US20230123778A1 - Triboelectric generating device and manufacturing method thereof - Google Patents
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Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/22—Methods relating to manufacturing, e.g. assembling, calibration
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
Definitions
- the present invention relates to a triboelectric power generating device and more particularly, to a triboelectric power generating device and a manufacturing method thereof, which does not require a physical space to generate friction motions unlike conventional pressured induced electric power generating devices, maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device, and effectively producing electricity.
- organic piezoelectric materials such as PVDF having excellent flexibility have a difficulty in producing a competitive product due to environmental hazards and high material cost.
- inorganic piezoelectric materials having poor flexibility have a durability problem that the material is ruptured by a continuous external pressure.
- triboelectric device not only a physical space is required to generate frictional motion between friction materials, but also a structure of the device is complicated and difficult to produce in large scale, and since the degree of abrasion due to friction of a material is large, a problem of low reliability in durability occurs.
- triboelectric materials have a disadvantage that it is difficult to produce in large scale due to the difficulty in joining an electrode and a friction material and the difference in the process method of applying the friction materials to the device. Therefore, it is required to develop a triboelectric generating device that is compensated for such disadvantages.
- a triboelectric device having a three-dimensional structure greatly improved an amount of generated current, and it was confirmed that triboelectric can be efficiently produced by rotating a disc electrode and triboelectric material having the shape of a bicycle wheel about a central axis, it showed that it is possible to efficiently produce electricity by grating a thin-film triboelectric material by micron unit and overlapping with the electrode, and then moving horizontally, and it was confirmed that a spring was attached to the grated triboelectric material and the electrode to make it possible to move horizontally between the material and the electrode and to convert high efficiency (up to 85%) physical energy into electric energy through energy conservation through the spring.
- a triboelectric device to be described in the present invention power is generated by removing a physically unnecessary structure between the triboelectric materials and using a phenomenon in which a contact between triboelectric material domains in nano units or maximum microns units is attached and detached by bending of the film. This is developed in terms of controlling the material surface shape of existing studies, and has also secured legitimacy by inheriting researches on utilizing various types of kinetic energy.
- the present invention provides a triboelectric power generating device which includes a triboelectric generation layer 300 including a friction portion having a junction structure which is located at a central portion and made of two or more different polymers, a first electrode 100 which is located to face one surface of the triboelectric generation layer 300 , and a second electrode 200 which is located to face the other surface of the triboelectric generation layer 300 .
- the present invention provides a manufacturing method of a triboelectric power generating device, which includes the steps of a) dissolving and dispersing, or dissolving and dispersing and then mixing, or melting and mixing two or more polymers having different dielectric properties in a solvent, respectively; b) masking a part of the surface of each of a first electrode and a second electrode having different materials; c) forming a triboelectric generation layer on the electrode by supplying a polymer solution which is mixed or unmixed in the step a) onto a unmasked exposed surface in one of the masked first and second electrodes; and d) laminating and then pressing the other electrode on which the triboelectric generation layer is not formed on the triboelectric generation layer.
- the triboelectric power generating device and the manufacturing method thereof according to the present invention does not require a physical space to generate friction motions unlike conventional pressured induced electric power generating devices, and maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device, and effectively producing electricity.
- FIG. 1 is a side cross-sectional schematic view of a triboelectric power generating device according to an example of the present invention.
- FIG. 2 A and FIG. 2 B are schematic views of an electrode masked according to the present invention.
- FIG. 3 is a side cross-sectional schematic view of a triboelectric power generating device according to another example of the present invention.
- FIGS. 4 and 5 are side cross-sectional schematic views of a triboelectric power generating device according to yet another example of the present invention.
- FIG. 6 is a graph of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to an example of the present invention.
- FIGS. 7 to 9 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to the comparative examples of the present invention.
- FIGS. 10 to 12 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to other examples of the present invention.
- FIG. 1 is a side cross-sectional schematic view of a triboelectric power generating device according to an exemplary embodiment of the present invention.
- a triboelectric power generating device according to the present invention includes a triboelectric generation layer 300 including a friction portion having a junction structure which is located at a central portion and made of two or more different polymers, a first electrode 100 which is located to face one surface of the triboelectric generation layer 300 , and a second electrode 200 which is located to face the other surface of the triboelectric generation layer 300 .
- the triboelectric power generating device is a device capable of converting all physical kinetic energy applied from the outside into electrical energy, can be utilized for wind power generation, tidal power generation, wave power generation and the like, and may be configured by a module in which a plurality of devices are repeatedly arranged and a generator in which a plurality of the modules are repeatedly arranged in order to implement each power generation method.
- the triboelectric power generating device can detect a physical motion, texture, hardness, or applied force and thus can be utilized even as a sensor.
- the triboelectric generation layer 300 is a triboelectric composite material in the form of a film including a friction portion for generating electricity, and the friction portion is formed of random junction portions in nanometers (nm) to micrometer ( ⁇ m) units.
- the junction portion may have a bulk-heterojunction structure in which two or more different materials are not uniformly contacted, or may have a multi junction structure, for example, a structure similar to an active layer of a bulk-heterojunction organic photovoltaics (see website).
- the multi junction structure is basically similar to the bulk-heterojunction structure, but may be a structure in which two or more materials are in contact with each other in a more regular shape (see website).
- the triboelectric generation layer 300 has a thickness of 1 nm to 10,000 ⁇ m, preferably 100 nm to 5,000 ⁇ m, and more preferably 1 to 1,000 ⁇ m.
- the thickness of the triboelectric generation layer 300 exceeds 10,000 ⁇ m, an electric field formed by the separation of charges generated at the junction portion does not affect a collector electrode, which may cause a problem that voltage and current cannot be generated.
- the thickness of the triboelectric generation layer 300 is less than 1 nm, a distance between the collector electrodes is too close, and thus a short phenomenon in devices may occur due to a tunneling phenomenon.
- the triboelectric generation layer (or the friction portion) is made of two or more different polymers having different dielectric properties, preferably two different polymers.
- the polymers may be materials that are inexpensive to manufacture and easy to mass-produce, that is, for example, polyamide, polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyester, polyurethane, polyvinyl butyral (PVB), polyacrylonitrile, natural rubber, polystyrene (PS), polyvinylidene chloride, polyethylene (PE), polypropylene (PP), polyimide, polyvinylchloride (PVC), and polydimethylsiloxane (PDMS), and preferably a mixture of PVC and PMMA, a mixture of PVC and PVA, a mixture of PVC and PVB, a mixture of PP and PMMA, and a mixture of PE and PMMA.
- PVA polyvinyl alcohol
- PMMA polymethylmethacrylate
- PVB polyurethane
- the mixing (including) ratio of the polymers is a weight ratio of 0.1:99.9 to 99.9:0.1.
- the mixing ratio of the polymers may be preferably a weight ratio of 20:80 to 80:20, more preferably a weight ratio of 40:60 to 60:40.
- each of the polymers preferably has a weight average molecular weight (Mw) of 10,000 to 5,000,000.
- the friction portion when the friction portion is composed of polymers having different dielectric properties, a binding between a backbone between polymers having different dielectric properties and a functional group is broken to form radicals, which means that a charge transfer between the two materials may occur due to a material transfer formed by electrons or radicals.
- the ionic monomolecules when ionic monomolecules are already present in the polymer or are formed due to friction, the ionic monomolecules may also migrate between heterogeneous polymers, which may cause a charge transfer. For this reason, charges between the two materials are separated to generate triboelectricity.
