Triboelectrictrification composition for triboelectric nanogenerator, and triboelectric nanogenerator comprising same

Abstract

The present invention relates to a triboelectrictrification composition for a triboelectric nanogenerator, and a triboelectric nanogenerator comprising same. One embodiment comprises a triboelectric nanogenerator in which a tribo-positive composition, comprising a graphene oxide-based nanomaterial, has been applied as a tribo-positive layer. In addition, one embodiment comprises a triboelectric nanogenerator in which a tribo-negative composition, comprising any one among fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2), has been applied as a tribo-negative layer.

Description

Triboelectric composition for triboelectric nanogenerator and triboelectric nanogenerator comprising the same

[0001] The present invention relates to a triboelectric composition for a triboelectric nanogenerator and a triboelectric nanogenerator comprising the same. One embodiment includes a triboelectric nanogenerator having a triboelectric anode composition comprising a graphene oxide-based nanomaterial applied as a triboelectric anode layer. In addition, one embodiment includes a triboelectric nanogenerator having a triboelectric anode composition comprising any one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2) applied as a triboelectric anode layer.

[0002] The present invention is the result of research supported by the 'Next-generation high-transparency and high-stretchability sensor using non-aqueous-based high-performance multi-functional ion-conducting non-ion-conducting polymer gel and its application to electrochemical display devices' project (No. 1711190086) of the National Research Foundation of Korea with funding from the government (Ministry of Science and ICT) from March 1, 2021 to February 29, 2024, and the 'Development of technology for manufacturing and utilizing piezoelectric fluorine-based copolymer resin' project (No. 1415185197) of the Korea Evaluation Institute of Industrial Technology with funding from the government (Ministry of Trade, Industry and Energy) from April 1, 2021 to December 31, 2024.

[0003] Triboelectric nanogenerators (TENGs) are devices that generate electrical energy by utilizing the static electricity generated when two dissimilar materials come into contact or rub against each other. Compared to traditional power generation methods, triboelectric nanogenerators are environmentally friendly because they operate from a renewable energy source, and their small size makes them suitable for a wide range of applications, leading to extensive research. These triboelectric nanogenerators can be used to power biosensors, implantable or external devices, and generate sustainable power using human movement.

[0004] However, triboelectric nanogenerators currently face technological limitations, including low power density and high internal impedance. To address these challenges, triboelectric compositions with high electromechanical conversion efficiency must be applied.

[0005] Related prior art literature includes Korean Patent Publication No. 10-2023-0134367.

[0006] The present invention aims to provide a triboelectric composition for a triboelectric nanogenerator having high power density and low impedance, and a triboelectric nanogenerator comprising the same.

[0007] In addition, the present invention has high sensitivity.

[0008] In addition, the present invention has high mechanical stability and durability.

[0009] In addition, the present invention has excellent efficiency even at low pressure.

[0010] In addition, the present invention has excellent sensitivity and can use various sources as power generation sources.

[0011] A triboelectric anode composition for a triboelectric nanogenerator according to an embodiment of the present invention comprises reduced graphene oxide functionalized with tetraethylenepentamine (rGO-TEPA) and a first polymer.

[0012] The content of the reduced graphene oxide functionalized with the above tetraethylene pentamine may be 1 to 10 parts by weight based on 100 parts by weight of the first polymer.

[0013]

[0014] A triboelectric cathode composition for a triboelectric nanogenerator according to an embodiment of the present invention comprises one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2), and a second polymer.

[0015] The content of the fluorine-functionalized graphite may be 5 to 15 parts by weight based on 100 parts by weight of the second polymer, the content of the perovskite material may be 5 to 10 parts by weight based on 100 parts by weight of the second polymer, and the content of the molybdenum sulfide may be 0.2 to 2.0 parts by weight based on 100 parts by weight of the second polymer. The perovskite material may be barium strontium titanate.

[0016]

[0017] A triboelectric nanogenerator according to an embodiment of the present invention includes a tribo-positive layer and a tribo-negative layer.

