CN116396513B - Composite film material, friction nano generator, and preparation method and application thereof - Google Patents

Composite film material, friction nano generator, and preparation method and application thereof Download PDF

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CN116396513B
CN116396513B CN202310380923.3A CN202310380923A CN116396513B CN 116396513 B CN116396513 B CN 116396513B CN 202310380923 A CN202310380923 A CN 202310380923A CN 116396513 B CN116396513 B CN 116396513B
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composite film
film material
reaction
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titanate
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CN116396513A (en
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卢殷
王宁
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04—Friction generators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/044—Elimination of an inorganic solid phase
    • C08J2201/0444—Salts
    • C08J2201/0446—Elimination of NaCl only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention provides a composite film material, a friction nano generator, a preparation method and application thereof. The preparation method of the composite film material comprises the following steps: step A: mixing and stirring calcium copper titanate-barium titanate, polydimethylsiloxane, a curing agent and a pore-forming agent to obtain a mixed solution; and (B) step (B): and coating the mixed solution on a substrate, and performing curing reaction to obtain the composite film material. The invention adopts copper calcium titanate-barium titanate (CCTO-BT) as the filler to prepare the high-dielectric composite film material, has lower dielectric loss, higher dielectric constant and higher surface potential, can effectively improve the output performance of the friction nano generator, can further widen the selection range of the friction nano generator, and has higher research significance and commercial value.

Description

Composite film material, friction nano generator, and preparation method and application thereof
Technical Field
The invention relates to the field of friction generators, in particular to a composite film material and a preparation method thereof, a friction nano generator prepared from the composite film material and a preparation method and application thereof.
Background
Triboelectric nano-generators (Triboelectric nanogenerator, TENGs) can collect and convert various forms of mechanical energy, particularly mechanical energy generated by low-frequency motion of a human body, into electric energy by using the coupling effect of triboelectric charging and electrostatic induction, and have proven to be a reliable and sustainable energy collector with the advantages of small volume, light weight, high efficiency, low cost, portability and the like. Furthermore, TENGs have a broad application prospect in the aspect of power supply of a wearable electronic system, however, in the practical application process, TNEG needs to be designed into equipment with good comfort, durability and high performance output, which is also a key for realizing practical application of a self-powered system.
At present, three methods for improving output power are mainly surface modification, structural design and selection of high-surface charge materials. The surface modification process is mainly to assist electron transport or to increase the relative capacitance (effective epsilon/d value, where epsilon is the relative dielectric constant and d is the film thickness) of the triboelectric material by grafting chemical groups. In general, the polymer-based dielectric material has the characteristics of good processability, high electronegativity, no toxicity, good biocompatibility, light weight and the like, and is remarkable in dielectric materials with high dielectric constant (k) and low dielectric loss. Meanwhile, the dielectric constant of the polymer can be adjusted by molecular design or addition of dielectric particles, such as BaTiO 3 (BT)、SrTiO 3 、Pb(Zr,Ti)O 3 (PZT), however, the volume fraction of filler particles is typically too high to meet the desired epsilon value, resulting in reduced comfort, processability and flexibility of the composite. In addition, the addition of conductive fillers such as Carbon Nanotubes (CNTs), graphene Nanoplatelets (GNs), etc., increases the dielectric loss tangent index if the doping amount exceeds the percolation threshold. Therefore, developing a triboelectric layer composite material with better cost-effectiveness, high stability and high output performance is particularly important for TENG applications.
Disclosure of Invention
The invention provides a polymer-based high-dielectric composite sponge film material, which is a copper calcium titanate-barium titanate/polydimethylsiloxane composite film, has high relative dielectric constant and low dielectric loss, and a friction nano generator prepared by using the composite film material has obviously improved output performance.
In order to solve the above-mentioned purpose, the technical scheme provided by the invention is as follows:
in one aspect, the present invention provides a method for preparing a composite film material, comprising:
step A: mixing and stirring calcium copper titanate-barium titanate, polydimethylsiloxane, a curing agent and a pore-forming agent to obtain a mixed solution;
and (B) step (B): and coating the mixed solution on a substrate, and performing curing reaction to obtain the composite film material.
