CN108511598A - The preparation method of PVDF/ graphene flexible piezoelectric materials and its flexible piezoelectric generator - Google Patents
The preparation method of PVDF/ graphene flexible piezoelectric materials and its flexible piezoelectric generator Download PDFInfo
- Publication number
- CN108511598A CN108511598A CN201810218379.1A CN201810218379A CN108511598A CN 108511598 A CN108511598 A CN 108511598A CN 201810218379 A CN201810218379 A CN 201810218379A CN 108511598 A CN108511598 A CN 108511598A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- graphene
- flexible piezoelectric
- graphenes
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
Abstract
The present invention provides a kind of preparation methods of PVDF/ graphenes flexible piezoelectric material, including：Step S1：PVDF Type of Collective objects are dissolved in organic solvent and obtains PVDF and birdss of the same feather flock together polymer solution, and graphene dispersing solution is added, obtain uniform graphene/PVDF Type of Collective object dispersion liquids；Step S2：So that PVDF/ graphene dispersing solutions is infiltrated a carrying fiber material, then the carrying fiber material is immersed in phase separation agent, and dry, obtains cured PVDF/ graphenes piezoelectric material.The present invention also provides the methods for preparing PVDF/ graphene flexible piezoelectric generators using the piezoelectric material.The present invention realizes rapid curing using phase separation, using graphene and phase separation while promoting polarization, and method simple and effective improves PVDF/ graphene flexible piezoelectric generator piezoelectric properties obtained.
Description
Technical field
The present invention relates to piezoelectric energy conversion arts, and in particular to a kind of flexible piezoelectric electricity generation material and piezoelectric generator
Preparation method.
Background technology
Piezoelectric generator is a kind of device converting mechanical energy to using piezoelectric effect electric energy, and flexible piezoelectric generator
So that human motion energy is collected into possibility.With the quietly rise of wearable device, more and more people conceive to utilize
Energy source of the flexible piezoelectric device as wearable device.Common piezoelectric material such as lead titanates, zinc oxide etc. has to people
The harmful heavy metal of body has rigidity, it is difficult to prepare flexible device.Polyvinylidene fluoride or PVDF
(Polyvinylidene Fluoride) is a kind of high molecular material flexible with piezoelectric properties, nontoxic, and chemistry
Stability is good, is commonly used by people for the preparation of flexible piezoelectric device all the time, if Liu Xia et al. was in ACS Nano the 11st in 2017
Roll up the Polymeric Nanofibers with Ultrahigh Piezoelectricity via Self- of the 5th phase
Method of electrostatic spinning is reported in mono- texts of Orientation of Nanocrystals, prepares the PVDF nanometers of high tension electricity coefficient
Line, but high voltage is needed to polarize, cause energy consumption higher.In Valentina Cauda et al. in ACS Applied in 2013
The Nanoconfinement delivered on Materials＆Interfaces periodicals:an Effective Way to Enhance
In PVDF Piezoelectric Properties, it was recently reported that the PVDF nano-pillars of high-voltage electricity phase are prepared using alumina formwork,
But alumina formwork is expensive, can consume template when PVDF nano-pillars are taken out causes to waste, and inefficiency cannot achieve
It is quickly continuous to prepare.
2016, graphene oxide and aluminium oxide was added in Sumanta Kumar Karan et al. in PVDF, with PMMA
(polymethyl methacrylate) is PVDF piezoelectric devices (the Advanced Energy that substrate prepares high-energy conversion efficiency
Materials2016,1601016).But existing aluminium oxide, graphene oxide+aluminium oxide be using metal cation with
In PVDF fluorine interaction inducing molecule be orientated to form polarization structure (β or γ phases), preparation method can not fast shaping, to
Reduce device preparation efficiency.
Marquis discloses a kind of graphenes of response PVDF/ certainly/elasticity at justice et al. in patent document (CN106370221A)
The preparation method of fabric compound sensor, the preparation method are defeated with strengthening electric current using fibre structure load graphene and PVDF
Go out, but the PVDF of piezoelectric phase in order to obtain, it needs to use high voltage polarization field, to need a large amount of energy consumptions.
In summary, the problems such as preparation method of existing flexible generator is there is poor efficiency, high energy consumption, therefore develop
The preparation method of a kind of energy saving and efficient flexible piezoelectric generator is current urgent problem to be solved.
Invention content
Present invention aims at provide a kind of PVDF/ graphene flexible piezoelectric materials and its flexible piezoelectric generator of preparing
Preparation method reduces energy consumption to improve the production efficiency of PVDF/ graphene flexible piezoelectric materials, and improves PVDF/ stones obtained
The content of the piezoelectricity crystal form of black alkene flexible piezoelectric generator and improve its piezoelectricity output performance.