[0018] The above triboelectric anode layer may include reduced graphene oxide-tetraethylenepentamine (rGO-TEPA) functionalized with tetraethylenepentamine and a first polymer, and the above triboelectric anode layer may include any one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2), and a second polymer.

[0019] The above-mentioned triboelectric anode layer may be manufactured by an electrospinning method using a first mixture in which the reduced graphene oxide functionalized with the tetraethylene pentamine and the first polymer are mixed.

[0020] The above-mentioned triboelectric cathode layer may be manufactured by a casting method using a second mixture in which any one of the above-mentioned fluorine-functionalized graphite, perovskite material, and molybdenum sulfide (MoS2) and a second polymer are mixed.

[0021] A triboelectric composition for a triboelectric nanogenerator according to an embodiment of the present invention and a triboelectric nanogenerator comprising the same have high power density and low impedance.

[0022] In addition, the present invention has high sensitivity.

[0023] In addition, the present invention has high mechanical stability and durability.

[0024] In addition, the present invention has excellent efficiency even at low pressure.

[0025] In addition, the present invention has excellent sensitivity and can use various sources as power generation sources.

[0026] Figure 1 is a conceptual diagram of a triboelectric nanogenerator according to an embodiment of the present invention.

[0027] Figure 2 is an SEM photograph of reduced graphene oxide functionalized with tetraethylene pentamine, anode comparative example 1, and anode examples 1 to 4.

[0028] Figure 3 shows the XRD analysis results of anode comparative example 1, reduced graphene oxide functionalized with tetraethylene pentamine, and anode embodiment 4.

[0029] Figure 4 is an SEM photograph of cathode example 3.

[0030] Figure 5 is an EDS result photograph of cathode example 3.

[0031] Figure 6 shows the XRD analysis results of silicone rubber, fluorine-functionalized graphite, and cathode example 3.

[0032] Figure 7 shows the results of measuring the dielectric constant and dielectric loss for cathode examples 1 to 3 and cathode comparative example 1.

[0033] Figure 8 shows the results of surface potential measurements over time for cathode examples 1 to 3 and cathode comparative example 1.

[0034] Figures 9(a) and (b) are SEM photographs of cathode examples 5 and 7, respectively.

[0035] Figure 10 shows the XRD analysis results of cathode examples 5 to 7 and cathode comparative example 2.

[0036] Figure 11 shows the results of measuring the dielectric constant and dielectric loss for cathode examples 5 to 7 and cathode comparative example 2.

[0037] Figures 12(a) and (b) are SEM photographs of cathode example 11 and cathode comparative example 3, respectively.

[0038] Figure 13 shows the XRD analysis results of cathode examples 8 to 11.

[0039] Figure 14 shows the results of measuring the dielectric constant and dielectric loss for cathode examples 8 to 11 and cathode comparative example 3.

[0040] Figure 15 shows the VOC and ISC measurement results of a triboelectric nanogenerator combined with positive electrode examples 1 to 4, positive electrode comparative example 1, negative electrode comparative example 1, and negative electrode examples 1 to 3.

[0041] Figure 16 shows the results of measuring electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode example 2 and negative electrode example 3.

[0042] Figure 17 shows the VOC, ISC, and Q measurement results of a triboelectric nanogenerator in which positive electrode examples 1 to 3, positive electrode comparative example 1, and negative electrode examples 5 to 7, and negative electrode comparative example 2 are combined.

[0043] Figure 18 shows the results of measuring electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode example 2 and negative electrode example 5.

[0044] Figure 19 shows the VOC and ISC measurement results of a triboelectric nanogenerator combined with positive electrode example 2, negative electrode examples 8 to 11, and negative electrode comparative example 3.

[0045] Figure 20 shows the results of measuring electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode example 2 and negative electrode example 11.

[0046] Figure 21 is the structural formula of reduced graphene oxide functionalized with tetraethylenepentamine.

[0047] Hereinafter, preferred embodiments of the present invention will be described with reference to the attached drawings. However, the embodiments of the present invention may be modified in various ways, and the scope of the present invention is not limited to the embodiments described below. Furthermore, the embodiments of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art.

