CN111662470B - Fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film and preparation method thereof - Google Patents
Fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film and preparation method thereof Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 100
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- 150000001768 cations Chemical class 0.000 claims description 6
- GPHGLYLDASNBBU-UHFFFAOYSA-N cobalt(2+) dinitrate pentahydrate Chemical compound O.O.O.O.O.[Co++].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPHGLYLDASNBBU-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention belongs to the technical field of multiferroic films, and particularly relates to a fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film which comprises a PVDF-TrFE film, wherein at least one layer of CFO/PVDF-TrFE composite film is attached to the PVDF-TrFE film; the preparation method comprises the following steps: dissolving PVDF-TrFE powder to obtain a solution A, and adding CFO nanoscale powder into the solution A to obtain a mixed solution B; then taking FTO conductive glass as a substrate, preparing a PVDF-TrFE film by carrying out spin coating on the FTO conductive glass by using the solution A, drying, and then carrying out spin coating on the PVDF-TrFE film by using the mixed solution B to prepare a CFO/PVDF-TrFE composite film; and then annealing the wet film to obtain the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film, and finally plating a platinum point electrode on the composite film. The cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film has excellent ferroelectric fatigue property, mild preparation condition, simple process steps and strong controllability.
Description
Technical Field
The invention relates to a multiferroic composite film and a preparation method thereof, in particular to a fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film and a preparation method thereof, and belongs to the technical field of multiferroic films.
Background
Polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) is a semi-crystalline organic matter with excellent performance and ideal film material. PVDF-TrFE has high elasticity and excellent piezoelectric ferroelectric property, and has wide application prospect in the fields of pressure and acceleration sensors, energy collection, ultrasonic sensors, nonvolatile memories, waveguides and the like. In particular, in recent years, as the semiconductor industry has developed, high density storage of organic ferroelectric films has become the focus of academia and industry. The problem of ferroelectric fatigue (as the number of ferroelectric film switches increases, the remnant polarization gradually decreases until the ferroelectric performance is lost) becomes a key factor for limiting whether the ferroelectric memory device can really go to commercial application, and the pure ferroelectric organic film often has poorer fatigue performance than the inorganic material.
Cobalt ferrite (CoFe) 2 O 4 CFO) is a spinel crystal structure, has the advantages of larger magnetocrystalline anisotropy, large coercive field, medium saturation magnetization, high magnetostriction property, high resistivity and the like, and has wide application prospects in the fields of permanent magnets, magnetic recording, wave absorbing materials and biomedicine.
The magneto-electric effect refers to a phenomenon that a material generates an electric polarization response in an external magnetic field or magnetization change caused by an external electric field (the latter is called an inverse magneto-electric effect). The room temperature magnetoelectric coupling performance of the single-phase magnetoelectric material is usually weak, so that the layered composite magnetoelectric material is always a hot spot for international research in recent years. Therefore, aiming at the defect of poor ferroelectric fatigue resistance of PVDF-TrFE ferroelectric polymer, it is necessary to design a fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film and a preparation method thereof so as to overcome the defect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film and the preparation method thereof, which have the advantages of excellent ferroelectric fatigue property, low cost of process equipment, simple process and strong controllability.
In order to achieve the above purpose, the technical scheme of the invention is that the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multi-layer composite film comprises a CFO/PVDF-TrFE composite film and a PVDF-TrFE film, wherein at least one layer of CFO/PVDF-TrFE composite film is attached to the PVDF-TrFE film.
The invention also provides a preparation method of the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film, which comprises the following steps:
s1, preparing CFO nano-scale powder;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film;
s2.1, dissolving PVDF-TrFE powder in a diethyl carbonate solvent, and fully stirring to obtain a solution A;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, and fully stirring to obtain a mixed solution B;
s2.3, taking FTO conductive glass as a substrate, and carrying out spin coating on the prepared solution A on the FTO conductive glass by utilizing a spin coater to prepare a PVDF-TrFE film;
s2.4, placing the spin-coated wet film in a drying oven for drying;
s2.5, spin-coating the prepared mixed solution B on the dried PVDF-TrFE film by using a spin coater to prepare a CFO/PVDF-TrFE composite film;
s2.6, placing the spin-coated wet film in a heat treatment furnace for annealing treatment to obtain a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film;
s2.7, manufacturing an electrode, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film manufactured in the step S2.6.