Copper Calcium Titanate (CCTO) has excellent electrical properties, such as a large relative dielectric constant (. Epsilon. -10) 4-5 ) And has good stability to temperatures (100-600K) and frequencies (up to 10 MHz). Research shows that CCTO may form strong internal polarization in the polymer material under the action of triboelectric field, so that charge induction on the bottom electrode is enhanced, and triboelectric output performance is further improved. And CCTO has inclined TiO 6 The octahedral centrosymmetric cubic perovskite structure can receive ions with different radii and adjustable dielectric constants to a greater extent. CCTO-based composite ceramic materials are introduced into the polymer to achieve relatively high dielectric constant, low dielectric loss and high breakdown field strength at the same time, so that the charge density and internal capacitance of TENG are greatly improved, and the output performance of the TENG is remarkably improved.
In the step A, the weight ratio of the copper calcium titanate to the barium titanate is 0.01-15 percent based on the weight of the polydimethylsiloxane. For example, the weight ratio of copper calcium titanate-barium titanate may be 0.01%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% and any value therebetween based on the weight of the polydimethylsiloxane. In some preferred embodiments, the weight ratio of copper calcium titanate-barium titanate is 1% to 6% and any value therebetween, based on the weight of the polydimethylsiloxane.
In the step A, the weight ratio of the polydimethylsiloxane to the curing agent is (5-20): 1. Preferably, the weight ratio of the polydimethylsiloxane to the curing agent is (8-12): 1. more preferably, the weight ratio of polydimethylsiloxane to curing agent is 10:1.
in the step A, the weight ratio of the polydimethylsiloxane to the pore-forming agent is (0.5-5): 1. Preferably, the weight ratio of polydimethylsiloxane to pore-forming agent is (0.5-1): 1. More preferably, the weight ratio of polydimethylsiloxane to pore former is 1:1.
The curing agent is at least one selected from the group consisting of dimethyl methyl hydrogen siloxane, trimethyl hydroxy silane, alkoxy silane and hydroxy silane, preferably dimethyl methyl hydrogen siloxane.
The pore-forming agent is selected from sodium chloride and/or sucrose, preferably sodium chloride.
In the preparation method of the composite film material, the step A also comprises the step of utilizing a solvent to dissolve the copper calcium titanate-barium titanate, wherein the solvent is at least one selected from toluene, tetrahydrofuran and methylene dichloride.
In some embodiments of the invention, the weight ratio of solvent to polydimethylsiloxane is (0.5 to 5): 1. preferably, the weight ratio of the solvent to the polydimethylsiloxane is (1-2): 1. More preferably, the weight ratio of solvent to polydimethylsiloxane is 1:1.
In the preparation method of the composite film material provided by the invention, the process of coating the mixed solution on the substrate in the step B comprises the following steps: spin-coating the mixed solution on a substrate at the spin-coating speed of 350-650 r/min for 20-50 s. Preferably, the spin-coating speed of spin-coating the mixed solution on the substrate is 450 r/min-550 r/min, and the spin-coating time is 25 s-35 s. More preferably, the spin speed of spin-coating the mixed solution onto the substrate is 500r/min and the spin time is 30s.
In the present invention, the material of the substrate may be any suitable substrate in the art, for example, an acrylic plate or a glass plate may be selected, and in the embodiment of the present invention, a glass plate is preferable.
In the step B, the conditions for performing the curing reaction after spin-coating the mixed solution on the substrate include: the curing temperature is 70-90 ℃ and the curing time is 1.5-3 h. Preferably, the curing temperature in the curing reaction process is 75-85 ℃ and the curing time is 2-2.5 h. More preferably, the curing temperature during the curing reaction is 80℃and the curing time is 2 hours.
In some embodiments of the invention, in step B, after the curing reaction, the steps further comprise: and (3) peeling the film body formed on the substrate, soaking the peeled film body in water at the temperature of 85-100 ℃, and drying the soaked film body to obtain the composite film material. Wherein, the conditions of the soaking process comprise: the water with the temperature of 85-100 ℃ is replaced every 9-12 h, and the total replacement is 4-6 times. In some embodiments of the present invention, the peeled film body is immersed in hot water at a temperature of 85-100 ℃ and water is replaced every 10 hours for 5 times, so that the pore-forming agent in the film body can be removed to form a sponge structure.
In some embodiments of the present invention, the method for preparing a composite film material provided by the present invention includes:
(1) And uniformly mixing and dispersing the copper calcium titanate-barium titanate, the solvent, the polydimethylsiloxane prepolymer, the curing agent and the pore-forming agent by a solution blending method. Wherein the mass ratio of the copper calcium titanate-barium titanate, the solvent, the polydimethylsiloxane prepolymer, the curing agent and the pore-forming agent is as described above.