To achieve the goals above, the present invention provides a kind of preparation method of PVDF/ graphenes flexible piezoelectric material,
It is characterized in that, including：Step S1：PVDF Type of Collective objects are dissolved in organic solvent and obtains PVDF and birdss of the same feather flock together polymer solution, and are added
Enter graphene dispersing solution, obtains uniform graphene/PVDF Type of Collective object dispersion liquids；Step S2：Make PVDF/ graphene dispersing solutions
A carrying fiber material is infiltrated, then the carrying fiber material is immersed in phase separation agent, and is dried, cured PVDF/ is obtained
Graphene flexible piezoelectric material.
The PVDF of step S1 polymer solutions of birdsing of the same feather flock together are uniform by ultrasonic mixing with graphene dispersing solution.
In the step S2, PVDF/ graphene dispersing solutions are completed using infusion process or spray coating method and infiltrate carrying fiber material.
The drying temperature of the step S2 is 40-120 DEG C.
The PVDF Type of Collective object is PVDF, the one of which in modified PVDF.
The organic solvent is N-Methyl pyrrolidone or dimethylformamide.
The carrying fiber is plant fiber or artificial fiber.
The phase separation agent is the mixture of water, salting liquid or water and alcohols solvent.
Mass percent of the PVDF Type of Collective object in the organic solvent is 1-10%, and the graphene is opposite
In PVDF Type of Collective objects solid content be 0.01-3%.
In addition, the present invention also provides a kind of preparation methods of PVDF/ graphenes flexible piezoelectric generator, which is characterized in that
Including：Step S1：PVDF/ graphene pressures made from preparation method according to above-mentioned PVDF/ graphenes flexible piezoelectric material are provided
Electric material；Step S2：Compliant conductive collector is arranged in PVDF/ graphene piezoelectric materials two sides in step sl, and is sealed
Dress, obtains PVDF/ graphene flexible piezoelectric generators.
The present invention realizes the rapid curing of PVDF/ graphene flexible piezoelectric materials using phase separation agent, so that PVDF/
The preparation process of graphene flexible piezoelectric material is simple, quickly, improves production efficiency.Due to not needing extra electric field etc., because
This does not need large-scale particular instrument such as electrostatic spinning machine, and high voltage polarization power supply etc. reduces energy consumption.Preparation process is completely in water simultaneously
It is carried out in phase, therefore environmental protection is at low cost.
The present invention utilizes the hydrogen bond in phase separation agent to polarize the fluorine in PVDF, and the big π of graphene is strong to carry out hydrogen in PVDF
Induce PVDF polarization, with it is existing using metal cation in PVDF fluorine interact inducing molecule be orientated to be formed it is polarized
POLARIZATION MECHANISM is different, and the collective effect of graphene and phase separation improves the content of piezoelectricity crystal form so that PVDF/ graphenes are flexible
The preparation of piezoelectric material is more efficiently quick, and PVDF/ graphene flexible piezoelectric generators obtained is made to generate piezoelectric voltage
Higher, energy density bigger improve the piezoelectricity output performance of generator.
The substrate that the present invention uses is the paper or fiber cloth of porous structure or textile structural, utilizes textile structural
Big specific surface area, substantially increases the piezoelectricity output performance of PVDF/ graphene flexible piezoelectric generators, while remaining former material
The flexibility of material.
Description of the drawings
Fig. 1 is the low range scanning electron microscope of the PVDF/ graphene flexible piezoelectric materials prepared according to the embodiment of the present invention 1
Figure；
Fig. 2 is the high magnification scanning electron microscope of the PVDF/ graphene flexible piezoelectric materials prepared according to the embodiment of the present invention 1
Figure；
Fig. 3 be the PVDF/ graphene flexible piezoelectric materials that are prepared according to the embodiment of the present invention 2 integrate after collector with show
The assembling circuit diagram of wave device；
Fig. 4 A be the PVDF/ graphene flexible piezoelectric generators both ends prepared according to the embodiment of the present invention 2 voltage and
The relation curve of time, wherein the voltage is pressed by finger forms；
Fig. 4 B are the partial enlarged view of the dotted box portion of Fig. 4 A；
Fig. 5 is that the PVDF/ graphene flexible piezoelectric generators prepared according to the embodiment of the present invention 2 are generated in bending
The relation curve of short circuit current and time；
Fig. 6 A-6B are that the PVDF/ graphenes piezoelectric material prepared according to the embodiment of the present invention 3 is preparing front and back photo
Comparison diagram, wherein Fig. 6 A are the facial tissue before preparing, and Fig. 6 B are the piezoelectric material being prepared；
Fig. 7 be according to an embodiment of the invention the voltage at PVDF/ graphenes flexible piezoelectric generator both ends made from 3 and when
Between relation curve, the wherein voltage generates after being under pressure by facial tissue.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The range of invention and is not intended to limit the present invention.
