CN107034550A - A kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material - Google Patents
A kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 230000005291 magnetic effect Effects 0.000 claims description 99
- 238000013019 agitation Methods 0.000 claims description 94
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- -1 polyethylene pyrrole Polymers 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052593 corundum Inorganic materials 0.000 abstract description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 19
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 122
- 239000010936 titanium Substances 0.000 description 45
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 32
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000006250 one-dimensional material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/10—Metal-oxide dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth titanates
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to the preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material, comprise the following steps：Internal layer, middle level are injected separately into three different syringes with outer layer spinning liquid, is nested together using the syringe needle of three different-diameters and constitutes one three layers coaxial spinning head, spinning is carried out using method of electrostatic spinning；Organic matter volatilizees after high temperature sintering, ultimately forms one-dimensional monokaryon duplex shell structure BaTiO3@TiO2@ Al2O3, wherein length is about 20~100um, and diameter is about 200~350nm；Wherein, internal layer about 80~130nm, middle level about 30~55nm, outer layer are 30 55nm.Compared with prior art, the present invention has the advantages that preparation cost is low, preparation technology is simple, each thickness degree is controllable, can volume production.
Description
Technical field
The present invention relates to functional material preparing technical field, and in particular to a kind of one-dimensional monokaryon duplex shell structure dielectric capacitance
The preparation method of equipment material.
Background technology
Dielectric capacitor is as important base electronic element, with discharge power is big, utilization ratio is high, discharge and recharge is fast
Degree is fast, steady performance, is widely used in the fields such as electric power systems and energy resource system.In passive electronic components side
Face, the usage amount accounting of dielectric capacitor is more than 40%.It is particularly embedding recently as making rapid progress that electronic equipment develops
Enter the rise of formula capacitor, dielectric capacitor develops to high energy storage, miniaturization and environmentally friendly direction.On the other hand
With the fast development of electric power and energy resource system, dielectric capacitor is in solar power generation, wind-power electricity generation, the grid-connected system of intelligent grid
The new energy fields such as system, electrical power transmission system, hybrid vehicle, and the field such as pacemaker, high frequency pulse power supply is all
More and more important role is played, is played the role of irreplaceable.But the volume energy density of conventional dielectric capacitor is relatively low,
It significantly limit its application.Application for example in high-dielectric composite material in terms of electronic component energy storage, to material
It is required that with high dielectric constant, high disruptive field intensity.It is well known that piezoelectric ceramics has high dielectric constant, its toughness, hit
Wear field strength relatively low；Polymer has high disruptive field intensity, excellent toughness；The two is combined and can obtain high dielectric composite wood
Material.Biaxially oriented polypropylene (BOPP) Kynoar (PVDF) its dielectric constant for enjoying researcher to pay close attention to is both less than 10, and
The dielectric constants of ceramic material are very remote, the erroneous matching of a dielectric properties may occur compound when and cause
The reduction of combination property.In order to solve the above problems, nucleocapsid structure is incorporated inside and outside two kinds due to its unique architectural characteristic
The property of material, and the respective deficiency that complements each other, are the important research directions that pattern determines property in recent years, and prolonged
Do not wane, be with a wide range of applications.
At present nucleocapsid structure is prepared mainly to be received another one-step method by chemical bond or other active forces by nano material
Rice material coats the ordered fabrication structure for the nanoscale to be formed.Normal conditions, researchers are by two steps or two
The method of the step above could be prepared, and the thickness and uniformity of the shell prepared are difficult to control to.[Xingyi Huang and
Pingkai Jiang,Core–Shell Structured High-k Polymer Nanocomposites for Energy
Storage and Dielectric Applications,Advanced Materials27.3(2015):546-554.], because
It is extremely urgent that this explores a kind of cheap, the simple to operate method for preparing nucleocapsid structure of one-step method.Especially prepare list
The one-dimensional material of core duplex shell structure is more difficult.In addition, one-dimensional nanostructured have big draw ratio, specific surface area it is big, with
And unique superiority, all it is widely applied in terms of medical science, magnetics, electricity.Electrostatic spinning is to prepare 1-dimention nano
By a kind of one-step method method that material is common, with mix accurate, process can control, cost it is low, it is simple to operate etc. excellent
Point.
Liu et al. prepares barium titanate nano line using electrostatic spinning, is then prepared again by the method for chemistry cladding
One-dimensional nucleocapsid structure Al2O3@BaTiO3[Shaohui Liu,Jiao Wang,Bo Shen,Jiwei Zhai,Haoshan
Hao and Limin Zhao,Poly(vinylidene fluoride)nanocomposites with a small
loading of core-shell structured BaTiO3@Al2O3nanofibers exhibiting high
discharged energy density and efficiency,Journal of Alloys and Compounds 696
(2017)136e142.].But such a method is difficult to control to the thickness ratio of nuclear shell, and the uniformity of the thickness of shell is also difficult
To control.And monokaryon duplex shell structure BaTiO is prepared using electrostatic spinning one-step method at present3@TiO2@Al2O3One-dimensional material, and
Nucleocapsid ratio and shell uniformity relevant report can be controlled very few well.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of preparation technology is simple,
The preparation method for the one-dimensional monokaryon duplex shell structure dielectric capacitor material that controllability is strong, purity is high.
