CN102954848A - Novel flexible mechanical sensor and preparation method thereof - Google Patents
Novel flexible mechanical sensor and preparation method thereof Download PDFInfo
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- CN102954848A CN102954848A CN2011102350472A CN201110235047A CN102954848A CN 102954848 A CN102954848 A CN 102954848A CN 2011102350472 A CN2011102350472 A CN 2011102350472A CN 201110235047 A CN201110235047 A CN 201110235047A CN 102954848 A CN102954848 A CN 102954848A
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Abstract
The invention relates to a novel flexible mechanical sensor which consists of a nanofiber film layer and a conductive film electrode layer. The nanofiber film layer is made of piezoelectric material polyvinylidene fluoride or polyvinylidene fluoride-fluoro-olefine copolymer, and the molar weight of the polyvinylidene fluoride in the polyvinylidene fluoride-fluoro-olefine copolymer is 55-85% and is preferably 70-80%. The invention further provides a preparation method of the flexible mechanical sensor.
Description
Technical field
The present invention relates to a kind of novel flexible mechanics sensor, specifically a kind of piezoelectricity sensor and preparation method thereof.
Background technology
Sensor is a kind of device or the device that can experience measured change information and change information is converted into the desired form output signal according to certain rule.Sensor is converted into other desired form signals with the signal of measuring, thereby perception, transmission and the processing of the information of realization are the fundamentals that realization automatically detects and automatically controls.Wherein, mechanics sensor is the most common a kind of.Prior art provides the mechanics sensor of various ways for various application, such as resistance-type, condenser type, piezoelectric type mechanics sensor.Wherein resistance-type and condenser type are that passive sensor needs additional power source, have increased like this complicacy of device circuitry designing and making.Piezoelectric transducer is active device, is widely used in multiple fields.
Piezoelectric sensing device material mostly is piezoelectric ceramics in the prior art, piezoelectric ceramics have good piezoelectric property and cost of material lower, but the mechanical property of stupalith (large such as hardness, elasticity is little, gas penetration potential is poor etc.) has limited the application of such devices aspect medical treatment, dress ornament and measuring of human health greatly.Piezoelectric polymeric materials take polyvinylidene fluoride (PVDF) as representative has overcome the difficulty of piezoelectric ceramics on using to a certain extent, yet the plasticity piezoelectricity macromolecule membrane that existing method for making obtains, still restrict the mechanical property of device, can't satisfy in fields such as medical treatment, dress ornaments the requirement to device high sensitivity and pliability, gas penetration potential fully.
Existing piezoelectric polymer masking technique flow process: mixed material → film forming → stretching → thermal treatment → corona polarizing → top electrode.Wherein film forming procedure utilizes existing fusion method or solvent evaporation method, and the gentle gas penetration potential of the film that obtains is poor and pliability is not enough.In addition, existing technology is for obtaining excellent sensitivity, and the processing that will stretch and polarize after the film forming so that operation increases, has increased the processing complexity, and correspondingly increased the equipment and process cost.
Therefore, improve the mechanical property of device, improve the sensitivity of device, provide a kind of satisfied medical treatment, dress ornament field application requirements softness, novel flexible mechanics sensor ventilative, that have biocompatibility and preparation method thereof is of great immediate significance.
Summary of the invention
The objective of the invention is to improve the mechanical property of senser element, take into account device sensitivity, provide the fields such as a kind of satisfied medical treatment, dress ornament to flexible mechanics sensor and the related manufacturing processes thereof of senser element in requirement aspect sensitivity, pliability, gas penetration potential and the biocompatibility.
Aspect first, the invention provides by nano-fiber film layer and conductive film electrode layer and form, it is characterized in that described nano-fiber film layer made by polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers; Described conductive film electrode layer is made by flexible porous electrode, it is configured on the surface and both sides, the back side of described nano-fiber film layer, the molar content of polyvinylidene fluoride is 55-85% in wherein said polyvinylidene fluoride-fluorinated olefin copolymers, preferred 70-80%.
