CN109400147A - A kind of leadless piezoelectric structured composite material and preparation method and application applied to high power density collection of energy device - Google Patents
A kind of leadless piezoelectric structured composite material and preparation method and application applied to high power density collection of energy device Download PDFInfo
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- CN109400147A CN109400147A CN201811421334.0A CN201811421334A CN109400147A CN 109400147 A CN109400147 A CN 109400147A CN 201811421334 A CN201811421334 A CN 201811421334A CN 109400147 A CN109400147 A CN 109400147A
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- 239000002131 composite material Substances 0.000 title claims abstract description 176
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 165
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- 239000000463 material Substances 0.000 claims abstract description 33
- 235000015895 biscuits Nutrition 0.000 claims abstract description 31
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- 238000005056 compaction Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims description 60
- 238000000498 ball milling Methods 0.000 claims description 47
- 229910002113 barium titanate Inorganic materials 0.000 claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 35
- 239000004332 silver Substances 0.000 claims description 35
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 18
- 230000005684 electric field Effects 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000002463 transducing effect Effects 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 12
- 238000007766 curtain coating Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 239000002023 wood Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 239000013530 defoamer Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
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- 238000005245 sintering Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
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- 239000011656 manganese carbonate Substances 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000001802 infusion Methods 0.000 claims 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical group CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims 1
- 241001233037 catfish Species 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 9
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- 238000002474 experimental method Methods 0.000 description 9
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- 230000005611 electricity Effects 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
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- 238000001035 drying Methods 0.000 description 4
- 241000252203 Clupea harengus Species 0.000 description 3
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- 230000010287 polarization Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006487 butyl benzyl group Chemical group 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
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- 230000005662 electromechanics Effects 0.000 description 1
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- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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Abstract
A kind of leadless piezoelectric structured composite material and preparation method and application applied to high power density collection of energy device, the present invention relates to a kind of leadless piezoelectric structured composite material and preparation method and applications.The invention solves the problems that existing leadless piezoelectric ceramics energy density is low, and the theory based on traditional solution body or random doping makes the collection of energy performance boost amplitude of material very limited.The chemical general formula of leadless piezoelectric structured composite material applied to high power density collection of energy device is (1-x) (Ba1‑yCay)(Ti1‑zMz)O3/xBaTiO3.Method: one, fine grain housing base powder is prepared；Two, casting slurry is prepared；Three, biscuit of ceramics is prepared；Four, textural composite ceramics are prepared；Five, the textural composite ceramics of high compaction are prepared；Six, preparation high-performance textural composite ceramics.Using: it is used as environment-friendly type high power density and energy harvester is miniaturized.
Description
Technical field
The present invention relates to a kind of leadless piezoelectric structured composite material and preparation method and applications.
Background technique
In recent years, technology of Internet of things, removable with the promotion of complex digital system integrated technology and microelectric technique level
Dynamic electronics and wearable device etc. are quickly grown, and application range has gradually covered health monitoring, climate monitoring, wild dynamic
The various fields such as object tracking, embedded system and military security.However, the development of these microelectronic devices energy supply device is opposite
Lag usually provides electric energy using chemical cell at present for it.Since chemical cell has, size is big, the service life is short, temperature is stable
Property difference and the disadvantages of need replacing, it has also become the bottleneck for restricting microelectronic device development, particularly with wireless sensor network and embedding
Embedded system, this defect show more obvious.Direct piezoelectric effect of the piezoelectric energy collecting device based on material, can be effective
Ground captures the vibrational energy for being widely present and discarding in environment, is recycled and be converted to recycling electric energy, has conversion
It is high-efficient, use condition is pervasive, energy supply stablize continue, structure is simple and is easy to the advantages that being miniaturized, is integrated, become numerous vibrations
The one kind to attract attention in energy collection mode, application prospect are very wide.
The height of piezoelectric material electric property directly decides the output power and energy conversion efficiency of collection of energy device.
Now widely used piezoelectric material is mainly the lead base ceramic material haveing excellent performance, however such material is being prepared and discarded
Cheng Zhonghui causes serious harm to environment.In environmentally friendly leadless piezoelectric system, barium phthalate base (BaTiO3) ceramics are
Most potential one of the system for replacing lead base ceramics, however the electric property of pure barium titanate ceramics is far below lead base ceramics.In recent years
Come, people are based on solid solution theory, by introducing the methods of new constituent element, ionic compartmentation and doping vario-property to BaTiO3Matrix system into
It has gone component design, and has been prepared for a series of barium titanate based ceramic of performance improvements using conventional solid-state method.But since heat is dynamic
The presence of mechanics limitation, the high tension electricity coefficient d obtained by above method is always using the substantial increase of permittivity ε as generation
Valence, can be seen that its g according to g=d/ ε will significantly deteriorate, i.e., coexisting for high tension performance and high dielectric property is unfavorable for material
Expect the effective promotion of electromechanical transducing coefficient d × g.The presence of this problem makes BaTiO3Base ceramics are difficult to meet high-performance at present
Practical application request in piezoelectric energy collecting device.
In conclusion existing BaTiO3Its energy density of based leadless piezoelectric ceramics is low, electromechanical transducing coefficient d33×g33Greatly
About 1.0 × 10-12m2/ N~9.0 × 10-12m2/ N, electromechanical coupling factor KtAbout 0.30~0.50, it is prepared with such material
Cantilever beam energy harvester its power density be about 0.6 μ W/mm3~1.7 μ W/mm3.It can be seen that being based on traditional solution body
Or the theory of random doping makes the collection of energy performance boost amplitude of material very limited.
Summary of the invention
The present invention is to solve existing leadless piezoelectric ceramics energy density is low, based on traditional solution body or random doping
The problem that theory makes the collection of energy performance boost amplitude of material very limited, and provide a kind of applied to high power density energy
Measure the leadless piezoelectric structured composite material and preparation method and application of collecting device.
The present invention is proposed crystal orientation texture theory and composite design policy integration in BaTiO3In matrix system, pass through preparation
Novel, edge [001]cHeight preferred orientation and contain low εrThe leadless piezoelectric structured diphase ceramic material of insert, so that electricity
Performance (such as d × g) is significantly promoted, to meet the output of piezoelectric energy collecting device high-power energy and high energy turn
Change the demand of efficiency.
The chemical general formula of leadless piezoelectric structured composite material that the present invention is applied to high power density collection of energy device is
(1-x)(Ba1-yCay)(Ti1-zMz)O3/xBaTiO3, wherein M be Sn or Hf, 0.01≤x≤0.20,0.01≤y≤0.12,
0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 5 μm~50 μm；The orientation crystal grain has nucleocapsid knot
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is with orthorhombic phase (O), rhombohedral phase (R), just
It hands over phase (O) and rhombohedral phase (R) coexists or (the Ba of orthorhombic phase (O) and tetragonal phase (T) coexisting structure1-yCay)(Ti1-zMz)O3, wherein
M is Sn or Hf, 0.01≤y≤0.12,0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 96% or more, electromechanical transducing coefficient d33×g33It is 16.0 × 10-12m2/ N or more, electromechanical coupling factor KtIt is 0.60 or more,
Energy conversion efficiency η is 95% or more.
