CN104505146B - Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material - Google Patents
Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material Download PDFInfo
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- CN104505146B CN104505146B CN201410670630.XA CN201410670630A CN104505146B CN 104505146 B CN104505146 B CN 104505146B CN 201410670630 A CN201410670630 A CN 201410670630A CN 104505146 B CN104505146 B CN 104505146B
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Abstract
The invention discloses a dielectric composite material with nano core-shell and inner crystal structures and a preparation method of the of dielectric composite material, and belongs to the technical field of dielectric composite materials. Nano-scale Ag particles serve as cores. A PbO inorganic insulating material forms a shell layer. The nano core-shell structures formed by the Ag particles and the PbO inorganic insulating material serves as second-phase particles to be uniformly distributed in sub-micron-scale PZN-PZT material crystal particles, so that the inner crystal structures are formed. Sub-micron-scale PZN-PZT ceramic powder serves as a base material and the nano-scale Ag particles serve as fillers. The dielectric composite material is prepared through steps of wet grinding, drying, roasting, secondary ball milling, compression molding and sintering. The dielectric composite material is applied to an energy storage device and can be integrated with the energy collection device for storing energy recycled by the energy collection device temporally. The dielectric composite material has significant economic and social values.
Description
Technical field
The invention belongs to dielectric composite material technical field is and in particular to a kind of can be applicable to having of energy storage device
Seepage flow type Ferroelectric Composites of high-k and low-dielectric loss and preparation method thereof.
Background technology
Under the historical background of energy crisis, how by the collection of energy discarded in environment and be converted to recycling
Electric energy is paid close attention to jointly by national governments, academia or even the public.Wherein, the collection of energy device based on piezo-electric effect,
The mechanical energy producing in environment can be converted to electric energy, there is dynamo-electric transformation efficiency height, output voltage is high, not done by electromagnetism
Disturb, without applied bias the features such as, thus have broad application prospects.Lot of domestic and international scholar is devoted to grinding of this work
Study carefully.At present, if the collection of energy of the researcher's extensive concern modified PZN-PZT material bodies of piezoelectric material body owner
System, by technological means such as doping, to obtaining high piezoelectric constant and low dielectric constant, improves the work of collection of energy device
Make efficiency.It should be noted that while energy collecting material is fast-developing, obtaining for the conversion of storage energy collecting device
The research of the energy storage material of electric energy is seriously delayed, particularly becomes to be grouped into the material system similar to energy collecting material,
Pertinent literature is there is no to report at present.This energy storage material requires in performance：Low dielectric loss and high dielectric constant, with
The performance requirement of energy collecting material is dramatically different.Design and prepare the energy for propulsion based on piezo-electric effect for this critical material
The miniaturization of amount collection system (include energy collection unit and energy storage units), integrated it is significant.
At present, in numerous energy storage material, inorganic-metallic composite forms flexibly adjustable, energy because of its material
Amount storage performance is excellent and widely paid close attention to.It is known that such composite bodies ties up to occurring near percolation threshold being situated between
The mutation of electrical property, can be described with formula (1)：
εr=ε0|(fc-f)/fc|-q(1)
Wherein, εr,ε0The dielectric constant of composite and matrix material respectively, q be dielectric constant critical exponent because
Son, f is the percentage by volume of metal filled amount, fcIt is percolation threshold.According to this theory it is easy to obtain near percolation threshold
Obtain high dielectric constant.But, a lot of research work of forefathers find, obtain the same of high dielectric constant near percolation threshold
When, its dielectric loss also can significantly increase, and leads to the material cannot practical application.Researcher proposes a lot of solutions,
Most effective of which be exactly using insulating polymeric material, Surface coating is carried out to metal filled particle, then using cladding after
Metallic particles is as filler particles.When but this method is only applicable to matrix material for high molecular polymer, for inorganic-gold
Belong to composite system, this method is simultaneously inapplicable.Main cause is that the synthesis temperature of such composite is generally greater than 1000
℃.Therefore, how to reduce the dielectric loss of inorganic-metallic composite, remain a big challenge at present.
In view of the foregoing it is apparent that energy stores dielectric composite material is existed significantly with energy collecting material in performance
Difference, cannot be obtained using same technological means.Therefore, in order to mate PZN-PZT base collection of energy material widely studied at present
Material system, and also to meet the high-k of energy storage material and low-dielectric loss requires.
Content of the invention
It is an object of the invention to provide a kind of dielectric composite material that can be applicable to energy storage device and its preparation side
Method.The dielectric composite material of the present invention is characterized by novel nano core-shell and interior crystalline structure.
A kind of dielectric composite material of the present invention is it is characterised in that this dielectric composite material has nano core-shell and interior crystalline substance
Type structure, as " core ", the inorganic insulating material such as PbO constitutes " shell " to the Ag metallic particles of nanoscale；This golden by Ag
The nano-core-shell structure that metal particles are constituted with inorganic insulating materials such as PbO is evenly distributed on submicron-scale as Second Phase Particle
PZN-PZT material grains be internally formed interior crystalline structure.The presence of this special construction makes the dielectric properties of material significantly
Degree lifting, is embodied in high-k and low-dielectric loss, can meet energy storage device performance requirement.Above-mentioned for realizing
Purpose, the present invention takes technical scheme below.