Aspect second, the invention provides a kind of method for preparing the piezoelectricity sensor, may further comprise the steps:
1) polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers are dissolved in the organic solvent, obtain 8-20% (w/v), the solution to be spun of preferred 10-15% (w/v), wherein said organic solvent is the good solvent of polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers, and the molar content of polyvinylidene fluoride is 55-85% in described polyvinylidene fluoride-fluorinated olefin copolymers, preferred 70-80%;
2) in electrostatic spinning apparatus with step 1) the solution electrostatic spinning to be spun that obtains, obtain fiber membrane at the reception pole plate of described electrostatic spinning apparatus; With
3) with step 2) in the fiber membrane that obtains dry 6-8h at ambient temperature, then the two-layer conductive film electrode of being made by flexible porous electrode is arranged on the surface and the back side of dry fiber membrane, thereby obtains the piezoelectricity sensor.
Beneficial effect of the present invention
1. novel mechanics sensor provided by the invention has good performance aspect sensitivity and the mechanical characteristics.
2. method provided by the invention unites two into one spinning membrane system and electric field polarization, compares with traditional handicraft (need to be to stretch first after-polarization operation of film in order to obtain high sensitivity), and operation reduces, and operates simpler.
3. method of the present invention organically combines nano-meter characteristic and the piezoelectric property of material, and the fiber membrane of making by method of the present invention not only has the characteristics of light weight softness, good permeability, also possesses good piezoelectric property.This piezoelectric fabric film has overcome the shortcomings such as the hardness that stupalith and plastic macromolecule film exist is high, gas penetration potential is poor, is equipped with flexible porous electrode and the pressure sensor that obtains having soft light weight, gas penetration potential and biocompatibility can satisfy the application requirements in medical, dress ornament and measuring of human health field better.
Description of drawings
Fig. 1 is electrostatic spinning technique work schematic diagram.
Fig. 2 is case study on implementation assembling senser element structural representation.
Fig. 3 for be respectively embodiment 3 (Fig. 3 a), the piezoelectric polymer nano-fiber film electromicroscopic photograph for preparing of embodiment 4 (Fig. 3 b), embodiment 5 (Fig. 3 c), embodiment 6 (Fig. 3 d), embodiment 7 (Fig. 3 e) and embodiment 8 (Fig. 3 f).
Fig. 4 is the single response curve of the pressure sensor of embodiment 5 preparations.
Fig. 5 is the response curve of pressure transducer under different frequency pressure of embodiment 5 preparations.
Fig. 6 is (A) BsPT[(1-x) BiScO
3-xPbTiO
3] piezoelectric ceramics, (B) cobalt acid lithium (LiCoO
2) piezoelectric ceramics, (C) P (VDF-TrFE) the film sample electromicroscopic photograph of solvent evaporation method preparation.
Embodiment
Definition and abbreviation
PVDF: polyvinylidene fluoride.
TrFE: trifluoro-ethylene.
P (VDF-TrFE): vinylidene fluoride-trifluoro-ethylene copolymer.
Membrane electrode: the membranaceous electrode with softness, porous structure.
ITO-PET membrane electrode: adopt magnetron sputtering technique, (Indium-Tin Oxide, ITO) the conductive film coating of sputter transparent indium tin oxide on the polyester PET base material and the high-tech product that obtains through the high temperature anneal.
Nano-fiber film: the nonwoven fabrics form film that the Nano grade fibre structure forms.
Environment temperature: generally refer to ambient temperature, namely 22～25 ℃.
Biocompatibility: refer to that in the present invention this device uses material harmless to animal and human's body.
Principle of the present invention
The present invention utilizes electrostatic spinning technique to prepare the inductive material of piezoelectric sensing device, and piezoelectric polymer solution is subject to stretching and the polarization of highfield in spinning process.Solution is rapidly distortion under high-strength stretching action, is forming continuous nano-scale fiber in the process that receives the pole plate motion; The fiber that forms simultaneously possesses piezoelectric property thereby polar crystal forms preferred orientation under the polarization of highfield, along with the volatilization of solvent just can obtain the piezoelectric polymer nano fibrous membrane receiving pole plate
Because piezoelectric membrane provided by the invention is nano-fiber film, possesses highly sensitive, the advantages such as light weight is soft, good permeability; Simultaneously, method provided by the invention unites two into one spinning membrane system and electric field polarization, compares with traditional handicraft (need to be to stretch first after-polarization operation of film in order to obtain high sensitivity), and operation reduces, and operates simpler.