The PVDF/ graphene flexible piezoelectric generators of the present invention are prepared based on following principle：
PVDF has α, beta, gamma, tetra- kinds of crystal forms of θ wherein only β and γ has piezoelectric effect, therefore to prepare high beta, gamma crystalline phase and contain
The PVDF of amount is the key that improve piezoelectric property.First with phase separation method in the present invention, due in phase separation agent hydrogen atom with
The hydrogen bond action that fluorine atom generates on PVDF strands, obtains the ordered structure of high orientation.Secondly, graphene is a kind of two dimension
Crystalline material, the big pi-electron cloud of huge specific surface area and surface interact with the H-shaped on PVDF strands at π-H,
Further obtain the PVDF strands with polarizability.In conjunction with graphene and phase separation method, the mutual increasing of the two is utilized
Pretend use so that PVDF generates high β phases, shows that high pressure is electrical, improves the piezoelectricity output of flexible piezoelectric device.
Embodiment 1 prepares PVDF/ graphene flexible piezoelectric generators
Step S1：It weighs 2.5g PVDF and is dissolved in 100ml NMP (N-Methyl pyrrolidone) solvent by stirring
PVDF solution (mass percents of the PVDF in nmp solvent is 2.5%) is obtained, measures the graphene dispersion of 20mg/ml later
Liquid 3ml (graphene is 3% relative to the solid content of PVDF), PVDF solution and graphene dispersing solution are put into jointly in ultrasonic pond
Ultrasonic disperse is more than 30min, obtains uniform graphene/PVDF dispersion liquids.Wherein, graphene contains in the graphene dispersing solution
Oxygen amount is 0-30%, and lateral dimension is 0.1-100 μm.
Step S2：The non-dust cloth (material is polyester fiber) of use for laboratory is cut into the size of 5*5cm, uses deionized water
After being cleaned with isopropanol, it is dried for standby.Wherein, non-dust cloth is one kind of artificial fiber.Clean non-dust cloth is immersed in step again
It in the PVDF/ graphene dispersing solutions obtained in rapid S1, is taken out after non-dust cloth is saturated with dispersion liquid, has PVDF/ to obtain load
The non-dust cloth of graphene dispersing solution.Dispersion liquid extra on non-dust cloth is then wiped, and in deionized water by its smooth placement,
The deionized water plays the role of phase separation, and the NMP in dispersion liquid is made rapidly to be diffused into water.Deng 1 point of immersion in water
Zhong Hou after that is, nmp solvent is mainly dissolved in water, takes out the graphene-supported non-dust cloths of cured PVDF/, is put into baking oven
It is dried at a temperature of 40 DEG C, obtains PVDF/ graphene flexible piezoelectric materials.
Step S3：Cut the aluminium foil of 2 pieces and PVDF/ graphene flexible piezoelectric material identical shapes as collector, respectively
The both sides of the PVDF/ graphene piezoelectric materials are attached to, finally encapsulation is fixed, and PVDF/ graphene flexible piezoelectric generators are obtained.
Fig. 1 is the low range scanning electron microscope of the PVDF/ graphene flexible piezoelectric materials prepared according to the embodiment of the present invention 1
Figure, it can be seen that non-dust cloth is the textile structural mutually wound, wherein with many apertures and gap.Fig. 2 is according to this hair
The high magnification scanning electron microscope (SEM) photograph of PVDF/ graphene flexible piezoelectric materials prepared by bright embodiment 1, from this figure, it can be seen that nothing
The dirt cloth surface uniform fold thin polymer film of PVDF/ graphenes.
Embodiment 2 prepares PVDF/ graphene flexible piezoelectric generators
Step S1：Uniform PVDF/ graphene dispersing solutions are obtained using method same as Example 1.
Step S2：The non-dust cloth of use for laboratory (material is polyester fiber) is equally cut into the size of 5*5cm, spend from
After sub- water and isopropanol cleaning, it is dried for standby.The PVDF/ graphene dispersing solutions obtained in step S1 are sprayed here with spray gun
It on non-dust cloth, is taken out after non-dust cloth is saturated with dispersion liquid, has the non-dust cloth of PVDF/ graphene dispersing solutions to obtain load.