- general-purpose solvents such as acetone, tetrahydrofuran (THF), toluene, dichloromethane, chloroform, toluene, hexane, cyclohexane, dimethyl sulfoxide, NMP, water, and the like, may be used. That is, a composite material such as a composite film or composite particles may be formed by dissolving and then mixing the different polymers in such a solvent, melting and mixing the polymers in the solvent, or water-borne or solvent-borne dispersing and then mixing the different polymers in aqueous and non-aqueous solvents (that is, emulsion polymerization).
- the triboelectric power generating device has a simple structure in which the triboelectric generation layer (or the triboelectric material composite) 300 , which is easy to mass-produce, is located (inserted) between both electrodes (the first electrode 100 and the second electrode 200 ) and then a coating layer 400 for water-proof/moisture-proof and a coating layer 500 for supporting are coated.
- the triboelectric generating device since the triboelectric generating device has a very simple structure as compared to existing triboelectric devices, which has a structure similar to existing commercially available pressured induced electric power generating devices, mass-productivity and reliability are high.
- the first electrode 100 and the second electrode 200 are made of conductive materials that allow electricity to flow by the charging phenomenon, and any conductive material that satisfies this may be applied without particular limitation.
- conductive materials may include copper, aluminum, gold, silver, carbon felt, carbon paper, a composite added with carbon nanotubes (CNT), and the like, and the electrode is not particularly limited in its form such as porous foam in addition to the usual film form.
- the first electrode 100 and the second electrode 200 may be formed of different materials, respectively.
- the first electrode 100 and the second electrode 200 have thicknesses of 20 nm to 5 mm, preferably 50 nm to 1 mm, and more preferably 100 nm to 100 um.
- the thickness of the first electrode 100 and the second electrode 200 exceeds 5 mm, the flexibility corresponding to the wind of the device may be lowered, and when the thickness thereof is less than 20 nm, the performance of the device may be deteriorated due to an increase in resistance.
- the first electrode 100 and the second electrode 200 may be configured such that one end of each electrode protrudes from the triboelectric generation layer 300 in order to couple (ground) the wire (see FIG. 2 A and FIG. 2 B ).
- the first electrode 100 and the second electrode 200 prevent a short phenomenon between both electrodes.
- other remaining external exposed surface except for a part facing the triboelectric generation layer 300 may be masked by a tape coated with an adhesive component or an insulating material such as PP or PE.
- FIG. 2 B are schematic views of an electrode masked according to the present invention, wherein the masking treatment of the electrode may be performed on both sides (a and b of FIG. 2 A ) as illustrated in FIG. 2 A , may also be performed only on one side as illustrated in FIG. 2 B , and may vary depending on the performance and the like of a target electrode.
- the content of basic roles of electrode not described above may comply with the content of electrode used in the conventional triboelectric device.
- FIG. 3 is a side cross-sectional schematic view of a triboelectric power generating device according to another example of the present invention.
- the triboelectric power generating device may further include at least a pair of first coating layers 400 which are located on the outer peripheral surface of each of the first and second electrodes 100 , 200 to prevent water, moisture, and oxygen, and the like, if necessary.
- the triboelectric generating device may further include at least a pair of second coating layers 500 which are located on the outer peripheral surface of each of the first coating layers 400 to be supported.
- the first coating layer 400 is a layer for improving water-proof, moisture-proof, oxygen blocking, weather resistance, durability, and the like of the triboelectric power generating device according to the present invention and blocking the inside of the device from the outside.
- the material thereof may include epoxy, polyester, polyurethane, a mixture of paraffin wax and polyolefin, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polyamide (PA), polyvinyl alcohol (PVAL), ethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), and mixtures thereof, and may be used without particular limitation so long as the material has at least one property of water-proof, moisture-proof, oxygen blocking, weather resistance, and durability.
- the second coating layer 500 basically has a function of supporting the triboelectric generating device, and may also have the function of the first coating layer 400 , and more precisely, is a layer for applying elasticity to the device.
- Example of the material of the second coating layer 500 may include polyimide, polyether ether ketone, mixtures thereof, and mixtures of at least one thereof and compounds constituting the first coating layer 400 , and any materials may be used without particular limitation so long as the material enables the triboelectric power generating device to have a supporting function such as flexibility and durableness.
- the thickness of the first coating layer 400 is 100 nm to 10 mm, preferably 1 um to 1 mm, and more preferably 10 to 100 um.
- both ends of the first coating layer 400 may be configured to protrude from both ends of the first and second electrodes 100 , 200 as illustrated in FIG. 3 in order to protect the entire device including the collector electrode from water, moisture, and oxygen.
- the thickness of the second coating layer 500 is 1 um to 10 mm, preferably 5 um to 5 mm, and more preferably 10 um to 1 mm.
- the lengths of the first coating layer 400 and the second coating layer 500 are the same, but this is only an example, and any one end or both ends of the second coating layer 500 may also be configured to protrude from the first coating layer 400 . With such a protruding configuration, the coating layer is completely coated (wrapped) once more by an outer support layer, thereby improving a blocking effect from the outside.
- FIGS. 4 and 5 are side cross-sectional schematic views of a triboelectric power generating device according to yet another exemplary embodiment of the present invention. Meanwhile, the triboelectric power generating device according to the present invention, if necessary, as illustrated in FIG.
- first interface layer 600 and a second interface layer 700 may further include a first interface layer 600 and a second interface layer 700 , including a material selected from the group consisting of polyamide, polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyester, polyurethane, polyvinyl butyral (PVB), polyacrylonitrile, natural rubber, polystyrene (PS), polyvinylidene chloride, polyethylene (PE), polypropylene (PP), polyimide, polyvinylchloride (PVC), and polydimethylsiloxane (PDMS), between the triboelectric generation layer 300 and the first electrode 100 , and between the triboelectric generation layer 300 and the second electrode 200 , respectively.
- PVA polyvinyl alcohol
- PMMA polymethylmethacrylate
- PVB polyurethane
- PVB polyvinyl butyral
- PS polyacrylonitrile
- PS polystyrene
- PS polyvinylidene chloride
- PE
- the triboelectric power generating device includes the first interface layer 600 and the second interface layer 700 formed of a plurality of layers which may be cross-laminated with the triboelectric generation layer 300 as necessary to improve the performance of the device as illustrated in FIG. 5 , and the order thereof is not limited to FIG. 5 , and may be formed in various combinations in consideration of device performance.
- the first interface layer 600 and the second interface layer 700 are to further improve an interaction with the triboelectric generation layer 300 and a generation degree of electricity by preventing charges from flowing reversely from the triboelectric generation layer 300 .
- the first interface layer 600 and the second interface layer 700 have different triboelectric polarities, and for example, when the first interface layer 600 is PMMA, the second interface layer 700 may be PVC.
- the other interface layer may be selected from the group consisting of PVC, PDMS, polypropylene, polyethylene, and polyvinylidine chloride.
- the thickness of the first interface layer 600 and the second interface layer 700 is 1 nm to 1 mm, preferably 50 nm to 500 um, and more preferably 100 nm to 100 um.
- the thicknesses of the first interface layer 600 and the second interface layer 700 are out of the above range, there may be a problem that the flexibility of the device is reduced, the generation performance of the device is lowered, or a function of blocking charges that move reversely from the triboelectric generation layer 300 is not properly performed.
- the widths (width ⁇ length, based on an appearance viewed from the top) of the triboelectric generation layer 300 , the first electrode 100 , the second electrode 200 , the first coating layer 400 , the second coating layer 500 , the first interface layer 600 , and the second interface layer 700 described so far are not particularly limited, and may vary depending on the size and characteristics of a target triboelectric power generating device.
