CN107195836A - A kind of Piezoelectric Driving self-charging battery barrier film and preparation method thereof - Google Patents
A kind of Piezoelectric Driving self-charging battery barrier film and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/46—Accumulators structurally combined with charging apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention proposes a kind of Piezoelectric Driving self-charging battery barrier film and preparation method thereof, and the barrier film is a kind of PVDF/BCT BZT Piezoelectric anisotropy films including fibrous piezoelectric BCT BZT and polymer P VDF；Wherein, BCT BZT are 0.5 (Ba0.7Ca0.3)TiO3‑0.5Ba(Ti0.8Zr0.2)O3, PVDF is polyvinylidene fluoride.0.5 (Ba is prepared using method of electrostatic spinning0.7Ca0.3)TiO3‑0.5Ba(Ti0.8Zr0.2)O3(being abbreviated as BCT BZT) nanofiber, and it is compound in the film as piezoelectric phase, obtain the PVDF/BCT BZT nano compound films with loose structure.The present invention carries out fibrous leadless piezoelectric material material BCT BZT and traditional SCPC diaphragm materials PVDF composite modified, so that the purer pvdf membrane of the composite diaphragm has more pore structures and Geng Gao piezoelectric response potential, so as to significantly improve the piezoelectricity of the SCPC, self-charging and chemical property.
Description
Technical field
The invention belongs to the technical field of high polymer material, and in particular to one kind is used for Piezoelectric Driving self-charging battery barrier film
PVDF/BCT-BZT Piezoelectric anisotropies film and the film preparation method
Background technology
, the leader that the seminar being made up of Xue Xin spaces and Wang Sihong etc. is taught in Georgia Institute of Technology Wang Zhonglin in 2012
Under, a kind of brand-new structure mechanism is proposed first, and this brand-new mechanism melts energy conversion with two processes of energy stores
Synthesize step realization.They make two kinds of structure fusions of nano generator and lithium battery into one using cleverly device structure design
Individual device cell --- self-charging energy unit (i.e. self-charging power cell, are abbreviated as SCPC).This fills certainly
Electric flux unit can directly utilize mechanical oscillation or deformation in surrounding environment to complete the process of self power generation and charging, realize
Mechanical energy is directly changed and stored in single device.Because self-charging energy unit is similar to battery, and its is basic
Structure is the structure based on battery, and self-charging energy unit is also referred to as self-charging battery.(Xue X,Wang S,Guo W,et
al.Hybridizing energy conversion and storage in a mechanical-to-
electrochemical process for self-charging power cell[J].Nano Letters,2012,12
(9):5048-5054.)
The structure design of self-charging battery is basic structure (including positive pole, barrier film, negative pole and the electrolysis in lithium ion battery
Liquid) basis on, use with piezo-electric effect polyvinylidene fluoride (PVDF) film substitution lithium ion battery in polyethylene
(PE) film as self-charging battery barrier film.Pvdf membrane after polarization has good piezo-electric effect, when it is by outside
When pressure, compressive deformation can occur in the vertical direction for pvdf membrane, and this to produce on PVDF thickness direction
One negative pole is pointed to by positive pole piezoelectric field.In the presence of the piezoelectric field, the lithium ion in electrolyte then can be from electricity
The positive pole in pond is nearby moved near negative pole by pvdf membrane, to shield piezoelectric field.The movement of lithium ion changes electrolyte
Being uniformly distributed for middle lithium ion, destroys the balance of the redox reaction at battery plus-negative plate, passes through this piezoelectricity electrochemistry
Process realizes the self-charging reaction of battery.As can be seen here, it is to influence the pass of SCPC performances as the PVDF base films of piezoelectricity barrier film
Key is constituted, therefore one high performance piezoelectricity barrier film of exploitation can be widely using extremely important to SCPC.