A kind of above-mentioned dielectric composite material with nano core-shell and interior crystalline structure, the chemical composition of this composite
For：Pb(Zn1/15Nb2/15Zr2/5Ti2/5)O3The numerical value of/xAg, x is 10.0vol.%～18.0vol.%.Further preferably wherein
Nano metal Ag particle containing 16.6vol.% in compound matrix material volume.
The dielectric composite material of nano core-shell and interior crystalline structure of having of the present invention can be used as being applied to energy accumulator
The dielectric composite material of part.
The preparation method of the above-mentioned dielectric composite material with novel nano core-shell and interior crystalline structure of the present invention, its feature
It is, as matrix material, the metal Ag particle of nanoscale is as filling for the PZN-PZT ceramic powder selecting submicron-scale
Thing, is prepared by ordinary sinter technique, specifically includes following steps：
(1) synthesize Ag2O presoma, this precursor can adopt AgNO3It is obtained with KOH reaction, its course of reaction is as follows：
AgNO3+KOH→AgOH↓+KNO3(2)
AgOH→Ag2O↓+H2O (3)
First by a certain amount of AgNO3Powder is dissolved in distilled water, treats AgNO3After powder is completely dissolved, to AgNO3Solution
In, add excessive KOH powder, reaction in above-mentioned (2), AgOH extremely unstable occur first, occurs rapidly above-mentioned at room temperature
(3) reaction in, generates sepia Ag2O precipitates.Using supercentrifuge under conditions of 4000r/min, centrifugation obtains palm fibre
Brown Ag2O powder, under the conditions of 80 DEG C, dry for standby.
(2) by the Ag obtaining2O and Pb3O4、ZnO、Nb2O5、ZrO2And TiO2Stoichiometrically weigh, Pb3O4、ZnO、
Nb2O5、ZrO2And TiO2It is submicron-scale, load weighted raw material is put in ball grinder, is placed in for medium with absolute ethyl alcohol
Ball milling 12 hours in planetary ball mill, then dry under the conditions of 80 DEG C；Dried powder is calcined at 800-900 DEG C 2 little
When, along with the furnace cooling.It is worthy of note that, in calcination process, Ag2O will resolve into Ag simple substance and O2, course of reaction is as follows：
Ag2O→Ag+O2↑ (4) are by the powder obtaining ball milling 12 hours again, under the conditions of 80 DEG C, dry for standby.
(3) each component powder do not need add binding agent, directly in the forming under the pressure of 100MPa, then 1000 DEG C-
1100 DEG C of sintering, are incubated 2 hours, obtain final product target composite.
The composite preparing, first passes around the polishing on surface, carries out micro-structural and thermal property test, so
Coat silver electrode afterwards, sample is carried out with the test of electrical property.
Wherein, best sample consists of：Pb(Zn1/15Nb2/15Zr2/5Ti2/5)O3/ 16.6vol.%Ag, its performance up to
Arrive：Permittivity εr=16600, dielectric loss tan δ=0.056, meets the requirement of energy storage device.
In the present invention, select the PZN-PZT ceramic powder of submicron-scale as matrix material, the metal of nanoscale
Ag particle, as filler, constructs the PZN-PZT/Ag dielectric composite material with novel nano-core-shell structure.This new
In clever nano-core-shell structure, as " core ", the inorganic insulating material such as PbO constitutes " shell " to the Ag metallic particles of nanoscale.
And this nano-core-shell structure can uniformly be distributed to inside ceramic crystalline grain, form stable interior crystalline structure.So-called interior crystalline substance
Type structure refers to that nanoscale Second Phase Particle enters matrix material intra-die.Specific to patent of the present invention, by Ag metallic particles
The nano-core-shell structure being constituted with inorganic insulating materials such as PbO is entered inside PZN-PZT material grains as Second Phase Particle.By
In this special nanostructured presence so that the interfacial polarization effect of this composite significantly increases, dielectric constant is significantly
Improve；What is more important inorganic insulating material will can effectively reduce the tunnelling electricity between Ag particle after metal Ag particle parcel
Stream, and then reduce the purpose of dielectric loss, it is the dielectric composite material being potentially applied to energy storage device.
Brief description
Fig. 1 is novel nano core-shell and interior crystalline structure schematic diagram.
Fig. 2 consists of Pb (Zn for present component1/15Nb2/15Zr2/5Ti2/5)O3The TEM photo of/16vol.%Ag.
Fig. 3 consists of Pb (Zn for present component1/15Nb2/15Zr2/5Ti2/5)O3The HRTEM photo of/16vol.%Ag.
Specific embodiment
It is further elucidated with substantive distinguishing features and the remarkable advantage of the present invention below by embodiment.It should be appreciated that the present invention
It is limited only to by no means stated embodiment.