(2) And (3) spin-coating the mixed solution obtained in the step (1) on a substrate, and curing. Wherein the spin coating and curing process reaction conditions are as described above.
(3) The film body is peeled from the substrate and then immersed in hot water to remove the pore-forming agent to form a sponge structure. Wherein the soaking process is as described above.
(4) And (3) drying the film body with the sponge structure obtained in the step (3) to obtain the composite film material.
In some embodiments of the present invention, the copper calcium titanate-barium titanate in step a may be obtained by a preparation method comprising:
step A1: ba (OH) 2 ·H 2 O, copper calcium titanate are dissolved in deionized water, and ultrasonic stirring is carried out to obtain a reaction solution;
step A2: and (3) placing the obtained reaction liquid into a reaction kettle for reaction, and carrying out pretreatment and impurity removal on the reacted material to obtain the copper calcium titanate-barium titanate.
In some embodiments of the invention, in step A1, ba (OH) 2 ·H 2 The mass ratio of O to copper calcium titanate is (2-4): 1. Preferably, ba (OH) 2 ·H 2 The mass ratio of O to copper calcium titanate is (3-3.2): 1. more preferably, ba (OH) 2 ·H 2 The mass ratio of O to copper calcium titanate is 3:1。
In some embodiments of the present invention, in step A1, the conditions of ultrasonic agitation include: the stirring speed is 400 r/min-1000 r/min, and the stirring time is 30 min-60 min. Preferably, the conditions of ultrasonic agitation include: the stirring speed is 600 r/min-800 r/min, and the stirring time is 40 min-50 min.
In some embodiments of the present invention, in step A2, the conditions under which the reaction liquid reacts in the reaction vessel include: the reaction temperature is 150-180 ℃ and the reaction time is 20-24 h. Preferably, the reaction conditions of the reaction liquid in the reaction kettle comprise: the reaction temperature is 160-170 ℃ and the reaction time is 22-23 h.
In some embodiments of the present invention, in step A2, the process of pretreating the reacted material comprises: and after the reacted materials are cooled, adding a solvent for washing, centrifuging and drying to obtain the copper calcium titanate-barium titanate precursor.
In some embodiments of the present invention, in step A2, the impurity removal process includes: and (3) carrying out high-temperature calcination on the copper calcium titanate-barium titanate precursor in a muffle furnace, wherein the calcination temperature is 850-1000 ℃ and the calcination time is 1.5-2.5 h. Preferably, the calcination temperature is 900 ℃ and the calcination time is 2 hours.
In another aspect, the present invention provides a composite film material prepared by any one of the above-described methods of preparation. Preferably, the thickness of the composite film material is 1.2 μm to 1.8 μm. More preferably, the thickness of the composite film material is 1.5 μm. Preferably, the surface potential of the composite film material is 2.5V-3.5V. More preferably, the surface potential of the composite film material may be up to 2.75V.
In still another aspect, the invention further provides any one of the preparation methods and the application of any one of the composite film materials in the preparation of the friction nano-generator.
In still another aspect, the present invention further provides a friction nano-generator, where the friction nano-generator uses any one of the composite film materials described above as a friction negative layer.
In some embodiments of the present invention, a first copper foil is attached to the triboelectric negative layer as the collector and a second copper foil is the triboelectric positive layer. In some embodiments, the first copper foil and the second copper foil have the same dimensions. Preferably, the composite film material as the triboelectric negative layer is cut into small-sized films having a gauge of 4.5cm×4.5 cm.
In some embodiments, the friction positive layer and the friction negative layer perform contact-separation action under the action of external force at the frequency of 1-4 Hz to generate alternating current signals with the same frequency, and the friction nano generator is obtained.
In still another aspect, the invention further provides a preparation method of any one of the composite film materials and/or application of any one of the composite film materials and/or any one of the friction nano generators in wearable equipment and commercial capacitors.
The invention has the beneficial effects that:
(1) The invention adopts copper calcium titanate-barium titanate (CCTO-BT) as the filler to prepare the high-dielectric composite film material, has lower dielectric loss, higher dielectric constant and higher surface potential, can effectively improve the output performance of the friction nano generator, can further widen the selection range of the friction nano generator, and has higher research significance and commercial value.
(2) The preparation method of the composite film material and the friction nano generator provided by the invention has the advantages of low cost, simple operation and simple and easily available required equipment.