Further, the steps between the step S2.5 and the step S2.6 include the following steps: and (3) placing the spin-coated wet film in a drying oven for drying, and then carrying out spin coating on the prepared mixed solution B on the dried CFO/PVDF-TrFE composite film by using a spin coater, thereby preparing a layer of CFO/PVDF-TrFE composite film.
Further, the PVDF-TrFE in the solution A is 5-7% in mass fraction.
Further, the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.085-0.1333 and g:0.2g.
Further, in step S2.4, the wet film is dried in a drying oven at 70-80 ℃ for 3-5min.
Further, the annealing treatment temperature is 130-140 ℃ and the treatment time is 1.5-2h.
Further, the preparation of the CFO nanoscale powder in step S1 includes the steps of:
s1.1, cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.75mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1.2, obtaining cobalt ferrite precursor sol;
s1.2, continuously stirring the obtained cobalt ferrite precursor sol for 2h to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5min to obtain cobalt ferrite xerogel;
s1.3, placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2h, so as to obtain cobalt ferrite presintered powder;
s1.4, placing the obtained cobalt ferrite presintered powder into a mortar for grinding for 30min to obtain CFO nanoscale powder.
Further, the particle size of the CFO nanoscale powder prepared in step S1 is 500-800nm.
Further, in step S2.2, after adding the CFO nano-sized powder into the solution a, stirring electrically, then dispersing ultrasonically, repeating for 2-3 times, so as to uniformly disperse the CFO nano-sized powder.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film, disclosed by the invention, the high-ferromagnetism nano-particle cobalt ferrite is uniformly mixed in the polyvinylidene fluoride-trifluoroethylene solution and then is subjected to spin coating to obtain the multilayer composite film with compact structure, the high magnetostriction coefficient of the cobalt ferrite and the plasticity of PVDF-TrFE are combined to prepare the film meeting the characteristics of high magnetoelectric effect, controllable shape and the like of a magnetoelectric material, the two-phase material is complementary in performance, and simultaneously, the better and reliable magnetoelectric coupling effect is obtained, so that the defect of poor fatigue resistance of the single-phase ferroelectric polymer polyvinylidene fluoride-trifluoroethylene is effectively overcome.
Drawings
Fig. 1 is a schematic structural diagram of a PVDF-TrFE film (a), a CFO (PVDF-TrFE)/PVDF-TrFE multilayer composite film (b) prepared in example 1, and a PVDF-TrFE/CFO (PVDF-TrFE) multilayer composite film (c) prepared in example 2;
FIG. 2 is an XRD pattern of PVDF-TrFE, cobalt Ferrite (CFO) and the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film prepared in example 1 and the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film prepared in example 2;
FIG. 3 is a fatigue characteristic curve of the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film prepared in example 1 of the present invention;
FIG. 4 shows the hysteresis loops before and after fatigue testing of the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film prepared in example 1 of the present invention;
FIG. 5 is a fatigue characteristic curve of a PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film prepared in example 2 of the present invention;
FIG. 6 shows the hysteresis loops before and after fatigue testing of a PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film prepared in example 2 of the present invention;
FIG. 7 shows hysteresis loops of CFO nanoscale powders prepared in accordance with the present invention;
fig. 8 is a graph showing fatigue characteristics of PVDF-TrFE film.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multi-layer composite film, which comprises a CFO/PVDF-TrFE composite film and a PVDF-TrFE film, wherein two layers of PVDF-TrFE films are attached to the CFO/PVDF-TrFE composite film.