A kind of preparation side of the leadless piezoelectric structured composite material applied to high power density collection of energy device of the present invention
Method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh powder, when M be Sn when, weigh
BaCO3Powder, CaCO3Powder, TiO2Powder and SnO2Powder weighs BaCO when M is Hf3Powder, CaCO3Powder, TiO2Powder
Body and HfO2Then weighed powder is placed in ball grinder by powder, dehydrated alcohol is added as ball-milling medium, utilization is planetary
Ball mill ball milling 12h~120h is dried after ball milling, and grinding uniformly, obtains fine grain raw material, fine grain raw material is placed in corundum crucible
In, under conditions of temperature is 1000 DEG C~1400 DEG C, heat preservation 2h~6h is calcined, and obtains fine grain housing base powder；(Ba1- yCay)(Ti1-zMz)O3In 0.01≤y≤0.12,0.01≤z≤0.15；
The fine grain housing base powder is orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase (O) and rhombohedral phase (R) coexist or
Orthorhombic phase (O) and tetragonal phase (T) coexisting structure；The fine grain housing base powder is pure perovskite phase, and partial size≤300nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by aqua system method or organic system method；Wherein M be Sn or Hf, 0.01≤x≤0.20,0.01≤
Y≤0.12,0.01≤z≤0.15；
The platy-monocrystal BaTiO3Template seed crystal partial size is 3 μm~45 μm, with a thickness of 0.5 μm~2 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:(0.01~1)；
The growth auxiliary agent is CuO, ZnO, Bi2O3、Li2CO3、MnO2Or MnCO3；
Three, biscuit of ceramics is prepared:
Casting slurry is cast using casting machine, obtains diaphragm, diaphragm is cut and laminated, by the sample after laminating
Successively carry out the even pressure of hot water and heating dumping, the biscuit of ceramics after obtaining dumping；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 100MPa~300MPa, biscuit of ceramics pressure maintaining 1min~6min after dumping is carried out cold
Biscuit after isostatic cool pressing, is then placed in high temperature furnace, in temperature be 1000 DEG C~1550 DEG C and sintering atmosphere is by equal static pressure
Under conditions of air, oxygen or nitrogen, it is sintered 1h~15h, obtains textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, are 50MPa~200MPa and temperature in pressure
Under conditions of 800 DEG C~1450 DEG C, heat-insulation pressure keeping 15min~240min is sintered, and obtains the textural composite of high compaction
Ceramics；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 500 DEG C~850 DEG C is obtained by the textural composite ceramics after silver, will
It is put into silicone oil by the textural composite ceramics after silver, it will be by the textural composite ceramics after silver using DC electric field or AC field
Along [001]cPolarization, when using DC electric field, poling temperature be -50 DEG C~90 DEG C with polarized electric field be 10kV/cm~
Under conditions of 70kV/cm, heat-insulation pressure keeping 1min~30min, when an alternating current field is used, poling temperature be -50 DEG C~50 DEG C,
Polarized electric field be 10kV/cm~70kV/cm and frequency be 0.1Hz~10Hz under conditions of polarize, obtain be applied to high function
The leadless piezoelectric structured composite material of rate density energy collecting device.
It is high that the leadless piezoelectric structured composite material that the present invention is applied to high power density collection of energy device is used as environment-friendly type
Energy harvester is miniaturized in power density, for micro- electricity of microsensor, movable electronic and wearable device in Internet of Things
Sub- device provides electric energy；When prepared by the leadless piezoelectric structured composite material applied to high power density collection of energy device
When cantilever beam energy harvester, power density is up to 4.0 μ W/mm3More than.
The leadless piezoelectric structured composite material applied to high power density collection of energy device prepares cantilever beam energy
When measuring collector, the confession of the microelectronic component of microsensor in Internet of Things, movable electronic and wearable device can be met
Electricity requires.
Principle:
On the one hand, the present invention is applied to the leadless piezoelectric structured composite material of high power density collection of energy device using life
The template seed crystal oriented growth technology preparation of long auxiliary agent auxiliary, crystal grain is along [001]cHeight-oriented (texture degree is higher than 96%),
With significant electromechanical transformation anisotropy, in its predominant direction [001]cOn can present than common No yield point ceramic monomer substantially
Spend the piezoelectric coefficient d improved33With electromechanical coupling factor Kt.In addition, case material (Ba in compound orientation crystal grain1-yCay)
(Ti1-zMz)O3Containing orthorhombic phase (O) or rhombohedral phase (R), when along [001]cWhen direction polarization, can be formed the overturning that is easy to polarize 4O or
The engineering Ancient-sacrifice configuration of person 4R, so that d33And KtIt further increases.On the other hand, the present invention is applied to high power density collection of energy
Its crystal grain of the leadless piezoelectric structured composite material of device is novel core-shell structure, and core is in [001]cDirection has extremely low Jie
Electric constant εr(130) sheet BaTiO3Monocrystal is as the second phase monomer.Series-parallel reason based on complex effect and capacitor
By according to formula g=d/ ε, introducing has low εrThe second phase monomer may make entire crystal grain to construct compound core-shell structure
Dielectric constant is effectively inhibited, and then is inhibited the dielectric constant of material entirety and significant promoted its g33Value.It therefore, will be brilliant
(1-x) (Ba is integrated in texture effect and composite design theory1-yCay)(Ti1-zMz)O3/xBaTiO3(wherein M=Sn or Hf,
0.01≤x≤0.20,0.01≤y≤0.12,0.01≤z≤0.15) in composite ceramic material, electromechanical transducing coefficient may be implemented
d33×g33With the significantly promotion of energy conversion efficiency η, and then d is obtained33×g33It is 16.0 × 10-12m2/ N or more, KtFor
0.60 or more, the leadless piezoelectric structured composite material that η is 95% or more, cantilever beam energy harvester its power constructed with this are close
Degree can achieve 4.0 μ W/mm3More than.
The invention has the advantages that: the material modification technology for being intended to break through traditional solution body, the present invention is by crystal orientation texture theory
Design is jointly used in composite design strategy and is prepared novel edge [001]cPreferred orientation and the nothing with core-shell structure
The piezoelectric structured composite material of lead, to significantly improve electromechanical transducing coefficient d simultaneously33×g33, electromechanical coupling factor KtAnd energy
Efficiency eta is measured, and then the power density of its energy harvester is significantly increased.With existing leadless piezoelectric ceramics monomer phase
Than (1-x) (Ba prepared by the present invention1-yCay)(Ti1-zMz)O3/xBaTiO3(wherein M=Sn or Hf, 0.01≤x≤0.20,
0.01≤y≤0.12,0.01≤z≤0.15) composite ceramic material its crystal grain edge [001]cThe degree of orientation is 96% or more, micro-structure
For core-shell structure.Specifically, the core of the composite grain is the BaTiO for having tetragonal phase (T) structure and sheet-like morphology being presented3,
Shell is to coexist with orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase (O) and rhombohedral phase (R) or orthorhombic phase (O) and tetragonal phase (T) are total to
Deposit (the Ba of structure1-yCay)(Ti1-zMz)O3.The d of the composite material33×g33Up to 16.0 × 10-12m2/ N or more, KtIt is reachable
0.60 or more, η are up to 95% or more.The leadless piezoelectric structured composite wood applied to high power density collection of energy device of preparation
Material can be used as environment-friendly type high power density micromation energy harvester and be widely applied, and discard by high efficiente callback and using in environment
Vibrational energy generate electricity, be the microelectronic components such as microsensor, movable electronic and wearable device in Internet of Things
Electric energy is provided.
Detailed description of the invention
Fig. 1 is the leadless piezoelectric structured composite material prepared by the present invention applied to high power density collection of energy device
Structural schematic diagram；1 is the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3；2 is with orthorhombic phases (O), rhombohedral phase
(R), orthorhombic phase (O) and rhombohedral phase (R) coexist or (the Ba of orthorhombic phase (O) and tetragonal phase (T) coexisting structure1-yCay)(Ti1-zMz)
O3, wherein M is Sn or Hf, 0.01≤y≤0.12,0.01≤z≤0.15；3 be texture direction；4 be polarization direction；
Fig. 2 is application and preparation of the present invention in the stream of the leadless piezoelectric structured composite material of high power density collection of energy device
Journey schematic diagram；
Fig. 3 is the leadless piezoelectric structured composite material applied to high power density collection of energy device prepared by embodiment one
XRD spectrum；
Fig. 4 is electromechanical transducing coefficient d33×g33Comparison diagram, a are the No yield point ceramics of comparative experiments preparation, and b is embodiment
The leadless piezoelectric structured composite material applied to high power density collection of energy device of one preparation；
Fig. 5 is electromechanical coupling factor KtComparison diagram, a are the No yield point ceramics of comparative experiments preparation, and b is the preparation of embodiment two
The leadless piezoelectric structured composite material applied to high power density collection of energy device；
Fig. 6 is the leadless piezoelectric structured composite material applied to high power density collection of energy device prepared by embodiment three
SEM picture, BT be with tetragonal phase (T) structure and present sheet-like morphology BaTiO3；
Fig. 7 is the leadless piezoelectric structured composite material applied to high power density collection of energy device of example IV preparation
XRD diagram piece.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further includes between each specific embodiment
Any combination.
