, and compression moulding obtains biscuit.Above-mentioned sand milling can be also
Sand mill progress can be used.In this case, can be according to Ag1-3xLaxNbO3Powder: ball: dehydrated alcohol=(0.8~1.0): (4.0
~4.5): (1.0~1.2) can be 3 hours for the time is sanded.Abrading-ball, such as iron ball, agate ball or zirconium oxide can be used
Ball etc..Polyvinyl alcohol (PVA), polyvinyl butyral (PVB) etc. can be used in the binder of above-mentioned addition.The additive amount of binder
It is the 3%~8% of ceramic powder quality.The pressure of above-mentioned compression moulding can be 150~200MPa.In the present invention, the ball
Mill is in ball grinder, and sand milling is carried out in sand mill, is all made of dehydrated alcohol and carries out respectively as medium ball milling 12 hours
With 3 hours and complete.Be conducive to that raw material is evenly dispersed, to obtain ingredient uniformly and the powder of refinement.It is possible thereby to further
Improve the energy-storage property for mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material.
Biscuit is subjected to plastic removal, i.e., excludes organic substance binder (for example, PVA) at a certain temperature, obtains raw material base
Body.Specifically, the temperature of plastic removal can be 700 DEG C~900 DEG C (preferably 850 DEG C~900 DEG C), and soaking time can be small for 2~3
When.The heating rate of plastic removal can be 1~3 DEG C/min.
Biscuit after plastic removal is put and is sintered at a certain temperature.Specifically, it in sintering process, can be sintered in oxygen,
Sintering temperature can be 1020 DEG C~1200 DEG C, and soaking time can be 2~3 hours.In the present invention, the heating rate of sintering can
Think 1~3 DEG C/min.Wherein, lead to oxygen sintering to be conducive to improve consistency, inhibit Ag2The decomposition of O has ensured that obtain accuracy
Learn the component of metering ratio.
In the present invention, gained is mixed into lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material crude product through upper and lower surfaces wear down extremely
0.15mm~0.20mm thickness (sanding and polishing processing), mixes lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic it is possible thereby to further increase
The energy storage density of material.
In the present invention, lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material surface covering electrodes (for example, silver electrode) are being mixed,
After obtain energy storage ceramic element.Specifically, the surface covering electrodes are dried for example including the screen printing of silver paste, silver ink firing (for example,
It is sintered 30 minutes for 600 DEG C in air) etc..
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Comparative example 1:
Energy storage ceramic material composition are as follows: AgNbO3(x=0)
(1) Ag needed for being calculated by above-mentioned chemical formula composition2O、Nb2O5, using with wet ball-milling method mixing, according to raw material: ball: nothing
Water-ethanol=1:4.5:1.7 mass ratio mixes 12 hours, is uniformly mixed each component.40 meshes are crossed after drying, in oxygen gas
Atmosphere lower lock block was raised to 850 DEG C of temperature with 8 hours, keeps the temperature 2 hours, synthesizes AgNbO3Powder；
It (2) will be in powder synthetic in step (1).According to raw material: ball: dehydrated alcohol=1:4.5:1.2 wet process, which is sanded, (to be sanded
Machine) discharge drying after 3 hours, crosses 40 meshes, and addition 3wt%PVA is granulated, and dry-pressing formed is diameter 13mm, and thickness is about
The green body of 2mm；
(3) 800 DEG C of green body for obtaining step (2) keep the temperature 2 hours, exclude the organic substance in biscuit, and plastic removal heating rate is 2
DEG C/min, plastic removal obtains raw material green body；
(4) the raw material green body that step (3) obtains is put into Muffle furnace small by being raised within 7 hours 1020 DEG C~1200 DEG C heat preservations 2
When obtain AgNbO3Energy storage ceramic material；
(5) AgNbO for obtaining step (4)3Energy storage ceramic material carries out XRD test, and test result is shown in Fig. 1；
(6) to gained AgNbO3Energy storage ceramic material has carried out surface SEM observation, and Fig. 2 gives AgNbO3Energy storage ceramic material
Surface topography figure；
(7) to AgNbO3The average grain size of energy storage ceramic material is calculated and is drawn, and Fig. 8 is obtained；
(8) AgNbO that will be sintered3Energy storage ceramic material two-side is polished to a thickness of 0.15mm, cleaning, drying, silk-screen printing
Silver paste, then dry, it is put into van-type electric furnace silver ink firing, silver ink firing condition is 600 DEG C of heat preservation 30min.Heating rate is 2 DEG C/min, is obtained
It is covered with the ceramics sample of electrode；
(9) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to the ceramics sample for being covered with electrode, obtains its phase transition temperature figure, surveys
Test result is shown in Fig. 9；
(10) ferroelectric hysteresis loop measurement, turnover electric field and energy storage at room temperature are carried out to the ceramics sample for being covered with electrode of this comparative example 1
The calculating of performance, the result is shown in Figure 1 0-12.