Dispersion liquid extra on non-dust cloth is then wiped, and in deionized water by its smooth placement, which plays phase point
From effect, so that the NMP in dispersion liquid is rapidly diffused into water.After impregnating 1 minute in water, i.e., nmp solvent is most of
After soluble in water, the graphene-supported non-dust cloths of cured PVDF/ are taken out, is put into baking oven and is dried at a temperature of 120 DEG C, obtained
PVDF/ graphene flexible piezoelectric materials.
Step S3：Cut the aluminium foil of 2 pieces and PVDF/ graphene flexible piezoelectric material identical shapes as collector, respectively
The both sides of the PVDF/ graphene piezoelectric materials are attached to, finally encapsulation is fixed, and PVDF/ graphene flexible piezoelectric generators are obtained.
Fig. 3 is the assembling of the PVDF/ graphene flexible piezoelectric generator and oscillograph that are prepared according to the embodiment of the present invention 2
Circuit diagram, the circuit can be used for measuring voltage output.Fig. 4 A are that the PVDF/ graphenes of 2 preparations according to an embodiment of the invention are soft
Property the voltage at piezoelectric generator both ends and the relation curve of time, the wherein voltage pressed and formed by finger, finger press when just
At the time of being that voltage generates；Fig. 4 B are the partial enlarged view of the dotted box portion of Fig. 4 A.From Fig. 4 A and Fig. 4 B this it appears that：
As finger presses, the PVDF/ graphene flexible piezoelectric generators both ends of the present embodiment can generate the voltage more than 10V.Fig. 5
Be according to an embodiment of the invention the 2 PVDF/ graphene flexible piezoelectric generators prepared in bending the short circuit current that generates with
The relation curve of time.As shown in figure 5, current peak is up to 0.8 μ A.
Embodiment 3 prepares PVDF/ graphene flexible piezoelectric generators
Step S1：It weighs 2.5g PVDF and is dissolved in 100mlDMF (dimethylformamide) solvent that (PVDF exists by stirring
Mass percent in DMF solvent is 2.5%), to obtain PVDF solution, measures the graphene dispersing solution 3ml of 20mg/ml later
PVDF solution and graphene dispersing solution are put into ultrasound point in ultrasonic pond by (solid content 3% of the graphene relative to PVDF) jointly
It dissipates more than 30min, obtains uniform PVDF/ graphene dispersing solutions.
Step S2：Household facial tissue is cut into the blockage of 5*5cm.Wherein, household facial tissue is one kind of plant fiber.Then
The PVDF/ graphene dispersing solutions obtained in step S1 are spread on facial tissue using infusion process, after facial tissue is saturated with dispersion liquid, are scraped
Extra dispersion liquid is wiped, in deionized water, which plays the role of phase separation, makes in dispersion liquid for smooth placement
DMF is rapidly diffused into water.Deng impregnating after five minutes in water, i.e., after solvent DMF is mainly dissolved in water, take out cured
Facial tissue graphene-supported PVDF/ is finally putting into baking oven and is dried at a temperature of 80 DEG C, obtains PVDF/ graphene flexible piezoelectrics
Material.
Step S3：Cut the aluminium foil of 2 pieces and PVDF/ graphene flexible piezoelectric material identical shapes as collector, respectively
The both sides of the PVDF/ graphene piezoelectric materials are attached to, finally encapsulation is fixed, and PVDF/ graphene flexible piezoelectric generators are obtained.
Fig. 6 A-6B are that the 3 PVDF/ graphenes piezoelectric materials prepared are preparing front and back photo according to an embodiment of the invention
Comparison diagram, wherein Fig. 6 A be prepare before facial tissue, Fig. 6 B are the piezoelectric material being prepared, it can be seen that color from white (such as
Shown in Fig. 6 A) become grey (as shown in Figure 6B).Fig. 7 is that PVDF/ graphenes made from 3 are flexible according to an embodiment of the invention
The voltage at piezoelectric generator both ends and the relation curve of time, the wherein voltage generate after being under pressure by facial tissue, and peak value is reachable
26V or more.This shows that the substrate of the PVDF/ graphene flexible piezoelectric generators of the present invention is not limited solely to woven fabric, and can be with
It is the arbitrary fiber insoluble in organic solvent.