Specific embodiment 1: illustrating present embodiment in conjunction with Fig. 1, present embodiment is applied to high power density energy
The chemical general formula for measuring the leadless piezoelectric structured composite material of collecting device is (1-x) (Ba1-yCay)(Ti1-zMz)O3/xBaTiO3,
Wherein M is Sn or Hf, 0.01≤x≤0.20,0.01≤y≤0.12,0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 5 μm~50 μm；The orientation crystal grain has nucleocapsid knot
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is with orthorhombic phase (O), rhombohedral phase (R), just
It hands over phase (O) and rhombohedral phase (R) coexists or (the Ba of orthorhombic phase (O) and tetragonal phase (T) coexisting structure1-yCay)(Ti1-zMz)O3, wherein
M is Sn or Hf, 0.01≤y≤0.12,0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 96% or more, electromechanical transducing coefficient d33×g33It is 16.0 × 10-12m2/ N or more, electromechanical coupling factor KtIt is 0.60 or more,
Energy conversion efficiency η is 95% or more.
Specific embodiment 2: illustrating present embodiment in conjunction with Fig. 2, it is close that present embodiment one kind is applied to high power
The preparation method for spending the leadless piezoelectric structured composite material of collection of energy device is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh powder, when M be Sn when, weigh
BaCO3Powder, CaCO3Powder, TiO2Powder and SnO2Powder weighs BaCO when M is Hf3Powder, CaCO3Powder, TiO2Powder
Body and HfO2Then weighed powder is placed in ball grinder by powder, dehydrated alcohol is added as ball-milling medium, utilization is planetary
Ball mill ball milling 12h~120h is dried after ball milling, and grinding uniformly, obtains fine grain raw material, fine grain raw material is placed in corundum crucible
In, under conditions of temperature is 1000 DEG C~1400 DEG C, heat preservation 2h~6h is calcined, and obtains fine grain housing base powder；(Ba1- yCay)(Ti1-zMz)O3In 0.01≤y≤0.12,0.01≤z≤0.15；
The fine grain housing base powder is orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase (O) and rhombohedral phase (R) coexist or
Orthorhombic phase (O) and tetragonal phase (T) coexisting structure；The fine grain housing base powder is pure perovskite phase, and partial size≤300nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by aqua system method or organic system method；Wherein M be Sn or Hf, 0.01≤x≤0.20,0.01≤
Y≤0.12,0.01≤z≤0.15；
The platy-monocrystal BaTiO3Template seed crystal partial size is 3 μm~45 μm, with a thickness of 0.5 μm~2 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:(0.01~1)；
The growth auxiliary agent is CuO, ZnO, Bi2O3、Li2CO3、MnO2Or MnCO3；
Three, biscuit of ceramics is prepared:
Casting slurry is cast using casting machine, obtains diaphragm, diaphragm is cut and laminated, by the sample after laminating
Successively carry out the even pressure of hot water and heating dumping, the biscuit of ceramics after obtaining dumping；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 100MPa~300MPa, biscuit of ceramics pressure maintaining 1min~6min after dumping is carried out cold
Biscuit after isostatic cool pressing, is then placed in high temperature furnace, in temperature be 1000 DEG C~1550 DEG C and sintering atmosphere is by equal static pressure
Under conditions of air, oxygen or nitrogen, it is sintered 1h~15h, obtains textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, are 50MPa~200MPa and temperature in pressure
Under conditions of 800 DEG C~1450 DEG C, heat-insulation pressure keeping 15min~240min is sintered, and obtains the textural composite of high compaction
Ceramics；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 500 DEG C~850 DEG C is obtained by the textural composite ceramics after silver, will
It is put into silicone oil by the textural composite ceramics after silver, it will be by the textural composite ceramics after silver using DC electric field or AC field
Along [001]cPolarization, when using DC electric field, poling temperature be -50 DEG C~90 DEG C with polarized electric field be 10kV/cm~
Under conditions of 70kV/cm, heat-insulation pressure keeping 1min~30min, when an alternating current field is used, poling temperature be -50 DEG C~50 DEG C,
Polarized electric field be 10kV/cm~70kV/cm and frequency be 0.1Hz~10Hz under conditions of polarize, obtain be applied to high function
The leadless piezoelectric structured composite material of rate density energy collecting device.
Present embodiment is the utility model has the advantages that be intended to break through the material modification technology of traditional solution body, this specific embodiment party
Crystal orientation texture theory and composite design strategy are jointly used in design and prepared novel edge [001] by formulacPreferred orientation and
Leadless piezoelectric structured composite material with core-shell structure, to significantly improve electromechanical transducing coefficient d simultaneously33×g33, machine
Electric coupling coefficient KtWith energy conversion efficiency η, and then the power density of its energy harvester is significantly increased.With it is existing unleaded
Piezoelectric ceramics monomer is compared, (1-x) (Ba of present embodiment preparation1-yCay)(Ti1-zMz)O3/xBaTiO3(wherein M=
Sn or Hf, 0.01≤x≤0.20,0.01≤y≤0.12,0.01≤z≤0.15) composite ceramic material its crystal grain edge [001]cIt takes
To degree 96% or more, micro-structure is core-shell structure.Specifically, the core of the composite grain be with tetragonal phase (T) structure and
The BaTiO of sheet-like morphology is presented3, shell is to coexist with orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase (O) and rhombohedral phase (R) or just
Hand over (the Ba of phase (O) and tetragonal phase (T) coexisting structure1-yCay)(Ti1-zMz)O3.The d of the composite material33×g33Reachable 16.0 ×
10-12m2/ N or more, KtUp to 0.60 or more, η up to 95% or more.Preparation is applied to high power density collection of energy device
Leadless piezoelectric structured composite material can be used as environment-friendly type high power density micromation energy harvester and be widely applied, by efficiently returning
Receive and generated electricity using the vibrational energy discarded in environment, in Internet of Things microsensor, movable electronic and can wear
It wears the microelectronic components such as equipment and electric energy is provided.
Specific embodiment 3: present embodiment is unlike specific embodiment two: TiO described in step 12
Partial size≤100nm of powder；SnO described in step 12Partial size≤100nm of powder；HfO described in step 12Powder
Partial size≤100nm.Other are identical with embodiment two.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: working as use in step 2
It when aqua system method prepares casting slurry, specifically carries out according to the following steps: fine grain housing base powder is placed in ball grinder,
Then sequentially add growth auxiliary agent, solvent, defoamer and dispersing agent into ball grinder, ball milling 6h~48h, then into ball grinder according to
Secondary addition adhesive and plasticiser, ball milling 6h~48h obtain matrix slurry, by platy-monocrystal BaTiO3Template seed crystal ultrasound point
It dissipates and is added in matrix slurry, continue ball milling 15min~90min, obtain mixed slurry, mixed slurry is placed in vacuum plant
Middle 1h~12h removes bubble removing, obtains casting slurry；
Mass ratio 1:(0.45~0.65 of the fine grain housing base powder and solvent)；The fine grain housing base powder
With mass ratio 1:(0.005~0.025 of defoamer)；The mass ratio 1:(0.005 of the fine grain housing base powder and dispersing agent
~0.03)；Mass ratio 1:(0.05~0.15 of the fine grain housing base powder and adhesive)；The fine grain housing base powder
Mass ratio 1:(0.10~0.16 of body and plasticiser).Other are identical as specific embodiment two or three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment two to four: the solvent
For distilled water；The defoamer is DFC-21；The dispersing agent is polyacrylate；The adhesive is polyethylene
Alcohol；The plasticiser is polyethylene glycol.Other are identical as one of specific embodiment two to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five: in step 2 when
It when preparing casting slurry using organic system method, specifically carries out according to the following steps: fine grain housing base powder is placed in ball milling
In tank, is then sequentially added into ball grinder and grow auxiliary agent, solvent and dispersing agent, ball milling 6h~48h, then successively into ball grinder
Adhesive is added and plasticiser, ball milling 6h~48h obtain matrix slurry, by platy-monocrystal BaTiO3Template seed crystal ultrasonic disperse
And be added in matrix slurry, continue ball milling 15min~90min, obtains mixed slurry, mixed slurry is placed in vacuum plant
1h~12h removes bubble removing, obtains casting slurry；
Mass ratio 1:(0.30~0.50 of the fine grain housing base powder and solvent)；The fine grain housing base powder
With mass ratio 1:(0.008~0.02 of dispersing agent)；The mass ratio 1:(0.03 of the fine grain housing base powder and adhesive~
0.06)；Mass ratio 1:(0.03~0.06 of the fine grain housing base powder and plasticiser).Other and specific embodiment two
It is identical to one of five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment two to six: the solvent
For dimethylbenzene-alcohol mixed solution；The dispersing agent is molten herring oil；The adhesive is polyvinyl butyral；Institute
The plasticiser stated is the mixture of polyalkylene glycol and BBP(Butyl Benzyl Phthalate.Other and specific embodiment two to six it
One is identical.