Embodiment 1:
Energy storage ceramic material composition are as follows: Ag0.97La0.01NbO3(x=0.01)
(1) preparation method of comparative example 1 is repeated by above-mentioned formula；
(2) XRD test is carried out to the present embodiment, test result is shown in Fig. 1；
(3) SEM test in surface is carried out to the present embodiment, Fig. 3 gives the surface topography figure of the present embodiment ceramics sample；
(4) average grain size of ceramics sample is calculated and is drawn, obtain Fig. 8；
(5) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to ceramics sample, obtains its phase transition temperature figure, test result is shown in figure
9；
(6) ferroelectric hysteresis loop measurement, the calculating of turnover electric field and energy-storage property at room temperature, knot are carried out to the ceramics sample of the present embodiment
Fruit sees Figure 10-12.
Embodiment 2:
Energy storage ceramic material composition are as follows: Ag0.94La0.02NbO3(x=0.02)
(1) preparation method of comparative example 1 is repeated by above-mentioned formula；
(2) XRD test is carried out to the present embodiment, test result is shown in Fig. 1；
(3) SEM test in surface is carried out to the present embodiment, Fig. 4 gives the surface topography figure of the present embodiment ceramics sample；
(4) average grain size of ceramics sample is calculated and is drawn, obtain Fig. 8；
(5) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to ceramics sample, obtains its phase transition temperature figure, test result is shown in figure
9；
(6) ferroelectric hysteresis loop measurement, the calculating of turnover electric field and energy-storage property at room temperature, knot are carried out to the ceramics sample of the present embodiment
Fruit sees Figure 10-12.
Embodiment 3:
Energy storage ceramic material composition are as follows: Ag0.91La0.03NbO3(x=0.03)
(1) preparation method of comparative example 1 is repeated by above-mentioned formula；
(2) XRD test is carried out to the present embodiment, test result is shown in Fig. 1；
(3) SEM test in surface is carried out to the present embodiment, Fig. 5 gives the surface topography figure of the present embodiment ceramics sample；
(4) average grain size of ceramics sample is calculated and is drawn, obtain Fig. 8；
(5) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to ceramics sample, obtains its phase transition temperature figure, test result is shown in figure
9；
(6) ferroelectric hysteresis loop measurement, the calculating of turnover electric field and energy-storage property at room temperature, knot are carried out to the ceramics sample of the present embodiment
Fruit sees Figure 10-12.
Embodiment 4:
Energy storage ceramic material composition are as follows: Ag0.88La0.04NbO3(x=0.04)
(1) it is obtained by the preparation method that above-mentioned formula repeats comparative example 1；
(2) XRD test is carried out to the present embodiment, test result is shown in Fig. 1；
(3) SEM test in surface is carried out to the present embodiment, Fig. 6 gives the surface topography figure of the present embodiment ceramics sample；
(4) average grain size of ceramics sample is calculated and is drawn, obtain Fig. 8；
(5) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to ceramics sample, obtains its phase transition temperature figure, test result is shown in figure
9；
(6) ferroelectric hysteresis loop measurement, the calculating of turnover electric field and energy-storage property at room temperature, knot are carried out to the ceramics sample of the present embodiment
Fruit sees Figure 10-12.
Embodiment 5:
Energy storage ceramic material composition are as follows: Ag0.88La0.04NbO3(x=0.05)
(1) it is obtained by the preparation method that above-mentioned formula repeats comparative example 1；
(2) XRD test is carried out to the present embodiment, test result is shown in Fig. 1；
(3) SEM test in surface is carried out to the present embodiment, Fig. 7 gives the surface topography figure of the present embodiment ceramics sample；
(4) average grain size of ceramics sample is calculated and is drawn, obtain Fig. 8；
(5) test that dielectric temperature spectrum and dielectric and magnetic has been carried out to ceramics sample, obtains its phase transition temperature figure, test result is shown in figure
9；
(6) ferroelectric hysteresis loop measurement, the calculating of turnover electric field and energy-storage property at room temperature, knot are carried out to the ceramics sample of the present embodiment
Fruit sees Figure 10-12.