The method for preparing the piezoelectricity sensor of the present invention mainly may further comprise the steps:
1. utilize the solution to be spun of organic solvent preparation polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers;
2. place electrostatic spinning apparatus that solution stretching to be spun is polarized solution to be spun, form the piezoelectric nano fiber membrane;
3. remove the residual particle of fiber membrane, and carry out drying and remove remaining solvent;
4. the fiber membrane of processing and conductive film electrode assembling are the piezoelectric sensing device.
Electrostatic spinning technique
The inventive method is based on electrostatic spinning technique, and electrostatic spinning technique is a kind of novel preparation nanofiber technology, and Fig. 1 is the structural representation of electrostatic spinning apparatus, and this device comprises:
High-voltage power supply 1;
The thrower 2 that links to each other with high-voltage power supply;
The reception pole plate 3 corresponding with shower nozzle 2.
Wherein thrower 2 comprises liquid storage cylinder 21 and the shower nozzle 22 that links to each other with the liquid storage cylinder end, receives pole plate corresponding with the position of shower nozzle 22.The positive pole of high-voltage power supply links to each other with shower nozzle 22, and negative pole links to each other and ground connection with reception pole plate 3, forms high voltage between shower nozzle 22 and the reception pole plate 3 thus, and the solution at shower nozzle 22 places sprays under the effect of high electric field and forms fiber, and is receiving film forming on the pole plate 3.
The piezoelectricity sensor
The structure of piezoelectricity senser element provided by the invention as shown in Figure 2, it comprises:
Piezoelectric nano fiber membrane 4;
Conductive film electrode 5;
Contact conductor 6.
The preferred embodiments of the invention
In the present invention, the conductive film electrode layer is preferably made by the conductive material of flexible porous structure, and the traditional material electrode that it can be selected from lithographic technique preparation comprises metal or metal conductive oxide film on the flexible substrates, such as the ITO-PET film etc.; The carbonaceous conductive film comprises the carbonaceous conductive adhesive tape, graphene film, carbon nano-tube film etc.; Conductive polymer film comprises polypyrrole, polyacetylene, doped and compounded material film etc.According to the present invention, not restriction of selection to the material of conductive film electrode layer, the material that those skilled in the art are can be according to concrete application choice suitable, as long as it can be combined with the nano-fiber film of the present invention's preparation and form the piezoelectric sensing device, the conductive film electrode layers thickness that is complementary with fiber membrane is generally 100-1000nm.
Nano-fiber film of the present invention is made by polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers, and preferred described nano-fiber film is made by electrostatic spinning.Therefore polyvinylidene fluoride is widely used in preparing piezoelectric device in the art because piezoelectric constant is high.The present invention also preferred polyvinylidene fluoride-fluorinated olefin copolymers of using prepares nano-fiber film, thereby makes fiber membrane have better mechanics and piezoelectric property.
For the consideration of biocompatibility, use fluorinated olefins among the present invention, preferred trifluoro-ethylene.The polymkeric substance that uses fluorinated olefins and vinylidene fluoride to form has good biocompatibility, and has good flexibility.
In polyvinylidene fluoride-fluorinated olefin copolymers, have preferably piezoelectric property in order to make final nano-fiber film, the molar content of polyvinylidene fluoride is 55-85%, preferred 70-80%.
Piezoelectricity sensor of the present invention is comprised of nano-fiber film layer and conductive film electrode layer, the conductive film electrode layer is configured in the both sides of fiber thin rete of the present invention, both can combine by means commonly known in the art, for example by attaching process as known in the art.
In the method for preparing the piezoelectricity sensor of the present invention (below abbreviation " method of the present invention "), organic solvent can be single solvent, also can be mixed solvent.Single solvent can be selected from any in acetone, butanone or the dimethyl formamide, preferred acetone or butanone.Mixed solvent can be selected from the mixed solvent that acetone or butanone and dimethyl formamide form, wherein acetone or the butanone content in mixed solvent be 50-70wt% (for example, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% etc.), preferred content of acetone is the acetone of 50-70wt% and the mixed solvent of dimethyl formamide.The selection of organic solvent is mainly based on following any consideration: 1. the good solvent of polymkeric substance: above-mentioned several solvents all are the common good solvents of polymkeric substance, can obtain uniform solution.2. the carrying out that is conducive to spinning process: spinning process requires solution to have certain viscosity, and solvent is volatile solvent, selects the suitable dimethyl formamide of volatile acetone or butanone and viscosity based on this.In addition, the ratio of mixed solvent also directly affects the carrying out of spinning process and the homogeneity of gained sample, experiment shows that 50-70wt% can effectively avoid the problems such as nozzle solution casting in the spinning process, jet shakiness, sample residual grains, therefore in the situation that use mixed solvent, preferred acetone or the content of butanone in mixed solvent are 50-70wt%.