- the manufacturing method of the triboelectric power generating device includes the steps of a) dissolving and dispersing, or dissolving and dispersing and then mixing, or melting and mixing two or more polymers having different dielectric properties in a solvent, respectively; b) masking a part of the surface of each of a first electrode and a second electrode having different materials; c) supplying a polymer solution which is mixed or unmixed in step a) onto the unmasked exposed surface of any one of the masked first and second electrodes (the second electrode 200 in the drawing), and then drying or curing the polymer solution to form a triboelectric generation layer (or a polymer composite film) 300 on the electrode; and d) laminating and then pressing the other electrode (the first electrode 100 in the drawing), on which the triboelectric generation layer 300 is not formed, on the top of the
- a process of annealing the triboelectric generation layer 300 may be performed, and the manufacturing method of the triboelectric power generating device further includes the steps of e) forming a first coating layer 400 on the outer peripheral surface of each of the first electrode 100 and the second electrode 200 , and f) forming a second coating layer 500 on the outer peripheral surface of each of the first coating layers 400 , if necessary.
- the triboelectric power generating device in order to manufacture the triboelectric power generating device, first, it needs to dissolve and disperse, dissolve, disperse, and then mix, or melt and mix two or more polymers having different dielectric properties in an solvent, respectively (in the case of emulsion polymerization, mixing a water-borne solution and a solvent-borne solution, step a).
- the polymer (material) constitutes a friction portion for generating electricity in the triboelectric power generating device, and the detailed description thereof complies with the contents of the polymers described in the triboelectric power generating device.
- a laminated-type triboelectric power generating device may be manufactured by sequentially supplying each polymer solution on an electrode.
- Dissolving/dispersing the polymer in the solvent is a unique process of the present invention for further improving the mass-productivity of the polymer.
- the solvent that can be used may include organic solvents, such as linear and cyclic alkane-based compounds, aromatic-based compounds, ketone-based compounds, linear and cyclic ether-based compounds, amine-based compounds, sulfide-based compounds, and halogen-based compounds. More specifically, examples of general solvents may include hexane, cyclohexane, toluene, acetone, diethyl ether, tetrahydrofuran (THF), N-methyl-2-pyrrolidone, dimethyl sulfoxide, dichloromethane, and chloroform.
- organic solvents such as linear and cyclic alkane-based compounds, aromatic-based compounds, ketone-based compounds, linear and cyclic ether-based compounds, amine-based compounds, sulfide-based compounds, and halogen-
- the concentration at which the polymer is dissolved in the solvent is 0.1 to 10,000 g/kg, preferably 1 to 5,000 g/kg, and more preferably 10 to 1,000 g/kg.
- concentration at which the polymer is dissolved in the solvent is out of the above range, an effect obtained by dissolving the polymer in the solvent may be insignificant or the mixing process may be difficult.
- the temperature at which the polymer is dissolved in the solvent is 0° C. to 70° C., preferably 10° C. to 50° C., and more preferably 25° C. to 40° C. When the temperature at which the polymer is dissolved in the solvent is out of the above range, there may be a problem that the polymer is insoluble or decomposed, or increases the risk of explosion.
- a mixing ratio of each polymer solution may be a weight ratio of 0.1:99.9 to 99.9:0.1, preferably a weight ratio of 20:80 to 80:20, and more preferably a weight ratio of 40:60 to 60:40.
- additives such as plasticizers and impact modifiers may be additionally added, if necessary.
- step b After preparing the electrodes (the first electrode and the second electrode) having different materials, a part of each surface is masked (step b).
- the first electrode and the second electrode should be made of different materials to enable the generation of triboelectricity.
- the reason for masking a part of the surface of the first and second electrodes with a tape is to prevent a short phenomenon between both electrodes and to keep an area of the triboelectric generation layer the same for each device, so that a part to which the polymer mixed solution is not to be applied (or supplied) is defined as a masking application portion.
- the detailed description of the electrodes and the masking complies with the contents of the electrodes and masking described in the triboelectric power generating device.
- each electrode After the surface of each electrode is masked, by supplying a polymer solution which is mixed or unmixed in step a) on a unmasked exposed surface in any one of the first and second electrodes (the second electrode 200 in the drawing), and then drying or curing the polymer solution to form a triboelectric generation layer (or a polymer composite film 300 ) on an electrode (step c).
- a polymer solution which is mixed or unmixed in step a) on a unmasked exposed surface in any one of the first and second electrodes (the second electrode 200 in the drawing), and then drying or curing the polymer solution to form a triboelectric generation layer (or a polymer composite film 300 ) on an electrode (step c).
- the method of supplying the polymer mixed solution on the electrode there are drop casting, screen printing, spin coating, rotogravure printing, spray coating, inkjet printing, and the like.
- the triboelectric generation layer 300 has a thickness of 1 nm to 10,000 ⁇ m, preferably 100 nm to 5,000 ⁇ m, and more preferably 1 to 1,000 ⁇ m.
- the thickness of the triboelectric generation layer 300 exceeds 10,000 ⁇ m, an electric field generated by the separation of charges generated at a junction portion does not affect a collector electrode, which may cause a problem that voltage and current cannot be generated.
- the thickness thereof is less than 1 nm, a distance between the collector electrodes is too close, which may cause a short phenomenon in devices due to a tunneling phenomenon.
- the manufacturing method of the triboelectric power generating device further includes the step of re-supplying the polymer mixed solution used in step c) one or more times, preferably 1 to 100 times, and more preferably 5 to 20 times onto the surface of the polymer composite film (the triboelectric generation layer) formed in step c) and then drying the solution, if necessary.
- this is a process for adjusting the thickness of the polymer composite film, as the concentration of the polymer in step a) is lowered, the number of re-supplying times may be increased. Therefore, when the concentration of the polymer is high, the re-supplying process of such a polymer mixed solution may not be performed.
- the other electrode (the first electrode 100 in the drawing) in which the triboelectric generation layer 300 is not formed is laminated and then pressed on the annealed triboelectric generation layer 300 .
- the pressing may be performed under a temperature of 40° C. to 250° C. and a pressure of 1 gF to 100 kgF by a general pressing method such as a roll-press method and a hot-press method.
- a process of annealing the triboelectric generation layer 300 is performed.
- the annealing process is a process in which the triboelectric generation layer 300 is made at a predetermined temperature, maintained at the corresponding temperature for a predetermined time, and then cooled to room temperature, and is used for optimizing the power generation efficiency according to the control of the total junction area by controlling the aggregation degree of polymers in the triboelectric generation layer 300 .
- the temperature, the required time, and the number of times of the annealing process may be arbitrarily changed in consideration of physical properties of the target power generating device, but the annealing process may be performed 1 to 24 times, preferably 1 to 10 times at a temperature of 30° C. to 250° C., preferably 50° C. to 150° C. for 1 to 3,600 seconds, preferably 10 to 180 seconds.
- the interface layers (the first interface layer 600 and the second interface layer 700 in FIG. 4 ) may be formed between the triboelectric generation layer 300 and the first electrode 100 , and between the triboelectric generation layer 300 and the second electrode 200 (alternatively, on both sides of the triboelectric generation layer 300 ), respectively.
- This is a phenomenon in which the polymer of the triboelectric generation layer 300 leaks up and down by heating during the annealing process, and is caused by a difference in density.
- the first interface layer 600 and the second interface layer 700 may be induced to be formed with polymers having opposite triboelectric polarities to each other.
- the interface layer may be intentionally formed at a time before forming the triboelectric generation layer (or the polymer composite film) 300 on the electrode.
- the first interface layer 600 and the second interface layer 700 may be formed of a plurality of layers to be cross-laminated with the triboelectric generation layer 300 , and the order thereof is not limited to FIG. 5 and may be formed in various combinations in consideration of device performance.
- the performance of the device may be further improved.
- the annealing process may be further performed, if necessary.