Embodiment 4 prepares modified PVDF/ graphene flexible piezoelectric materials
Step S1：It weighs 2.5g PVDF and 0.2g PDMS (dimethyl silicone polymer) and is dissolved in by stirring
PVDF-PDMS solution (mass percents of the PVDF in nmp solvent is 2.5%) is obtained in 100ml DMF solvents, is measured later
The graphene dispersing solution 3ml (graphene is 3% relative to the solid content of PVDF) of 20mg/ml, by PVDF-PDMS solution and graphite
It is more than 30min that alkene dispersion liquid is put into ultrasonic disperse in ultrasonic pond jointly, obtains uniform PVDF-PDMS/ graphene dispersing solutions.Its
In, PVDF, which is added, in PDMS so that PVDF is modified, therefore PVDF-PDMS is a kind of modified PVDF.
Step S2：Blotting paper is cut into the size of 5*5cm.Wherein, blotting paper is one kind of plant fiber, then will water suction
In the PVDF-PDMS/ graphene dispersing solutions that paper submergence obtains in step sl, taken out after blotting paper is saturated with dispersion liquid, to
Obtaining load has the blotting paper of PVDF-PDMS/ graphene dispersing solutions.Then wipe extra dispersion liquid on blotting paper, and by its
In deionized water, which plays the role of phase separation, and the NMP in dispersion liquid is made rapidly to be diffused into for smooth placement
In water.After impregnating 1 minute in water, i.e., after nmp solvent is mainly dissolved in water, take out cured PVDF-PDMS/ graphenes
The blotting paper of load is put into baking oven and is dried at a temperature of 80 DEG C, obtains modified PVDF/ graphene flexible piezoelectric materials.
Embodiment 5 prepares PVDF/ graphene flexible piezoelectric generators
Step S1：It weighs 10g PVDF and is dissolved in 100ml nmp solvents by stirring, obtaining PVDF solution, (PVDF exists
Mass percent in nmp solvent be 10%) measure later 0.25mg/ml graphene dispersing solution 4ml (graphene relative to
0.01%) solid content of PVDF is that PVDF solution and graphene dispersing solution are put into ultrasonic disperse in ultrasonic pond jointly is more than
30min obtains uniform PVDF/ graphene dispersing solutions.
Step S2：Burlap is cut into the size of 5*5cm, after being cleaned with deionized water and isopropanol, is dried for standby.Its
In, burlap is one kind of plant fiber.Recycle spray gun that the PVDF/ graphene dispersing solutions obtained in step S1 are sprayed on burlap
On, it is taken out after burlap is saturated with dispersion liquid, has the burlap of PVDF/ graphene dispersing solutions to obtain load.Then wipe burlap
Upper extra dispersion liquid, and in deionized water by its smooth placement.After impregnating 1 minute in water, i.e., nmp solvent is most of
After soluble in water, the graphene-supported burlaps of cured PVDF/ are taken out, is put into baking oven and is dried at a temperature of 80 DEG C, obtained
PVDF/ graphene flexible piezoelectric materials.
Step S3：Cut the goldleaf of 2 pieces and PVDF/ graphene flexible piezoelectric material identical shapes as collector, respectively
The both sides of the PVDF/ graphene piezoelectric materials are attached to, finally encapsulation is fixed, and PVDF/ graphene flexible piezoelectric generators are obtained.
Embodiment 6 prepares PVDF/ graphene flexible piezoelectric generators
Step S1：It weighs 2.5g PVDF and is dissolved in 100ml nmp solvents by stirring, obtaining PVDF solution, (PVDF exists
Mass percent in nmp solvent is that 2.5%), (graphene is opposite by the graphene dispersing solution 1ml of measurement 0.25mg/ml later
PVDF solid contents 3%), it is more than 30min that PVDF solution and graphene dispersing solution are put into ultrasonic disperse in ultrasonic pond jointly, is obtained
Uniform PVDF/ graphene dispersing solutions.
Step S2：The cotton of use for laboratory is cut into the size of 5*5cm, after being cleaned with deionized water and isopropanol, is dried
It is dry spare.Wherein, cotton is one kind of plant fiber.The PVDF/ graphene dispersing solutions for recycling spray gun that will be obtained in step S1
It is sprayed on cotton, is taken out after cotton is saturated with dispersion liquid, have the cotton of PVDF/ graphene dispersing solutions to obtain load.With
Wipe extra dispersion liquid on cotton afterwards, and by its smooth aqueous solution (1 for being placed on ethyl alcohol:1) in.Deng the aqueous solution in ethyl alcohol
After middle immersion 1 minute, i.e., after nmp solvent is mainly dissolved in water, the graphene-supported cottons of cured PVDF/ is taken out, are put into
Baking oven is dried at a temperature of 80 DEG C, obtains PVDF/ graphene flexible piezoelectric materials.