(3) The friction nano generator prepared by the invention can charge a commercial capacitor, can lighten 58 red Light Emitting Diodes (LEDs) at the same time, and can be well attached to shoes to monitor the movement conditions of a human body, such as walking, jogging and rope skipping.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic view of a (CCTO-BT) Scanning Electron Microscope (SEM) of copper calcium titanate-barium titanate prepared in example 1 of the present invention.
Fig. 2 is a schematic diagram of TENG provided in embodiment 1 of the present invention.
Fig. 3 is a schematic diagram of the working process of the positive friction layer and the negative friction layer provided in embodiment 1 of the present invention.
FIG. 4 is a graph showing the open circuit voltage (V) of a friction nano-generator tested at 1Hz, 2Hz, 3Hz, 4Hz, respectively, based on TENG of the composite film material prepared in example 2 of the present invention OC ) Short-circuit current (I) SC ) And the charge amount (Q) SC ) Is a variation of the schematic diagram.
FIG. 5 shows the connection of TENG of the composite film material prepared according to example 2 to different load resistances at a frequency of 4Hz (10 3 Ω～10 9 Ω) is shown.
Fig. 6 is a graph showing the open circuit voltage and current density change of the friction nano-generators at 4Hz frequency at different CCTO-BT additions in examples 1 to 6 and comparative example 1 of the present invention.
FIG. 7 is a schematic diagram of Kelvin Probe Force Microscopy (KPFM) test surface potentials of the composite film materials prepared in example 2 and comparative example 1 of the present invention.
FIG. 8 (a) is a graph showing the change in capacitance of the composite film materials prepared in example 2 and comparative examples 1 to 4 according to the present invention.
FIG. 8 (b) is a graph showing the change in dielectric loss of the composite film materials prepared in example 2 and comparative examples 1 to 4 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a dielectric composite sponge film based on copper calcium titanate-barium titanate (CCTO-BT) and Polydimethylsiloxane (PDMS), which comprises the following steps:
s1: ba (OH) 2 ·H 2 O (0.0189 mol) was dissolved in 40mL deionized water, CCTO particles (0.0063 mol) were slowly added to the solution, stirred for 2h, sonicated for 30min to allow for sufficient dispersion, transferred to a reaction kettle, and reacted in a constant temperature oven at 180℃for 24h. After cooling the solid precipitate obtained by the reaction, centrifugally washing the solid precipitate with deionized water and absolute ethyl alcohol for 6 times, and drying the solid precipitate at 60-80 ℃ overnight. Then sintering at 900 ℃ for 2 hours to obtain the CCTO-BT composite material, wherein an SEM schematic diagram of a microscopic morphology diagram of the CCTO-BT obtained by the step is shown in figure 1. From FIG. 1, the CCTO-BT prepared in this example is granular and has an average particle size of 250nm.
S2: dispersing CCTO-BT into PDMS taking toluene as a solvent, carrying out ultrasonic stirring, wherein the CCTO-BT accounts for 1wt% of the PDMS, adding NaCl with the same mass as the PDMS after stirring and dispersing uniformly, and adding dimethyl methyl hydrogen siloxane after stirring uniformly to obtain a mixed solution.
S3: spin-coating the mixed solution obtained in the step S2 on a glass plate at a rotating speed of 500r/min for 30S, drying at 80 ℃ for 2h, peeling off a film body formed on the glass plate after drying, soaking in hot water, changing water every 10h, and exchanging for 5 times to obtain a composite film material with an average thickness of 1.5 mu m, as shown in figure 2. From fig. 2, the composite sponge film material based on copper calcium titanate-barium titanate (CCTO-BT) and Polydimethylsiloxane (PDMS) prepared in this example has good flexibility and uniform surface pore distribution.
S4: cutting the composite film material obtained in the step S3 into a film with the size of 4.5cm multiplied by 4.5cm, attaching one copper foil serving as a collector electrode to the film to serve as a friction negative electrode layer material, and attaching the other copper foil with the same size to serve as a friction positive electrode layer material.
S5: under the action of external force, the friction positive layer and the friction negative layer respectively perform contact-separation movement at frequencies of 1Hz, 2Hz, 3Hz and 4Hz, and can generate alternating current signals with the same frequency, thus forming the friction nano generator, as shown in figure 3.
Example 2
This example uses the same preparation as example 1, except that: in the step S2, the CCTO-BT accounts for 2wt% of the PDMS.