Specific embodiment 8: unlike one of present embodiment and specific embodiment two to seven: the diformazan
The mass ratio of dimethylbenzene and ethyl alcohol is 1:(0.7~1.3 in benzene-alcohol mixed solution)；The polyalkylene glycol and adjacent benzene
Mass ratio 1:(0.7~1.3 of polyalkylene glycol and BBP(Butyl Benzyl Phthalate in the mixture of dioctyl phthalate butyl benzyl).Other
It is identical as one of specific embodiment two to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment two to eight: being made in step 3
What standby biscuit of ceramics specifically carried out according to the following steps: under conditions of being cast a height of 30 μm~400 μm of the edge of a knife, utilizing casting machine
Casting slurry is cast, 1h~for 24 hours and dry is stood after curtain coating on platform, obtains diaphragm, diaphragm is cut, in temperature
Under conditions of being 5MPa~50MPa for 60 DEG C~90 DEG C and pressure, the diaphragm after multilayer is cut is laminated, after being laminated
Sample, it is in 60 DEG C~90 DEG C of water that the sample after laminating, which is placed in temperature, and in pressure be 20MPa~50MPa and temperature is
Under conditions of 60 DEG C~90 DEG C, pressure-maintaining and heat-preservation 15min~90min carries out the even pressure of hot water, and the sample after obtaining the even pressure of hot water will be warm
Sample after the even pressure of water is placed in Muffle furnace, under conditions of temperature is 500 DEG C~600 DEG C, is kept the temperature 0.5h~6h, is obtained dumping
Biscuit of ceramics afterwards.Other are identical as one of specific embodiment two to eight.
Specific embodiment 10: the leadless piezoelectric structured composite material for being applied to high power density collection of energy device is used as
Energy harvester is miniaturized in environment-friendly type high power density, in Internet of Things microsensor, movable electronic and wearable set
Standby microelectronic component provides electric energy；When described is applied to the leadless piezoelectric structured compound of high power density collection of energy device
When material prepares cantilever beam energy harvester, power density is up to 4.0 μ W/mm3More than.
Beneficial effects of the present invention are verified using following embodiments:
A kind of embodiment one: preparation of the leadless piezoelectric structured composite material applied to high power density collection of energy device
Method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh BaCO3Powder, CaCO3Powder,
TiO2Powder and SnO2Powder obtains weighed powder, and then weighed powder is placed in ball grinder, and dehydrated alcohol is added and makees
It is dried after ball milling for ball-milling medium using planetary ball mill ball milling 72h, grinding uniformly, obtains fine grain raw material, by fine grain original
Material is placed in corundum crucible, and under conditions of temperature is 1150 DEG C, heat preservation 3h is calcined, and obtains fine grain housing base powder；Its
Middle M is Sn, y=0.02, z=0.043；
The fine grain housing base powder is orthorhombic phase (O) structure；The fine grain housing base powder is pure perovskite phase,
And partial size≤200nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by organic system method；Wherein M is Sn, x=0.06, y=0.02, z=0.043；
The platy-monocrystal BaTiO3Template seed crystal partial size is 5 μm~15 μm, with a thickness of 0.5 μm~1.5 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:0.1；
The growth auxiliary agent is CuO；
It when preparing casting slurry using organic system method, specifically carries out according to the following steps: by fine grain housing base powder
Be placed in ball grinder, then sequentially add growth auxiliary agent, solvent and dispersing agent into ball grinder, ball milling for 24 hours, then into ball grinder
Adhesive and plasticiser are sequentially added, ball milling for 24 hours, obtains matrix slurry, by platy-monocrystal BaTiO3Template seed crystal ultrasonic disperse
And be added in matrix slurry, continue ball milling 30min, obtain mixed slurry, mixed slurry is placed in 4h in vacuum plant and is removed
Bubble obtains casting slurry；
The mass ratio 1:0.33 of the fine grain housing base powder and solvent；The fine grain housing base powder and dispersing agent
Mass ratio 1:0.01；The mass ratio 1:0.04 of the fine grain housing base powder and adhesive；The fine grain housing base powder
The mass ratio 1:0.04 of body and plasticiser；
The solvent is dimethylbenzene-alcohol mixed solution；Dimethylbenzene and second in the dimethylbenzene-alcohol mixed solution
The mass ratio of alcohol is 1:1；The dispersing agent is molten herring oil；The adhesive is polyvinyl butyral；The modeling
Agent is the mixture of polyalkylene glycol and BBP(Butyl Benzyl Phthalate；The polyalkylene glycol and phthalic acid fourth
The mass ratio 1:1 of polyalkylene glycol and BBP(Butyl Benzyl Phthalate in the mixture of benzyl ester；
Three, biscuit of ceramics is prepared:
Under conditions of the curtain coating edge of a knife is 100 μm a height of, casting slurry is cast using casting machine, in platform after curtain coating
Upper standing 6h and drying, obtain diaphragm, diaphragm are cut, and under conditions of temperature is 75 DEG C and pressure is 30MPa, multilayer is cut
Diaphragm after cutting is laminated, the sample after being laminated, and the sample after laminating is placed in the water that temperature is 75 DEG C, in pressure
Under conditions of being 75 DEG C for 40MPa and temperature, pressure-maintaining and heat-preservation 30min carries out the even pressure of hot water, and the sample after obtaining the even pressure of hot water will
Sample after the even pressure of hot water is placed in Muffle furnace, under conditions of temperature is 600 DEG C, keeps the temperature 3h, the ceramics element after obtaining dumping
Base；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 200MPa, the biscuit of ceramics pressure maintaining 2min after dumping is subjected to isostatic cool pressing, then will
Biscuit after isostatic cool pressing is placed in high temperature furnace, under conditions of temperature is 1400 DEG C and sintering atmosphere is air, is sintered 6h, is obtained
To textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, in pressure be 150MPa and temperature is 1200 DEG C
Under conditions of, heat-insulation pressure keeping 45min is sintered, and obtains the textural composite ceramics of high compaction；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 550 DEG C is obtained by the textural composite ceramics after silver, will be by after silver
Textural composite ceramics be put into silicone oil, will be by the textural composite ceramics after silver along [001] using DC electric fieldcPolarization, in pole
Change that temperature is 20 DEG C and under conditions of polarized electric field is 50kV/cm, heat-insulation pressure keeping 10min obtains being applied to high power density energy
Measure the leadless piezoelectric structured composite material of collecting device；
TiO described in step 12Partial size≤100nm of powder；SnO described in step 12The partial size of powder≤
100nm；
The change of leadless piezoelectric structured composite material manufactured in the present embodiment applied to high power density collection of energy device
General formula is (1-x) (Ba1-yCay)(Ti1-zMz)O3/xBaTiO3, wherein M=Sn, x=0.06, y=0.02, z=0.043；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 8 μm~18 μm；The orientation crystal grain has nucleocapsid knot
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is the (Ba with orthorhombic phase (O) structure1- yCay)(Ti1-zMz)O3, wherein M is Sn, y=0.02, z=0.043；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 98%, electromechanical transducing coefficient d33×g33It is 18.1 × 10-12m2/ N, electromechanical coupling factor KtIt is 0.67, energy conversion efficiency
It is 98%.