Step S3：Cut the copper foil of 2 pieces and PVDF/ graphene flexible piezoelectric material identical shapes as collector, respectively
The both sides of the PVDF/ graphene piezoelectric materials are attached to, finally encapsulation is fixed, and PVDF/ graphene flexible piezoelectric generators are obtained.
Embodiment 7 prepares PVDF/ graphene flexible piezoelectric materials
Step S1：It weighs 2.5g PVDF and is dissolved in 100ml nmp solvents by stirring, obtaining PVDF solution, (PVDF exists
Mass percent in nmp solvent is that 2.5%), (graphene is opposite by the graphene dispersing solution 1ml of measurement 0.25mg/ml later
PVDF solid contents 3%), it is more than 30min that PVDF solution and graphene dispersing solution are put into ultrasonic disperse in ultrasonic pond jointly, is obtained
Uniform PVDF/ graphene dispersing solutions.
Step S2：The non-dust cloth (material is polyester fiber) of use for laboratory is cut into the size of 5*5cm, uses deionized water
After being cleaned with isopropanol, it is dried for standby.Spray gun is recycled to be sprayed on the PVDF/ graphene dispersing solutions obtained in step S1 dustless
It on cloth, is taken out after non-dust cloth is saturated with dispersion liquid, has the non-dust cloth of PVDF/ graphene dispersing solutions to obtain load.Then scrape
Dispersion liquid extra on non-dust cloth is wiped, and will be in its smooth aqueous solution (brine concentration 1mol/L) for being placed on salt.Deng eating
After being impregnated 1 minute in salting liquid, i.e., after nmp solvent is mainly dissolved in solution, take out the graphene-supported nothings of cured PVDF/
Dirt cloth is put into baking oven and is dried at a temperature of 80 DEG C, obtains PVDF/ graphene flexible piezoelectric materials.
Embodiment 8 prepares PVDF/ graphene flexible piezoelectric materials
Step S1：It weighs 1g PVDF and is dissolved in 100ml nmp solvents by stirring, obtaining PVDF solution, (PVDF exists
Mass percent in nmp solvent is that 1%), (graphene is with respect to PVDF by the graphene dispersing solution 4ml of measurement 0.25mg/ml later
Solid content 0.1%), it is more than 30min that PVDF solution and graphene dispersing solution are put into ultrasonic disperse in ultrasonic pond jointly, is obtained
Even PVDF/ graphene dispersing solutions.
Step S2：The non-dust cloth (material is polyester fiber) of use for laboratory is cut into the size of 5*5cm, uses deionized water
After being cleaned with isopropanol, it is dried for standby.Spray gun is recycled to be sprayed on the PVDF/ graphene dispersing solutions obtained in step S1 dustless
It on cloth, is taken out after non-dust cloth is saturated with dispersion liquid, has the non-dust cloth of PVDF/ graphene dispersing solutions to obtain load.Then scrape
Dispersion liquid extra on non-dust cloth is wiped, and in deionized water by its smooth placement.After impregnating 1 minute in water, i.e., NMP is molten
After agent is mainly dissolved in water, the graphene-supported non-dust cloths of cured PVDF/ are taken out, is put into baking oven and is dried at a temperature of 80 DEG C
It is dry, obtain PVDF/ graphene flexible piezoelectric materials.
Above-described, only presently preferred embodiments of the present invention is not limited to the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.Made by i.e. every claims applied according to the present invention and description
Simply, equivalent changes and modifications fall within the claims of patent of the present invention.The not detailed description of the present invention is
Routine techniques content.
Claims (10)
1. a kind of preparation method of PVDF/ graphenes flexible piezoelectric material, which is characterized in that including：
Step S1：PVDF Type of Collective objects are dissolved in organic solvent and obtains PVDF and birdss of the same feather flock together polymer solution, and graphene point is added
Dispersion liquid obtains uniform graphene/PVDF Type of Collective object dispersion liquids；
Step S2：So that PVDF/ graphene dispersing solutions is infiltrated a carrying fiber material, then the carrying fiber material is immersed in phase point
It from agent, and dries, obtains cured PVDF/ graphenes flexible piezoelectric material.
2. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that the step
The PVDF of rapid S1 polymer solutions of birdsing of the same feather flock together are uniform by ultrasonic mixing with graphene dispersing solution.
3. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that the step
In rapid S2, PVDF/ graphene dispersing solutions are completed using infusion process or spray coating method and infiltrate carrying fiber material.
4. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that the step
The drying temperature of rapid S2 is 40-120 DEG C.
5. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that described
PVDF Type of Collective objects are PVDF, the one of which in modified PVDF.
6. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that described to have
Solvent is N-Methyl pyrrolidone or dimethylformamide.
7. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that described negative
It is plant fiber or artificial fiber to carry fiber.
8. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that the phase
Release agent is the mixture of water, salting liquid or water and alcohols solvent.
9. the preparation method of PVDF/ graphenes flexible piezoelectric material according to claim 1, which is characterized in that described
Mass percent of the PVDF Type of Collective object in the organic solvent is 1-10%, and the graphene is relative to PVDF Type of Collective
The solid content of object is 0.01-3%.
10. a kind of preparation method of PVDF/ graphenes flexible piezoelectric generator, which is characterized in that including：
Step S1：PVDF/ graphene piezoelectric materials made from any one according to claim 1-9 are provided；
Step S2：Compliant conductive collector is arranged in PVDF/ graphene piezoelectric materials two sides in step sl, and is packaged,
Obtain PVDF/ graphene flexible piezoelectric generators.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810218379.1A CN108511598B (en) | 2018-03-16 | 2018-03-16 | PVDF/graphene flexible piezoelectric material and preparation method of flexible piezoelectric generator thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810218379.1A CN108511598B (en) | 2018-03-16 | 2018-03-16 | PVDF/graphene flexible piezoelectric material and preparation method of flexible piezoelectric generator thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108511598A true CN108511598A (en) | 2018-09-07 |
| CN108511598B CN108511598B (en) | 2020-04-03 |
Family
ID=63376622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810218379.1A Active CN108511598B (en) | 2018-03-16 | 2018-03-16 | PVDF/graphene flexible piezoelectric material and preparation method of flexible piezoelectric generator thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108511598B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN112216787A (en) * | 2020-09-22 | 2021-01-12 | 电子科技大学 | Flexible piezoelectric generator based on PVDF/DAST composite fiber material and preparation method thereof |
| CN113725351A (en) * | 2021-07-16 | 2021-11-30 | 浙江百安医疗科技有限公司 | Polyvinylidene fluoride flower-like graphene composite piezoelectric film and preparation method thereof |
| TWI830926B (en) * | 2020-06-19 | 2024-02-01 | 國立臺灣科技大學 | Electrical responsive graphene-pvdf material and the manufacturing method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966844A (en) * | 2014-05-23 | 2014-08-06 | 青岛大学 | Preparation method of graphene electroconductive composite fiber |
| CN105037763A (en) * | 2015-07-31 | 2015-11-11 | 中国地质大学（北京） | Preparing method for modified graphene oxide-piezoelectric polymer energy-storing thin-film device |
| US20160181952A1 (en) * | 2014-12-19 | 2016-06-23 | Samsung Electronics Co., Ltd. | Energy generating device, and method of manufacturing the same |
| CN105708425A (en) * | 2016-04-06 | 2016-06-29 | 姜凯 | Development of flexible resistance type pressure transducer capable of being applied to human body pulse detection |
| CN106370290A (en) * | 2016-08-23 | 2017-02-01 | 东华大学 | PVDF nanometer fiber/graphene/elastic fiber piezoelectric sensor and its preparation method |
| CN106370221A (en) * | 2016-08-23 | 2017-02-01 | 东华大学 | Self-responsive PVDF/ graphene /elastic fabric composite sensor preparation method |
| CN107732003A (en) * | 2017-09-25 | 2018-02-23 | 中国地质大学（北京） | A kind of preparation method of the PAH/PAMAM self-assembled multilayer films based on piezoelectric membrane |
-
2018
- 2018-03-16 CN CN201810218379.1A patent/CN108511598B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966844A (en) * | 2014-05-23 | 2014-08-06 | 青岛大学 | Preparation method of graphene electroconductive composite fiber |
| US20160181952A1 (en) * | 2014-12-19 | 2016-06-23 | Samsung Electronics Co., Ltd. | Energy generating device, and method of manufacturing the same |
| CN105037763A (en) * | 2015-07-31 | 2015-11-11 | 中国地质大学（北京） | Preparing method for modified graphene oxide-piezoelectric polymer energy-storing thin-film device |
| CN105708425A (en) * | 2016-04-06 | 2016-06-29 | 姜凯 | Development of flexible resistance type pressure transducer capable of being applied to human body pulse detection |
| CN106370290A (en) * | 2016-08-23 | 2017-02-01 | 东华大学 | PVDF nanometer fiber/graphene/elastic fiber piezoelectric sensor and its preparation method |
| CN106370221A (en) * | 2016-08-23 | 2017-02-01 | 东华大学 | Self-responsive PVDF/ graphene /elastic fabric composite sensor preparation method |