- the description of the material, the thickness, and the like of the first coating layer 400 and the second coating layer 500 complies with the contents described in the triboelectric power generating device.
- PMMA was dissolved in tetrahydrofuran (THF) at room temperature at a concentration of 0.1 g/mL
- PVC was also dissolved in THF at room temperature at the same concentration of 0.1 g/mL
- the PMMA solution and the PVC solution were mixed at a weight ratio of 1:1 to prepare a polymer mixed solution.
- a PMMA-PVC polymer mixed solution was bar-coated and dried to form a triboelectric generation layer, and then the PMMA-PVC polymer mixed solution was additionally bar-coated 5 times on the upper side (surface) of the triboelectric generation layer and dried.
- a triboelectric generation layer was annealed at 70° C. to 90° C. for about 5 seconds by using a laminator (Kolami-320S, Kolami, in Korea) and pressed at a pressure of about 1 kgF to prepare a triboelectric power generating device.
- a triboelectric power generating device was prepared in the same manner as in Example 1, except that the PVC and PMMA layers were sequentially coated one time and laminated without mixing the PVC and PMMA solutions.
- a triboelectric power generating device was prepared in the same manner as in Example 2, except that the PVC and PMMA layers were alternately coated 3 times and laminated.
- a triboelectric power generating device was prepared in the same manner as in Example 2, except that the PVC and PMMA layers were alternately coated 5 times and laminated.
- a triboelectric power generating device was prepared in the same manner as in Example 1, except that drop casting, drying, and annealing processes were excluded by not using the polymer mixed solution.
- a triboelectric power generating device was prepared in the same manner as in Example 1, except that a PMMA polymer solution was used by excluding a PVC solution instead of a PMMA-PVC polymer mixed solution (that is, the triboelectric generation layer was configured by only a PMMA polymer).
- a triboelectric power generating device was prepared in the same manner as in Example 1, except that a PVC polymer solution is used by excluding the PMMA solution instead of a PMMA-PVC polymer mixed solution (that is, the triboelectric generation layer was configured by only a PVC polymer)
- FIG. 6 is a graph of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to an example of the present invention
- FIGS. 7 to 9 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to the comparative examples of the present invention.
- FIG. 6 corresponds to Example 1
- FIGS. 7 to 9 correspond to Comparative Examples 1 to 3, respectively.
- FIGS. 10 to 12 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to other examples of the present invention, and FIGS. 10 to 12 correspond to Examples 2 to 4, respectively.
- the laminated-type triboelectric power generating devices prepared in Examples 2 to 4 as in Example 1 for the triboelectric power generating device which is not a laminated type, it can be confirmed that the electricity is immediately generated depending on an impact/change applied to the device (see FIGS. 10 to 12 ). In addition, it can be confirmed that as the number of laminated layers increases, the voltage and overall current amount of electricity generated increases.
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Abstract
Disclosed are a triboelectric power generating device and a manufacturing method thereof, which does not require a physical space to generate friction motions unlike conventional pressured induced electric power generating devices, maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device, and effectively producing electricity. The triboelectric power generating device includes a triboelectric generation layer including a friction portion having a junction structure which is located at a central portion and made of two or more different polymers, a first electrode which is located to face one surface of the triboelectric generation layer, and a second electrode which is located to face the other surface of the triboelectric generation layer.
Description
- This application is a Divisional of U.S. application Ser. No. 16/764,903 filed May 18, 2020, which is National Stage of International Application No. PCT/KR2018/013687 filed Nov. 12, 2018, claiming priority based on Korean Patent Application No. 10-2017-0156387 filed Nov. 22, 2017, the contents of which are incorporated by reference in their entireties.
- The present invention relates to a triboelectric power generating device and more particularly, to a triboelectric power generating device and a manufacturing method thereof, which does not require a physical space to generate friction motions unlike conventional pressured induced electric power generating devices, maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device, and effectively producing electricity.
- In the case of general pressured induced electric power generating devices, organic piezoelectric materials such as PVDF having excellent flexibility have a difficulty in producing a competitive product due to environmental hazards and high material cost. In addition, inorganic piezoelectric materials having poor flexibility have a durability problem that the material is ruptured by a continuous external pressure. In the case of triboelectric device, not only a physical space is required to generate frictional motion between friction materials, but also a structure of the device is complicated and difficult to produce in large scale, and since the degree of abrasion due to friction of a material is large, a problem of low reliability in durability occurs. In addition, existing triboelectric materials have a disadvantage that it is difficult to produce in large scale due to the difficulty in joining an electrode and a friction material and the difference in the process method of applying the friction materials to the device. Therefore, it is required to develop a triboelectric generating device that is compensated for such disadvantages.
- Here, when describing the history of the development of the conventional triboelectric devices that have been conducted so far, in 2012, it was confirmed that different types of triboelectric materials were bilayered, and then electrodes face the outside, thereby producing electricity through vertical and horizontal movement between the triboelectric materials. In 2013, it was possible to produce electricity even by intersecting different types of triboelectric materials, and individual triboelectric devices were formed in a multiple layer (parallel structure) to improve power generation efficiency. In 2014, a triboelectric device having a three-dimensional structure greatly improved an amount of generated current, and it was confirmed that triboelectric can be efficiently produced by rotating a disc electrode and triboelectric material having the shape of a bicycle wheel about a central axis, it showed that it is possible to efficiently produce electricity by grating a thin-film triboelectric material by micron unit and overlapping with the electrode, and then moving horizontally, and it was confirmed that a spring was attached to the grated triboelectric material and the electrode to make it possible to move horizontally between the material and the electrode and to convert high efficiency (up to 85%) physical energy into electric energy through energy conservation through the spring.
- In 2015, it showed that a structure was improved so that the friction materials could move smoothly even with little energy applied by inserting a steel rod between the friction materials for the use of a bearing, and nevertheless, triboelectric power generation efficiency was not lowered significantly. In addition, it was found that a hybrid system can supply the amount of voltage or current more stably by connecting an electromagnetic generator (AC) and a triboelectric element (AC) in series or in parallel. In addition, it was confirmed that power can be produced simultaneously from light and kinetic energy by connecting a solar cell (DC) and the triboelectric device (AC). Thereafter, researches are being conducted to improve the power generation efficiency through micro- or nano-unit patterning between the triboelectric materials, and the efficiency has been further improved by changing the material or the shape (vertical, horizontal, rotational, bent, etc.) of receiving the kinetic energy. The latest notable research result showed the possibility of use as a wind generator by fixing one side of the triboelectric device to a substrate and leaving the other side shaken in the wind.
- Unlike all the triboelectric devices introduced above, in a triboelectric device to be described in the present invention, power is generated by removing a physically unnecessary structure between the triboelectric materials and using a phenomenon in which a contact between triboelectric material domains in nano units or maximum microns units is attached and detached by bending of the film. This is developed in terms of controlling the material surface shape of existing studies, and has also secured legitimacy by inheriting researches on utilizing various types of kinetic energy.
- Therefore, it is an object of the present invention to provide a triboelectric generating device and a manufacturing method thereof, which does not require a physical space to generate a friction motion unlike conventional pressured induced electric power generating devices, and maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device and effectively producing electricity.
- In order to achieve the object, the present invention provides a triboelectric power generating device which includes a
triboelectric generation layer 300 including a friction portion having a junction structure which is located at a central portion and made of two or more different polymers, afirst electrode 100 which is located to face one surface of thetriboelectric generation layer 300, and asecond electrode 200 which is located to face the other surface of thetriboelectric generation layer 300. - In addition, the present invention provides a manufacturing method of a triboelectric power generating device, which includes the steps of a) dissolving and dispersing, or dissolving and dispersing and then mixing, or melting and mixing two or more polymers having different dielectric properties in a solvent, respectively; b) masking a part of the surface of each of a first electrode and a second electrode having different materials; c) forming a triboelectric generation layer on the electrode by supplying a polymer solution which is mixed or unmixed in the step a) onto a unmasked exposed surface in one of the masked first and second electrodes; and d) laminating and then pressing the other electrode on which the triboelectric generation layer is not formed on the triboelectric generation layer.