The purpose of the present invention can be achieved through the following technical solutions：A kind of one-dimensional monokaryon duplex shell structure dielectric capacitance
The preparation method of equipment material, the preparation method comprises the following steps：
(1) internal layer spinning solution, middle level spinning solution and outer layer spinning solution are injected separately into three different syringes, use three
The syringe needle of different-diameter, which is nested together, constitutes one three layers coaxial spinning head, and spinning is carried out using method of electrostatic spinning, and coaxial
Precursor fibre is obtained on receiver board below spinning head；
(2) precursor fibre obtained by step (1) carries out high temperature sintering after drying, produces the one-dimensional monokaryon duplex shell structure
Dielectric capacitor material.
Described internal layer spinning solution includes following synthesis step：
(a) by Ba (COOH)2It is dissolved in CH3CH2In COOH, ultrasound, magnetic agitation are until Ba (COOH)2It is dissolved completely in
CH3CH2In COOH, solution A is obtained, is stood；
(b) by C16H36O4Ti adds C5H8O2In, magnetic agitation obtains solution B, stands；
(c) polyethylene pyrrole network alkanone is added into CH3CH2In OH, magnetic agitation is completely dissolved up to polyethylene pyrrole network alkanone,
Solution C is obtained, is stood；
(d) solution A, solution B, solution C are mixed, magnetic agitation obtains internal layer colloidal solution, standing produces the internal layer
Spinning solution.
Ba described in step (a) (COOH)2With CH3CH2COOH mass ratio is 1：(3~7), ultrasonic time be 20~
40min, the temperature of magnetic agitation described in step (a) is 40~80 DEG C, and mixing time is 20~40min, described in step (a)
The temperature of standing is 20~30 DEG C, and time of repose is 0.5~2h；
C described in step (b)16H36O4Ti and C5H8O2Mass ratio be 1：(1.5~3), magnetic force is stirred described in step (b)
The temperature mixed is 20~30 DEG C, and the magnetic agitation time is 0.5~2h, and the temperature stood described in step (b) is 20~30 DEG C, quiet
The time is put for 0.5~2h；
PVP and CH in step (c)3CH2OH mass ratio is 1：(1.5~4), the temperature of magnetic agitation described in step (c)
For 30~80 DEG C, the magnetic agitation time is 20~30min, and the temperature stood described in step (c) is 20~30 DEG C, time of repose
For 0.5~2h；
Solution A described in step (d), solution B, the mass ratio of solution C are 1:1:2, magnetic agitation described in step (d)
Temperature is 20~30 DEG C, and the magnetic agitation time is 1~3h, and the dwell temperature of the internal layer colloidal solution is 20~30 DEG C, is stood
Time is 1~3 day.
Described middle level spinning solution includes following synthesis step：
(I) by C16H36O4Ti adds C5H8O2In, ultrasound, magnetic agitation so that C16H36O4Ti is completely dissolved in C5H8O2In,
Solution D is obtained, is stood；
(II) PVP is added into CH3CH2In OH, magnetic agitation is until PVP is dissolved completely in CH3CH2In OH, solution E is obtained,
Stand；
(III) solution D and solution E are mixed, magnetic agitation obtains middle level colloidal solution, standing produces middle level spinning solution.
C described in step (I)16H36O4Ti and C5H8O2Mass ratio be 1：(1~3), ultrasonic time is 8~15min, step
Suddenly the temperature of magnetic agitation described in (I) is 20~30 DEG C, and the magnetic agitation time is 20~40min, is stood described in step (I)
Temperature is 20~30 DEG C, and time of repose is 0.5~2h；
PVP and CH described in step (II)3CH2OH mass ratio is 1：(1.5~4), magnetic agitation described in step (II)
Temperature be 30~80 DEG C, the magnetic agitation time be 20~40min；Dwell temperature described in step (II) is 20~30 DEG C, quiet
The time is put for 0.5~2h；
The mass ratio of solution D and solution E described in step (III) is 1:2, the temperature of magnetic agitation described in step (III)
For 20~30 DEG C, the magnetic agitation time is 1~3h, and the dwell temperature of the middle level colloidal solution is 20~30 DEG C, time of repose
For 1~3 day.
Described outer layer spinning solution includes following synthesis step：
(X) by C9H21AlO3Add CH3CH2In OH, ultrasound, magnetic agitation are until C9H21AlO3It is dissolved completely in CH3CH2OH
In, solution F is obtained, is stood；
(Y) PVP is added into CH3CH2In OH, magnetic agitation is until PVP is dissolved completely in CH3CH2In OH, solution G is obtained,
Stand；
(Z) solution F and solution G is mixed, magnetic agitation obtains outer layer colloidal solution, standing produces outer layer spinning solution.