Utilize the leadless piezoelectric structured composite material for being applied to high power density collection of energy device described in the present embodiment
Cantilever beam energy harvester is prepared, power density is up to 4.8 μ W/mm3。
Comparative experiments prepares No yield point ceramics: this comparative experiments is unlike embodiment one: piece is not added in step 2
Shape monocrystalline BaTiO3Template seed crystal, but the isometric BaTiO identical in quality with it is added3Powder, thus guarantee No yield point ceramics with
The total component of textured ceramic is identical.Other are the same as example 1.
Fig. 3 is the leadless piezoelectric structured composite material applied to high power density collection of energy device prepared by embodiment one
XRD spectrum.Wherein, chemical formula is 0.94 (Ba0.98Ca0.02)(Ti0.957Sn0.043)O3/0.06BaTiO3；It can be seen by figure
Out, which has pure Perovskite Phase structure, can be seen that textured ceramic with the comparison of common No yield point ceramics
(001) and the intensity at (002) peak is very strong, and other non-{ 001 } peak intensities are very weak, show strong [001]cPreferred orientation.
Using the Lotgering factor (F00l) analysis method calculate, the degree of orientation F of the textural composite material00lIt is 98%.For texture
For ceramics, F00lValue range be 0 < F001< 1, F001Bigger, ceramic [001]cThe degree of orientation is higher.The present embodiment system
The F of standby leadless piezoelectric structured composite material001It is 98%, illustrates the material grains along [001]cHeight preferred orientation, and this
Phase structure is that orthorhombic phase (O) accounts for leading to the leadless piezoelectric structured composite material of embodiment preparation at room temperature, can guarantee to polarize
The presence of the farmland 4O configuration afterwards, these are a big advantages of the invention.
Fig. 4 is electromechanical transducing coefficient d33×g33Comparison diagram, a are the No yield point ceramics of comparative experiments preparation, and b is embodiment
The leadless piezoelectric structured composite material applied to high power density collection of energy device of one preparation.As seen from the figure, identical
Common its d of No yield point ceramic monomer of component33×g33Only 4.6 × 10-12m2/ N, and pass through the present embodiment and integrate crystal orientation texture
0.94 (the Ba prepared with composite design0.98Ca0.02)(Ti0.957Sn0.043)O3/0.06BaTiO3Leadless piezoelectric structured composite wood
Material, d33×g33Up to 18.1 × 10-12m2/ N improves as many as 3.9 times than common No yield point monomer.In addition, the numerical value is remote
Higher than at present it has been reported that different leadless piezoelectric ceramics systems, or even it is more taller than part lead base system.This is also the present invention
A big advantage, i.e. the leadless piezoelectric structured composite material has the electromechanical conversion coefficient that increases substantially.
The experiment proved that its power density of cantilever beam energy harvester prepared with the present embodiment material is up to 4.8 μ W/
mm3。
A kind of embodiment two: preparation of the leadless piezoelectric structured composite material applied to high power density collection of energy device
Method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh BaCO3Powder, CaCO3Powder,
TiO2Powder and SnO2Powder obtains weighed powder, and then weighed powder is placed in ball grinder, and dehydrated alcohol is added and makees
It is dried after ball milling for ball-milling medium using planetary ball mill ball milling 96h, grinding uniformly, obtains fine grain raw material, by fine grain original
Material is placed in corundum crucible, and under conditions of temperature is 1200 DEG C, heat preservation 2h is calcined, and obtains fine grain housing base powder；Its
Middle M is Sn, y=0.02, z=0.043；
The fine grain housing base powder is orthorhombic phase (O) structure；The fine grain housing base powder is pure perovskite phase,
And partial size≤200nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by aqua system method；Wherein M is Sn, x=0.04, y=0.02, z=0.043；
The platy-monocrystal BaTiO3Template seed crystal partial size is 5 μm~15 μm, with a thickness of 0.5 μm~1.5 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:0.2；
The growth auxiliary agent is CuO；
It when preparing casting slurry using aqua system method, specifically carries out according to the following steps: by fine grain housing base powder
It is placed in ball grinder, is then sequentially added into ball grinder and grow auxiliary agent, solvent, defoamer and dispersing agent, ball milling 36h, then to
Adhesive and plasticiser are sequentially added in ball grinder, ball milling 36h obtains matrix slurry, by platy-monocrystal BaTiO3Template seed crystal
Ultrasonic disperse is simultaneously added in matrix slurry, is continued ball milling 45min, is obtained mixed slurry, mixed slurry is placed in vacuum plant
Middle 6h removes bubble removing, obtains casting slurry；
The mass ratio 1:0.55 of the fine grain housing base powder and solvent；The fine grain housing base powder and defoamer
Mass ratio 1:0.01；The mass ratio 1:0.01 of the fine grain housing base powder and dispersing agent；The fine grain housing base powder
The mass ratio 1:0.08 of body and adhesive；The mass ratio 1:0.12 of the fine grain housing base powder and plasticiser；
The solvent is distilled water；The defoamer is DFC-21；The dispersing agent is polyacrylate；It is described
Adhesive be polyvinyl alcohol；The plasticiser is polyethylene glycol；
Three, biscuit of ceramics is prepared:
Under conditions of the curtain coating edge of a knife is 200 μm a height of, casting slurry is cast using casting machine, in platform after curtain coating
Upper standing 18h and drying, obtain diaphragm, diaphragm are cut, under conditions of temperature is 80 DEG C and pressure is 25MPa, by multilayer
Diaphragm after cutting is laminated, the sample after being laminated, and the sample after laminating is placed in the water that temperature is 85 DEG C, is being pressed
Under conditions of power is 30MPa and temperature is 85 DEG C, pressure-maintaining and heat-preservation 40min carries out the even pressure of hot water, the sample after obtaining the even pressure of hot water,
Sample after the even pressure of hot water is placed in Muffle furnace, under conditions of temperature is 550 DEG C, keeps the temperature 3h, the ceramics after obtaining dumping
Biscuit；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 180MPa, the biscuit of ceramics pressure maintaining 3min after dumping is subjected to isostatic cool pressing, then will
Biscuit after isostatic cool pressing is placed in high temperature furnace, under conditions of temperature is 1350 DEG C and sintering atmosphere is air, is sintered 4h, is obtained
To textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, in pressure be 200MPa and temperature is 1175 DEG C
Under conditions of, heat-insulation pressure keeping 60min is sintered, and obtains the textural composite ceramics of high compaction；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 600 DEG C is obtained by the textural composite ceramics after silver, will be by after silver
Textural composite ceramics be put into silicone oil, will be by the textural composite ceramics after silver along [001] using AC fieldcPolarization, in pole
Change temperature be 30 DEG C, polarized electric field is 50kV/cm and frequency be 0.1Hz under conditions of polarize, obtain be applied to high power
The leadless piezoelectric structured composite material of density energy collecting device；
TiO described in step 12Partial size≤50nm of powder；SnO described in step 12The partial size of powder≤
100nm；
The change of leadless piezoelectric structured composite material manufactured in the present embodiment applied to high power density collection of energy device
General formula is (1-x) (Ba1-yCay)(Ti1-zMz)O3/xBaTiO3, wherein M=Sn, x=0.04, y=0.02, z=0.043；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 11 μm~25 μm；The orientation crystal grain has nucleocapsid
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is the (Ba with orthorhombic phase (O) structure1- yCay)(Ti1-zMz)O3, wherein M is Sn, y=0.02, z=0.043；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 97%, electromechanical transducing coefficient d33×g33It is 17.7 × 10-12m2/ N, electromechanical coupling factor KtIt is 0.62, energy conversion efficiency
η is 96%.