- The triboelectric power generating device and the manufacturing method thereof according to the present invention does not require a physical space to generate friction motions unlike conventional pressured induced electric power generating devices, and maximizes a surface area by the junction friction portion of a friction material composite that is inexpensive and easy to mass-produce, thereby improving the durability of a generating device, and effectively producing electricity.
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FIG. 1 is a side cross-sectional schematic view of a triboelectric power generating device according to an example of the present invention. -
FIG. 2A andFIG. 2B are schematic views of an electrode masked according to the present invention. -
FIG. 3 is a side cross-sectional schematic view of a triboelectric power generating device according to another example of the present invention. -
FIGS. 4 and 5 are side cross-sectional schematic views of a triboelectric power generating device according to yet another example of the present invention. -
FIG. 6 is a graph of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to an example of the present invention. -
FIGS. 7 to 9 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to the comparative examples of the present invention. -
FIGS. 10 to 12 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to other examples of the present invention. - Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
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FIG. 1 is a side cross-sectional schematic view of a triboelectric power generating device according to an exemplary embodiment of the present invention. As illustrated inFIG. 1 , a triboelectric power generating device according to the present invention includes atriboelectric generation layer 300 including a friction portion having a junction structure which is located at a central portion and made of two or more different polymers, afirst electrode 100 which is located to face one surface of thetriboelectric generation layer 300, and asecond electrode 200 which is located to face the other surface of thetriboelectric generation layer 300. - The triboelectric power generating device according to the present invention is a device capable of converting all physical kinetic energy applied from the outside into electrical energy, can be utilized for wind power generation, tidal power generation, wave power generation and the like, and may be configured by a module in which a plurality of devices are repeatedly arranged and a generator in which a plurality of the modules are repeatedly arranged in order to implement each power generation method. In addition, the triboelectric power generating device according to the present invention can detect a physical motion, texture, hardness, or applied force and thus can be utilized even as a sensor.
- The
triboelectric generation layer 300 is a triboelectric composite material in the form of a film including a friction portion for generating electricity, and the friction portion is formed of random junction portions in nanometers (nm) to micrometer (μm) units. The junction portion may have a bulk-heterojunction structure in which two or more different materials are not uniformly contacted, or may have a multi junction structure, for example, a structure similar to an active layer of a bulk-heterojunction organic photovoltaics (see website). Meanwhile, the multi junction structure is basically similar to the bulk-heterojunction structure, but may be a structure in which two or more materials are in contact with each other in a more regular shape (see website). Thus, despite the extremely short travel distances of each polarized triboelectric material, a surface area is maximized, thereby improving the reliability of the material durability and efficiently producing electricity. - Meanwhile, the
triboelectric generation layer 300 has a thickness of 1 nm to 10,000 μm, preferably 100 nm to 5,000 μm, and more preferably 1 to 1,000 μm. When the thickness of thetriboelectric generation layer 300 exceeds 10,000 μm, an electric field formed by the separation of charges generated at the junction portion does not affect a collector electrode, which may cause a problem that voltage and current cannot be generated. When the thickness of thetriboelectric generation layer 300 is less than 1 nm, a distance between the collector electrodes is too close, and thus a short phenomenon in devices may occur due to a tunneling phenomenon. - The triboelectric generation layer (or the friction portion) is made of two or more different polymers having different dielectric properties, preferably two different polymers. The polymers may be materials that are inexpensive to manufacture and easy to mass-produce, that is, for example, polyamide, polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyester, polyurethane, polyvinyl butyral (PVB), polyacrylonitrile, natural rubber, polystyrene (PS), polyvinylidene chloride, polyethylene (PE), polypropylene (PP), polyimide, polyvinylchloride (PVC), and polydimethylsiloxane (PDMS), and preferably a mixture of PVC and PMMA, a mixture of PVC and PVA, a mixture of PVC and PVB, a mixture of PP and PMMA, and a mixture of PE and PMMA. When the polymers are used in two kinds of mixture (i.e., when the triboelectric generation layer includes two different polymers), the mixing (including) ratio of the polymers is a weight ratio of 0.1:99.9 to 99.9:0.1. Despite including one of the two polymers in a small amount, the effect according to the present invention occurs, and the mixing ratio of the polymers may be preferably a weight ratio of 20:80 to 80:20, more preferably a weight ratio of 40:60 to 60:40. In addition, each of the polymers preferably has a weight average molecular weight (Mw) of 10,000 to 5,000,000.
- As such, when the friction portion is composed of polymers having different dielectric properties, a binding between a backbone between polymers having different dielectric properties and a functional group is broken to form radicals, which means that a charge transfer between the two materials may occur due to a material transfer formed by electrons or radicals. In addition, when ionic monomolecules are already present in the polymer or are formed due to friction, the ionic monomolecules may also migrate between heterogeneous polymers, which may cause a charge transfer. For this reason, charges between the two materials are separated to generate triboelectricity.
- Meanwhile, in order to more increase the mass-productivity of the polymer materials, general-purpose solvents, such as acetone, tetrahydrofuran (THF), toluene, dichloromethane, chloroform, toluene, hexane, cyclohexane, dimethyl sulfoxide, NMP, water, and the like, may be used. That is, a composite material such as a composite film or composite particles may be formed by dissolving and then mixing the different polymers in such a solvent, melting and mixing the polymers in the solvent, or water-borne or solvent-borne dispersing and then mixing the different polymers in aqueous and non-aqueous solvents (that is, emulsion polymerization).
- Accordingly, the triboelectric power generating device according to the present invention has a simple structure in which the triboelectric generation layer (or the triboelectric material composite) 300, which is easy to mass-produce, is located (inserted) between both electrodes (the
first electrode 100 and the second electrode 200) and then acoating layer 400 for water-proof/moisture-proof and acoating layer 500 for supporting are coated. Thus, since the triboelectric generating device has a very simple structure as compared to existing triboelectric devices, which has a structure similar to existing commercially available pressured induced electric power generating devices, mass-productivity and reliability are high. - Next, the
first electrode 100 and thesecond electrode 200 are made of conductive materials that allow electricity to flow by the charging phenomenon, and any conductive material that satisfies this may be applied without particular limitation. Examples of such conductive materials may include copper, aluminum, gold, silver, carbon felt, carbon paper, a composite added with carbon nanotubes (CNT), and the like, and the electrode is not particularly limited in its form such as porous foam in addition to the usual film form. - However, the
first electrode 100 and thesecond electrode 200 may be formed of different materials, respectively. In addition, thefirst electrode 100 and thesecond electrode 200 have thicknesses of 20 nm to 5 mm, preferably 50 nm to 1 mm, and more preferably 100 nm to 100 um. When the thickness of thefirst electrode 100 and thesecond electrode 200 exceeds 5 mm, the flexibility corresponding to the wind of the device may be lowered, and when the thickness thereof is less than 20 nm, the performance of the device may be deteriorated due to an increase in resistance. - Meanwhile, the
first electrode 100 and thesecond electrode 200 may be configured such that one end of each electrode protrudes from thetriboelectric generation layer 300 in order to couple (ground) the wire (seeFIG. 2A andFIG. 2B ). In addition, in the present invention, thefirst electrode 100 and thesecond electrode 200 prevent a short phenomenon between both electrodes. Further, in order to identically maintain the area of thetriboelectric generation layer 300 for each device, other remaining external exposed surface except for a part facing thetriboelectric generation layer 300 may be masked by a tape coated with an adhesive component or an insulating material such as PP or PE.FIG. 2A andFIG. 2B are schematic views of an electrode masked according to the present invention, wherein the masking treatment of the electrode may be performed on both sides (a and b ofFIG. 2A ) as illustrated inFIG. 2A , may also be performed only on one side as illustrated inFIG. 2B , and may vary depending on the performance and the like of a target electrode. In addition, the content of basic roles of electrode not described above may comply with the content of electrode used in the conventional triboelectric device. -
FIG. 3 is a side cross-sectional schematic view of a triboelectric power generating device according to another example of the present invention. On the other hand, the triboelectric power generating device, as illustrated inFIG. 3 , may further include at least a pair of first coating layers 400 which are located on the outer peripheral surface of each of the first andsecond electrodes - Specifically, the
first coating layer 400 is a layer for improving water-proof, moisture-proof, oxygen blocking, weather resistance, durability, and the like of the triboelectric power generating device according to the present invention and blocking the inside of the device from the outside. Examples of the material thereof may include epoxy, polyester, polyurethane, a mixture of paraffin wax and polyolefin, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyethylene naphthalate (PEN), polyamide (PA), polyvinyl alcohol (PVAL), ethylene vinyl alcohol (EVOH), polyvinylidene chloride (PVDC), and mixtures thereof, and may be used without particular limitation so long as the material has at least one property of water-proof, moisture-proof, oxygen blocking, weather resistance, and durability. - In addition, the
second coating layer 500 basically has a function of supporting the triboelectric generating device, and may also have the function of thefirst coating layer 400, and more precisely, is a layer for applying elasticity to the device. Example of the material of thesecond coating layer 500 may include polyimide, polyether ether ketone, mixtures thereof, and mixtures of at least one thereof and compounds constituting thefirst coating layer 400, and any materials may be used without particular limitation so long as the material enables the triboelectric power generating device to have a supporting function such as flexibility and durableness. - The thickness of the
first coating layer 400 is 100 nm to 10 mm, preferably 1 um to 1 mm, and more preferably 10 to 100 um. When the thickness of thefirst coating layer 400 is out of the above range, there may be a problem that the flexibility of the device is reduced or a function such as water-proof/moisture-proof is not sufficiently performed. Meanwhile, both ends of thefirst coating layer 400 may be configured to protrude from both ends of the first andsecond electrodes FIG. 3 in order to protect the entire device including the collector electrode from water, moisture, and oxygen. - In addition, the thickness of the
second coating layer 500 is 1 um to 10 mm, preferably 5 um to 5 mm, and more preferably 10 um to 1 mm. When the thickness of thesecond coating layer 500 is out of the above range, there may be a problem that the flexibility of the device is reduced or the function of supporting the device is not be sufficiently performed. Meanwhile, inFIG. 3 , the lengths of thefirst coating layer 400 and thesecond coating layer 500 are the same, but this is only an example, and any one end or both ends of thesecond coating layer 500 may also be configured to protrude from thefirst coating layer 400. With such a protruding configuration, the coating layer is completely coated (wrapped) once more by an outer support layer, thereby improving a blocking effect from the outside. -
FIGS. 4 and 5 are side cross-sectional schematic views of a triboelectric power generating device according to yet another exemplary embodiment of the present invention. Meanwhile, the triboelectric power generating device according to the present invention, if necessary, as illustrated inFIG. 4 , may further include afirst interface layer 600 and asecond interface layer 700, including a material selected from the group consisting of polyamide, polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), polyester, polyurethane, polyvinyl butyral (PVB), polyacrylonitrile, natural rubber, polystyrene (PS), polyvinylidene chloride, polyethylene (PE), polypropylene (PP), polyimide, polyvinylchloride (PVC), and polydimethylsiloxane (PDMS), between thetriboelectric generation layer 300 and thefirst electrode 100, and between thetriboelectric generation layer 300 and thesecond electrode 200, respectively. In addition, the triboelectric power generating device according to the present invention includes thefirst interface layer 600 and thesecond interface layer 700 formed of a plurality of layers which may be cross-laminated with thetriboelectric generation layer 300 as necessary to improve the performance of the device as illustrated inFIG. 5 , and the order thereof is not limited toFIG. 5 , and may be formed in various combinations in consideration of device performance. - The
first interface layer 600 and thesecond interface layer 700 are to further improve an interaction with thetriboelectric generation layer 300 and a generation degree of electricity by preventing charges from flowing reversely from thetriboelectric generation layer 300. Thefirst interface layer 600 and thesecond interface layer 700 have different triboelectric polarities, and for example, when thefirst interface layer 600 is PMMA, thesecond interface layer 700 may be PVC. Specifically, when any one of thefirst interface layer 600 and thesecond interface layer 700 is selected from the group consisting of PMMA, polyamide, polyvinyl alcohol, polybutyral, and polystyrene, the other interface layer may be selected from the group consisting of PVC, PDMS, polypropylene, polyethylene, and polyvinylidine chloride. - In addition, the thickness of the
first interface layer 600 and thesecond interface layer 700 is 1 nm to 1 mm, preferably 50 nm to 500 um, and more preferably 100 nm to 100 um. When the thicknesses of thefirst interface layer 600 and thesecond interface layer 700 are out of the above range, there may be a problem that the flexibility of the device is reduced, the generation performance of the device is lowered, or a function of blocking charges that move reversely from thetriboelectric generation layer 300 is not properly performed. - Meanwhile, the widths (width×length, based on an appearance viewed from the top) of the
triboelectric generation layer 300, thefirst electrode 100, thesecond electrode 200, thefirst coating layer 400, thesecond coating layer 500, thefirst interface layer 600, and thesecond interface layer 700 described so far are not particularly limited, and may vary depending on the size and characteristics of a target triboelectric power generating device. - Next, a manufacturing method of a triboelectric power generating device according to the present invention will be described with reference to
FIGS. 1 and 3 . The manufacturing method of the triboelectric power generating device includes the steps of a) dissolving and dispersing, or dissolving and dispersing and then mixing, or melting and mixing two or more polymers having different dielectric properties in a solvent, respectively; b) masking a part of the surface of each of a first electrode and a second electrode having different materials; c) supplying a polymer solution which is mixed or unmixed in step a) onto the unmasked exposed surface of any one of the masked first and second electrodes (thesecond electrode 200 in the drawing), and then drying or curing the polymer solution to form a triboelectric generation layer (or a polymer composite film) 300 on the electrode; and d) laminating and then pressing the other electrode (thefirst electrode 100 in the drawing), on which thetriboelectric generation layer 300 is not formed, on the top of thetriboelectric generation layer 300. - Meanwhile, after at least one of steps c) and d) is performed, a process of annealing the
triboelectric generation layer 300 may be performed, and the manufacturing method of the triboelectric power generating device further includes the steps of e) forming afirst coating layer 400 on the outer peripheral surface of each of thefirst electrode 100 and thesecond electrode 200, and f) forming asecond coating layer 500 on the outer peripheral surface of each of the first coating layers 400, if necessary. - According to the present invention, in order to manufacture the triboelectric power generating device, first, it needs to dissolve and disperse, dissolve, disperse, and then mix, or melt and mix two or more polymers having different dielectric properties in an solvent, respectively (in the case of emulsion polymerization, mixing a water-borne solution and a solvent-borne solution, step a). The polymer (material) constitutes a friction portion for generating electricity in the triboelectric power generating device, and the detailed description thereof complies with the contents of the polymers described in the triboelectric power generating device. On the other hand, when the polymer is not mixed after being dissolved and dispersed in each solvent, a laminated-type triboelectric power generating device may be manufactured by sequentially supplying each polymer solution on an electrode.