Step (X) described C9H21AlO3With CH3CH2OH mass ratio is 1：(1.5~4), ultrasonic time is 20~40min,
The temperature of magnetic agitation described in step (X) is 40~80 DEG C, and the magnetic agitation time is 20~40min, quiet described in step (X)
It is 20~30 DEG C to put temperature, and time of repose is 0.5~2h；
PVP and CH described in step (Y)3CH2OH mass ratio is 1：(1.5~4), magnetic agitation described in step (Y)
Temperature is 30~80 DEG C, and the magnetic agitation time is 20~40min；Dwell temperature described in step (Y) is 20~30 DEG C, during standing
Between be 0.5~2h；
Solution F and solution G mass ratio described in step (Z) are 1:2, the temperature of magnetic agitation is described in step (Z)
20~30 DEG C, the magnetic agitation time is 1~3h, and the dwell temperature of the middle level colloidal solution is 20~30 DEG C, and time of repose is 1
~3 days.
The syringe needle of three different-diameters described in step (1) includes internal layer syringe needle, middle level syringe needle and outer layer syringe needle, described interior
0.23~0.33mm, the external diameter of layer syringe needle are 0.45~0.71mm；The internal diameter of middle level syringe needle is that 0.51~0.9mm, external diameter are
0.81~1.26mm；The internal diameter of outer layer syringe needle is that 1.12~1.69mm, external diameter are 1.48~2.11mm, and internal layer syringe needle is arranged on
Middle level needle wall, middle level syringe needle is arranged on outer layer needle wall.
It is 1 to control the internal layer syringe needle, middle level syringe needle and outer layer syringe needle to spray the ratio between speed of solution by syringe pump：
(0.3~1)：(0.3~1), the voltage that the method for electrostatic spinning is used for 10~20kV, the coaxial spinning head and receiver board
Distance is 10~20cm, by controlling injection rate, can control internal layer, middle level and outer layer thickness, be allowed to uniform, controllable.
The drying temperature of the precursor fibre is 40~90 DEG C, and drying time is 8~20h, and the high temperature sintering is in horse
Not carried out in stove, be that 4~6 DEG C/min rises to 500~700 DEG C of 0.5~3h of insulation according to programming rate, be finally cooled to 20~30
DEG C, produce the one-dimensional monokaryon duplex shell structure dielectric capacitor material.
The present invention prepares the material of monokaryon duplex shell structure, relative to multi-step chemical method, electrostatic spinning technique have energy consumption it is low,
The advantages of convenient and swift, morphology controllable.In order to improve the application of dielectric capacitor under high voltages, the monokaryon bivalve
Dielectric capacitor material is divided into internal layer, middle level and the part of outer layer three.Thirdly partial effect is respectively：Internal layer has high dielectric
Constant improves polarization；Internal layer has transitional function for the intermediate layer of appropriate dielectric constant；Outer layer is that high-insulativity and relatively low dielectric are normal
Several layers.
The chemical reaction occurred in calcination process is as follows：
The chemical reaction that internal layer occurs：
PVP→C
2C16H36O4Ti+(46+x)O2→2TiOx+32CO2↑+36H2O
Ba(OOCCH3)2→Ba(OOC)2+2CH3↑
C+O2→CO2↑
2TiOx+(2-x)O2→2TiO2
Ba(OOC)2→BaCO3+CO2↑
BaCO3+TiO2→BaTiO3+CO2↑
The chemical reaction that middle level occurs：
PVP→C
2C16H36O4Ti+(46+x)O2→2TiOx+32CO2↑+36H2O
2TiOx+(2-x)O2→2TiO2
The chemical reaction that middle level occurs：
PVP→C
C9H21AlO3+O2→Al2O3+CO2↑+36H2O
Compared with prior art, beneficial effects of the present invention are embodied in：Utilize the syringe needle of three truncated different-diameter sizes
Be nested together three layers of coaxial spinning head of composition, and core shell structure (PVP+Ba (COOH) is prepared for using the method for electrostatic spinning2+
C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+C9H21AlO3) be presoma fiber, by high temperature sintering, be finally cooled to
Room temperature obtains one-dimensional monokaryon duplex shell structure BaTiO3@TiO2@Al2O3.Cost is low, preparation technology is simple, core with preparing for this method
Shell thickness is controllable, can volume production the advantages of.
Brief description of the drawings
Fig. 1 is the schematic diagram for preparing one-dimensional monokaryon duplex shell structure device therefor；
Fig. 2 one-dimensional monokaryon duplex shell structure BaTiO obtained by preparing3@TiO2@Al2O3X-ray diffraction (XRD) analysis chart
Spectrum；
Fig. 3 one-dimensional monokaryon duplex shell structure BaTiO obtained by preparing3@TiO2@Al2O3SEM (SEM)；
Fig. 4 one-dimensional monokaryon duplex shell structure BaTiO obtained by preparing3@TiO2@Al2O3Transmission electron microscope (TEM) collection of illustrative plates.