FIG. 4 is open circuit voltage (V) of a friction nano-generator tested at 1Hz, 2Hz, 3Hz, 4Hz frequency, respectively, based on TENG of the composite film material prepared in this example OC ) Short-circuit current (I) SC ) And the charge amount (Q) SC ) Is a variation of the schematic diagram. As can be seen from FIG. 4, V at a frequency of 4Hz OC The peak value of (C) can reach 291.14V, Q SC Up to 80nC and is substantially independent of frequency. And, as the frequency increases, the corresponding I SC The value increased from 11.27. Mu.A at 1Hz to 35.49. Mu.A at 4 Hz.
FIG. 5 shows a TENG of a composite film material prepared according to this example connecting different load resistances at a frequency of 4Hz (10 3 Ω～10 9 Ω) is shown. At an external load of 70MΩ, a maximum power density of 1.34Wm is reached -2 The corresponding voltages and currents were 211.7V and 10.16 ua, respectively.
Example 3
This example uses the same preparation as example 1, except that: in the step S2, the CCTO-BT accounts for 3wt% of the PDMS.
Example 4
This example uses the same preparation as example 1, except that: in the step S2, CCTO-BT accounts for 4wt% of PDMS.
Example 5
This example uses the same preparation as example 1, except that: in the step S2, the CCTO-BT accounts for 5wt% of the PDMS.
Example 6
This example uses the same preparation as example 1, except that: in the step S2, CCTO-BT accounts for 6wt% of PDMS.
Comparative example 1
In this comparative example, pure PDMS sponge was used as a dielectric material, and a friction nano-generator was prepared according to step S4 and step S5 in example 1.
Fig. 6 is a graph showing the open circuit voltage and current density changes of the friction nano-generators at 4Hz frequency at different CCTO-BT additions in examples 1 to 6 and comparative example 1. As can be seen from fig. 6, when the CCTO-BT particle concentration is lower than 2wt%, the triboelectric output tends to increase with increasing CCTO-BT addition; when the concentration ratio of CCTO-BT particles is higher than 2wt%, the triboelectric output tends to decrease along with the increase of the CCTO-BT addition amount, and an electric field generated by friction charges acts on the CCTO-BT/PDMS composite material to form strong polarization of the CCTO-BT particles, so that the charge induction of the bottom electrode is enhanced, and compared with the pure PDMS adopted in comparative example 1 (the CCTO-BT addition amount is 0 wt%), the CCTO-BT composite material has higher output performance. Along with the increase of the addition amount of the CCTO-BT, when the addition amount of the CCTO-BT is more than 2wt%, the CCTO-BT particles are mutually agglomerated, a leakage current path is formed in the composite layer, and the leakage current reduces the friction charge on the surface of the dielectric material and the induction charge on the bottom electrode, so that the friction electricity output performance is reduced.
FIG. 7 is a schematic diagram of Kelvin Probe Force Microscopy (KPFM) test surface potentials of the composite film materials prepared in example 2 and comparative example 1. As can be seen from fig. 7, the surface potential of the composite thin film material prepared according to the method of example 2 was 2.75V, and the surface potential of the pure PDMS sponge prepared according to comparative example 1 was 0.445V, indicating that the addition of CCTO-BT can increase the surface potential of the thin film material, thereby improving the frictional properties.
Comparative example 2
This example uses the same preparation as example 1, except that: and replacing the CCTO-BT in the step S2 with a single material CCTO, wherein the weight ratio is unchanged.
Comparative example 3
This example uses the same preparation as example 1, except that: replacing CCTO-BT in step S2Changing to single material Ba (OH) 2 ·H 2 O, the weight ratio is unchanged.
Comparative example 4
This example uses the same preparation as example 1, except that: replacing CCTO-BT in step S2 with single material TiO 2 The weight ratio is unchanged.
FIG. 8 (a) is a graph showing the change in capacitance of the composite film materials prepared in example 2 and comparative examples 1 to 4. FIG. 8 (b) is a graph showing the change in dielectric loss of the composite film materials prepared in example 2 and comparative examples 1 to 4. As can be seen from fig. 8 (a) and 8 (b), the CCTO-BT/PDMS based sponge film prepared in example 2 had the highest capacitance value and the lowest dielectric loss at a test frequency of 1,000hz was 0.0009.