Modification for SCPC PVDF base piezoelectricity barrier films at present mainly has two methods, and a kind of is the means using etching
Obtain porous pure β phases PVDF thin film (Kim Y S, Xie Y, Wen X, et al.Highly porous piezoelectric
PVDF membrane as effective lithium ion transfer channels for enhanced self-
charging power cell[J].Nano Energy,2015,14:77-86. and Xing L, Nie Y, Xue X, et
al.PVDF mesoporous nanostructures as the piezo-separator for a self-charging
power cell[J].Nano Energy,2014,10:44-52.), another is that piezoelectricity is carried out on the basis of PVDF thin film
Phase it is compound, the report of the current direction is also seldom, only 2014 Nian Zhang rocks seminars propose by PZT nano particles and PVDF
It is compound to obtain in the research that PVDF-PZT nano compound films are applied to Piezoelectric Driving self-charging battery, text being to use directly
The PVDF-PZT that PVDF powders are coated with again after being well mixed with PZT nano particles in DMF, dry method is obtained is nano combined
Film.(Zhang Y,Zhang Y,Xue X,et al.PVDF-PZT nanocomposite film based self-
charging power cell[J].Nanotechnology,2014,25(10):105401.).Selected in text as piezoelectricity
Mutually compound PZT nano particles, although so that SCPC piezoelectricity output improves, but laminated film porosity not
Height, and the doping of nanoparticle can hinder the transmission of lithium ion in the film on the contrary to a certain extent.
Li Cheng in 2015 propose the method (Li that a kind of utilization electrostatic spinning prepares BCT-BZT nano short fibers
Cheng, Miaomiao Yuan, Long Gu etc.Wireless power-free and implantable
Nanosystem for resistance-based biodetection.Nano Energy (2015) 15,598-606), but
The relation and laminated film of its relation of milling time and fibre length to chopped fiber, the proportioning of fiber and film porosity
The problems such as influence of thickness, is not directed to.
The optimum process condition that the present invention is determined according to early stage many experiments, first by BCT- that average length is 5-6 μm
BZT piezoelectric fabrics and piezoelectricity barrier film of the compound obtained films with loose structure of PVDF as self-charging battery, and determine
Suitable BCT-BZT fibers and the proportioning of PVDF matrixes and its influence to laminated film porosity, and suitable piezoelectricity
The parameters such as membrane thicknesses.Wherein, the nanofiber for this random orientation that spinning is obtained can be in polymer compared to nano particle
Middle generation more continuous and quick ionic conduction path, the mode phase of laminated film is prepared with traditional doped nanoparticle
Than it is an advantage of the present invention that the chopped fiber club shaped structure that BCT-BZT piezoelectrics are first made into uniqueness is answered with PVDF again
Close, transport of the lithium ion in barrier film is greatly facilitated in this, simultaneously because stacking and the PVDF solidification of fiber, the laminated film
Also there is preferable pore structure, so that the SCPC using PVDF/BCT-BZT nano compound films as barrier film has excellent pressure
Electricity, self-charging and chemical property.At present, it is not combined both at home and abroad on BCT-BZT piezoelectric fabrics and PVDF polymer also
Piezoelectric membrane is used for the report of Piezoelectric Driving self-charging battery.
The content of the invention
Technical problem：It is used for Piezoelectric Driving self-charging battery barrier film and preparation method thereof, the pressure the invention provides one kind
Electric drive self-charging battery barrier film PVDF/BCT-BZT porosity and the purer PVDF thin film of piezoelectric response potential is greatly increased, together
When by it be applied to Piezoelectric Driving self-charging battery when, use the battery of laminated film compared with the battery using pure PVDF as barrier film
Piezoelectricity, self-charging and chemical property be obviously improved.Present invention also offers a kind of PVDF/BCT-BZT Piezoelectric anisotropies are thin
The preparation method of film.