[0048]

[0049] Triboelectric anode composition for triboelectric nanogenerator

[0050] A triboelectric anode composition for a triboelectric nanogenerator according to an embodiment of the present invention comprises reduced graphene oxide functionalized with tetraethylenepentamine (rGO-TEPA) and a first polymer.

[0051]

[0052] The reduced graphene oxide functionalized with the above tetraethylene pentamine is a material that readily attracts electrons to its surroundings or readily releases electrons. In the present invention, it can perform the function of readily releasing electrons upon contact with a negative triboelectric material. The reduced graphene oxide functionalized with the above tetraethylene pentamine can be expressed by the structural formula of Fig. 21.

[0053]

[0054] In one embodiment, the content of the reduced graphene oxide functionalized with tetraethylene pentamine may be 1 to 10 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the first polymer. If the content is too low or too high, the power generation efficiency may decrease.

[0055]

[0056] The above first polymer enables the bipolar triboelectric material to form a certain shape so that it can be used as a triboelectric anode layer, and the reduced graphene oxide functionalized with the tetraethylene pentamine is evenly dispersed so that it has a high current density.

[0057] The above first polymer may be a polymer resin cured by a curing agent, and preferably, the polymer resin may be polyurethane (PU).

[0058]

[0059] The above triboelectric anode composition for the triboelectric nanogenerator can be manufactured into a film-shaped triboelectric layer by being cured and dried, and can be used as a triboelectric nanogenerator by placing it on an electrode.

[0060] A method for manufacturing a triboelectric layer for a triboelectric nanogenerator according to an embodiment of the present invention comprises the steps of mixing reduced graphene oxide functionalized with tetraethylenepentamine (rGO-TEPA), a first polymer, and a solvent to manufacture a mixture, and the steps of forming the mixture into a sheet shape. Next, the method may further comprise the step of disposing the triboelectric layer manufactured by the above method on an electrode.

[0061]

[0062] In the step of preparing a mixture by mixing the reduced graphene oxide functionalized with tetraethylene pentamine, the first polymer, and the solvent, the reduced graphene oxide and the first polymer are those described above. In this step, the content of the reduced graphene oxide functionalized with tetraethylene pentamine may be 1 to 10 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the first polymer.

[0063] The solvent is not particularly limited as long as it can dissolve the first polymer. The solvent may be an organic solvent, and preferably N,N-dimethylformamide (DMF) or tetrahydrofuran (THF).

[0064] This step can be performed by stirring the mixture in a stirrer while heating. In this case, the temperature of the mixture can be 50 to 70°C, and the process can be performed for 5 to 10 hours.

[0065]

[0066] The step of forming the above mixture into a sheet shape may be performed by electrospinning the mixture. In one embodiment, by using the electrospinning method, the electrical characteristics of the reduced graphene oxide functionalized with tetraethylene pentamine can be well expressed, and power generation can be generated in response to low pressure, thereby increasing power generation efficiency.

[0067] The sheets manufactured at this stage may have a thickness of several tens of µm.

[0068]

[0069] The manufacturing of the triboelectric layer has been completed through the above process. Next, a further step of placing the triboelectric layer on an electrode can be performed. The electrode can be formed of a conductive material, such as a metal or alloy. This step can be performed by attaching the triboelectric layer and electrode using an adhesive, or by applying pressure or heat.

[0070] In another embodiment, this step may be omitted by casting the mixture onto an electrode in the step of forming the mixture into a film shape.

[0071]

[0072] The triboelectric layer manufactured in this way can be used as a triboelectric anode layer or a triboelectric cathode layer, and preferably can be used as a triboelectric anode layer.

[0073]

[0074] Triboelectric cathode composition for triboelectric nanogenerator

[0075] A triboelectric cathode composition for a triboelectric nanogenerator according to an embodiment of the present invention comprises one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2), and a second polymer.

[0076] The present invention may include any one of fluorine-functionalized graphite, perovskite material, and molybdenum sulfide (MoS2), each of which is described below.