By calculating C max ＝ε 0 ·S·ε r /d PDMS (ε 0 Is vacuum dielectric constant, S is effective electrode area, epsilon r Is the relative dielectric constant of the film, d PDMS Thickness of PDMS composite film) under the condition of test frequency of 100Hz, the composite film materials prepared in example 2 and comparative examples 1-4 (the added materials respectively correspond to CCTO-BT/PDMS, pure PDMS, CCTO/PDMS, BT/PDMS and TiO 2 PDMS) was 54.3, 31.88,3.85,3.42,3.07, respectively. Thus, the composite film material prepared by simultaneous addition of CCTO-BT prepared in example 2 had the best dielectric enhancement compared to comparative examples 1-4, and the corresponding triboelectric output performance was the best.
The present invention is not limited to the above embodiments, but the scope of the invention is defined by the claims.

Claims (9)

1. A method of preparing a composite film material, the method comprising:
step A: mixing and stirring calcium copper titanate-barium titanate, polydimethylsiloxane, a curing agent and a pore-forming agent to obtain a mixed solution;
and (B) step (B): coating the mixed solution on a substrate, carrying out curing reaction, stripping a film body formed on the substrate, soaking the film body in water with the temperature of 85-100 ℃, and drying the soaked film body to obtain the composite film material;
the preparation method of the copper calcium titanate-barium titanate comprises the following steps:
step A1: ba (OH) 2 •H 2 O, copper calcium titanate are dissolved in deionized water, and ultrasonic stirring is carried out to obtain a reaction solution;
step A2: placing the obtained reaction liquid into a reaction kettle for reaction, and carrying out pretreatment and impurity removal on the reacted material to obtain the copper calcium titanate-barium titanate;
in step A1, ba (OH) 2 •H 2 The mass ratio of O to copper calcium titanate is (2-4) 1;
in step A1, the ultrasonic agitation conditions include: stirring speed is 400 r/min-1000 r/min, and stirring time is 30 min-60 min;
in the step A2, the reaction conditions of the reaction solution in the reaction kettle include: the reaction temperature is 150-180 ℃ and the reaction time is 20-24 hours;
in step A2, the impurity removal process includes: the calcination temperature is 850-1000 ℃, and the calcination time is 1.5-2.5 h.
2. The method according to claim 1, wherein in the step a, the weight ratio of the copper calcium titanate-barium titanate is 0.01% to 15% based on the weight of the polydimethylsiloxane; and/or, in the step A, the weight ratio of the polydimethylsiloxane to the curing agent is (5-20): 1; and/or the weight ratio of the polydimethylsiloxane to the pore-forming agent is (0.5-5): 1; and/or the number of the groups of groups,
the curing agent is at least one selected from dimethyl methyl hydrogen siloxane, alkoxy silane and hydroxy silane; and/or the number of the groups of groups,
the pore-forming agent is selected from sodium chloride and/or sucrose; and/or the number of the groups of groups,
the step A also comprises a solvent, wherein the solvent is used for dispersing the copper calcium titanate-barium titanate, the solvent is at least one selected from toluene, tetrahydrofuran and methylene dichloride, and the weight ratio of the solvent to the polydimethylsiloxane is (0.5-5): 1.
3. the method according to claim 1 or 2, wherein in step B, the process of coating the mixed liquid on the substrate comprises: spin-coating the mixed solution on the substrate at the spin-coating speed of 350-650 r/min for 20-50 s; and/or the number of the groups of groups,
in step B, the conditions of the curing reaction include: the curing temperature is 70-90 ℃ and the curing time is 1.5-3 h; and/or the number of the groups of groups,
in step B, the conditions of the soaking process include: the water with the temperature of 85-100 ℃ is replaced every 9-12 h, and the total replacement is 4-6 times.
4. A composite film material prepared by the preparation method of any one of claims 1 to 3.
5. The composite film material according to claim 4, wherein the thickness of the composite film material is 1.2 μm to 1.8 μm and the surface potential is 2.5. 2.5V to 3.5V.
6. A method for producing a composite film material according to any one of claims 1 to 3 or the use of a composite film material according to claim 4 for producing a friction nano-generator.
7. A friction nano-generator, characterized in that the friction nano-generator uses the composite film material as described in claim 4 or 5 as a friction negative layer.
8. The triboelectric nano-generator according to claim 7, wherein a first copper foil is attached as a collector to the triboelectric negative layer and a second copper foil is used as a triboelectric positive layer; and, a step of, in the first embodiment,
and under the frequency of 1-4 Hz, the friction positive layer and the friction negative layer perform contact-separation action to generate alternating current signals with the same frequency, and the friction nano generator is obtained.
9. Use of the composite film material of claim 4 or 5 or the tribo-nano-generator of claim 7 or 8 in wearable devices and commercial capacitors.
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