| CN107732003A (en) * | 2017-09-25 | 2018-02-23 | 中国地质大学（北京） | A kind of preparation method of the PAH/PAMAM self-assembled multilayer films based on piezoelectric membrane |
Non-Patent Citations (2)
| Title |
|---|
| MOHAMMAD MAHDIABOLHASANI等: "PVDF/graphene composite nanofibers with enhanced piezoelectric performance for development of robust nanogenerators", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
| XIAOYU YUAN等: "A novel PVDF/graphene composite membrane based on electrospun nano fibrous film for oil/water emulsion separation", 《COMPOSITES COMMUNICATIONS 》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485884A (en) * | 2018-11-02 | 2019-03-19 | 北京石油化工学院 | The preparation method of polyvinylidene difluoride film |
| CN109485884B (en) * | 2018-11-02 | 2021-07-09 | 北京石油化工学院 | Preparation method of polyvinylidene fluoride film |
| TWI830926B (en) * | 2020-06-19 | 2024-02-01 | 國立臺灣科技大學 | Electrical responsive graphene-pvdf material and the manufacturing method thereof |
| CN112216787A (en) * | 2020-09-22 | 2021-01-12 | 电子科技大学 | Flexible piezoelectric generator based on PVDF/DAST composite fiber material and preparation method thereof |
| CN113725351A (en) * | 2021-07-16 | 2021-11-30 | 浙江百安医疗科技有限公司 | Polyvinylidene fluoride flower-like graphene composite piezoelectric film and preparation method thereof |
| CN113725351B (en) * | 2021-07-16 | 2024-04-30 | 浙江百安医疗科技有限公司 | Polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108511598B (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108511598A (en) | The preparation method of PVDF/ graphene flexible piezoelectric materials and its flexible piezoelectric generator | |
| Nie et al. | Enhanced performance of a cellulose nanofibrils-based triboelectric nanogenerator by tuning the surface polarizability and hydrophobicity | |
| Xu et al. | A coupled photo-piezo-catalytic effect in a BST-PDMS porous foam for enhanced dye wastewater degradation | |
| Wu et al. | High-performance nanogenerators based on flexible cellulose nanofibril/MoS2 nanosheet composite piezoelectric films for energy harvesting | |
| Mansouri et al. | Investigation on the electrospun PVDF/NP-ZnO nanofibers for application in environmental energy harvesting | |
| CN105810455B (en) | A kind of preparation method of graphene/polyaniline composite film electrode | |
| CN105118688B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material | |
| CN103367629B (en) | Nano generator and preparation method thereof and fiber array preparation method | |
| CN105898981B (en) | A kind of stretchable electrode and preparation method thereof based on conductive fabric | |
| CN107195470B (en) | The nanotube-shaped composite material and preparation method of nickel cobalt iron ternary metal oxide | |
| CN111600511B (en) | Preparation method of one-dimensional carboxylated carbon material-based photovoltaic and wet gas power generation device | |
| CN109341902A (en) | It is a kind of using graphene as pliable pressure sensor of electrode material and preparation method thereof | |
| Kim et al. | Microwave-welded single-walled carbon nanotubes as suitable electrodes for triboelectric energy harvesting from biomaterials and bioproducts | |
| CN106876147A (en) | Self-charging energy device based on fabric and preparation method thereof | |
| CN105543991A (en) | Graphene fibers of helical structure and preparation method and application of graphene fibers | |
| CN109755035A (en) | A kind of preparation method of imitative shell stratiform high strength graphite alkene combination electrode material | |
| CN106971865A (en) | A kind of Polymerization of Polyaniline/carbon Nanotube with high specific capacitance/bafta composite and flexible electrode and its preparation and application | |
| Wang et al. | Intelligent nanomaterials for solar energy harvesting: from polar bear hairs to unsmooth nanofiber fabrication | |
| CN103388197B (en) | A kind of preparation method of graphene fiber | |
| CN103762356B (en) | Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application | |
| CN108462402B (en) | A kind of friction nanometer power generator and preparation method thereof based on leaf and leaf dusty material | |
| Zu et al. | Humidity-resistant, durable, wearable single-electrode triboelectric nanogenerator for mechanical energy harvesting | |
| CN108505213A (en) | A kind of preparation method of amino graphene/polyunsymfluorethylepiezoelectric piezoelectric nanometer electrospinning film | |
| CN114530287B (en) | Fabric wet power generation material based on molybdenum disulfide, preparation method and application thereof | |
| Guo et al. | Triboelectric nanogenerator-based near-field electrospinning system for optimizing PVDF fibers with high piezoelectric performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |