CN109265880A - A kind of core-shell structured powder and dielectric composite material as made from it - Google Patents
A kind of core-shell structured powder and dielectric composite material as made from it Download PDFInfo
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- CN109265880A CN109265880A CN201810962538.9A CN201810962538A CN109265880A CN 109265880 A CN109265880 A CN 109265880A CN 201810962538 A CN201810962538 A CN 201810962538A CN 109265880 A CN109265880 A CN 109265880A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
Abstract
The present invention relates to a kind of core-shell structured powder and dielectric composite materials as made from it.The core-shell structured powder includes: BaTiO3The metallic shell component of nuclear structure and its Surface Creation；The particle size of the metallic shell component is 20nm~100nm, preferably 20-80nm；The tenor is the 1-9vol% of core-shell structured powder.There is lower dielectric loss using polymer matrix composite made of the core-shell structured powder, effectively avoid nano nickel from forming conductive network and reduce leakage current, while composite material dielectric constant with higher and preferable mechanical property.The preparation method have the characteristics that simply, conveniently, easily industrialization.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of core-shell structured powder, preparation method and by
Its dielectric composite material obtained.
Background technique
Recent years, the polymer based nanocomposites of high dielectric constant, low-dielectric loss and good mechanical performance
It receives significant attention.High dielectric polymer based composites combine the advantages of conventional dielectric material and polymer are without matrix,
Have the characteristics that easy processing, mechanical property be good and low production cost, causes the extensive research of home and abroad expert and seminar.
Currently, the polymer matrix composite of high dielectric constant obtains extensively in the high energy-storage capacitor such as inserted thin film capacitor
Using.
However, being gathered by high dielectric constant prepared by the functions such as conductive nano body, ferroelectric ceramics phase and polymer matrix bluk recombination
Close object based composites there are problems that such as in practical applications:
(1) conductive particle exceed seep near threshold Polymeric dielectric performance it is unstable, high dielectric constant is often with higher
Dielectric loss.To conductor function phase/polymer composites research and development of the high dielectric constant based on seepage theory
Through doing a lot of work, but there is a critical issue not to be resolved, i.e. the reproducibility (stability problem) of dielectric properties.It is high
Conductor function phase/polymer composites dielectric properties of dielectric constant to its influence factor, (especially join by the related of conductor
Amount) it is very sensitive, if function phase dosage can cause the change dramatically of system conductivity exceeding the micro variation for seeping near threshold, give
The stability of the conductor function phase of high dielectric constant/polymer composites production control and material property brings greatly tired
Difficult and challenge.
In addition, conductor function phase/polymer composites dielectric constant reaches most near conductive filler percolation threshold
When high level, dielectric loss is especially big, reduces conductor function phase/polymer composites breakdown voltage and service performance.
(2) when ferroelectric ceramics function phase volume fraction >=45%, ferroelectric ceramics function phase/polymer composites ability
High dielectric constant is obtained, ferroelectric ceramics function phase/polymer composites mechanical strength and toughness is seriously reduced, increases
Dielectric loss.
Since tensile strength, impact flexibility reduction and dielectric loss increase, so that polymer matrix composite is difficult to reality
Engineer application.It is simple to obtain by metal and carbon nanometer conductive particle or ferroelectricity particle with stable dielectric constant and low
The polymer-based dielectric composite material of dielectric loss.
Summary of the invention
In order to solve the problems, such as exist in current technology, chemical reduction method is utilized the present invention provides a kind of, in barium titanate
Nano grain surface discrete deposits nano-metal particle (such as Ni-BaTiO3、Ag-BaTiO3、Mn-BaTiO3), obtain core-shell structure
Powder；Core-shell structured powder is compounded to form composite material with polymeric matrix (PVDF) again；Prepared composite material is in filler
Under lower content, dielectric constant with higher and lower dielectric loss.
The present invention adopts the following technical scheme that realization.
A kind of core-shell structured powder, including BaTiO3The metallic shell component of nuclear structure and its Surface Creation, the metal
The particle size of shell structurre is 20nm~100nm, preferably 20-80nm, such as 30nm, 50nm；The metal volume content is core
The 1-9vol% of shell structure powder, such as 2.5vol%, 6vol%；The metal is one of nickel, silver, manganese.
