CN104505146A - 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
- Publication number
- CN104505146A CN104505146A CN201410670630.XA CN201410670630A CN104505146A CN 104505146 A CN104505146 A CN 104505146A CN 201410670630 A CN201410670630 A CN 201410670630A CN 104505146 A CN104505146 A CN 104505146A
- Authority
- CN
- China
- Prior art keywords
- composite material
- dielectric composite
- shell
- powder
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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, be specifically related to a kind ofly can be applicable to seepage flow type Ferroelectric Composites with high-k and low-dielectric loss of energy storage device and preparation method thereof.
Background technology
Under the historical background of energy crisis, how the collection of energy of discarding in environment is converted to recycling electric energy and is jointly paid close attention to by national governments, academia and even the public.Wherein, based on the collection of energy device of piezoelectric effect, the mechanical energy produced can be converted to electric energy in environment, have that dynamo-electric transformation efficiency is high, output voltage is high, by electromagnetic interference, without the need to features such as applied bias, thus have broad application prospects.Lot of domestic and international scholar is devoted to the research of this work.At present, if the PZN-PZT material system that the collection of energy piezoelectric material body owner of researcher's extensive concern is modified, by technological means such as doping, to obtaining high piezoelectric constant and low dielectric constant, improve the operating efficiency of collection of energy device.It should be noted that, while energy collecting material fast development, transform for stored energy collecting device the research obtaining the energy storage material of electric energy seriously delayed, particularly become to be grouped into the material system similar to energy collecting material, there is no pertinent literature report at present.This energy storage material requires in performance: low dielectric loss and high dielectric constant, significantly different from the performance requirement of energy collecting material.Design and prepare this critical material for advance based on the energy collecting system (comprising energy collection unit and energy storage units) of piezoelectric effect miniaturization, to be integratedly significant.
At present, in numerous energy storage material, inorganic-metallic composite is because of its material composition adjustable, stored energy excellent performance and being paid close attention to widely flexibly.As everyone knows, such composite bodies ties up to the sudden change occurring dielectric property near percolation threshold, can describe with formula (1):
ε
r=ε
0|(f
c-f)/f
c|
-q(1)
Wherein, ε
r, ε
0be the dielectric constant of composite material and basis material respectively, q is the critical exponent factor of dielectric constant, and f is the percentage by volume of metal filled amount, f
cit is percolation threshold.Theoretical according to this, be easy near percolation threshold, obtain high dielectric constant.But a lot of research work of forefathers find, obtain high dielectric constant near percolation threshold while, its dielectric loss also can significantly increase, cause material cannot practical application.Researcher proposes a lot of solution, wherein be the most effectively exactly use insulating polymeric material Surface coating is carried out to metal filled particle, then use coated after metallic particles as filler particles.But this method is only applicable to basis material when being high molecular polymer, and for inorganic-metallic composite system, this method is also inapplicable.Main cause is, the synthesis temperature of such composite material is generally higher than 1000 DEG C.Therefore, how to reduce the dielectric loss of inorganic-metallic composite, remain a large challenge at present.
In sum, can find out that stored energy dielectric composite material exists significant difference with energy collecting material in performance, same technological means cannot be used to obtain.Therefore, in order to mate the PZN-PZT base energy collecting material system of extensively research at present, simultaneously also in order to meet high-k and the low-dielectric loss requirement of energy storage material.
Summary of the invention
The object of the present invention is to provide a kind of dielectric composite material that can be applicable to energy storage device and preparation method thereof.Dielectric composite material of the present invention is characterised in that to have novel nano core-shell and interior crystalline structure.
A kind of dielectric composite material of the present invention, is characterized in that, this dielectric composite material has nano core-shell and interior crystalline structure, and the Ag metallic particles of nanoscale is as " core ", and the inorganic insulating materials such as PbO form " shell "; The PZN-PZT material grains inside that this nano-core-shell structure be made up of inorganic insulating materials such as Ag metallic particles and PbO is evenly distributed on submicron-scale as Second Phase Particle forms interior crystalline structure.The existence of this special construction makes the dielectric property of material significantly promote, and is embodied in high-k and low-dielectric loss, can meets energy storage device performance requirement.For achieving the above object, the present invention takes following technical scheme.
Above-mentioned a kind of dielectric composite material with nano core-shell and interior crystalline structure, the chemical composition of this composite material is: Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3the numerical value of/xAg, x is 10.0vol.% ~ 18.0vol.%.Nano metal Ag particle further containing 16.6vol.% in preferred wherein compound matrix material volume.
The dielectric composite material with nano core-shell and interior crystalline structure of the present invention can be used as the dielectric composite material being applied to energy storage device.