[0077]

[0078] Hereinafter, a triboelectric cathode composition for a triboelectric nanogenerator comprising fluorine-functionalized graphite is described.

[0079]

[0080] The above fluorine-functionalized graphite is a material that easily attracts electrons to its surroundings or easily releases electrons, and in the present invention, it can perform the function of easily attracting electrons by coming into contact with a positive triboelectric material. The above fluorine-functionalized graphite can be expressed by the following chemical formula 1. Here, x is preferably 1.1 to increase electron capture efficiency.

[0081] [Chemical Formula 1]

[0082] (CF x ) n

[0083] (Here, X is 0.5 to 1.5, n is a natural number)

[0084]

[0085] In one embodiment, the content of the fluorine-functionalized graphite may be 5 to 17 parts by weight, preferably 13 to 17 parts by weight, based on 100 parts by weight of the first polymer. If the content of the fluorine-functionalized graphite is too high, there is a problem in that curing does not occur and a film cannot be formed, and if the content is too low, there is a problem in that the power density is low and the impedance increases.

[0086]

[0087] The above second polymer can be used as a film-shaped triboelectric layer in which the negative triboelectric material has a certain shape, and the fluorine-functionalized graphite is evenly dispersed to have a high current density.

[0088] The second polymer may be a variety of polymer resins cured by a curing agent, and preferably, the polymer resin may be silicone rubber. Silicone rubber has superior tensile strength and wear resistance, is chemically stable, and has excellent processability compared to other polymer materials. The silicone rubber may be PDMS (polydimethylsiloxane) or PDMS containing a platinum catalyst. The PDMS containing the platinum catalyst is Ecoflex from Smooth-On. TM By specifying the second polymer in this way, even when the content of fluorine-functionalized graphite is high, it can be cured and maintain a certain shape.

[0089]

[0090] Hereinafter, a triboelectric cathode composition for a triboelectric nanogenerator including a perovskite material is described.

[0091]

[0092] The above perovskite material is a material that easily attracts electrons to its surroundings or easily releases electrons, and in the present invention, it can perform the function of easily attracting electrons by coming into contact with a positive triboelectric material. The above perovskite material is barium strontium titanate and can be expressed by chemical formula 2.

[0093] [Chemical Formula 2]

[0094] Ba x Sr - xTiO3

[0095] (x is a natural number)

[0096]

[0097] In one embodiment, the content of the perovskite material may be 5 to 10 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the second polymer. If the content of the perovskite material is too high or too low, there is a problem of low power density and increased impedance.

[0098]

[0099] The above second polymer enables the negative triboelectric material to form a certain shape and be used as an electrode, and the above fluorocarbon is evenly distributed to have a high current density.

[0100] The second polymer may be a variety of polymer resins cured by a curing agent, and preferably, the polymer resin may be silicone rubber. Silicone rubber has superior tensile strength and wear resistance, is chemically stable, and has excellent processability compared to other polymer materials. The silicone rubber may be PDMS (polydimethylsiloxane) or PDMS containing a platinum catalyst. The PDMS containing the platinum catalyst is Ecoflex from Smooth-On. TM By specifying the second polymer in this way, it can be cured and maintain a certain shape even when the content of fluorocarbon is high.

[0101]

[0102] Hereinafter, a triboelectric cathode composition for a triboelectric nanogenerator containing molybdenum sulfide (MoS2) is described.

[0103]

[0104] The above molybdenum sulfide (MoS2) is a material that easily attracts electrons to the surroundings or easily releases electrons, and in the present invention, it can perform the function of easily attracting electrons by coming into contact with a positive triboelectric material.

[0105] In one embodiment, the content of the molybdenum sulfide may be 0.2 to 2.0 parts by weight, preferably 1 to 1.5 parts by weight, based on 100 parts by weight of the second polymer. If the content is too high, there is a problem of non-curing, and if the content is too low, there is a problem of reduced power generation efficiency.

[0106] In one embodiment, the average particle size of the molybdenum sulfide may be 50 to 100 nm. If the particle size exceeds this size, dispersion may be difficult, resulting in a decrease in power generation efficiency.