- Dissolving/dispersing the polymer in the solvent is a unique process of the present invention for further improving the mass-productivity of the polymer. Examples of the solvent that can be used may include organic solvents, such as linear and cyclic alkane-based compounds, aromatic-based compounds, ketone-based compounds, linear and cyclic ether-based compounds, amine-based compounds, sulfide-based compounds, and halogen-based compounds. More specifically, examples of general solvents may include hexane, cyclohexane, toluene, acetone, diethyl ether, tetrahydrofuran (THF), N-methyl-2-pyrrolidone, dimethyl sulfoxide, dichloromethane, and chloroform.
- The concentration at which the polymer is dissolved in the solvent is 0.1 to 10,000 g/kg, preferably 1 to 5,000 g/kg, and more preferably 10 to 1,000 g/kg. When the concentration at which the polymer is dissolved in the solvent is out of the above range, an effect obtained by dissolving the polymer in the solvent may be insignificant or the mixing process may be difficult. In addition, the temperature at which the polymer is dissolved in the solvent is 0° C. to 70° C., preferably 10° C. to 50° C., and more preferably 25° C. to 40° C. When the temperature at which the polymer is dissolved in the solvent is out of the above range, there may be a problem that the polymer is insoluble or decomposed, or increases the risk of explosion.
- At this time, a mixing ratio of each polymer solution may be a weight ratio of 0.1:99.9 to 99.9:0.1, preferably a weight ratio of 20:80 to 80:20, and more preferably a weight ratio of 40:60 to 60:40. Meanwhile, when performing step a) of mixing the different polymer solutions, in order to reinforce the flexibility and impact strength of each polymer material, additives such as plasticizers and impact modifiers may be additionally added, if necessary.
- Next, after preparing the electrodes (the first electrode and the second electrode) having different materials, a part of each surface is masked (step b). The first electrode and the second electrode should be made of different materials to enable the generation of triboelectricity. The reason for masking a part of the surface of the first and second electrodes with a tape is to prevent a short phenomenon between both electrodes and to keep an area of the triboelectric generation layer the same for each device, so that a part to which the polymer mixed solution is not to be applied (or supplied) is defined as a masking application portion. In addition, the detailed description of the electrodes and the masking complies with the contents of the electrodes and masking described in the triboelectric power generating device.
- After the surface of each electrode is masked, by supplying a polymer solution which is mixed or unmixed in step a) on a unmasked exposed surface in any one of the first and second electrodes (the
second electrode 200 in the drawing), and then drying or curing the polymer solution to form a triboelectric generation layer (or a polymer composite film 300) on an electrode (step c). As the method of supplying the polymer mixed solution on the electrode, there are drop casting, screen printing, spin coating, rotogravure printing, spray coating, inkjet printing, and the like. In addition, thetriboelectric generation layer 300 has a thickness of 1 nm to 10,000 μm, preferably 100 nm to 5,000 μm, and more preferably 1 to 1,000 μm. When the thickness of thetriboelectric generation layer 300 exceeds 10,000 μm, an electric field generated by the separation of charges generated at a junction portion does not affect a collector electrode, which may cause a problem that voltage and current cannot be generated. When the thickness thereof is less than 1 nm, a distance between the collector electrodes is too close, which may cause a short phenomenon in devices due to a tunneling phenomenon. - Meanwhile, the manufacturing method of the triboelectric power generating device further includes the step of re-supplying the polymer mixed solution used in step c) one or more times, preferably 1 to 100 times, and more preferably 5 to 20 times onto the surface of the polymer composite film (the triboelectric generation layer) formed in step c) and then drying the solution, if necessary. As this is a process for adjusting the thickness of the polymer composite film, as the concentration of the polymer in step a) is lowered, the number of re-supplying times may be increased. Therefore, when the concentration of the polymer is high, the re-supplying process of such a polymer mixed solution may not be performed.
- In addition, it is described in the present specification that the polymer solution and the mixed solution are first prepared, and then the surface of the electrode is masked, but this is only for convenience of description and the order thereof may be changed or proceed simultaneously.
- When the triboelectric generation layer is formed on the electrode as described above, the other electrode (the
first electrode 100 in the drawing) in which thetriboelectric generation layer 300 is not formed is laminated and then pressed on the annealedtriboelectric generation layer 300. The pressing may be performed under a temperature of 40° C. to 250° C. and a pressure of 1 gF to 100 kgF by a general pressing method such as a roll-press method and a hot-press method. - On the other hand, after at least one of steps c) and d) is performed, a process of annealing the
triboelectric generation layer 300 is performed. The annealing process is a process in which thetriboelectric generation layer 300 is made at a predetermined temperature, maintained at the corresponding temperature for a predetermined time, and then cooled to room temperature, and is used for optimizing the power generation efficiency according to the control of the total junction area by controlling the aggregation degree of polymers in thetriboelectric generation layer 300. The temperature, the required time, and the number of times of the annealing process may be arbitrarily changed in consideration of physical properties of the target power generating device, but the annealing process may be performed 1 to 24 times, preferably 1 to 10 times at a temperature of 30° C. to 250° C., preferably 50° C. to 150° C. for 1 to 3,600 seconds, preferably 10 to 180 seconds. - Meanwhile, when the annealing process is performed, as illustrated in
FIG. 4 , the interface layers (thefirst interface layer 600 and thesecond interface layer 700 inFIG. 4 ) may be formed between thetriboelectric generation layer 300 and thefirst electrode 100, and between thetriboelectric generation layer 300 and the second electrode 200 (alternatively, on both sides of the triboelectric generation layer 300), respectively. This is a phenomenon in which the polymer of thetriboelectric generation layer 300 leaks up and down by heating during the annealing process, and is caused by a difference in density. Thefirst interface layer 600 and thesecond interface layer 700 may be induced to be formed with polymers having opposite triboelectric polarities to each other. - Meanwhile, in addition to the method formed by the annealing process, the interface layer may be intentionally formed at a time before forming the triboelectric generation layer (or the polymer composite film) 300 on the electrode. Accordingly, as illustrated in
FIG. 5 , thefirst interface layer 600 and thesecond interface layer 700 may be formed of a plurality of layers to be cross-laminated with thetriboelectric generation layer 300, and the order thereof is not limited toFIG. 5 and may be formed in various combinations in consideration of device performance. Here, when the triboelectric device is configured as illustrated inFIG. 5 , the performance of the device may be further improved. - Meanwhile, after forming the
first coating layer 400 in step e) or even after forming thesecond coating layer 500 in step f), the annealing process may be further performed, if necessary. In addition, the description of the material, the thickness, and the like of thefirst coating layer 400 and thesecond coating layer 500 complies with the contents described in the triboelectric power generating device. - Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are illustrative of the present invention and the present invention is not limited to the following examples.
- First, PMMA was dissolved in tetrahydrofuran (THF) at room temperature at a concentration of 0.1 g/mL, and PVC was also dissolved in THF at room temperature at the same concentration of 0.1 g/mL, and then the PMMA solution and the PVC solution were mixed at a weight ratio of 1:1 to prepare a polymer mixed solution.
- Next, after bonding an aluminum electrode having a size of 4.3 cm×9 cm×10 μm on the surface of a PET coated paper coated with an acrylic adhesive and washing the surface of the electrode with acetone, in the form as illustrated in
FIG. 2 , two electrode films were prepared, in which the remaining portion except for an area (exposed electrode) of 4.3 cm×8 cm was masked by a Scotch tape. - Subsequently, on the surface of one exposed (unmasked) electrode film, a PMMA-PVC polymer mixed solution was bar-coated and dried to form a triboelectric generation layer, and then the PMMA-PVC polymer mixed solution was additionally bar-coated 5 times on the upper side (surface) of the triboelectric generation layer and dried.