Wherein, 1 is coaxial syringe, and 2 be internal layer spinning solution, and 3 be middle level spinning solution, and 4 be outer layer spinning solution, and 5 be internal layer pin
Head, 6 be middle level syringe needle, and 7 be outer layer syringe needle, and 8 be receiver board, and 9 be syringe, and 10 be DC high-voltage power supply, and 11 be precursor fibre.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
1. prepare internal layer spinning liquid：According to mol ratio Ba：Ti=1：1 ratio weighs Ba (COOH) respectively2、
C16H36O4Ti.By Ba (COOH)2It is dissolved in CH3CH2In COOH solution, the two mass ratio is 1：3, ultrasonic 30min, then in temperature
For magnetic agitation 30min at 40 DEG C until Ba (COOH)2It is dissolved completely in CH3CH2In COOH, by obtained solution A at room temperature
Stand 0.5h；By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, wherein the mass ratio of the two is 1：1.5, then at room temperature
Magnetic agitation 0.5h, 0.5h is stood by obtained solution B at room temperature；PVP is added into ethanol (CH3CH2OH in), the two quality
Than for 1：1.5, then again temperature be 30 DEG C at magnetic agitation 30min until PVP be dissolved completely in CH3CH2In OH, by what is obtained
Solution C stands 0.5h at room temperature；It is 1 in mass ratio by tri- groups of solution of A, B, C：1：2 mix, at room temperature magnetic agitation 1h,
The colloidal solution of a transparent clear stable is obtained, the solution is finally stood 1 day at room temperature, that is, obtains internal layer spinning solution
Body.
2. prepare middle level spinning liquid：By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, the two mass ratio is 1：1, surpass
Sound 10min, then asks lower magnetic agitation 30min until C in room temperature16H36O4Ti is completely dissolved and C5H8O2In, by obtained solution
A stands 0.5h at room temperature；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：1.5, then temperature is 30 DEG C again
Lower magnetic agitation 30min is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 0.5h at room temperature；By A, B
Two groups of solution are 1 in mass ratio:2 mixing, magnetic agitation 1h, obtains the colloidal solution of a transparent clear stable at room temperature,
The solution is finally stood 1 day at room temperature, that is, obtains middle level spinning liquid.
3. prepare outer layer spinning liquid：By C9H21AlO3Add CH3CH2In OH, the two mass ratio is 1：1.5, ultrasound
30min, then temperature be at 40 DEG C magnetic agitation 30min until C9H21AlO3It is dissolved completely in CH3CH2In OH, by what is obtained
Solution A stands 0.5h at room temperature；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：1.5, then temperature is again
Magnetic agitation 30min at 30 DEG C is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 0.5h at room temperature；
It is 1 in mass ratio by tri- groups of solution of A, B：2 mixing, magnetic agitation 1h, obtains the colloid of a transparent clear stable at room temperature
Solution, finally stands 1 day at room temperature by the solution, that is, obtains outer layer spinning liquid.
4. in the inner tube that the stratum nucleare solution prepared is added to coaxial spinning, shell layer spinning solution adds the outer tube of coaxial spinning
In, electrostatic spinning is then carried out, (PVP+Ba (COOH) is obtained2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+
C9H21AlO3) be presoma fiber.The device specifically used is as shown in Figure 1.By internal layer spinning solution 2, middle level spinning solution 3 and outer
Layer spinning solution 4 is injected separately into three syringes 9, is nested together using the syringe needle of three different-diameters and is constituted three layers of coaxial spinning head
1, the syringe needles of three different-diameters is respectively internal layer syringe needle 5, middle level syringe needle 6 and outer layer syringe needle 7, wherein, the internal diameter of internal layer syringe needle
It is 0.45mm for 0.23mm, external diameter；The internal diameter of middle level syringe needle is that 0.51mm, external diameter are 0.81mm；The internal diameter of outer layer syringe needle is
1.12mm, external diameter are 1.48mm；Receiver board 8 is provided with the lower 10cm of coaxial spinning head 1, and by receiver board 8 and coaxial spinneret
First 1 is connected to the two ends of 10kV DC high-voltage power supply, syringe pump control internal layer spinning solution 2, middle level spinning solution 3 and outer layer spinning
The ratio between speed that liquid sprays from coaxial spinning head 1 is 1：0.3：1, spinning is carried out using method of electrostatic spinning, on receiver board
To precursor fibre 11.
5. by obtained (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+C9H21AlO3) be before
The fiber for driving body dries 8h at 40 DEG C, and dried precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, according to
Programming rate is that 5 DEG C/min rises to 500 DEG C of insulation 0.5h, is finally cooled to room temperature and obtains one-dimensional monokaryon duplex shell structure BaTiO3@
TiO2@Al2O3.By the one-dimensional monokaryon duplex shell structure BaTiO of gained3@TiO2@Al2O3Carry out X-ray diffraction analysis, ESEM
Detection and transmission electron microscope detection, obtained testing result difference is as shown in Figure 2, Figure 3, Figure 4.