Utilize the leadless piezoelectric structured composite material for being applied to high power density collection of energy device described in the present embodiment
Cantilever beam energy harvester is prepared, power density is up to 4.4 μ W/mm3。
Fig. 5 is electromechanical coupling factor KtComparison diagram, a are the No yield point ceramics of comparative experiments preparation, and b is the preparation of embodiment two
The leadless piezoelectric structured composite material applied to high power density collection of energy device.Wherein, chemical formula 0.96
(Ba0.98Ca0.02)(Ti0.957Sn0.043)O3/0.04BaTiO3；As seen from the figure, the common No yield point ceramics of same composition are single
Its K of bodytOnly 0.30, and pass through the 0.96 (Ba that the present embodiment integrates crystal orientation texture and composite design and prepares0.98Ca0.02)
(Ti0.957Sn0.043)O3/0.04BaTiO3Leadless piezoelectric structured composite material, KtUp to 0.62, it is mentioned than common No yield point monomer
It is high more than 2 times.This is also a big advantage of the invention, i.e., the leadless piezoelectric structured composite material has the electromechanics increased substantially
The coefficient of coup.
The experiment proved that its power density of cantilever beam energy harvester prepared with the present embodiment material is up to 4.4 μ W/
mm3。
A kind of embodiment three: preparation of the leadless piezoelectric structured composite material applied to high power density collection of energy device
Method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh BaCO3Powder, CaCO3Powder,
TiO2Powder and SnO2Powder obtains weighed powder, and then weighed powder is placed in ball grinder, and dehydrated alcohol is added and makees
It is dried after ball milling for ball-milling medium using planetary ball mill ball milling 120h, grinding uniformly, obtains fine grain raw material, by fine grain original
Material is placed in corundum crucible, and under conditions of temperature is 1225 DEG C, heat preservation 2h is calcined, and obtains fine grain housing base powder；Its
Middle M is Sn, y=0.05, z=0.07；
The fine grain housing base powder is at room temperature based on orthorhombic phase (O) structure；The fine grain housing base powder is
Pure perovskite phase, and partial size≤200nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by organic system method；Wherein M is Sn, x=0.06, y=0.05, z=0.07；
The platy-monocrystal BaTiO3Template seed crystal partial size is 5 μm~15 μm, with a thickness of 0.5 μm~1.5 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:0.4；
The growth auxiliary agent is Li2CO3；
It when preparing casting slurry using organic system method, specifically carries out according to the following steps: by fine grain housing base powder
It is placed in ball grinder, is then sequentially added into ball grinder and grow auxiliary agent, solvent and dispersing agent, ball milling 16h, then into ball grinder
Adhesive and plasticiser are sequentially added, ball milling 16h obtains matrix slurry, by platy-monocrystal BaTiO3Template seed crystal ultrasonic disperse
And be added in matrix slurry, continue ball milling 30min, obtain mixed slurry, mixed slurry is placed in 4h in vacuum plant and is removed
Bubble obtains casting slurry；
The mass ratio 1:0.42 of the fine grain housing base powder and solvent；The fine grain housing base powder and dispersing agent
Mass ratio 1:0.015；The mass ratio 1:0.05 of the fine grain housing base powder and adhesive；The fine grain housing base powder
The mass ratio 1:0.05 of body and plasticiser；
The solvent is dimethylbenzene-alcohol mixed solution；Dimethylbenzene in the solvent xylene-alcohol mixed solution
Mass ratio with ethyl alcohol is 1:1；The dispersing agent is molten herring oil；The adhesive is polyvinyl butyral；It is described
Plasticiser be polyalkylene glycol and BBP(Butyl Benzyl Phthalate mixture；The polyalkylene glycol and O-phthalic
The mass ratio 1:1 of polyalkylene glycol and BBP(Butyl Benzyl Phthalate in the mixture of sour butyl benzyl；
Three, biscuit of ceramics is prepared:
Under conditions of the curtain coating edge of a knife is 150 μm a height of, casting slurry is cast using casting machine, in platform after curtain coating
Upper standing 8h and drying, obtain diaphragm, diaphragm are cut, and under conditions of temperature is 75 DEG C and pressure is 25MPa, multilayer is cut
Diaphragm after cutting is laminated, the sample after being laminated, and the sample after laminating is placed in the water that temperature is 80 DEG C, in pressure
Under conditions of being 80 DEG C for 40MPa and temperature, pressure-maintaining and heat-preservation 45min carries out the even pressure of hot water, and the sample after obtaining the even pressure of hot water will
Sample after the even pressure of hot water is placed in Muffle furnace, under conditions of temperature is 600 DEG C, keeps the temperature 2h, the ceramics element after obtaining dumping
Base；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 250MPa, the biscuit of ceramics pressure maintaining 3min after dumping is subjected to isostatic cool pressing, then will
Biscuit after isostatic cool pressing is placed in high temperature furnace, under conditions of temperature is 1300 DEG C and sintering atmosphere is oxygen, is sintered 6h, is obtained
To textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, in pressure be 100MPa and temperature is 1200 DEG C
Under conditions of, heat-insulation pressure keeping 30min is sintered, and obtains the textural composite ceramics of high compaction；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 550 DEG C is obtained by the textural composite ceramics after silver, will be by after silver
Textural composite ceramics be put into silicone oil, will be by the textural composite ceramics after silver along [001] using DC electric fieldcPolarization, in pole
Change that temperature is 25 DEG C and under conditions of polarized electric field is 55kV/cm, heat-insulation pressure keeping 20min obtains being applied to high power density energy
Measure the leadless piezoelectric structured composite material of collecting device；
TiO described in step 12Partial size≤50nm of powder；SnO described in step 12The partial size of powder≤
100nm；
The change of leadless piezoelectric structured composite material manufactured in the present embodiment applied to high power density collection of energy device
General formula is (1-x) (Ba1-yCay)(Ti1-zMz)O3/xBaTiO3, wherein M=Sn, x=0.06, y=0.05, z=0.07；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 7 μm~17 μm；The orientation crystal grain has nucleocapsid knot
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is the (Ba with orthorhombic phase (O) structure1- yCay)(Ti1-zMz)O3, wherein M is Sn, y=0.05, z=0.07；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 96.5%, electromechanical transducing coefficient d33×g33It is 16.2 × 10-12m2/ N, electromechanical coupling factor KtIt is 0.64, energy conversion effect
Rate η is 97%.
Utilize the leadless piezoelectric structured composite material for being applied to high power density collection of energy device described in the present embodiment
Cantilever beam energy harvester is prepared, power density is up to 4.1 μ W/mm3。
Fig. 6 is the leadless piezoelectric structured composite material applied to high power density collection of energy device prepared by embodiment three
SEM picture, BT be with tetragonal phase (T) structure and present sheet-like morphology BaTiO3.Wherein, chemical formula 0.94
(Ba0.95Ca0.05)(Ti0.93Sn0.07)O3/0.06BaTiO3；The leadless piezoelectric structured composite material is 7 μm~17 μm by partial size
Orientation crystal grain is formed.Apparent core-shell structure is presented in its crystal grain, and core is along [001]cThe BaTiO of height preferential arrangement3Sheet
Template seed crystal, shell are the (Ba with epitaxy relationship0.95Ca0.05)(Ti0.93Sn0.07)O3.This is also of the invention one big
Feature, i.e. prepared leadless piezoelectric structured composite material are by novel, edge [001]cPreferred orientation and have core-shell structure
Crystal grain composition, and orientation effect and complex effect are superimposed with increasing substantially conducive to electromechanical transformation performance.