The preparation method of the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film comprises the following steps:
s1, preparing nanoscale cobalt ferrite powder;
s1.1, cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.75mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1.2, obtaining cobalt ferrite precursor sol;
s1.2, continuously stirring the obtained cobalt ferrite precursor sol for 2h to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5min to obtain cobalt ferrite xerogel;
s1.3, placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2h, so as to obtain cobalt ferrite presintered powder;
s1.4, grinding the obtained cobalt ferrite presintered powder in a mortar for 30min to obtain CFO nanoscale powder with the particle size range of 500-800 nm;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film;
s2.1, dissolving vinylidene fluoride in diethyl carbonate solvent, and fully stirring to obtain solution A, wherein the mass fraction of the solution A is guaranteed to be 7%;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, electrically stirring for 1h, then performing ultrasonic dispersion for 20min, and repeating for 2-3 times to obtain a uniformly mixed solution B, wherein the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.1333 and g:0.2 g;
s2.3, selecting FTO conductive glass as a substrate, carrying out spin coating on the prepared mixed solution B on the FTO conductive glass by using a spin coater, and preparing the CFO/PVDF-TrFE composite film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.4, placing the spin-coated wet film in a drying oven at 80 ℃ for drying for 5min;
s2.5, spin-coating the prepared solution A on the dried CFO/PVDF-TrFE composite film by using a spin coater, and preparing the PVDF-TrFE film by controlling spin-coating rotation speed and time; the initial rotation speed of the spin coating is 300r/s for 20s; accelerating to 3000r/s, and then continuously spin-coating for 40s;
s2.6, repeating the steps S2.4 and S2.5, and preparing a layer of PVDF-TrFE film on the dried PVDF-TrFE film to obtain a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film;
s2.7, placing the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film in a heat treatment furnace for annealing treatment at 140 ℃ for 2 h;
s2.8, manufacturing an upper electrode of the composite multilayer film, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film obtained in the step S2.7 to obtain the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film.
The structure of the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film prepared in this embodiment is shown in FIG. 1 (b), and the thickness is about 1. Mu.m. The XRD pattern is shown in figure 2; as can be seen from fig. 2: in the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film of the embodiment, a spinel single-phase structure peak of cobalt ferrite crystals and a b-phase peak of PVDF-TrFE appear. Ferroelectric fatigue characteristic curves and ferroelectric hysteresis loops of the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film prepared by the implementation are respectively shown in fig. 3 and 4; as can be seen from fig. 3: the fatigue characteristics of the CFO (PVDF-TrFE)/PVDF-TrFE/PVDF-TrFE multilayer composite film of this example were that when the number of turns reached 10 5 At the beginning of the switch polarization value became significantly smaller, only 10 compared with pure PVDF-TrFE 6 Equivalent (as in fig. 8); as can be seen from fig. 4: the residual polarization before and after polarization is respectively: 4.37 Mu C/cm 2 、0.03 μC/cm 2， The coercive fields before and after polarization are respectively: 563.8 kV/cm, 53.4. 53.4 kV/cm.
Example 2
The embodiment provides a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multi-layer composite film, which comprises a CFO/PVDF-TrFE composite film and a PVDF-TrFE film, wherein two layers of CFO/PVDF-TrFE composite films are attached to the PVDF-TrFE film.