[0107]

[0108] The above second polymer enables the negative triboelectric material to form a certain shape and be used as a triboelectric layer, and the above molybdenum sulfide is evenly distributed to have a high current density.

[0109] The second polymer may be a variety of polymer resins cured by a curing agent, and preferably, the polymer resin may be silicone rubber. Silicone rubber has superior tensile strength and wear resistance, is chemically stable, and has excellent processability compared to other polymer materials. The silicone rubber may be PDMS (polydimethylsiloxane) or PDMS containing a platinum catalyst. The PDMS containing the platinum catalyst is Ecoflex from Smooth-On. TMBy specifying the second polymer in this way, it can be hardened and maintain a certain shape even when the content of molybdenum sulfide is high.

[0110]

[0111] The above triboelectric cathode composition for the triboelectric nanogenerator can be manufactured into a film-shaped triboelectric layer by being cured and dried, and can be used as a triboelectric nanogenerator by placing it on an electrode.

[0112] A method for manufacturing a triboelectric nanogenerator according to an embodiment of the present invention comprises the steps of: mixing a second polymer with one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2) to prepare a mixture; forming the mixture into a film shape; and drying the mixture formed into a film shape. Next, the method may further include the step of disposing the triboelectric layer manufactured by the above method on a current collector.

[0113]

[0114] In the step of preparing a mixture by mixing one of fluorine-functionalized graphite, perovskite material and molybdenum sulfide (MoS2) and a second polymer, one of the fluorine-functionalized graphite, perovskite material and molybdenum sulfide (MoS2) and the second polymer may be as described above.

[0115]

[0116] The step of forming the above mixture into a film shape can be performed using a general method for manufacturing films using polymer resins. In one embodiment, the film shape can be manufactured using a melt casting method. In this step, the thickness of the film can be controlled using a doctor blade or the like.

[0117]

[0118] Next, a step of drying the mixture formed into the film shape is performed. This step can be performed by leaving the mixture at room temperature (20 to 30°C) for 20 to 30 hours. The thickness of the triboelectric layer (film) after drying can be 200 to 250 µm. If necessary, the triboelectric layer can be cut into a certain size.

[0119]

[0120] The above process has completed the manufacturing of the triboelectric layer. A further step may be performed to place the triboelectric layer on an electrode. The electrode may be formed of a conductive material, such as a metal or alloy. This step may be performed by attaching the triboelectric layer and electrode using an adhesive, or by applying pressure or heat.

[0121] In another embodiment, this step may be omitted by casting the mixture onto an electrode in the step of forming the mixture into a film shape.

[0122]

[0123] The triboelectric layer manufactured in this way can be used as an anode layer or a cathode layer, and preferably can be used as a cathode layer.

[0124]

[0125] triboelectric nanogenerator

[0126] FIG. 1 is a conceptual diagram of a triboelectric nanogenerator (100) according to an embodiment of the present invention. Referring to FIG. 1, the triboelectric nanogenerator according to an embodiment of the present invention includes a triboelectric anode layer (120) and a triboelectric cathode layer (110). In addition, the triboelectric nanogenerator may include an electrode (130`) disposed on the triboelectric anode layer (120) and an electrode (130`) disposed on the triboelectric cathode layer (110). In addition, the triboelectric nanogenerator may further include a support plate (140, 140`) disposed on the other surface of each of the electrodes (130, 130`) to protect them. The triboelectric anode layer (120) and the triboelectric cathode layer (110) may be electrically connected to each other so that electrons may move between them, and for this purpose, may be directly or indirectly connected to each other. One embodiment may further include a spacer (150) disposed between the triboelectric anode layer (120) and the triboelectric cathode layer (110). Through this, the triboelectric anode layer (120) and the triboelectric cathode layer (110) may be configured to be normally disposed at a constant interval and to come into contact with each other when pressure is applied from the outside.