Technical scheme：Above-mentioned technical problem is solved, provided by the present invention for Piezoelectric Driving self-charging battery barrier film
PVDF/BCT-BZT Piezoelectric anisotropy films, it includes fibrous piezoelectric BCT-BZT and polymer P VDF.Surveyed through experiment
It is fixed, both can be with enhanced film by being compounded with the BCT-BZT piezoelectric fabrics that mass percent is 10~30% in PVDF thin film
Piezoelectricity potential can obtain porous structure again.Contrasted by the SCPC with not compound pure PVDF thin film assembling, with
PVDF/BCT-BZT nano compound films show higher piezoelectricity potential, lower electro transfer impedance for the SCPC of barrier film
Lower inducing capacity fading, while also presenting a self-charging effect driven well by piezoelectricity potential.This method is operated
Simply, to experiment condition control is nor very high, and using common apparatus, BCT-BZT is novel lead-free piezoresistive material in addition
Material, it is more environmentally friendly more harmless than traditional leaded PZT systems piezoelectric, it is adapted to popularization and application, and the uniqueness obtained by electrostatic spinning
BCT-BZT chopped fibers structure be more beneficial for the biography of lithium ion in the film than conventional compound in the form of nano particle
It is defeated, so exploitation PVDF/BCT-BZT Piezoelectric anisotropies film has great to the practical application for promoting the self-charging battery of Piezoelectric Driving
Meaning.
The Piezoelectric Driving self-charging battery barrier film of the present invention is a kind of including fibrous piezoelectric BCT-BZT and polymerization
Thing PVDF PVDF/BCT-BZT Piezoelectric anisotropy films；Wherein, BCT-BZT is 0.5 (Ba0.7Ca0.3)TiO3-0.5Ba
(Ti0.8Zr0.2)O3, PVDF is polyvinylidene fluoride.
The preparation method for Piezoelectric Driving self-charging battery barrier film of the present invention comprises the following steps：
Step 1, sol-gel process prepared composition is used for 0.5 (Ba0.7Ca0.3)TiO3-0.5Ba(Ti0.8Zr0.2)O3Referred to as
BCT-BZT colloidal sols；
Step 2, the BCT-BZT colloidal sols obtained to step 1 carry out electrostatic spinning and heat treatment operation, become BCT-BZT
Piezoelectric fabric；
Step 3, the BCT-BZT piezoelectric fabrics grinding for obtaining step 2 turn into chopped fiber rod；
Step 4, BCT-BZT piezoelectricity chopped fiber rods and PVDF powder that step 3 is obtained are dissolved in DMF solvent, are passed through
0.5~1.5h of magnetic agitation, obtains uniform solution mixing；
Step 5, step 4 resulting solution mixed into ultrasonically treated 0.5~1.5h；
Step 6, in the substrate of glass thoroughly cleaned with alcohol and acetone, by step 5 resulting solution mixing scraper
It is uniformly coated to above；
Step 7, the coated solution of step 6 mixed together it is put into 80~90 DEG C of air blast together with following substrate of glass and does
Dry case drying, makes DMF solvent volatilize completely；
Step 8, through fully dry after, film is taken off from substrate of glass, you can obtain PVDF/BCT-BZT piezoelectricity answer
Close film.
Piezoelectric anisotropy film obtained by the step 8, is placed on 2~3h of polarization in 80~100 DEG C of high voltage electric fields, makes
Electricdomain is along direction of an electric field orientations.
Piezoelectric anisotropy film after polarization, is made into a diameter of 19mm disk, is used as piezoelectricity barrier film assembling self-charging
Battery.
Milling time is 0.5~1.5h in the step 3 so that the length of fiber rod is 5~6um, to keep more single
Spontaneous polarization orientation.
In mixed solution described in the step 4, piezoelectric BCT-BZT mass percent is 10~30%.
Described in the step 6 with painting work of the scraper to solution, wherein the scraper selected is highly 20~90 μm.
The structure design of described Piezoelectric Driving self-charging battery be lithium ion battery basic structure (including positive pole,
Barrier film, negative pole and electrolyte) basis on, using the porous compound PVDF/BCT-BZT films with piezo-electric effect replace lithium from
Polyethylene (PE) film is as the barrier film of self-charging battery in sub- battery, and the present invention is not intended to limit both positive and negative polarity and electrolyte etc. in battery
The selection of composition.