The performance parameter for the energy storage ceramic material that table 1 is 1-5 of the embodiment of the present invention and prepared by comparative example 1:
| x | Average grain size/μm | Energy storage density Wrec (/J/cm3) | Energy storage efficiency η/% | |
| Embodiment 1 | 0.01 | 3.07μm | 3.0J/cm3 | 51% |
| Embodiment 2 | 0.02 | 2.73μm | 3.5J/cm3 | 59% |
| Embodiment 3 | 0.03 | 2.16μm | 3.9J/cm3 | 66% |
| Embodiment 4 | 0.04 | 1.79μm | 4.6J/cm3 | 69% |
| Embodiment 5 | 0.05 | 1.68μm | 3.8J/cm3 | 75% |
| Comparative example 1 | 0 | 4.73μm | 2.4J/cm3 | 40% |
。
It is single it will be seen from figure 1 that having no the generation of the second phase in the energy storage ceramic material of embodiment 1-5 preparation
Perovskite structure, (220) peak and (008) peak of (020) peak and (114) peak and 46 ° for being cleaved from 32 ° or so or so splitting
As can be seen that the diffraction maximum of XRD is deviated to high angle with the increase of La content.This is because La ionic radius ratio Ag ion
Radius is small, into after the position A of niobic acid silver perovskite structure, so that unit cell volume becomes smaller, so that XRD peak position is deviated to high angle；
From Fig. 2-7 it is found that the surface topography of the energy storage ceramic material of comparative example 1 and embodiment 1-5 is finer and close, as La content increases
Add, crystallite dimension gradually decreases；
It is obtained by Fig. 8, the average grain size of pure niobic acid silver is 4.73 μm in comparative example 1, by the table of the ceramics of Examples 1 to 5
Face pattern, it can be seen that as La content increases, crystal grain is gradually decreased, when the incorporation of 0.05mol, average crystal grain ruler
It is very little to refine to 1.68 μm.Therefore, this will make the disruptive field intensity of ceramics be largely increased, so that it is close to further increase energy storage
Degree；
The phase transition temperature test result of the energy storage ceramic material of comparative example 1 and embodiment 1-5 is shown in Fig. 9, it can be seen that sub- ferroelectric phase
(M1) inhibited, sub- ferroelectric phase (M1) room temperature is reduced to hereinafter, the increase of antiferroelectric phase region, illustrates to increase with La content, anti-iron
Electrically enhancing；
The ferroelectric hysteresis loop figure of the energy storage ceramic material of comparative example 1 and embodiment 1-5, turnover electric field intensity map and energy-storage property test and
As shown in figs. 10-12, with the increase of La content, ferroelectric hysteresis loop becomes narrower oblique to calculated result, and Wrec and η gradually increase
Add.When La content reaches 0.04mol, reverse snapback electric field is significantly improved, maximum polarization Pmax not too big decline,
Still close to 40C/cm2, but reverse snapback electric field significantly improves, and obtains releasable energy storage density Wrec up to 4.6J/cm3, energy storage
Efficiency is much higher than pure AgNbO up to 69%3Energy-storage property (Wrec=2.4J/cm3, η=40%).
To sum up, pure AgNbO can be made by doped lanthanum in the present invention3The energy storage density highest of (comparative example 1) improves
48%, energy storage efficiency highest improves 42%, significantly improve its energy-storage property.
Claims (10)
1. one kind mixes lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material, which is characterized in that described to mix the unleaded anti-iron of lanthanum niobate silver
Electric energy storage ceramic material is single perovskite structure, and composition general formula is Ag1-3xLaxNbO3, wherein 0.01≤x≤0.08, it is excellent
It is selected as 0.03≤x≤0.04.
2. according to claim 1 mix lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material, which is characterized in that described to mix lanthanum
The energy density of niobic acid silver lead-free anti-ferroelectric energy storage ceramic material is in 3.0~4.6J/cm3Between, energy storage efficiency 51~75% it
Between.
3. according to claim 2 mix lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material, which is characterized in that when x=0.04
When, the energy density for mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material is 4.6 J/cm3, energy storage efficiency 69%.
4. a kind of preparation side as claimed in any one of claims 1-3 for mixing lanthanum niobate silver lead-free anti-ferroelectric energy storage ceramic material
Method characterized by comprising
Select Ag2O powder, Nb2O5Powder, La2O3Powder is as material powder, according to composition general formula Ag1-3xLaxNbO3Ingredient is simultaneously
Mixing, keeps the temperature 2~3 hours in oxygen-containing atmosphere, at 850 DEG C~900 DEG C, obtains Ag1-3xLaxNbO3Powder；
In gained Ag1-3xLaxNbO3Binder is added in powder and is granulated, then repressed molding, obtains biscuit；
It by gained biscuit after plastic removal, is sintered in oxygen-containing atmosphere, at 1020 DEG C~1200 DEG C, obtains described mixing lanthanum niobium
Sour silver lead-free anti-ferroelectric energy storage ceramic material.
5. the preparation method according to claim 4, which is characterized in that the binder is polyvinyl alcohol, polyvinyl alcohol contracting
At least one of butyraldehyde, additional amount Ag1-3xLaxNbO3The 3%~8% of powder quality.
6. preparation method according to claim 4 or 5, which is characterized in that the pressure of the compression moulding is 150~200
MPa。
7. the preparation method according to any one of claim 4-6, which is characterized in that the temperature of the plastic removal is 700 DEG C
~900 DEG C, the time is 2~3 hours；Preferably, the heating rate of the plastic removal is 1~3 DEG C/min.
8. the preparation method according to any one of claim 4-7, which is characterized in that the oxygen-containing atmosphere is air atmosphere
Or oxygen atmosphere.
9. the preparation method according to any one of claim 4-8, which is characterized in that the heating rate of the sintering is 1
~3 DEG C/min.
10. the preparation method according to any one of claim 4-9, which is characterized in that it is unleaded that gained is mixed lanthanum niobate silver
After Anti-ferroelectric energy storage ceramic material is polishing to specific thickness, silver electrode is coated on its surface；Preferably, the specific thickness is
0.15~0.20 mm.
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