In the method for the invention, the typical structure of the electrostatic spinning apparatus that adopts as shown in fig. 1, it can adopt commercially available device, for example, Japan adds the NEU-010 nanofiber spinning equipment of technology company limited, the electrospinning device that Beijing Kang Sente Science and Technology Ltd. makes, the Electrospun equipment of the good farsighted Science and Technology Ltd. in Jinan etc.In the preferred embodiment of method of the present invention, in electrostatic spinning apparatus shown in Figure 1, typical spinning process condition is: under the voltage of 9-18kv, will solution spinning 4h be spun with the fltting speed of 1.2-1.6ml/h, reception pole plate at electrostatic spinning apparatus obtains the fiber membrane that thickness is 30-50 μ m, then with the fiber membrane dry 6-8h under environment temperature (for example, about 22 ℃) that obtains.
In preferred embodiments, the sensitivity of the piezoelectricity senser element by method of the present invention preparation is 30-65mV/N.
Embodiment
Following examples all adopt electrostatic spinning apparatus as shown in Figure 1, and wherein shower nozzle 22 internal diameters are 0.84mm, and shower nozzle 22 and the vertical range that receives between the pole plate 3 are 100-200mm, are traditionally arranged to be 150mm.PVDF and P (VDF-TrFE) buy from U.S. Sigma Aldrich and French PIEZOTECH S.A.S company respectively.
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 9kV that the high-voltage power supply output voltage is set, and it is 1.2mL/h that thrower solution fltting speed is set, and obtains the fiber membrane that thickness is the 30-40 micron at the reception pole plate behind the 4h.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and obtaining its sensitivity through the overcorrect test is 30mV/N.
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 18kV that the high-voltage power supply output voltage is set, and it is 1.2mL/h that thrower solution fltting speed is set, and obtains the fiber membrane that thickness is the 30-40 micron at the reception pole plate behind the 4h.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 37mV/N.
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of P (VDF-TrFE) (PVDF: the TrFE mol ratio is 55: 45) powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h, Fig. 3 (a) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 30.9mV/N.
Embodiment 4
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of P (VDF-TrFE) (PVDF: the TrFE mol ratio is 70: 30) powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h, Fig. 3 (b) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 55mV/N.
Embodiment 5
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of P (VDF-TrFE) (PVDF: the TrFE mol ratio is 77: 23) powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h, Fig. 3 (c) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, utilizes response curve that test macro obtains senser element as shown in Figure 4 and Figure 5, and its measurement sensitivity is 60.5mV/N.
Embodiment 6
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h, Fig. 3 (d) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, is 40.6mV/N through its measurement sensitivity of overcorrect.
Embodiment 7
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 10% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 30-40 micron at the reception pole plate behind the 4h, Fig. 3 (e) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 30mV/N.
Embodiment 8
Take mass ratio as 4: 6 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 15% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, it is 1.6mL/h that thrower solution fltting speed is set, obtain the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h, Fig. 3 (f) is the electron scanning micrograph of tunica fibrosa.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 42mV/N.
Embodiment 9
Take mass ratio as 5: 5 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, and it is 1.6mL/h that thrower solution fltting speed is set, and obtains the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 40mV/N.
Take mass ratio as 3: 7 dimethyl formamide and the acetone intermixture as solvent, a certain amount of PVDF powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, and it is 1.6mL/h that thrower solution fltting speed is set, and obtains the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 42mV/N.