Beneficial effect：PVDF/BCT-BZT Piezoelectric anisotropies for Piezoelectric Driving self-charging battery barrier film prepared by the present invention
Film, not only with the piezoelectric response potential of enhanced film but also can obtain porous structure.By thin with not compound pure PVDF
The SCPC of film assembling is contrasted, and the SCPC using PVDF/BCT-BZT nano compound films as barrier film shows higher piezoelectricity
Potential, lower electro transfer impedance and lower inducing capacity fading, are driven by piezoelectricity potential well while also presenting one
Self-charging effect.This method is simple to operate, and the control to experiment condition is nor very high, using common apparatus, in addition
BCT-BZT is novel lead-free piezoelectric, more environmentally friendly more harmless than traditional leaded PZT systems piezoelectric, is adapted to popularization and application, and
And the unique BCT-BZT chopped fibers structure obtained by electrostatic spinning is compound more favourable in the form of nano particle than routine
In the transmission of lithium ion in the film so that the Piezoelectric Driving self-charging electricity by barrier film of PVDF/BCT-BZT Piezoelectric anisotropies film
Pond has excellent piezoelectricity, self-charging and chemical property.
Brief description of the drawings
Fig. 1 is the SEM figures of the PVDF/BCT-BZT laminated films prepared by the method for the invention,
Fig. 2 is the structural representation of the SCPC using PVDF/BCT-BZT laminated films,
Fig. 3 is that the piezoelectric voltage using the SCPC of PVDF/BCT-BZT laminated films under the effect of different ambient pressures is defeated
Go out,
Fig. 4 is the typical self-charging figure of the SCPC using PVDF/BCT-BZT laminated films,
Fig. 5 is the cycle life contrast that pure PVDF barrier films and PVDF/BCT-BZT composite diaphragms are used for after SCPC.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：PVDF/BCT-BZT piezoelectricity in present embodiment for Piezoelectric Driving self-charging battery is answered
The preparation method for closing film is followed the steps below：
Step 1, use routine sol-gel process prepared composition for 0.5 (Ba0.7Ca0.3)TiO3-0.5Ba
(Ti0.8Zr0.2)O3The colloidal sol of (being abbreviated as BCT-BZT)；
Step 2, the colloidal sol obtained to step 1 carry out electrostatic spinning and heat treatment operation, become BCT-BZT piezoelectricity fine
Dimension；
Step 3, the piezoelectric fabric for obtaining step 2 are first crumbed, then grind 0.5~1.5h by hand so that the length of fiber rod
Spend for 5~6um；
Step 4, BCT-BZT piezoelectricity chopped fiber and PVDF powder that step 3 is obtained are dissolved in DMF solvent, and control is mixed
The mass percent for closing piezoelectric BCT-BZT in solution is 10~30%, and by 0.5~1.5h of magnetic agitation, makes solution
It is well mixed；
Step 5, by the ultrasonically treated 0.5~1.5h of step 4 resulting solution；
Step 6, in the substrate of glass thoroughly cleaned with alcohol and acetone, by step 5 resulting solution thickness be 20
~90 μm of scraper is uniformly coated to above；
Step 7, the coated solution of step 6 together with following substrate of glass is together put into 80~90 DEG C of air dry ovens
Drying, makes DMF solvent volatilize completely；
Step 8, after fully drying, film is gently taken off from substrate of glass with tweezers, you can obtain PVDF/BCT-
BZT Piezoelectric anisotropy films；
Step 9, step 8 gained film is placed in 80~100 DEG C of electric fields with 300V 2~3h of high voltage polarization, makes electricdomain edge
Direction of an electric field orientations；
Step 10, step 9 is polarized after a diameter of 19mm of film knock disk, be assembled into as piezoelectricity barrier film from filling
The main composition of battery, wherein self-charging battery includes：LiCoO2Positive pole, carbon based negative electrodes, PVDF/BCT-BZT Piezoelectric anisotropies
Film is barrier film and LiPF6The electrolyte of base.