The preparation method of the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film comprises the following steps:
s1, preparing nanoscale cobalt ferrite powder:
s1.1: cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.5 mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1, obtaining cobalt ferrite precursor sol;
s1.2: continuously stirring the obtained cobalt ferrite precursor sol for 2-3 h to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5min to obtain cobalt ferrite xerogel;
s1.3: placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2-3 h, so as to obtain cobalt ferrite presintered powder;
s1.4: grinding the obtained cobalt ferrite presintered powder in a mortar for 20-30 min to obtain CFO nanoscale powder with the particle size range of 500-800 nm;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film:
s2.1, dissolving vinylidene fluoride in diethyl carbonate solvent, and fully stirring to obtain solution A, wherein the mass fraction of the solution A is guaranteed to be 7%;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, firstly stirring for 1h electrically, then dispersing for 20min by ultrasonic, and repeating for 2-3 times to obtain a uniform mixed solution B, wherein the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.1333 and g:0.2 g;
s2.3, selecting FTO conductive glass as a substrate, carrying out spin coating on the prepared solution A on the FTO conductive glass by using a spin coater, and preparing a PVDF-TrFE film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.4, placing the spin-coated wet film in a drying oven at 80 ℃ for drying for 5min;
s2.5, carrying out spin coating on the prepared mixed solution B on the dried PVDF-TrFE film by using a spin coater, and preparing the CFO/PVDF-TrFE composite film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.6, repeating the steps S2.4 and S2.5, and preparing a layer of CFO/PVDF-TrFE composite film on the dried CFO/PVDF-TrFE composite film to obtain a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film;
s2.7, placing the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film in a heat treatment furnace for annealing treatment at 140 ℃ for 2 h;
s2.8, manufacturing an upper electrode of the composite multilayer film, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film obtained in the step S2.7 to obtain the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film. In the embodiment, two layers of CFO/PVDF-TrFE composite films are spin-coated on the PVDF-TrFE film, so that the clean and smooth surface of the film is ensured, and the stability of a platinum electrode coating can be ensured.
The structure of the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film prepared by the implementation is shown in (c) of figure 1, the thickness is about 1.5 mu m, and the XRD pattern is shown in figure 2; as can be seen from fig. 2: in the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film of the embodiment, both spinel single-phase structural peaks of cobalt ferrite crystals and b-phase peaks of PVDF-TrFE appear. Ferroelectric fatigue characteristic curves and hysteresis loops of the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite films prepared by the implementation are shown in fig. 5 and 6 respectively; as can be seen from fig. 5: the fatigue characteristics of the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film of this example are that when flippedUp to 10 9 When the switch polarization value starts to be obviously reduced, which is far better than that of pure PVDF-TrFE 10 5 10 of example 1 6 The method comprises the steps of carrying out a first treatment on the surface of the The electric domain pinning and de-pinning model (Domain Pinning and Depinning Models) can be used to explain the mechanism of fatigue occurrence, polarization fatigue originating from electron injection during polarization inversion, with electron injection under high electric fields resulting in electric domain phase separation at and inside the interface electrode. Because a certain interface charge exists between the platinum electrode and the surface of the film, the interface charge triggers the needle-shaped electric domain to nucleate and turn over; the needle tip also collects positively charged interface charges or oxygen vacancies, and a certain depolarization field can be generated because the tip charges cannot be completely shielded; the CFO nano-scale particles are introduced to fully make up the defects in the film, so that the leakage current in the film is reduced; the CFO nano-scale particles are doped, which is equivalent to introducing more free charges, so that domain pinning effect at an interface can be counteracted, the polarization occurrence efficiency of the polymer film is fully improved, and the conductivity is enhanced; the dipole-oriented polarization of the CFO and PVDF-TrFE matrix is enhanced at low frequencies, so the fatigue properties of the films of examples 1 and 2 are superior to those of pure PVDF-TrFE; in the embodiment 2, the platinum electrode is directly contacted with the CFO/PVDFTrFE layer, electrons are directly injected into the layer in the test process, a certain potential difference is formed at the interface, free charges contained in the CFO nano particles can be overturned under the action of an electric field after an electric domain is slowly formed on the surface of the film, the domain pinning effect is inhibited, and the material fatigue is reduced, so that the fatigue property of the thin film of the embodiment 2 is far better than that of the embodiment 1 and the pure PVDF-TrFE. As can be seen from fig. 6: the residual polarization before and after polarization was 6.9. Mu.C/cm, respectively 2 、7.8 μC/cm 2 The coercive fields before and after polarization are respectively: 564 kV/cm, 574, kV/cm.
Example 3
The embodiment provides a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multi-layer composite film, which comprises a CFO/PVDF-TrFE composite film and a PVDF-TrFE film, wherein a layer of CFO/PVDF-TrFE composite film is attached to the PVDF-TrFE film.