The present invention also provides a kind of preparation methods of core-shell structured powder, comprising: is added to barium titanate nano particle and contains
In the ethylene glycol solution of nitrate, thermal reduction processing is cooling, is centrifuged, dry, obtains core-shell structured powder.
The partial size of the barium titanate is 300nm~1 μm, density 6.2g/cm3。
The nitrate is one or more of nickel nitrate, silver nitrate, manganese nitrate.
The mass ratio of the barium titanate nano particle and the nitrate is (45-55): (5-15), preferably 50:(5-15).
The temperature of the thermal reduction processing is 110~160 DEG C, and preferably 120-160 DEG C, the time is 0.2~1h.
During the thermal reduction, system heating rate is 5-6 DEG C/min.
The present invention also provides a kind of polymer-based dielectric composite materials, are a film, are by above-mentioned core-shell structured powder
With PVDF is compound obtains；The film thickness is 30 μm~150 μm, and the core-shell structured powder is in dielectric composite material
Volume fraction is 5%-20%.
Resulting polymers base dielectric composite material dielectric constant with higher of the present invention and lower dielectric loss, with
Ni-BaTiO3For the polymer-based dielectric composite material that core-shell structure particles are prepared:
Work as Ni-BaTiO3When volume fraction of the core-shell structure particles in dielectric composite material is 5%, Ni-BaTiO3Nucleocapsid
For the dielectric constant of the PVDF base dielectric composite material of structure powder up to 52 (100Hz), dielectric loss is only 0.03 (100Hz)；
Work as Ni-BaTiO3When volume fraction of the core-shell structure particles in dielectric composite material is 20%, Ni-BaTiO3Core
For the dielectric constant of the PVDF base dielectric composite material of shell structure up to 3000 (100Hz), dielectric loss is only 0.87 (100Hz).
The present invention also provides a kind of preparation methods of polymer-based dielectric composite material, comprising:
(1) above-mentioned core-shell structured powder is added in PVDF resin solution, ultrasonic vibration, magnetic agitation, is obtained uniform steady
Fixed suspension；
(2) suspension is applied on glass plate, drying obtains Ni-BaTiO3The polymer matrix composite wood of core-shell structure
Material.
Wherein, the core-shell structured powder and PVDF mass ratio are 1:(20~50).
The drying temperature is 60~75 DEG C.
The PVDF resin solution is added in NN- dimethylformamide (DMF) solvent by Kynoar PVDF, is added
Heat, the obtained mixed liquor of magnetic agitation.Wherein, the molecular weight of the PVDF is 28~600,000, density 1.76g/cm3, melt
Melting temperature is 165 DEG C.The mass ratio of the PVDF and DMF is 1:5.The magnetic agitation is carried out at 30~40 DEG C of temperature,
Time is 2~3h.
The invention has the following advantages that
1, the present invention proposes the preparation method of a kind of core-shell structured powder and its polymer-based dielectric composite material, low cost
It is honest and clean, easy to operate.
2, the PVDF base dielectric composite material of core-shell structured powder prepared by the present invention has lower dielectric loss, effectively
Ground avoids semiconductor function phase factor and contacts with each other and form leakage and lead.
3, the PVDF base dielectric composite material dielectric constant with higher of core-shell structured powder prepared by the present invention.
4, the PVDF base dielectric composite material system of core-shell structured powder prepared by the present invention have higher force intensity and
Toughness.
Detailed description of the invention
Fig. 1 is 1vol%Ni discrete deposits in BaTiO3The scanning electron microscopic picture of nano grain surface.
Fig. 2 is the discrete deposits of 2.5vol%Ni in BaTiO3The scanning electron microscopic picture of nano grain surface.
Fig. 3 is 6vol%Ni discrete deposits in BaTiO3The scanning electron microscopic picture of nano grain surface.
Fig. 4 is 9vol%Ni discrete deposits in BaTiO3The scanning electron microscopic picture of nano grain surface.
Fig. 5 is the Ni-BaTiO of different content Ni3The dielectric constant of/PVDF composite material.