Embodiment two：Present embodiment is ground from step 3 unlike embodiment one to piezoelectric fabric
1h is ground, it is other identical with embodiment one.
Embodiment three：Controlled in step 4 unlike one of present embodiment and embodiment one or two
Piezoelectric BCT-BZT mass percent is 20% in mixed solution.It is other identical with one of embodiment one or two.
Embodiment four：To mixed in step 4 unlike one of present embodiment and embodiment one to three
Solution magnetic agitation 1h is closed, it is other identical with one of embodiment one to three.
Embodiment five：Stirred in step 5 unlike one of present embodiment and embodiment one to four
1h ultrasonically treated to mixed solution again afterwards.It is other identical with one of embodiment one to four.
Embodiment six：Selected in step 6 unlike one of present embodiment and embodiment one to five
Highly solution is coated for 30 μm of scraper.It is other identical with one of embodiment one to five.
Embodiment seven：Dried in step 7 unlike one of present embodiment and embodiment one to six
Temperature selection be 85 DEG C.It is other identical with one of embodiment one to six.
Embodiment eight：Polarized in step 9 unlike one of present embodiment and embodiment one to seven
Temperature is 90 DEG C, and the polarization time is 2.5h.It is other identical with one of embodiment one to seven.
Embodiment nine：Assembled in step 10 unlike one of present embodiment and embodiment one to eight
It is negative pole that CNTs is selected during self-charging battery.It is other identical with one of embodiment one to eight.
Using following experimental verifications effect of the present invention：
PVDF/BCT-BZT Piezoelectric anisotropy films for Piezoelectric Driving self-charging battery
Experiment：This experiment is divided into experimental group and control group.Experimental group is the Piezoelectric anisotropy film for preparing PVDF/BCT-BZT,
Control group is to prepare pure PVDF thin film.
The PVDF/BCT-BZT for Piezoelectric Driving self-charging battery of experimental group Piezoelectric anisotropy film, specifically by with
What lower step was completed：
Step 1, use routine sol-gel process prepared composition for 0.5 (Ba0.7Ca0.3)TiO3-0.5Ba
(Ti0.8Zr0.2)O3The colloidal sol of (being abbreviated as BCT-BZT)；
Step 2, the colloidal sol obtained to step 1 carry out electrostatic spinning and heat treatment operation, become BCT-BZT piezoelectricity fine
Dimension；
Micro alcohol is added in step 3, present mortar, the fabric crumbed by hand is poured into mortar, 1h is ground.
Step 4,0.4g BCT-BZT piezoelectric fabrics are dissolved in 12mL DMF solvents in 1.6g PVDF powder, that is, mixed
The mass percent for closing piezoelectric BCT-BZT in solution is 20%, then by magnetic stirrer 1h, to being completely dissolved.
Step 5, by the ultrasonically treated 1h of the mixed solution being stirred.
Step 6, first thoroughly clean substrate of glass with alcohol and acetone, then with thickness be 30 μm of scraper by step 5 ultrasound
Good mixed solution is uniformly coated in substrate.
Step 7, by coated solution together with following substrate of glass be put into 85 DEG C of air dry ovens dry, make
DMF solvent volatilizees completely.
Step 8, after fully drying, film is gently taken off from substrate of glass with tweezers, you can obtain PVDF/BCT-
BZT Piezoelectric anisotropy films, its pattern is as shown in Figure 1, it can be seen that the length of BCT-BZT fibers rod is maintained at 5~6 μm in film
Between, and film has good pore structure.
Step 9, film is cut to long 4cm, wide 3cm rectangular sheet, and copper foil is stained with respectively in the upper and lower surface of film,
Two wires are drawn again and are respectively connected to the both positive and negative polarity of high voltage power supply, and are put into polarization, polarizing voltage in 90 DEG C of thermostatic drying chamber
For 300V, after the 2.5h that polarizes, the temperature of drying box is closed, power strength is maintained, power supply is closed after it is cooled to room temperature.