[0127] At least one of the triboelectric anode layer and the triboelectric cathode layer comprises the triboelectric anode composition or the triboelectric cathode composition described above. Preferably, the triboelectric anode layer may comprise reduced graphene oxide functionalized with tetraethylenepentamine (rGO-TEPA) and a first polymer. In addition, preferably, the triboelectric cathode layer may comprise any one of fluorine-functionalized graphite, a perovskite material, and molybdenum sulfide (MoS2), and a second polymer.

[0128] The above triboelectric nanogenerator may include other components commonly used in the field, without particular limitation.

[0129]

[0130] Example: Fabrication of a triboelectric anode layer

[0131] Bipolar Example 1 (PUAFG01): Polyurethane is Selectophore from Sigma-Aldrich TM was prepared, and reduced graphene oxide functionalized with tetraethylenepentamine was prepared from Sigma-Aldrich. N,N-dimethylformamide (DMF, 99.8%) as a solvent was prepared from Acros Organics, and tetrahydrofuran (THF > purity 99%) was prepared from Daejung Chemical Industry Co., Ltd. 1 g of polyurethane and 0.01 g of reduced graphene oxide functionalized with tetraethylenepentamine were added to 9 g of a solvent containing DMF and THF in a volume ratio of 4:6 and stirred at 60°C and 500 rpm for 8 hours. The mixture was electrospun into a sheet shape using an electrospinning machine under the following conditions: voltage 10 kV, tip-to-collector distance 12 cm, discharge rate 1 mL / h, collector speed 100 rpm, temperature 10-12°C, and relative humidity 40-50%. The above electrospun sheet was manufactured on a collector wrapped with aluminum foil. The sheet-shaped mixture was placed in an oven and dried at 80°C for 10 hours. Through this, a triboelectric anode layer was manufactured in which 1 part by weight of reduced graphene oxide functionalized with tetraethylene pentamine was used for 100 parts by weight of polyurethane. The thickness of the triboelectric anode layer manufactured in this way was 30-40±2 µm.

[0132]

[0133] Positive electrode embodiment 2 (PUAFG02): A triboelectric positive electrode layer was manufactured in the same manner as in Positive electrode embodiment 1, except that 0.02 g of reduced graphene oxide functionalized with tetraethylene pentamine was added to 100 parts by weight of polyurethane, thereby producing a triboelectric positive electrode layer in which 2 parts by weight of reduced graphene oxide functionalized with tetraethylene pentamine was added to 100 parts by weight of polyurethane.

[0134]

[0135] Anode Example 3 (PUAFG05): A triboelectric anode layer was manufactured in the same manner as in Anode Example 1, except that 0.05 g of reduced graphene oxide functionalized with tetraethylene pentamine was added to 100 parts by weight of polyurethane, thereby producing a triboelectric anode layer in which 5 parts by weight of reduced graphene oxide functionalized with tetraethylene pentamine was added to 100 parts by weight of polyurethane.

[0136]

[0137] Anode Example 4 (PUAFG010): A triboelectric anode layer was manufactured in the same manner as in Anode Example 1, except that 0.10 g of reduced graphene oxide functionalized with tetraethylene pentamine was added to 100 parts by weight of polyurethane, thereby producing 10 parts by weight of reduced graphene oxide functionalized with tetraethylene pentamine.

[0138]

[0139] Bipolar Comparative Example 1 (PU): It was manufactured in the same manner as in Bipolar Example 1, except that reduced graphene oxide functionalized with tetraethylene pentamine was not added.

[0140]

[0141] Example: Fabrication of a triboelectric cathode layer (fluorine-functionalized graphite)

[0142] Cathode Example 1 (EC5FG): Fluorine-functionalized graphite was prepared from Sigma-Aldrich, and silicone rubber was Ecoflex from Smooth-On. TM -00-30 was prepared. 0.5 g of fluorine-functionalized graphite was mixed with 10 g of silicone rubber mixed with components A and B, and the mixture was thoroughly stirred to prepare a mixture. Next, the mixture was poured onto sandpaper, and the thickness was 235 ± 5 µm using a doctor blade, and then dried at room temperature (20 to 25°C) for 24 hours. Through this, a triboelectric negative electrode layer was prepared in which 5 parts by weight of fluorine-functionalized graphite was used per 100 parts by weight of silicone rubber. The thickness of the prepared triboelectric negative electrode layer was 235 ± 5 µm.