Fig. 6 is the Ni-BaTiO of different content Ni3The dielectric loss of/PVDF composite material.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1:Ni-BaTiO3The preparation (Ni content 2.5vol%) of core-shell structured powder
(1) it weighs 5g nickel nitrate and is dissolved in 150ml ethylene glycol solution, obtain nickel nitrate mixed solution；
(2) synthetic reaction.150ml ethylene glycol solution is added into three-necked flask, then 50g barium titanate nano particle is added
Into three-necked flask, finally above-mentioned nickel nitrate mixed solution is added dropwise in three-necked flask, control heating zone with 5 DEG C/
Min heating rate is warming up to 120 DEG C, keeps the temperature 120 DEG C/40min, is then cooled to room temperature with 3 DEG C/min rate.
(3) it is centrifuged.Slurry after synthesis is separated with centrifugal separator, adds water, stirring is centrifuged again, repeats above-mentioned behaviour
Make three times.
(4) slurry after centrifugation is subjected to 40 DEG C of drying 12h.
(5) examine: the particle size of gained Ni shell structurre is 20-50nm.
Embodiment 2:Ni-BaTiO3The preparation (Ni content 6vol%) of core-shell structured powder
(1) nickel nitrate for weighing 8g is dissolved in 150ml ethylene glycol solution, obtains nickel nitrate mixed solution；
(2) synthetic reaction.150ml ethylene glycol solution is added into three-necked flask, then 50g barium titanate nano particle is added
Into three-necked flask, finally above-mentioned nickel nitrate mixed solution is added dropwise in three-necked flask, control heating zone with 5 DEG C/
Min heating rate is warming up to 140 DEG C, keeps the temperature 140 DEG C/20min, is then cooled to room temperature with 3 DEG C/min rate.
(3) it is centrifuged.Slurry after synthesis is separated with centrifugal separator, adds water, stirring is centrifuged again, repeats above-mentioned behaviour
Make three times.
(4) slurry after centrifugation is subjected to 40 DEG C of drying 12h.
(5) examine: the particle size of gained Ni shell structurre is 30-80nm.
Embodiment 3:Ni-BaTiO3The preparation (Ni content 9vol%) of core-shell structured powder
(1) it weighs 15g nickel nitrate and is dissolved in 150ml ethylene glycol solution, obtain nickel nitrate mixed solution；
(2) synthetic reaction.150ml ethylene glycol solution is added into three-necked flask, then 50g barium titanate nano particle is added
Into three-necked flask, finally above-mentioned nickel nitrate mixed solution is added dropwise in three-necked flask, control heating zone with 5 DEG C/
Min heating rate is warming up to 160 DEG C, keeps the temperature 160 DEG C/30min, is then cooled to room temperature with 3 DEG C/min rate.
(3) it is centrifuged.Slurry after synthesis is separated with centrifugal separator, adds water, stirring is centrifuged again, repeats above-mentioned behaviour
Make three times.
(4) slurry after centrifugation is subjected to 40 DEG C of drying 12h.
(5) examine: the particle size of gained Ni shell structurre is 50-80nm.
The preparation of 4 polymer-based dielectric composite material of embodiment
By 1 gained Ni-BaTiO of embodiment3Polymer-based dielectric composite material is further prepared in core-shell structured powder
Film, comprising:
By 1 gained Ni-BaTiO of above-described embodiment3The PVDF resin that concentration 0.2g/ml is added in core-shell structured powder 1.5g is molten
In liquid, ultrasonic vibration, magnetic agitation obtains the suspension of stable homogeneous；Suspension is applied on clean glass plate, dry
It is dry, obtain Ni-BaTiO3The polymer matrix composite film of core-shell structure.
The drying temperature is 70 DEG C, and the time of heating is 12h.
The polymer-based dielectric composite material film with a thickness of 30-150 μm.
The PVDF resin solution is that 10gNN- dimethylformamide (DMF) solvent is added by 2g Kynoar PVDF
In, it heats, magnetic agitation is obtained.The magnetic agitation is carried out at 30 DEG C of temperature, time 2h.