Synthesis Ag2O presoma, this precursor adopts AgNO3It is obtained with KOH reaction, its course of reaction is as follows：
AgNO3+KOH→AgOH↓+KNO3(2)
AgOH→Ag2O↓+H2O (3)
First by a certain amount of AgNO3Powder is dissolved in distilled water, treats AgNO3After powder is completely dissolved, to AgNO3Solution
In, add excessive KOH powder, reaction in above-mentioned (2), AgOH extremely unstable occur first, occurs rapidly above-mentioned at room temperature
(3) reaction in, generates sepia Ag2O precipitates.Using supercentrifuge under conditions of 4000r/min, centrifugation obtains palm fibre
Brown Ag2O powder, under the conditions of 80 DEG C, dry for standby.
Pb3O4、ZnO、Nb2O5、ZrO2And TiO2It is submicron-scale.
Embodiment 1：
By chemical formula Pb (Zn1/15Nb2/15Zr2/5Ti2/5)O3/ 12vol.%Ag weighs Ag2O、Pb3O4、ZnO、Nb2O5、ZrO2
And TiO2, and ball milling 12 hours in ethanol.Calcine at 850 DEG C 2 hours after mixture drying, ball milling in ethanol again
After 12 hours, direct pressing shaping under 100MPa, then at 1050 DEG C, sintering obtains composite in 2 hours.
Embodiment 2：
By chemical formula Pb (Zn1/15Nb2/15Zr2/5Ti2/5)O3/ 16vol.%Ag weighs Ag2O、Pb3O4、ZnO、Nb2O5、ZrO2
And TiO2, the other the same as in Example 1.
Embodiment 3：
By chemical formula Pb (Zn1/15Nb2/15Zr2/5Ti2/5)O3/ 16.5vol.%Ag weighs Ag2O、Pb3O4、ZnO、Nb2O5、
ZrO2And TiO2, the other the same as in Example 1.
Embodiment 4：
By chemical formula Pb (Zn1/15Nb2/15Zr2/5Ti2/5)O3/ 16.6vol.%Ag weighs Ag2O、Pb3O4、ZnO、Nb2O5、
ZrO2And TiO2, the other the same as in Example 1.
Table 1 above-described embodiment performance comparison table
Claims (5)
1. a kind of dielectric composite material is it is characterised in that this dielectric composite material has nano core-shell and interior crystalline structure, nanometer
The Ag metallic particles of yardstick constitutes " shell " as " core ", PbO inorganic insulating material；This by Ag metallic particles and PbO no
The PZN-PZT material that the nano-core-shell structure that machine insulating materials is constituted is evenly distributed on submicron-scale as Second Phase Particle is brilliant
Grain is internally formed interior crystalline structure；The chemical composition of this composite is：Pb(Zn1/15Nb2/15Zr2/5Ti2/5)O3The number of/xAg, x
It is worth for 10.0vol.%～18.0vol.%.
2. according to claim 1 a kind of dielectric composite material it is characterised in that the chemical composition of this composite is：Compound
Nano metal Ag particle containing 16.6vol.% in matrix material volume.
3. a kind of method of the dielectric composite material described in preparation claim 1 or 2 is it is characterised in that comprise the following steps：
(1) synthesize Ag2O presoma；
(2) by the Ag obtaining2O and Pb3O4、ZnO、Nb2O5、ZrO2And TiO2Stoichiometrically weigh, Pb3O4、ZnO、Nb2O5、
ZrO2And TiO2It is submicron-scale, load weighted raw material is put in ball grinder, planet ball is placed in for medium with absolute ethyl alcohol
Ball milling 12 hours in grinding machine, then dry under the conditions of 80 DEG C；Dried powder is calcined 2 hours at 800-900 DEG C, with stove
Cooling；By the powder obtaining ball milling 12 hours again, under the conditions of 80 DEG C, dry for standby；
(3) each component powder does not need to add binding agent, directly in the forming under the pressure of 100MPa, then at 1000 DEG C -1100
DEG C sintering, be incubated 2 hours, obtain final product target composite.
4. according to claim 3 method it is characterised in that synthesis Ag2O presoma, this precursor adopts AgNO3With KOH reaction
It is obtained, its course of reaction is as follows：
AgNO3+KOH→AgOH↓+KNO3(2)
AgOH→Ag2O↓+H2O (3)
First by a certain amount of AgNO3Powder is dissolved in distilled water, treats AgNO3After powder is completely dissolved, to AgNO3In solution, plus
Enter excessive KOH powder, reaction in above-mentioned (2) occurs first, AgOH extremely unstable, at room temperature in rapid generation above-mentioned (3)
Reaction, generates sepia Ag2O precipitates；Using supercentrifuge under conditions of 4000r/min, centrifugation obtains sepia
Ag2O powder, under the conditions of 80 DEG C, dry for standby.
5. the application of the dielectric composite material described in claim 1 or 2, for energy storage device.
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