The preparation method of the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film comprises the following steps:
s1, preparing nanoscale cobalt ferrite powder:
s1.1: cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.5 mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1, obtaining cobalt ferrite precursor sol;
s1.2: continuously stirring the obtained cobalt ferrite precursor sol for 2-3 h to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5min to obtain cobalt ferrite xerogel;
s1.3: placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2-3 h, so as to obtain cobalt ferrite presintered powder;
s1.4: grinding the obtained cobalt ferrite presintered powder in a mortar for 20-30 min to obtain CFO nanoscale powder with the particle size range of 500-800 nm; when the particle size exceeds 1 mu m, the spin coating quality of the surface of the film is poor, the leakage current in the film is large, and the performance of the film is greatly affected;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film:
s2.1, dissolving vinylidene fluoride in diethyl carbonate solvent, and fully stirring to obtain solution A, wherein the mass fraction of the solution A is guaranteed to be 7%;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, firstly stirring for 1h electrically, then dispersing for 20min by ultrasonic, and repeating for 2-3 times to obtain a uniform mixed solution B, wherein the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.1333 and g:0.2 g;
s2.3, selecting FTO conductive glass as a substrate, carrying out spin coating on the prepared solution A on the FTO conductive glass by using a spin coater, and preparing a PVDF-TrFE film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.4, placing the spin-coated wet film in a drying oven at 80 ℃ for drying for 5min;
s2.5, carrying out spin coating on the prepared mixed solution B on the dried PVDF-TrFE film by using a spin coater, and preparing the CFO/PVDF-TrFE composite film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.6, placing the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film in a heat treatment furnace for annealing treatment at 140 ℃ for 2 h;
s2.7, manufacturing an upper electrode of the composite multilayer film, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film obtained in the step S2.7 to obtain the PVDF-TrFE/CFO (PVDF-TrFE) multilayer composite film.
Example 4
The embodiment provides a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multi-layer composite film, which comprises a CFO/PVDF-TrFE composite film and a PVDF-TrFE film, wherein two layers of CFO/PVDF-TrFE composite films are attached to the PVDF-TrFE film.
The preparation method of the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film comprises the following steps:
s1, preparing nanoscale cobalt ferrite powder:
s1.1: cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.5 mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1, obtaining cobalt ferrite precursor sol;
s1.2: continuously stirring the obtained cobalt ferrite precursor sol for 2-3 h to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5min to obtain cobalt ferrite xerogel;
s1.3: placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2-3 h, so as to obtain cobalt ferrite presintered powder;
s1.4: grinding the obtained cobalt ferrite presintered powder in a mortar for 20-30 min to obtain CFO nanoscale powder with the particle size range of 500-800 nm;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film:
s2.1, dissolving vinylidene fluoride in diethyl carbonate solvent, and fully stirring to obtain solution A, wherein the mass fraction of the solution A is ensured to be 5%;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, firstly stirring for 1h electrically, then dispersing for 20min by ultrasonic, and repeating for 2-3 times to obtain a uniform mixed solution B, wherein the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.085g:0.2 g;
s2.3, selecting FTO conductive glass as a substrate, carrying out spin coating on the prepared solution A on the FTO conductive glass by using a spin coater, and preparing a PVDF-TrFE film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.4, placing the spin-coated wet film in a drying oven at 70 ℃ for drying for 3min;
s2.5, carrying out spin coating on the prepared mixed solution B on the dried PVDF-TrFE film by using a spin coater, and preparing the CFO/PVDF-TrFE composite film by controlling spin coating rotation speed and time; the initial rotation speed of spin coating is 300r/s for 20s, and spin coating is continuously carried out for 40s after the spin coating is accelerated to 3000 r/s;
s2.6, repeating the steps S2.4 and S2.5, and preparing a layer of CFO/PVDF-TrFE composite film on the dried CFO/PVDF-TrFE composite film to obtain a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film;
s2.7, placing the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite wet film in a heat treatment furnace for annealing treatment at 130 ℃ for 1.5 h;
s2.8, manufacturing an upper electrode of the composite multilayer film, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film obtained in the step S2.7 to obtain the PVDF-TrFE/CFO (PVDF-TrFE)/CFO (PVDF-TrFE) multilayer composite film.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film is characterized in that: the membrane comprises a CFO/PVDF-TrFE composite membrane and a PVDF-TrFE composite membrane, wherein two or more layers of the CFO/PVDF-TrFE composite membrane are attached to the PVDF-TrFE composite membrane, the two or more layers of the CFO/PVDF-TrFE composite membrane are positioned on the same side of the PVDF-TrFE composite membrane, and a platinum point electrode is plated on the outermost layer of the CFO/PVDF-TrFE composite membrane.