From Fig. 2 monokaryon duplex shell structures BaTiO3@TiO2@Al2O3X-ray diffraction (XRD) analysis collection of illustrative plates in we can see
Go out monokaryon duplex shell structure BaTiO3@TiO2@Al2O3Main titanium dioxide and the metatitanic acid of perovskite structure by sharp perovskite structure
Barium is constituted, and should be aluminum oxide is that amorphous phase does not have obvious XRD peaks to occur；
From the one-dimensional monokaryon duplex shell structure BaTiO of Fig. 33@TiO2@Al2O3SEM (SEM) it can be seen that should
Material has big draw ratio, about tens microns of its length, and diameter is about 150-300 nanometers；
The one-dimensional monokaryon duplex shell structure BaTiO from Fig. 43@TiO2@Al2O3Transmission electron microscope (TEM) collection of illustrative plates can be seen
Go out, change material and be made up of respectively internal layer, middle level and the part of outer layer three, BaTiO is corresponded to respectively3、TiO2And Al2O3。
Embodiment 2
1. prepare internal layer spinning liquid：According to mol ratio Ba：Ti=1：1 ratio weighs Ba (COOH) respectively2、
C16H36O4Ti.By Ba (COOH)2It is dissolved in CH3CH2In COOH solution, the two mass ratio is 1：4, ultrasonic 20min, then in temperature
For magnetic agitation 20min at 50 DEG C until Ba (COOH)2It is dissolved completely in CH3CH2In COOH, by obtained solution A at 20 DEG C
Stand 1h；By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, wherein the mass ratio of the two is 1：2, the then magnetic force at 20 DEG C
1h is stirred, obtained solution B is stood into 1h at 20 DEG C；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：2,
Then again temperature be 50 DEG C at magnetic agitation 20min until PVP be dissolved completely in CH3CH2In OH, by obtained solution C at 20 DEG C
Lower standing 1h；It is 1 in mass ratio by tri- groups of solution of A, B, C：1：2 mixing, the magnetic agitation 1.5h at 20 DEG C, obtain one it is transparent
The colloidal solution of clear stable, finally stands 1-3 days at 20 DEG C by the solution, that is, obtains internal layer spinning liquid.
2. prepare middle level spinning liquid：By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, the two mass ratio is 1：1.5,
Ultrasonic 10min, then asks lower magnetic agitation 20min until C at 20 DEG C16H36O4Ti is completely dissolved and C5H8O2In, it is molten by what is obtained
Liquid A stands 1h at 20 DEG C；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：2, then again temperature be 50 DEG C at
Magnetic agitation 20min is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 1h at 20 DEG C；By two groups of A, B
Solution is 1 in mass ratio：2 mixing, the magnetic agitation 1.5h at 20 DEG C obtains the colloidal solution of a transparent clear stable, most
The solution is stood 1.5 days at 20 DEG C afterwards, that is, obtains middle level spinning liquid.
3. prepare outer layer spinning liquid：By C9H21AlO3Add CH3CH2In OH, the two mass ratio is 1：2, ultrasonic 20min,
Then temperature be at 50 DEG C magnetic agitation 20min until C9H21AlO3It is dissolved completely in CH3CH2In OH, by obtained solution A
1h is stood at 20 DEG C；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：2, then temperature is magnetic at 50 DEG C again
Power stirring 20min is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 1h at 20 DEG C；Tri- groups of A, B is molten
Liquid is 1 in mass ratio：2 mixing, the magnetic agitation 1.5h at 20 DEG C obtains the colloidal solution of a transparent clear stable, finally
The solution is stood 1.5 days at 20 DEG C, that is, obtains outer layer spinning liquid.
4. in the inner tube that the stratum nucleare solution prepared is added to coaxial spinning, shell layer spinning solution adds the outer tube of coaxial spinning
In, electrostatic spinning is then carried out, (PVP+Ba (COOH) is obtained2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+
C9H21AlO3) be presoma fiber, same as Example 1 using equipment, difference is, the internal diameter of internal layer syringe needle is
0.26mm, external diameter are 0.51mm；The internal diameter of middle level syringe needle is that 0.51mm, external diameter are 0.81mm；The internal diameter of outer layer syringe needle is
1.25mm, external diameter are 1.61mm, and the injection rate of internal layer spinning solution, middle level spinning solution and outer layer spinning solution is 1:1:0.3, use
Voltage be 13kV, the distance of receiver board and coaxial spinneret is 13cm.
5. by obtained (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+C9H21AlO3) be before
The fiber for driving body dries 100h at 50 DEG C, and dried precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, is pressed
It is that 5 DEG C/min rises to 550 DEG C of insulation 1h according to programming rate, is finally cooled to 20 DEG C and obtains one-dimensional monokaryon duplex shell structure BaTiO3@
TiO2@Al2O3。
Embodiment 3
(1) internal layer spinning liquid is prepared：According to mol ratio Ba：Ti=1：1 ratio weighs Ba (COOH) respectively2、
C16H36O4Ti.By Ba (COOH)2It is dissolved in CH3CH2In COOH solution, the two mass ratio is 1：5, ultrasonic 40min, then in temperature
For magnetic agitation 40min at 70 DEG C until Ba (COOH)2It is dissolved completely in CH3CH2In COOH, by obtained solution A at 30 DEG C
Stand 1.5h；By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, wherein the mass ratio of the two is 1：2.5, then at 30 DEG C
Magnetic agitation 1.5h, 1.5h is stood by obtained solution B at 30 DEG C；PVP is added into ethanol (CH3CH2OH in), the two quality
Than for 1：3, then again temperature be 70 DEG C at magnetic agitation 25min until PVP be dissolved completely in CH3CH2It is molten by what is obtained in OH
Liquid C stands 1.5h at 30 DEG C；It is 1 in mass ratio by tri- groups of solution of A, B, C：1：2 mixing, the magnetic agitation 2.5h at 30 DEG C,
The colloidal solution of a transparent clear stable is obtained, the solution is finally stood 2 days at 30 DEG C, that is, obtains internal layer spinning solution
Body.