The above-mentioned preparation method with the dielectric composite material of novel nano core-shell and interior crystalline structure of the present invention, it is characterized in that, select the PZN-PZT ceramic powder of submicron-scale as basis material, the metal A g particle of nanoscale is as filler, prepared by ordinary sinter technique, specifically comprise the following steps:
(1) Ag is synthesized
2o presoma, this precursor can adopt AgNO
3obtained with KOH reaction, its course of reaction is as follows:
AgNO
3+KOH→AgOH↓+KNO
3(2)
AgOH→Ag
2O↓+H
2O (3)
First by a certain amount of AgNO
3powder is dissolved in distilled water, treats AgNO
3after powder dissolves completely, to AgNO
3in solution, add excessive KOH powder, reaction in above-mentioned (2) first occurs, AgOH extremely unstable, at room temperature reaction in above-mentioned (3) occurs rapidly, generate sepia Ag
2o precipitates.Use supercentrifuge under the condition of 4000r/min, centrifugation obtains sepia Ag
2o powder, under 80 DEG C of conditions, dry for standby.
(2) Ag will obtained
2o and Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2stoichiometrically weigh, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2being submicron-scale, load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 12 hours with absolute ethyl alcohol, then dries under 80 DEG C of conditions; Dried powder is calcined 2 hours at 800-900 DEG C, cools with stove.It is worthy of note, in calcination process, Ag
2o will resolve into Ag simple substance and O
2, course of reaction is as follows:
Ag
2o → Ag+O
2↑ (4) by the powder that obtains ball milling 12 hours again, under 80 DEG C of conditions, dry for standby.
(3) each component powder does not need to add binding agent, directly at the forming under the pressure of 100MPa, then at 1000 DEG C-1100 DEG C sintering, is incubated 2 hours, obtains target composite material.
The composite material prepared, first passes through the polishing on surface, carries out micro-structural and thermal property test, then applies silver electrode, sample is carried out to the test of electrical property.
Wherein, best sample consists of: Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3/ 16.6vol.%Ag, its performance can reach: DIELECTRIC CONSTANT ε
r=16600, dielectric loss tan δ=0.056, meet the requirement of energy storage device.
In the present invention, select the PZN-PZT ceramic powder of submicron-scale as basis material, the metal A g particle of nanoscale, as filler, constructs the PZN-PZT/Ag dielectric composite material with novel nano-core-shell structure.In this novel nano-core-shell structure, the Ag metallic particles of nanoscale is as " core ", and the inorganic insulating materials such as PbO form " shell ".And this nano-core-shell structure can be distributed to ceramic crystalline grain inside uniformly, form stable interior crystalline structure.In so-called, crystalline structure refers to that nanoscale Second Phase Particle enters basis material intra-die.Specific to patent of the present invention, the nano-core-shell structure be made up of inorganic insulating materials such as Ag metallic particles and PbO enters PZN-PZT material grains inside as Second Phase Particle.Due to the existence of this special nanostructure, the interfacial polarization effect of this composite material is significantly strengthened, and dielectric constant increases substantially; The tunnelling current that what is more important inorganic insulating material will can effectively reduce after metal A g particle encapsulation between Ag particle, and then reach the object reducing dielectric loss, be the potential dielectric composite material being applied to energy storage device.
Accompanying drawing explanation
Fig. 1 is novel nano core-shell and interior crystalline structure schematic diagram.
Fig. 2 is that present component consists of Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3the TEM photo of/16vol.%Ag.
Fig. 3 is that present component consists of Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3the HRTEM photo of/16vol.%Ag.
Embodiment
Substantive distinguishing features of the present invention and remarkable advantage is illustrated further below by embodiment.It is noted that the present invention is only confined to stated embodiment by no means.
Synthesis Ag
2o presoma, this precursor adopts AgNO
3obtained with KOH reaction, its course of reaction is as follows:
AgNO
3+KOH→AgOH↓+KNO
3(2)
AgOH→Ag
2O↓+H
2O (3)
First by a certain amount of AgNO
3powder is dissolved in distilled water, treats AgNO
3after powder dissolves completely, to AgNO
3in solution, add excessive KOH powder, reaction in above-mentioned (2) first occurs, AgOH extremely unstable, at room temperature reaction in above-mentioned (3) occurs rapidly, generate sepia Ag
2o precipitates.Use supercentrifuge under the condition of 4000r/min, centrifugation obtains sepia Ag
2o powder, under 80 DEG C of conditions, dry for standby.
Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2be submicron-scale.
Embodiment 1:
By chemical formula Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3/ 12vol.%Ag weighs Ag
2o, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2, and ball milling 12 hours in ethanol.Calcine 2 hours at 850 DEG C after mixture drying, ball milling is after 12 hours in ethanol again, and under 100MPa, direct pressing is shaping, and then at 1050 DEG C, sintering obtains composite material in 2 hours.