The experiment proved that its power density of cantilever beam energy harvester prepared with the present embodiment material is up to 4.1 μ W/
mm3。
A kind of example IV: preparation of the leadless piezoelectric structured composite material applied to high power density collection of energy device
Method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh BaCO3Powder, CaCO3Powder,
TiO2Powder and HfO2Powder obtains weighed powder, and then weighed powder is placed in ball grinder, and dehydrated alcohol is added and makees
It is dried after ball milling for ball-milling medium using planetary ball mill ball milling 72h, grinding uniformly, obtains fine grain raw material, by fine grain original
Material is placed in corundum crucible, and under conditions of temperature is 1250 DEG C, heat preservation 2h is calcined, and obtains fine grain housing base powder；Its
Middle M is Hf, y=0.06, z=0.07；
The fine grain housing base powder is orthorhombic phase (O) and rhombohedral phase (R) coexisting structure；The fine grain housing base powder
Body is pure perovskite phase, and partial size≤300nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain shell base
Body powder and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and life
Long auxiliary agent prepares casting slurry by aqua system method；Wherein M is Hf, x=0.05, y=0.06, z=0.07；
The platy-monocrystal BaTiO3Template seed crystal partial size is 5 μm~15 μm, with a thickness of 0.5 μm~1.5 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:0.2；
The growth auxiliary agent is CuO；
It when preparing casting slurry using aqua system method, specifically carries out according to the following steps: by fine grain housing base powder
Be placed in ball grinder, then sequentially add growth auxiliary agent, solvent, defoamer and dispersing agent into ball grinder, ball milling for 24 hours, then to
Adhesive and plasticiser are sequentially added in ball grinder, ball milling for 24 hours, obtains matrix slurry, by platy-monocrystal BaTiO3Template seed crystal
Ultrasonic disperse is simultaneously added in matrix slurry, is continued ball milling 30min, is obtained mixed slurry, mixed slurry is placed in vacuum plant
Middle 8h removes bubble removing, obtains casting slurry；
The mass ratio 1:0.6 of the fine grain housing base powder and solvent；The fine grain housing base powder and defoamer
Mass ratio 1:0.02；The mass ratio 1:0.02 of the fine grain housing base powder and dispersing agent；The fine grain housing base powder
The mass ratio 1:0.1 of body and adhesive；The mass ratio 1:0.15 of the fine grain housing base powder and plasticiser；
The solvent is distilled water；The defoamer is DFC-21；The dispersing agent is polyacrylate；It is described
Adhesive be polyvinyl alcohol；The plasticiser is polyethylene glycol；
Three, biscuit of ceramics is prepared:
Under conditions of the curtain coating edge of a knife is 180 μm a height of, casting slurry is cast using casting machine, in platform after curtain coating
Upper standing 12h and drying, obtain diaphragm, diaphragm are cut, under conditions of temperature is 80 DEG C and pressure is 20MPa, by multilayer
Diaphragm after cutting is laminated, the sample after being laminated, and the sample after laminating is placed in the water that temperature is 80 DEG C, is being pressed
Under conditions of power is 30MPa and temperature is 80 DEG C, pressure-maintaining and heat-preservation 60min carries out the even pressure of hot water, the sample after obtaining the even pressure of hot water,
Sample after the even pressure of hot water is placed in Muffle furnace, under conditions of temperature is 550 DEG C, keeps the temperature 3h, the ceramics after obtaining dumping
Biscuit；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 250MPa, the biscuit of ceramics pressure maintaining 3min after dumping is subjected to isostatic cool pressing, then will
Biscuit after isostatic cool pressing is placed in high temperature furnace, under conditions of temperature is 1400 DEG C and sintering atmosphere is air, is sintered 4h, is obtained
To textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, in pressure be 150MPa and temperature is 1200 DEG C
Under conditions of, heat-insulation pressure keeping 30min is sintered, and obtains the textural composite ceramics of high compaction；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces carry out sanding and polishing
And silver paste is coated, burning infiltration silver electrode under conditions of temperature is 550 DEG C is obtained by the textural composite ceramics after silver, will be by after silver
Textural composite ceramics be put into silicone oil, will be by the textural composite ceramics after silver along [001] using DC electric fieldcPolarization, in pole
Change that temperature is 25 DEG C and under conditions of polarized electric field is 60kV/cm, heat-insulation pressure keeping 10min obtains being applied to high power density energy
Measure the leadless piezoelectric structured composite material of collecting device；
TiO described in step 12Partial size≤50nm of powder；HfO described in step 12The partial size of powder≤
100nm；
The change of leadless piezoelectric structured composite material manufactured in the present embodiment applied to high power density collection of energy device
General formula is (1-x) (Ba1-yCay)(Ti1-zMz)O3/xBaTiO3, wherein M=Hf, x=0.05, y=0.06, z=0.07；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]c
The orientation crystal grain of preferred orientation forms；The orientation size of microcrystal is 9 μm~20 μm；The orientation crystal grain has nucleocapsid knot
Structure, core are the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is total with orthorhombic phase (O) and rhombohedral phase (R)
Deposit (the Ba of structure1-yCay)(Ti1-zMz)O3, wherein M=Hf, y=0.06, z=0.07；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cOrientation
Degree is 98%, electromechanical transducing coefficient d33×g33It is 16.1 × 10-12m2/ N, electromechanical coupling factor KtIt is 0.61, energy conversion efficiency
η is 96%.
Fig. 7 is the leadless piezoelectric structured composite material applied to high power density collection of energy device of example IV preparation
XRD diagram piece.Wherein, chemical formula is 0.95 (Ba0.94Ca0.06)(Ti0.93Hf0.07)O3/0.05BaTiO3；It can be seen by figure
Out, which with pure Perovskite Phase structure and has strong [001]cOrientation.Using the Lotgering factor
(F00l) analysis method calculate, the degree of orientation F of the textured ceramic composite material00lAlso it is up to 98%.The textured ceramic is at room temperature
Phase structure is that orthorhombic phase (O) and rhombohedral phase (R) coexist, and can guarantee the presence of the farmland 4R and 4O configuration after polarization.
Claims (10)
1. a kind of leadless piezoelectric structured composite material applied to high power density collection of energy device, it is characterised in that be applied to
The chemical general formula of the leadless piezoelectric structured composite material of high power density collection of energy device is (1-x) (Ba1-yCay)(Ti1-zMz)
O3/xBaTiO3, wherein M is Sn or Hf, 0.01≤x≤0.20,0.01≤y≤0.12,0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is by along [001]cPreferentially take
To orientation crystal grain composition；The orientation size of microcrystal is 5 μm~50 μm；The orientation crystal grain has core-shell structure, core
For the BaTiO with tetragonal phase (T) structure and presentation sheet-like morphology3, shell is with orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase
(O) and rhombohedral phase (R) coexists or (the Ba of orthorhombic phase (O) and tetragonal phase (T) coexisting structure1-yCay)(Ti1-zMz)O3, wherein M be
Sn or Hf, 0.01≤y≤0.12,0.01≤z≤0.15；
The leadless piezoelectric structured composite material applied to high power density collection of energy device is along [001]cThe degree of orientation is
96% or more, electromechanical transducing coefficient d33×g33It is 16.0 × 10-12m2/ N or more, electromechanical coupling factor KtIt is 0.60 or more, energy
Efficiency eta is 95% or more.