Step 10, step 9 is polarized after a diameter of 19mm of film knock disk, be assembled into as piezoelectricity barrier film from filling
Battery.Piezoelectric Driving self-charging battery need to complete assembling in vacuum glove box, and its primary structure includes：LiCoO2For just
Pole, CNTs is negative pole, and PVDF/BCT-BZT Piezoelectric anisotropies film is barrier film and LiPF6The electrolyte of base, schematic diagram such as Fig. 2.
The preparation method of the pure PVDF piezoelectric membranes of control group is：
Step 1：The PVDF powder for weighing 2g is dissolved in 12mL DMF solution, by magnetic stirrer 1h, to complete
Dissolving.
Step 5, by the ultrasonically treated 1h of the mixed solution being stirred.
Step 6, first thoroughly clean substrate of glass with alcohol and acetone, then with thickness be 30 μm of scraper by step 5 ultrasound
Good mixed solution is uniformly coated in substrate.
Step 7, by coated solution together with following substrate of glass be put into 85 DEG C of air dry ovens dry, make
DMF solvent volatilizees completely.
Step 8, after fully drying, film is gently taken off from substrate of glass with tweezers, you can obtain pure PVDF pressures
Electric laminated film.
Step 9, film is cut to long 4cm, wide 3cm rectangular sheet, and copper foil is stained with respectively in the upper and lower surface of film,
Two wires are drawn again and are respectively connected to the both positive and negative polarity of high voltage power supply, and are put into polarization, polarizing voltage in 90 DEG C of thermostatic drying chamber
For 300V, after the 2.5h that polarizes, the temperature of drying box is closed, power strength is maintained, power supply is closed after it is cooled to room temperature.
Step 10, step 9 is polarized after a diameter of 19mm of film knock disk, be assembled into as piezoelectricity barrier film from filling
Battery.Piezoelectric Driving self-charging battery need to complete assembling in vacuum glove box, and its primary structure includes：LiCoO2For just
Pole, CNTs is negative pole, and PVDF/BCT-BZT Piezoelectric anisotropies film is barrier film and LiPF6The electrolyte of base,
Fig. 3 can be seen that the output voltage and the size of external energy using the SCPC of PVDF/BCT-BZT piezoelectric membranes
It is directly proportional, when applying 588mJ external force, it responds voltage and is up to 7V, shows good piezoelectric property.
Fig. 4 is a typical self-charging battery based on PVDF/BCT-BZT nanometer combined electrodes in periodic machinery
The part of red shade is battery in periodic machinery pressure masterpiece in self-charging cyclic process schematic diagram under pressure effect, figure
With the process of lower charging, voltage is kept rising, and the electric current circulated by outside batteries is 0, and blue shading part is shown
It is discharge process of the energy of storage when electric current is 1 μ A.It is 294mJ frequencies when acting on the energy size on self-charging battery
During for 0.5Hz, 950mV has been risen to from initial 800mV by the voltage of 600s self-charging batteries.When charging process terminates
Afterwards, battery has returned to initial voltage when discharge current is 0.01mA by 120s.By can be calculated in PVDF/BCT-
The capacity stored in BZT nanometer combined electrode self-charging batteries is 0.35 μ Ah.
In Fig. 5, the SCPC containing laminated film and pure PVDF thin film is circulated 80 times respectively, and with the initial of compound SCPC
Discharge capacity is the discharge capacity Q ' of standardizationdWhen, the capacity of initial pure PVDF thin film is only compound 87.6%, while 80
After secondary circulation terminates, the capacity attenuation of laminated film is only 32.8%, and pure PVDF decay illustrates to select PVDF/ more than 50%
BCT-BZT laminated films can improve the SCPC of pure PVDF barrier films cycle performance and service life, and this is due to that its is porous
Structure can produce more lithium ion transport passages, so as to promote electrochemical reaction.