Embodiment 11
Take butanone as solvent, a certain amount of P (VDF-TrFE) (PVDF: the TrFE mol ratio is 77: 23) powder dissolution is mixed with the solution to be spun that concentration is 12% (w/v).The solution for preparing is placed in the liquid storage cylinder of thrower, open the device for spinning power supply, it is 12kV that the high-voltage power supply output voltage is set, and it is 1.6mL/h that thrower solution fltting speed is set, and obtains the fiber membrane that thickness is the 40-50 micron at the reception pole plate behind the 4h.Fiber membrane that spinning obtains is through the drying of 6-8h, and itself and two-layer ITO-PET film combinations are up and down obtained as shown in Figure 2 senser element, and its measurement sensitivity is 57mV/N.
As can be seen from Figure 3, the nano-fiber film by method of the present invention preparation is porous membrane, and therefore the senser element good permeability of nano-fiber film preparation, light weight are soft thus.Piezoelectric ceramics and plastic macromolecule membrane structure ((A) BsPT[(1-x) BiScO with prior art among Fig. 6
3-xPbTiO
3] piezoelectric ceramics, (B) cobalt acid lithium (LiCoO
2) piezoelectric ceramics, (C) P (VDF-TrFE) film of solvent evaporation method preparation) compare, the structure of nano-fiber film of the present invention is having very large improvement and raising aspect gas penetration potential and the flexibility.
Response curve from Fig. 4 and Fig. 5 can find out, the response curve of prepared according to the methods of the invention piezoelectricity senser element and sensitivity meet the application requirements for the piezoelectric sensor in medical treatment, dress ornament field fully.
Claims (10)
1. piezoelectricity sensor, it is comprised of nano-fiber film layer and conductive film electrode layer, it is characterized in that described nano-fiber film layer made by polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers; Described conductive film electrode layer is made by flexible porous electrode, it is configured on the surface and both sides, the back side of described nano-fiber film layer, the molar content of polyvinylidene fluoride is 55-85% in wherein said polyvinylidene fluoride-fluorinated olefin copolymers, preferred 70-80%.
2. the sensor described in according to claim 1 is characterized in that described fluorinated olefins is ethylene fluoride, preferred trifluoro-ethylene.
3. piezoelectricity sensor according to claim 1 and 2 is characterized in that described conductive film electrode is to be selected from following any: be applied to metal or metal conductive oxide film on the flexible substrates; The carbonaceous conductive film; Conductive polymer film.
4. each described piezoelectricity sensor according to claim 1-3, wherein said conductive film electrode is the ITO-PET film.
5. each described piezoelectricity sensor according to claim 1-4, the sensitivity that it is characterized in that described piezoelectricity sensor is 30-65mV/N.
6. method for preparing the piezoelectricity sensor may further comprise the steps:
1) polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers are dissolved in the organic solvent, obtain 8-20% (w/v), the solution to be spun of preferred 10-15% (w/v), wherein said organic solvent is the good solvent of polyvinylidene fluoride or polyvinylidene fluoride-fluorinated olefin copolymers, and the molar content of polyvinylidene fluoride is 55-85% in described polyvinylidene fluoride-fluorinated olefin copolymers, preferred 70-80%;
2) in electrostatic spinning apparatus with step 1) the solution electrostatic spinning to be spun that obtains, obtain fiber membrane at the reception pole plate of described electrostatic spinning apparatus; With
3) with step 2) in the fiber membrane that obtains dry 6-8h at ambient temperature, then the two-layer conductive film electrode of being made by flexible porous electrode is arranged on the surface and the back side of dry fiber membrane, thereby obtains the piezoelectricity sensor.
7. the method described in according to claim 6 is characterized in that described fluorinated olefins is ethylene fluoride, preferred trifluoro-ethylene.
8. according to claim 6 or 7 described methods, it is characterized in that described organic solvent is single solvent or mixed solvent, wherein said single solvent is selected from any in acetone, butanone and the dimethyl formamide, preferred acetone or butanone; Described mixed solvent is selected from the mixed solvent that any and dimethyl formamide in acetone and the butanone form, wherein acetone or the butanone content in described mixed solvent is 50-70wt%, and preferred content of acetone is the acetone of 50-70wt% and the mixed solvent of dimethyl formamide.
9. each described method according to claim 6-8 is characterized in that described conductive film electrode is to be selected from following any: the metal on the flexible substrates or metal conductive oxide film; The carbonaceous conductive film; Conductive polymer film.
10. method according to claim 9 is characterized in that described conductive film electrode is the ITO-PET film.
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