(2) middle level spinning liquid is prepared：By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, the two mass ratio is 1：
2.5, ultrasonic 10min, then ask lower magnetic agitation 40min until C at 30 DEG C16H36O4Ti is completely dissolved and C5H8O2In, it will obtain
Solution A stand 1.5h at 30 DEG C；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：3, then temperature is again
Magnetic agitation 40min at 70 DEG C is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 1.5h at 30 DEG C；
It is 1 in mass ratio by two groups of solution of A, B：2 mixing, the magnetic agitation 2.5h at 30 DEG C obtains the glue of a transparent clear stable
Liquid solution, finally stands 2 days at 30 DEG C by the solution, that is, obtains middle level spinning liquid.
(3) outer layer spinning liquid is prepared：By C9H21AlO3Add CH3CH2In OH, the two mass ratio is 1：3, ultrasound
40min, then temperature be at 70 DEG C magnetic agitation 40min until C9H21AlO3It is dissolved completely in CH3CH2In OH, by what is obtained
Solution A stands 1.5h at 30 DEG C；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：3, then temperature is 70 again
Magnetic agitation 40min at DEG C is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 1.5h at 30 DEG C；Will
Tri- groups of solution of A, B are 1 in mass ratio：2 mixing, the magnetic agitation 2h at 30 DEG C, the colloid for obtaining a transparent clear stable is molten
Liquid, finally stands 2 days at 30 DEG C by the solution, that is, obtains outer layer spinning liquid.
(4) the stratum nucleare solution prepared is added in the inner tube of coaxial spinning, shell layer spinning solution adds the outer of coaxial spinning
Guan Zhong, then carries out electrostatic spinning, obtains (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+
C9H21AlO3) be presoma fiber.Same as Example 1 using equipment, difference is, the internal diameter of internal layer syringe needle is
0.3mm, external diameter are 0.55mm；The internal diameter of middle level syringe needle is that 0.7mm, external diameter are 1.06；The internal diameter of outer layer syringe needle is 1.45, external diameter
For 1.81mm.The voltage used is 16kV, and the distance of receiver board and coaxial spinneret is 16cm.
(5) by obtained (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+C9H21AlO3) be before
The fiber for driving body dries 8-20h at 40-90 DEG C, and dried precursor fibre is placed in alumina dry pot and is placed in Muffle
Stove, is that 5 DEG C/min rises to 650 DEG C of insulation 2h according to programming rate, is finally cooled to 30 DEG C and obtains one-dimensional monokaryon duplex shell structure
BaTiO3@TiO2@Al2O3。
Embodiment 4
(1) internal layer spinning liquid is prepared：According to mol ratio Ba：Ti=1：1 ratio weighs Ba (COOH) respectively2、
C16H36O4Ti.By Ba (COOH)2It is dissolved in CH3CH2In COOH solution, the two mass ratio is 1：7, ultrasonic 30min, then in temperature
For magnetic agitation 30min at 80 DEG C until Ba (COOH)2It is dissolved completely in CH3CH2In COOH, by obtained solution A at room temperature
Stand 2h；By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, wherein the mass ratio of the two is 1：3, then magnetic force at room temperature
2h is stirred, obtained solution B is stood into 2h at room temperature；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：4,
Then again temperature be 80 DEG C at magnetic agitation 30min until PVP be dissolved completely in CH3CH2In OH, by obtained solution C in room temperature
Lower standing 2h；It is 1 in mass ratio by tri- groups of solution of A, B, C：1：2 mixing, magnetic agitation 3h at room temperature, obtain one it is transparent clear
Stable colloidal solution, finally stands 3 days by the solution, that is, obtains internal layer spinning liquid at room temperature clearly.
(2) middle level spinning liquid is prepared：By C16H36O4Ti adds acetylacetone,2,4-pentanedione (C5H8O2) in, the two mass ratio is 1：3,
Ultrasonic 10min, then asks lower magnetic agitation 30min until C in room temperature16H36O4Ti is completely dissolved and C5H8O2In, it is molten by what is obtained
Liquid A stands 2h at room temperature；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：4, then again temperature be 80 DEG C at
Magnetic agitation 30min is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 2h at room temperature；By two groups of A, B
Solution is 1 in mass ratio：2 mixing, magnetic agitation 3h, obtains the colloidal solution of a transparent clear stable, finally at room temperature
The solution is stood 3 days at room temperature, that is, obtains middle level spinning liquid.