2. a kind of leadless piezoelectric structured composite material applied to high power density collection of energy device as described in claim 1
Preparation method, it is characterised in that a kind of leadless piezoelectric structured composite material applied to high power density collection of energy device
Preparation method is completed by the following steps:
One, fine grain housing base powder is prepared:
It is (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3Stoichiometric ratio weigh powder, when M be Sn when, weigh BaCO3Powder
Body, CaCO3Powder, TiO2Powder and SnO2Powder weighs BaCO when M is Hf3Powder, CaCO3Powder, TiO2Powder and
HfO2Then weighed powder is placed in ball grinder by powder, dehydrated alcohol is added as ball-milling medium, utilizes planetary type ball-milling
Machine ball milling 12h~120h is dried after ball milling, and grinding uniformly, obtains fine grain raw material, fine grain raw material is placed in corundum crucible,
Under conditions of temperature is 1000 DEG C~1400 DEG C, heat preservation 2h~6h is calcined, and obtains fine grain housing base powder；(Ba1-yCay)
(Ti1-zMz)O3In 0.01≤y≤0.12,0.01≤z≤0.15；
The fine grain housing base powder is orthorhombic phase (O), rhombohedral phase (R), orthorhombic phase (O) and rhombohedral phase (R) coexist or orthogonal
Phase (O) and tetragonal phase (T) coexisting structure；The fine grain housing base powder is pure perovskite phase, and partial size≤300nm；
Two, casting slurry is prepared:
It is (1-x) (Ba according to chemical general formula1-yCay)(Ti1-zMz)O3/xBaTiO3Stoichiometric ratio weigh fine grain housing base powder
Body and platy-monocrystal BaTiO3Template seed crystal, then by fine grain housing base powder, platy-monocrystal BaTiO3Template seed crystal and growth help
Agent prepares casting slurry by aqua system method or organic system method；Wherein M be Sn or Hf, 0.01≤x≤0.20,0.01≤y≤
0.12,0.01≤z≤0.15；
The platy-monocrystal BaTiO3Template seed crystal partial size is 3 μm~45 μm, with a thickness of 0.5 μm~2 μm；
The mass ratio of the fine grain housing base powder and growth auxiliary agent is 100:(0.01~1)；
The growth auxiliary agent is CuO, ZnO, Bi2O3、Li2CO3、MnO2Or MnCO3；
Three, biscuit of ceramics is prepared:
Casting slurry is cast using casting machine, obtains diaphragm, diaphragm is cut and laminated, successively by the sample after laminating
Carry out the even pressure of hot water and heating dumping, the biscuit of ceramics after obtaining dumping；
Four, textural composite ceramics are prepared:
Under conditions of pressure is 100MPa~300MPa, biscuit of ceramics pressure maintaining 1min~6min after dumping is carried out cold etc. quiet
Pressure, then the biscuit after isostatic cool pressing is placed in high temperature furnace, temperature be 1000 DEG C~1550 DEG C and sintering atmosphere be air,
Under conditions of oxygen or nitrogen, it is sintered 1h~15h, obtains textural composite ceramics；
Five, the textural composite ceramics of high compaction are prepared:
Textural composite ceramics are placed in the high-pressure bottle of hot isostatic press, in pressure be 50MPa~200MPa and temperature is 800
DEG C~1450 DEG C under conditions of, heat-insulation pressure keeping 15min~240min is sintered, obtain high compaction textural composite ceramics；
Six, preparation high-performance textural composite ceramics:
The textural composite ceramics of high compaction are respectively perpendicular to [001]cUpper and lower surfaces sanding and polishing and coat
Silver paste, burning infiltration silver electrode under conditions of temperature is 500 DEG C~850 DEG C are obtained by the textural composite ceramics after silver, will be by after silver
Textural composite ceramics be put into silicone oil, will be by the textural composite ceramics edge after silver using DC electric field or AC field
[001]cPolarization, when using DC electric field, in poling temperature be -50 DEG C~90 DEG C and polarized electric field is 10kV/cm~70kV/
Under conditions of cm, heat-insulation pressure keeping 1min~30min is -50 DEG C~50 DEG C, polarizes in poling temperature when an alternating current field is used
Electric field be 10kV/cm~70kV/cm and frequency be 0.1Hz~10Hz under conditions of polarize, obtain be applied to high power it is close
Spend the leadless piezoelectric structured composite material of collection of energy device.
3. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 2
The preparation method of material, it is characterised in that TiO described in step 12Partial size≤100nm of powder；SnO described in step 12
Partial size≤100nm of powder；HfO described in step 12Partial size≤100nm of powder.
4. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 2
The preparation method of material, it is characterised in that in step 2 when preparing casting slurry using aqua system method, specifically press following step
Suddenly it carries out: fine grain housing base powder is placed in ball grinder, growth auxiliary agent is then sequentially added into ball grinder, solvent, is gone
Infusion and dispersing agent, ball milling 6h~48h, then adhesive and plasticiser are sequentially added into ball grinder, ball milling 6h~48h is obtained
Matrix slurry, by platy-monocrystal BaTiO3Template seed crystal ultrasonic disperse is simultaneously added in matrix slurry, and continuation ball milling 15min~
90min obtains mixed slurry, and mixed slurry is placed in 1h~12h in vacuum plant and removes bubble removing, obtains casting slurry；
Mass ratio 1:(0.45~0.65 of the fine grain housing base powder and solvent)；The fine grain housing base powder with go
Mass ratio 1:(0.005~0.025 of infusion)；The mass ratio 1:(0.005 of the fine grain housing base powder and dispersing agent~
0.03)；Mass ratio 1:(0.05~0.15 of the fine grain housing base powder and adhesive)；The fine grain housing base powder
With mass ratio 1:(0.10~0.16 of plasticiser).
5. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 4
The preparation method of material, it is characterised in that the solvent is distilled water；The defoamer is DFC-21；The dispersing agent is
Polyacrylate；The adhesive is polyvinyl alcohol；The plasticiser is polyethylene glycol.
6. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 2
The preparation method of material, it is characterised in that in step 2 when preparing casting slurry using organic system method, specifically press following step
Suddenly it carries out: fine grain housing base powder is placed in ball grinder, growth auxiliary agent, solvent are then sequentially added into ball grinder and divide
Powder, ball milling 6h~48h, then adhesive and plasticiser are sequentially added into ball grinder, ball milling 6h~48h obtains matrix slurry,
By platy-monocrystal BaTiO3Template seed crystal ultrasonic disperse is simultaneously added in matrix slurry, is continued ball milling 15min~90min, is obtained
Mixed slurry is placed in 1h~12h in vacuum plant and removes bubble removing, obtains casting slurry by mixed slurry；
Mass ratio 1:(0.30~0.50 of the fine grain housing base powder and solvent)；The fine grain housing base powder with point
Mass ratio 1:(0.008~0.02 of powder)；The mass ratio 1:(0.03 of the fine grain housing base powder and adhesive~
0.06)；Mass ratio 1:(0.03~0.06 of the fine grain housing base powder and plasticiser).
7. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 6
The preparation method of material, it is characterised in that the solvent is dimethylbenzene-alcohol mixed solution；The dispersing agent is molten catfish
Oil；The adhesive is polyvinyl butyral；The plasticiser is polyalkylene glycol and BBP(Butyl Benzyl Phthalate
Mixture.
8. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 7
The preparation method of material, it is characterised in that the mass ratio of dimethylbenzene and ethyl alcohol is 1 in the dimethylbenzene-alcohol mixed solution:
(0.7~1.3)；Polyalkylene glycol and adjacent benzene two in the mixture of the polyalkylene glycol and BBP(Butyl Benzyl Phthalate
Mass ratio 1:(0.7~1.3 of formic acid butyl benzyl).
9. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device according to claim 2
The preparation method of material, it is characterised in that prepare what biscuit of ceramics specifically carried out according to the following steps in step 3: in the curtain coating edge of a knife
Under conditions of a height of 30 μm~400 μm, casting slurry is cast using casting machine, after curtain coating on platform stand 1h~
It is for 24 hours and dry, diaphragm is obtained, diaphragm is cut, under conditions of temperature is 60 DEG C~90 DEG C and pressure is 5MPa~50MPa,
Diaphragm after multilayer is cut laminates, the sample after being laminated, and it is 60 DEG C~90 that the sample after laminating, which is placed in temperature,
DEG C water in, under conditions of pressure is 20MPa~50MPa and temperature is 60 DEG C~90 DEG C, pressure-maintaining and heat-preservation 15min~90min
The even pressure of hot water is carried out, the sample after the even pressure of hot water is placed in Muffle furnace by the sample after obtaining the even pressure of hot water, is 500 in temperature
DEG C~600 DEG C under conditions of, keep the temperature 0.5h~6h, the biscuit of ceramics after obtaining dumping.
10. a kind of leadless piezoelectric structured composite wood applied to high power density collection of energy device as described in claim 1
The application of material, it is characterised in that the leadless piezoelectric structured composite material applied to high power density collection of energy device is used as environmental protection
Energy harvester is miniaturized in type high power density, is microsensor, movable electronic and wearable device in Internet of Things
Microelectronic component provides electric energy；When the leadless piezoelectric structured composite material applied to high power density collection of energy device
When preparing cantilever beam energy harvester, power density is up to 4.0 μ W/mm3More than.
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| CN116237225A (en) * | 2023-02-10 | 2023-06-09 | 之江实验室 | High-sensitivity flexible piezoelectric ultrasonic transducer and preparation method thereof |
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