Purpose that the embodiment above is merely to illustrate that and the example lifted, rather than for being limited, it is all
Any modification, equivalent substitution for being made under teachings of the present application and claims etc., should be included in the application will
In the range of asking protection.
Claims (7)
1. a kind of Piezoelectric Driving self-charging battery barrier film, it is characterised in that the barrier film is a kind of including fibrous piezoelectric
BCT-BZT and polymer P VDF PVDF/BCT-BZT Piezoelectric anisotropy films；Wherein, BCT-BZT is 0.5 (Ba0.7Ca0.3)
TiO3-0.5Ba(Ti0.8Zr0.2)O3, PVDF is polyvinylidene fluoride.
2. a kind of preparation method as claimed in claim 1 for Piezoelectric Driving self-charging battery barrier film, it is characterized in that be,
The preparation method comprises the following steps：
Step 1, sol-gel process prepared composition is used for 0.5 (Ba0.7Ca0.3)TiO3-0.5Ba(Ti0.8Zr0.2)O3Abbreviation BCT-
BZT colloidal sols；
Step 2, the BCT-BZT colloidal sols obtained to step 1 carry out electrostatic spinning and heat treatment operation, become BCT-BZT piezoelectricity
Fiber；
Step 3, the BCT-BZT piezoelectric fabrics grinding for obtaining step 2 turn into chopped fiber rod；
Step 4, BCT-BZT piezoelectricity chopped fiber rods and PVDF powder that step 3 is obtained are dissolved in DMF solvent, pass through magnetic force
0.5~1.5h is stirred, uniform solution mixing is obtained；
Step 5, step 4 resulting solution mixed into ultrasonically treated 0.5~1.5h；
Step 6, in the substrate of glass thoroughly cleaned with alcohol and acetone, step 5 resulting solution mixing is uniform with scraper
Ground is coated on above；
Step 7, the coated solution of step 6 is mixed together it is put into 80~90 DEG C of air dry ovens together with following substrate of glass
Drying, makes DMF solvent volatilize completely；
Step 8, through fully dry after, film is taken off from substrate of glass, you can obtain PVDF/BCT-BZT Piezoelectric anisotropies thin
Film.
3. the preparation method according to claim 2 for Piezoelectric Driving self-charging battery barrier film, it is characterised in that described
Piezoelectric anisotropy film obtained by step 8, is placed on 2~3h of polarization in 80~100 DEG C of high voltage electric fields, makes electricdomain along electric field side
To orientations.
4. the preparation method according to claim 3 for Piezoelectric Driving self-charging battery barrier film, it is characterised in that described
Piezoelectric anisotropy film after polarization, is made into a diameter of 19mm disk, and self-charging battery is assembled as piezoelectricity barrier film.
5. the preparation method according to claim 2 for Piezoelectric Driving self-charging battery barrier film, it is characterised in that step
Milling time is 0.5~1.5h in 3 so that the length of fiber rod is 5~6um, to keep more single spontaneous polarization to be orientated.
6. the preparation method according to claim 2 for Piezoelectric Driving self-charging battery barrier film, it is characterised in that in step
In mixed solution described in rapid 4, piezoelectric BCT-BZT mass percent is 10~30%.
7. the preparation method according to claim 2 for Piezoelectric Driving self-charging battery barrier film, it is characterised in that step
Described in 6 with painting work of the scraper to solution, wherein the scraper selected is highly 20~90 μm.
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| CN109097841A (en) * | 2018-07-24 | 2018-12-28 | 哈尔滨理工大学 | A kind of anisotropy nanofiber Kynoar based composite dielectric and preparation method thereof |
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| CN115262088A (en) * | 2022-07-18 | 2022-11-01 | 河南师范大学 | Preparation method of PVDF (polyvinylidene fluoride) composite film for improving piezoelectric/triboelectric output performance |
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