2. The preparation method of the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film is characterized by comprising the following steps of:
s1, preparing CFO nano-scale powder;
s2, preparing a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film;
s2.1, dissolving PVDF-TrFE powder in a diethyl carbonate solvent, and fully stirring to obtain a solution A;
s2.2, adding CFO nano-scale powder into the solution A which is continuously stirred, and fully stirring to obtain a mixed solution B;
s2.3, taking FTO conductive glass as a substrate, and carrying out spin coating on the prepared solution A on the FTO conductive glass by utilizing a spin coater to prepare a PVDF-TrFE film;
s2.4, placing the spin-coated wet film in a drying oven at 70-80 ℃ for drying for 3-5min;
s2.5, spin-coating the prepared mixed solution B on the dried PVDF-TrFE film by using a spin coater to prepare a CFO/PVDF-TrFE composite film;
placing the spin-coated wet film in a drying oven for drying, and then using a spin coater to spin-coat the prepared mixed solution B on the dried CFO/PVDF-TrFE composite film, thereby preparing a layer of CFO/PVDF-TrFE composite film;
s2.6, placing the spin-coated wet film in a heat treatment furnace for annealing treatment to obtain a cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film;
s2.7, manufacturing an electrode, and plating a platinum point electrode on the cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film manufactured in the step S2.6.
3. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: the PVDF-TrFE in the solution A is 5-7% by mass.
4. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: the dosage ratio of CFO and PVDF-TrFE in the mixed solution B is 0.085-0.1333g:0.2g.
5. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: the treatment temperature of the annealing treatment is 130-140 ℃ and the treatment time is 1.5-2h.
6. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: the preparation of CFO nanoscale powder in step S1 comprises the steps of:
s1.1, cobalt nitrate pentahydrate and ferric nitrate nonahydrate are mixed according to the mole ratio of 1.05:1 is dissolved in a glycol methyl ether solvent to obtain a solution C, wherein the concentration of the solution C is 0.75mol/L; dissolving citric acid in a continuously stirred solution C, wherein the molar ratio of the citric acid to cations in the solution is 1:1.2, obtaining cobalt ferrite precursor sol;
s1.2, continuously stirring the obtained cobalt ferrite precursor sol for 2 hours to obtain stable cobalt ferrite sol, and then drying in a drying oven at 80 ℃ for 5 minutes to obtain cobalt ferrite xerogel;
s1.3, placing the obtained cobalt ferrite xerogel into a heat treatment furnace, wherein the annealing temperature is 800 ℃, and the heat preservation time is 2 hours, so as to obtain cobalt ferrite presintered powder;
s1.4, placing the obtained cobalt ferrite presintered powder into a mortar for grinding for 30min to obtain CFO nanoscale powder.
7. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: the particle size of the CFO nanoscale powder prepared in the step S1 is 500-800nm.
8. The method for preparing the fatigue-resistant cobalt ferrite/polyvinylidene fluoride-trifluoroethylene multilayer composite film according to claim 2, which is characterized in that: in the step S2.2, after the CFO nano-scale powder is added into the solution A, electric stirring is performed, ultrasonic dispersion is performed again, and the process is repeated for 2-3 times, so that the CFO nano-scale powder is uniformly dispersed.
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