Embodiment 2:
By chemical formula Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3/ 16vol.%Ag weighs Ag
2o, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2, the other the same as in Example 1.
Embodiment 3:
By chemical formula Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3/ 16.5vol.%Ag weighs Ag
2o, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2, the other the same as in Example 1.
Embodiment 4:
By chemical formula Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3/ 16.6vol.%Ag weighs Ag
2o, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2, the other the same as in Example 1.
Table 1 above-described embodiment performance comparison table
Claims (6)
1. a dielectric composite material, is characterized in that, this dielectric composite material has nano core-shell and interior crystalline structure, and the Ag metallic particles of nanoscale is as " core ", and PbO inorganic insulating material forms " shell "; The PZN-PZT material grains inside that this nano-core-shell structure be made up of Ag metallic particles and PbO inorganic insulating material is evenly distributed on submicron-scale as Second Phase Particle forms interior crystalline structure.
2. according to a kind of dielectric composite material of claim 1, it is characterized in that, the chemical composition of this composite material is: Pb (Zn
1/15nb
2/15zr
2/5ti
2/5) O
3the numerical value of/xAg, x is 10.0vol.% ~ 18.0vol.%.
3. according to a kind of dielectric composite material of claim 1, it is characterized in that, the chemical composition of this composite material is: the nano metal Ag particle containing 16.6vol.% in compound matrix material volume.
4. the method for any dielectric composite material of preparation described in claim 1-3, is characterized in that, comprise the following steps:
(1) Ag is synthesized
2o presoma;
(2) Ag will obtained
2o and Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2stoichiometrically weigh, Pb
3o
4, ZnO, Nb
2o
5, ZrO
2and TiO
2being submicron-scale, load weighted raw material is put into ball grinder, is that medium is placed in planetary ball mill ball milling 12 hours with absolute ethyl alcohol, then dries under 80 DEG C of conditions; By dried powder 800 ?calcining 2 hours at 900 DEG C, cool with stove; By the powder that obtains ball milling 12 hours again, under 80 DEG C of conditions, dry for standby;
(3) each component powder does not need to add binding agent, directly at the forming under the pressure of 100MPa, then at 1000 DEG C-1100 DEG C sintering, is incubated 2 hours, obtains target composite material.
5. according to the method for claim 4, it is characterized in that, synthesis Ag
2o presoma, this precursor adopts AgNO
3obtained with KOH reaction, its course of reaction is as follows:
AgNO
3+KOH→AgOH↓+KNO
3(2)
AgOH→Ag
2O↓+H
2O (3)
First by a certain amount of AgNO
3powder is dissolved in distilled water, treats AgNO
3after powder dissolves completely, to AgNO
3in solution, add excessive KOH powder, reaction in above-mentioned (2) first occurs, AgOH extremely unstable, at room temperature reaction in above-mentioned (3) occurs rapidly, generate sepia Ag
2o precipitates.Use supercentrifuge under the condition of 4000r/min, centrifugation obtains sepia Ag
2o powder, under 80 DEG C of conditions, dry for standby.
6. the dielectric composite material described in claim 1-3 is used for energy storage device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410670630.XA CN104505146B (en) | 2014-11-20 | 2014-11-20 | Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410670630.XA CN104505146B (en) | 2014-11-20 | 2014-11-20 | Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104505146A true CN104505146A (en) | 2015-04-08 |
CN104505146B CN104505146B (en) | 2017-02-22 |
Family
ID=52946887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410670630.XA Expired - Fee Related CN104505146B (en) | 2014-11-20 | 2014-11-20 | Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104505146B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106041061A (en) * | 2016-07-06 | 2016-10-26 | 同济大学 | High-performance low-loss compound magnetic powder core and preparation method thereof |
CN110698725A (en) * | 2019-10-10 | 2020-01-17 | 深圳市峰泳科技有限公司 | Inorganic filler, preparation method thereof and application thereof in dielectric material |
CN112723877A (en) * | 2020-12-29 | 2021-04-30 | 北京工业大学 | Ceramic-metal lead-free piezoelectric composite material with micron inner crystal structure and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1676331A (en) * | 2004-03-29 | 2005-10-05 | 佳能株式会社 | Dielectric member, piezoelectric member, ink jet head, ink jet recording apparatus, and production methods thereof |
CN1750995A (en) * | 2003-07-11 | 2006-03-22 | 艾布尔光子学有限公司 | A ferroelectric ceramic compound, a ferroelectric ceramic single crystal, and preparation processes thereof |
KR100579661B1 (en) * | 2003-12-19 | 2006-05-15 | 재단법인서울대학교산학협력재단 | Actuator and Method for fabrication thereof |