- Thereafter, one masked electrode film was laminated on the electrode surface coated with the PMMA-PVC polymer mixed solution, and then a triboelectric generation layer was annealed at 70° C. to 90° C. for about 5 seconds by using a laminator (Kolami-320S, Kolami, in Korea) and pressed at a pressure of about 1 kgF to prepare a triboelectric power generating device.
- A triboelectric power generating device was prepared in the same manner as in Example 1, except that the PVC and PMMA layers were sequentially coated one time and laminated without mixing the PVC and PMMA solutions.
- A triboelectric power generating device was prepared in the same manner as in Example 2, except that the PVC and PMMA layers were alternately coated 3 times and laminated.
- A triboelectric power generating device was prepared in the same manner as in Example 2, except that the PVC and PMMA layers were alternately coated 5 times and laminated.
- A triboelectric power generating device was prepared in the same manner as in Example 1, except that drop casting, drying, and annealing processes were excluded by not using the polymer mixed solution.
- A triboelectric power generating device was prepared in the same manner as in Example 1, except that a PMMA polymer solution was used by excluding a PVC solution instead of a PMMA-PVC polymer mixed solution (that is, the triboelectric generation layer was configured by only a PMMA polymer).
- A triboelectric power generating device was prepared in the same manner as in Example 1, except that a PVC polymer solution is used by excluding the PMMA solution instead of a PMMA-PVC polymer mixed solution (that is, the triboelectric generation layer was configured by only a PVC polymer)
- After a multimeter (UT61E, UNI-T Co., Ltd., China) was connected with both electrodes of the triboelectric power generating devices prepared in Example 1 and Comparative Examples 1 to 3 with wires, changes in voltage depending on an impact applied to the devices were measured. That is, the device was bent up and down three times per second (3 Hz) for 20 seconds after a first pause of 10 seconds, and subsequently, after a pause of 10 to 20 seconds, the remaining process except for the first pause was additionally repeated 2 times.
-
FIG. 6 is a graph of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to an example of the present invention andFIGS. 7 to 9 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to the comparative examples of the present invention. Here,FIG. 6 corresponds to Example 1 andFIGS. 7 to 9 correspond to Comparative Examples 1 to 3, respectively. First, in the case of the triboelectric power generating device prepared in Example 1 (using the polymer composite film), as illustrated inFIG. 6 , it could be confirmed that electricity was immediately generated depending on an impact/change applied to the device. - On the other hand, in the case of the device prepared in Comparative Example 1 (without using the polymer composite film), as illustrated in
FIG. 7 , it can be seen that triboelectricity was not generated at all. In the case of the device prepared in Comparative Example 2 (using only the PMMA polymer), as illustrated inFIG. 8 , it can be confirmed that electricity was generated, but it is significantly less than Example 1. In the case of the device prepared in Comparative Example 3 (using only the PVC polymer), as illustrated inFIG. 9 , it can be confirmed that only a very small amount of electricity is generated. - After a multimeter (UT61E, UNI-T Co., Ltd., China) was connected with both electrodes of the laminated-type triboelectric power generating devices prepared in Examples 2 to 4 with wires, voltage changes depending on an impact applied to the devices are measured. That is, the device was bent up and down three times per second for 20 seconds after a first pause of 10 seconds, and subsequently, after a pause of 10 to 20 seconds, the remaining process except for the first pause is additionally repeated 2 times.
-
FIGS. 10 to 12 are graphs of measuring a voltage and a current according to an impact applied to a triboelectric power generating device according to other examples of the present invention, andFIGS. 10 to 12 correspond to Examples 2 to 4, respectively. In the laminated-type triboelectric power generating devices prepared in Examples 2 to 4, as in Example 1 for the triboelectric power generating device which is not a laminated type, it can be confirmed that the electricity is immediately generated depending on an impact/change applied to the device (seeFIGS. 10 to 12 ). In addition, it can be confirmed that as the number of laminated layers increases, the voltage and overall current amount of electricity generated increases.
Claims (8)
1. A manufacturing method of a triboelectric power generating device comprising:
a) dissolving and dispersing, or dissolving and dispersing and then mixing, or melting and mixing two or more polymers having different dielectric properties in a solvent, respectively;
b) masking a part of the surface of each of a first electrode and a second electrode having different materials;
c) forming a triboelectric generation layer on the electrode by supplying a polymer solution which is mixed or unmixed in step a) onto a non-masked exposed surface in one of the masked first and second electrodes, and then drying or curing the solution; and
d) laminating and then pressing the other electrode which is not formed with the triboelectric generation layer on the triboelectric generation layer.
2. The manufacturing method of the triboelectric power generating device of claim 1 , wherein after at least one of steps c) and d) is performed, a process of annealing the triboelectric generation layer is performed.
3. The manufacturing method of the triboelectric power generating device of claim 1 , wherein the solvent is selected from the group consisting of linear and cyclic alkane-based compounds, aromatic-based compounds, ketone-based compounds, linear and cyclic ether-based compounds, amine compounds, sulfide-based compounds, and halogen-based compounds.
4. The manufacturing method of the triboelectric power generating device of claim 1 , wherein a mixing ratio of each polymer solution is a weight ratio of 0.1:99.9 to 99.9:0.1.
5. The manufacturing method of the triboelectric power generating device of claim 1 , further comprising:
e) forming a first coating layer on the outer peripheral surface of each of the first electrode and the second electrode; and
f) forming a second coating layer on the outer peripheral surface of each of the first coating layers.
6. The manufacturing method of the triboelectric power generating device of claim 5 , wherein the first coating layer is selected from the group consisting of epoxy, polyester, polyurethane, a mixture of paraffin wax and polyolefin, polyethylene terephthalate, polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyethylene naphthalate, polyamide, polyvinyl alcohol, ethylene vinyl alcohol, polyvinylidene chloride, and mixtures thereof, and the second coating layer is selected from the group consisting of polyimide, polyether ether ketone, mixtures thereof, and mixtures of at least one thereof and compounds constituting the first coating layer.
7. The manufacturing method of the triboelectric power generating device of claim 1 , further comprising:
re-supplying the polymer mixed solution used in step c) one time or more onto the surface of the triboelectric generation layer formed in step c) and then drying the solution.
8. The manufacturing method of the triboelectric power generating device of claim 1 , wherein a laminated-type triboelectric power generating device is prepared by dissolving and dispersing the polymer in each solvent and then sequentially supplying each polymer solution onto the electrode without mixing.
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KR20210077157A (en) * | 2019-12-17 | 2021-06-25 | 송찰스기석 | Triboelectric power generating device with separation membrane and method for preparing the same |
KR102437360B1 (en) * | 2020-08-19 | 2022-08-26 | 인하대학교 산학협력단 | A novel large-area electrified complex film comprising fluoropolymers and sulfur polymers, a method for preparing the same and triboelectric generateor using the same |
KR102680489B1 (en) * | 2021-12-16 | 2024-07-03 | 한국화학연구원 | Film-type friction layer for triboelectric nano power generator and manufacturing method thereof |
KR102623192B1 (en) * | 2021-12-23 | 2024-01-11 | 연세대학교 산학협력단 | Electrode structure for high-sensitivity protrusion-type pressure sensor and method for manufacturing the same |
KR20230166734A (en) | 2022-05-31 | 2023-12-07 | 숙명여자대학교산학협력단 | Triboelectric power generating device with wrinkles and method for preparing the same |
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