(3) outer layer spinning liquid is prepared：By C9H21AlO3Add CH3CH2In OH, the two mass ratio is 1：4, ultrasound
30min, then temperature be at 80 DEG C magnetic agitation 30min until C9H21AlO3It is dissolved completely in CH3CH2In OH, by what is obtained
Solution A stands 2h at room temperature；PVP is added into ethanol (CH3CH2OH in), the two mass ratio is 1：4, then temperature is 80 DEG C again
Lower magnetic agitation 30min is until PVP is dissolved completely in CH3CH2In OH, obtained solution B is stood into 2h at room temperature；By A, B tri-
Group solution is 1 in mass ratio：2 mixing, magnetic agitation 3h, obtains the colloidal solution of a transparent clear stable, most at room temperature
The solution is stood 3 days at room temperature afterwards, that is, obtains outer layer spinning liquid.
(4) the stratum nucleare solution prepared is added in the inner tube of coaxial spinning, shell layer spinning solution adds the outer of coaxial spinning
Guan Zhong, then carries out electrostatic spinning, obtains (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+
C9H21AlO3) be presoma fiber.The internal diameter of internal layer syringe needle is that 0.33mm, external diameter are 0.71mm；The internal diameter of middle level syringe needle is
0.9mm, external diameter are 1.26mm；The internal diameter of outer layer syringe needle is that 1.69mm, external diameter are 2.11mm.The voltage used receives for 20kV
The distance of plate and coaxial spinneret is 20cm.
(5) by obtained (PVP+Ba (COOH)2+C16H36O4Ti)@(PVP+C16H36O4Ti)@(PVP+C9H21AlO3) be before
The fiber for driving body dries 8-20h at 40-90 DEG C, and dried precursor fibre is placed in alumina dry pot and is placed in Muffle
Stove, is that 5 DEG C/min rises to 700 DEG C of insulation 3h according to programming rate, is finally cooled to room temperature and obtains one-dimensional monokaryon duplex shell structure
BaTiO3@TiO2@Al2O3。
Claims (10)
1. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material, it is characterised in that the preparation method
Comprise the following steps：
(1) internal layer spinning solution, middle level spinning solution and outer layer spinning solution are injected separately into three different syringes, use three differences
The syringe needle of diameter, which is nested together, constitutes one three layers coaxial spinning head, and spinning is carried out using method of electrostatic spinning, and in coaxial spinneret
Precursor fibre is obtained on receiver board below head；
(2) precursor fibre obtained by step (1) carries out high temperature sintering after drying, produces the one-dimensional monokaryon duplex shell structure electricity and is situated between
Matter capacitor material.
2. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 1, it is special
Levy and be, described internal layer spinning solution includes following synthesis step：
(a) by Ba (COOH)2It is dissolved in CH3CH2In COOH, ultrasound, magnetic agitation are until Ba (COOH)2It is dissolved completely in
CH3CH2In COOH, solution A is obtained, is stood；
(b) by C16H36O4Ti adds C5H8O2In, magnetic agitation obtains solution B, stands；
(c) polyethylene pyrrole network alkanone is added into CH3CH2In OH, magnetic agitation is completely dissolved up to polyethylene pyrrole network alkanone, is obtained
Solution C, stands；
(d) solution A, solution B, solution C are mixed, magnetic agitation obtains internal layer colloidal solution, standing produces the internal layer spinning
Liquid.
3. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 2, it is special
Levy and be, Ba described in step (a) (COOH)2With CH3CH2COOH mass ratio is 1：(3~7), ultrasonic time be 20~
40min, the temperature of magnetic agitation described in step (a) is 40~80 DEG C, and mixing time is 20~40min, described in step (a)
The temperature of standing is 20~30 DEG C, and time of repose is 0.5~2h；
C described in step (b)16H36O4Ti and C5H8O2Mass ratio be 1：(1.5~3), magnetic agitation described in step (b)
Temperature is 20~30 DEG C, and the magnetic agitation time is 0.5~2h, and the temperature stood described in step (b) is 20~30 DEG C, during standing
Between be 0.5~2h；
PVP and CH in step (c)3CH2OH mass ratio is 1：(1.5~4), the temperature of magnetic agitation described in step (c) is 30
~80 DEG C, the magnetic agitation time is 20~30min, and the temperature stood described in step (c) is 20~30 DEG C, and time of repose is
0.5~2h；
Solution A described in step (d), solution B, the mass ratio of solution C are 1:1:2, the temperature of magnetic agitation described in step (d)
For 20~30 DEG C, the magnetic agitation time is 1~3h, and the dwell temperature of the internal layer colloidal solution is 20~30 DEG C, time of repose
For 1~3 day.
4. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 1, it is special
Levy and be, described middle level spinning solution includes following synthesis step：
(I) by C16H36O4Ti adds C5H8O2In, ultrasound, magnetic agitation so that C16H36O4Ti is completely dissolved in C5H8O2In, obtain molten
Liquid D, stands；
(II) PVP is added into CH3CH2In OH, magnetic agitation is until PVP is dissolved completely in CH3CH2In OH, solution E is obtained, is stood；
(III) solution D and solution E are mixed, magnetic agitation obtains middle level colloidal solution, standing produces middle level spinning solution.
5. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 4, it is special
Levy and be, C described in step (I)16H36O4Ti and C5H8O2Mass ratio be 1：(1~3), ultrasonic time is 8~15min, step
(I) temperature of magnetic agitation described in is 20~30 DEG C, and the magnetic agitation time is 20~40min, and temperature is stood described in step (I)
Spend for 20~30 DEG C, time of repose is 0.5~2h；
PVP and CH described in step (II)3CH2OH mass ratio is 1：(1.5~4), the temperature of magnetic agitation described in step (II)
Spend for 30~80 DEG C, the magnetic agitation time is 20~40min；Dwell temperature described in step (II) is 20~30 DEG C, during standing
Between be 0.5~2h；
The mass ratio of solution D and solution E described in step (III) is 1:2, the temperature of magnetic agitation described in step (III) is 20
~30 DEG C, the magnetic agitation time is 1~3h, and the dwell temperature of the middle level colloidal solution is 20~30 DEG C, time of repose is 1~
3 days.
6. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 1, it is special
Levy and be, described outer layer spinning solution includes following synthesis step：
(X) by C9H21AlO3Add CH3CH2In OH, ultrasound, magnetic agitation are until C9H21AlO3It is dissolved completely in CH3CH2In OH,
Solution F is obtained, is stood；
(Y) PVP is added into CH3CH2In OH, magnetic agitation is until PVP is dissolved completely in CH3CH2In OH, solution G is obtained, is stood；
(Z) solution F and solution G is mixed, magnetic agitation obtains outer layer colloidal solution, standing produces outer layer spinning solution.
7. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 6, it is special
Levy and be, step (X) described C9H21AlO3With CH3CH2OH mass ratio is 1：(1.5~4), ultrasonic time is 20~40min,
The temperature of magnetic agitation described in step (X) is 40~80 DEG C, and the magnetic agitation time is 20~40min, quiet described in step (X)
It is 20~30 DEG C to put temperature, and time of repose is 0.5~2h；
PVP and CH described in step (Y)3CH2OH mass ratio is 1：(1.5~4), the temperature of magnetic agitation described in step (Y)
For 30~80 DEG C, the magnetic agitation time is 20~40min；Dwell temperature described in step (Y) is 20~30 DEG C, and time of repose is
0.5~2h；
Solution F and solution G mass ratio described in step (Z) are 1:2, the temperature of magnetic agitation described in step (Z) be 20~
30 DEG C, the magnetic agitation time is 1~3h, and the dwell temperature of the middle level colloidal solution is 20~30 DEG C, and time of repose is 1~3
My god.
8. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 1, it is special
Levy and be, the syringe needle of three different-diameters described in step (1) includes internal layer syringe needle, middle level syringe needle and outer layer syringe needle, described interior
0.23~0.33mm, the external diameter of layer syringe needle are 0.45~0.71mm；The internal diameter of middle level syringe needle is that 0.51~0.9mm, external diameter are
0.81~1.26mm；The internal diameter of outer layer syringe needle is that 1.12~1.69mm, external diameter are 1.48~2.11mm, and internal layer syringe needle is arranged on
Middle level needle wall, middle level syringe needle is arranged on outer layer needle wall.
9. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 8, it is special
Levy and be, it is 1 to control the internal layer syringe needle, middle level syringe needle and outer layer syringe needle to spray the ratio between speed of solution by syringe pump：
(0.3~1)：(0.3~1), the voltage that the method for electrostatic spinning is used for 10~20kV, the coaxial spinning head and receiver board
Distance is 10~20cm.
10. a kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material according to claim 1, it is special
Levy and be, the drying temperature of the precursor fibre is 40~90 DEG C, and drying time is 8~20h, and the high temperature sintering is in Muffle
Carried out in stove, be that 4~6 DEG C/min rises to 500~700 DEG C of 0.5~3h of insulation according to programming rate, be finally cooled to 20~30
DEG C, produce the one-dimensional monokaryon duplex shell structure dielectric capacitor material.
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| CN201710281938.9A CN107034550A (en) | 2017-04-26 | 2017-04-26 | A kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material |
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| CN110683860A (en) * | 2019-11-18 | 2020-01-14 | 萍乡学院 | Ceramic hollow ball with double-shell structure and preparation method thereof |
| CN111785446A (en) * | 2020-08-11 | 2020-10-16 | 广东工业大学 | Two-dimensional material-based cardiac pacemaker connecting wire and preparation method thereof |
| CN111892805A (en) * | 2020-07-09 | 2020-11-06 | 盐城工学院 | High-temperature-resistant and high-dielectric polymer-based composite dielectric material, and preparation method and application thereof |
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| CN111785446A (en) * | 2020-08-11 | 2020-10-16 | 广东工业大学 | Two-dimensional material-based cardiac pacemaker connecting wire and preparation method thereof |
| CN112652822A (en) * | 2020-12-23 | 2021-04-13 | 深圳市言九电子科技有限公司 | Cylindrical lithium ion accumulator and its manufacturing process |
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