CN102714099A (en) * | 2009-11-30 | 2012-10-03 | Oc欧瑞康巴尔斯公司 | Core-shell nanoparticles in electronic battery applications |
-
2014
- 2014-11-20 CN CN201410670630.XA patent/CN104505146B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1750995A (en) * | 2003-07-11 | 2006-03-22 | 艾布尔光子学有限公司 | A ferroelectric ceramic compound, a ferroelectric ceramic single crystal, and preparation processes thereof |
KR100579661B1 (en) * | 2003-12-19 | 2006-05-15 | 재단법인서울대학교산학협력재단 | Actuator and Method for fabrication thereof |
CN1676331A (en) * | 2004-03-29 | 2005-10-05 | 佳能株式会社 | Dielectric member, piezoelectric member, ink jet head, ink jet recording apparatus, and production methods thereof |
CN102714099A (en) * | 2009-11-30 | 2012-10-03 | Oc欧瑞康巴尔斯公司 | Core-shell nanoparticles in electronic battery applications |
Non-Patent Citations (2)
Title |
---|
张正杰 等: "Ag掺杂PZN-PZT微观结构及电学性能影响", 《压电与声光》 * |
张永强,王瑾: "Ag与Ag2O粉末微电极的循环伏安和电化学阻抗对比研究", 《河南教育学院学报》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106041061A (en) * | 2016-07-06 | 2016-10-26 | 同济大学 | High-performance low-loss compound magnetic powder core and preparation method thereof |
CN106041061B (en) * | 2016-07-06 | 2018-06-26 | 同济大学 | A kind of preparation method of the low-loss composite magnetic powder core of high-performance |
CN110698725A (en) * | 2019-10-10 | 2020-01-17 | 深圳市峰泳科技有限公司 | Inorganic filler, preparation method thereof and application thereof in dielectric material |
CN110698725B (en) * | 2019-10-10 | 2021-05-18 | 深圳市峰泳科技有限公司 | Inorganic filler, preparation method thereof and application thereof in dielectric material |
CN112723877A (en) * | 2020-12-29 | 2021-04-30 | 北京工业大学 | Ceramic-metal lead-free piezoelectric composite material with micron inner crystal structure and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104505146B (en) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Simultaneously enhanced energy storage density and efficiency in novel BiFeO3-based lead-free ceramic capacitors | |
CN104478431B (en) | Ion modification titanium dioxide ceramic material and preparation method with high-k | |
CN108329027B (en) | Fine-grain energy storage medium ceramic material with double-layer core-shell structure and preparation method thereof | |
CN107698252B (en) | Application of ceramic material as high-temperature stable piezoelectric energy collecting material and preparation method thereof | |
CN107602115B (en) | Lead-free high-energy-storage-density wide-temperature-range stable ceramic material and preparation method thereof | |
CN103787653B (en) | A kind of carbon modification CaCu 3ti 4o 12the preparation method of high dielectric material | |
CN103553589B (en) | Method for preparing CaCu3Ti4O12 ceramic material | |
CN106587997A (en) | SrTiO<3>-based lead-free high-energy-density ceramic material and preparation method thereof | |
CN107954712A (en) | A kind of low-loss, giant dielectric CCTO ceramic materials and preparation method thereof | |
CN104505146A (en) | Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material | |
CN111039671B (en) | Composite for preparing ceramic material, preparation method thereof and ceramic capacitor | |
CN105777112B (en) | A kind of Ti is applied acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof | |
CN103172363B (en) | Preparation method of high-dielectric-constant perovskite CaCu3Ti4O12 (CCTO) pressure-sensitive material | |
CN102992761B (en) | A kind of piezoceramic material and preparation method being applied to collection of energy device | |
CN113620702A (en) | Yb (Yb)3+Doped giant dielectric constant low-loss ceramic and preparation method thereof | |
CN106699177B (en) | Lead-free piezoelectric energy collecting material with high power generation characteristic and preparation method thereof | |
CN102432291A (en) | Capacitor antiferroelectric ceramic material with positive voltage coefficient, and manufacturing method thereof | |
CN109957194A (en) | A kind of laminated film and preparation method thereof | |
CN109659427B (en) | Transition metal coated In2O3(ZnO)5Preparation method of core-shell structure thermoelectric material | |
Yang et al. | Enhancement of energy storage performances in BaTiO3-based ceramics via introducing Bi (Mg2/3Sb1/3) O3 | |
CN112142466A (en) | Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof | |
CN103708826A (en) | Low dielectric-loss barium strontium titanate pyroelectric ceramic and preparation method thereof | |
CN110483038A (en) | A kind of antiferroelectric lead-free ceramics and its preparation method and application | |
CN109400153A (en) | It is a kind of to collect the quaternary series ceramic material with high transducing coefficient and preparation applied to piezoelectric energy | |
Jadhav et al. | Electrochemical supercapacitors of bismuth ferrites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170222 Termination date: 20211120 |
|
CF01 | Termination of patent right due to non-payment of annual fee |