Similarly, 2/3 gained Ni-BaTiO of above-described embodiment34 the method system of embodiment can also be used in core-shell structured powder
Obtain dielectric composite material.
Nickel nitrate in above-described embodiment 1-3 is replaced with into silver nitrate or manganese nitrate, same available corresponding Ag-
BaTiO3Core-shell structured powder, Mn-BaTiO3Core-shell structured powder, and be further prepared Following the procedure of Example 4 corresponding multiple
Condensation material.
Validity check
By Ni-BaTiO obtained by embodiment 1-33The scanning electron microscopic picture of core-shell structured powder is shown in Fig. 2-4.
Dielectric constant, the dielectric loss of PVDF base dielectric composite material as made from embodiment 1-3 are shown in Fig. 5, Fig. 6.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of core-shell structured powder characterized by comprising BaTiO3The metallic shell component of nuclear structure and its Surface Creation；
The particle size of the metallic shell component is 20nm~100nm, preferably 20-80nm；The tenor is core-shell structure powder
The 1-9vol% of body.
2. a kind of preparation method of core-shell structured powder characterized by comprising being added to barium titanate nano particle containing nitric acid
In the ethylene glycol solution of salt, thermal reduction processing is cooling, is centrifuged, dry, obtains core-shell structured powder.
3. preparation method according to claim 2, which is characterized in that the nitrate is nickel nitrate, silver nitrate, manganese nitrate
One or more of.
4. preparation method according to claim 2 or 3, which is characterized in that the barium titanate nano particle and the nitric acid
The mass ratio of salt is (45-55): (5-15), preferably 50:(5-15).
5. according to any preparation method of claim 2-4, which is characterized in that the temperature of the thermal reduction processing is 110
~160 DEG C, preferably 120-160 DEG C.
6. a kind of polymer-based dielectric composite material, which is characterized in that the core-shell structured powder as described in claim 1 is answered with PVDF
Close obtained film；Volume fraction of the core-shell structured powder in dielectric composite material is 5-20%.
7. a kind of preparation method of polymer-based dielectric composite material characterized by comprising
(1) core-shell structured powder described in claim 1 is added in PVDF resin solution, ultrasonic vibration, magnetic agitation, is obtained
One stable suspension；
(2) suspension is applied on glass plate, drying obtains the polymer matrix composite of core-shell structure.
8. preparation method according to claim 7, which is characterized in that the mass ratio of the core-shell structured powder and PVDF is
1:(20~50).
9. preparation method according to claim 7 or 8, which is characterized in that the drying temperature is 60~75 DEG C.
10. according to any preparation method of claim 7-9, which is characterized in that the PVDF resin solution is by poly- inclined
Vinyl fluoride PVDF is added in NN- solvent dimethylformamide, heating, the obtained mixed liquor of magnetic agitation.
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Cited By (3)
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| CN109721894A (en) * | 2018-12-27 | 2019-05-07 | 中国科学院福建物质结构研究所 | Ceramic Composite dielectric film and preparation method thereof applied to capacitor |
| CN109971153A (en) * | 2019-04-04 | 2019-07-05 | 上海安费诺永亿通讯电子有限公司 | A kind of polymer matrix composites and preparation method thereof |
| CN110452421A (en) * | 2019-08-30 | 2019-11-15 | 中南大学 | A kind of dielectric composite material based on core-shell structure filler |
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| CN109721894A (en) * | 2018-12-27 | 2019-05-07 | 中国科学院福建物质结构研究所 | Ceramic Composite dielectric film and preparation method thereof applied to capacitor |
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| CN110452421B (en) * | 2019-08-30 | 2021-05-07 | 中南大学 | Dielectric composite material based on core-shell structure filler |
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Denomination of invention: The invention relates to a core-shell structure powder and a dielectric composite prepared from it Effective date of registration: 20211227 Granted publication date: 20210305 Pledgee: SHANGHAI GUOCI NEW MATERIAL TECHNOLOGY Co.,Ltd. Pledgor: SHANDONG SINOCERA FUNCTIONAL MATERIAL Co.,Ltd. Registration number: Y2021980016312 |
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