[0143]

[0144]

[0145] Cathode Example 2 (EC10FG): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 1, except that 1.0 g of fluorine-functionalized graphite was added to 10 parts by weight of fluorine-functionalized graphite per 100 parts by weight of silicone rubber.

[0146]

[0147] Cathode Example 3 (EC15FG): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 1, except that 1.5 g of fluorine-functionalized graphite was added to 100 parts by weight of silicone rubber, thereby producing 15 parts by weight of fluorine-functionalized graphite.

[0148]

[0149] Cathode Example 4 (EC20FG): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 1, except that 2.0 g of fluorine-functionalized graphite was added to 100 parts by weight of silicone rubber, thereby producing 20 parts by weight of fluorine-functionalized graphite.

[0150]

[0151] Cathode Comparative Example 1 (EC): Manufactured in the same manner as Cathode Example 1, except that fluorine-functionalized graphite was not added.

[0152]

[0153] Example: Fabrication of a triboelectric cathode layer (barium strontium titanate)

[0154] Cathode Example 5 (EC5): Barium strontium titanate powder was prepared from Sigma-Aldrich, and silicone rubber was Ecoflex from Smooth-On. TM-00-30 was prepared. 0.55 g of barium strontium titanate powder was mixed with 10 g of silicone rubber A component, and then 1 g of silicone rubber B component was added and sufficiently stirred to prepare a mixture. Next, the mixture was poured onto sandpaper, and after being ground to a thickness of 30±5 µm using a doctor blade, it was dried at room temperature (20 to 25°C) for 24 hours. Through this, a triboelectric negative electrode layer containing 5 parts by weight of barium strontium titanate per 100 parts by weight of silicone rubber was prepared. The thickness of the prepared triboelectric negative electrode layer was 20±10 µm.

[0155]

[0156] Cathode Example 6 (EC7.5): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 5, except that 0.825 g of barium strontium titanate powder was added to produce a triboelectric cathode layer in which 7.5 parts by weight of barium strontium titanate was added to 100 parts by weight of silicone rubber.

[0157]

[0158] Cathode Example 7 (EC10): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 5, except that 1.1 g of barium strontium titanate powder was added to 10 parts by weight of barium strontium titanate per 100 parts by weight of silicone rubber.

[0159]

[0160] Cathode Comparative Example 2 (EC0): Manufactured in the same manner as Cathode Example 5, except that barium strontium titanate powder was not added.

[0161]

[0162] Example: Preparation of a triboelectric cathode layer (molybdenum sulfide)

[0163] Cathode Example 8 (EC0.2): Molybdenum sulfide (diameter 90 nm) was prepared from Sigma-Aldrich, and silicone rubber was Ecoflex from Smooth-On. TM-00-30 was prepared. P-60 standard sandpaper was prepared to provide roughness to the surface of the triboelectric cathode layer. 0.02 g of molybdenum sulfide was mixed with 10 g of silicone rubber mixed with parts A and B, and the mixture was prepared by sufficiently stirring. Next, the mixture was poured onto sandpaper, and the thickness was 230±5 µm using a doctor blade, and then dried at room temperature (20 to 25°C) for 8 hours. Through this, a triboelectric cathode layer containing 0.2 parts by weight of molybdenum sulfide per 100 parts by weight of silicone rubber was prepared.

[0164]

[0165] Cathode Example 9 (EC0.5): A triboelectric cathode layer was manufactured in the same manner as Cathode Example 8, except that 0.05 g of molybdenum sulfide was added to 100 parts by weight of silicone rubber, thereby producing a 0.5 part by weight triboelectric cathode layer.

[0166]

[0167] Cathode Example 10 (EC1): A triboelectric cathode layer was manufactured in the same manner as in Cathode Example 8, except that 0.10 g of molybdenum sulfide was added to 100 parts by weight of silicone rubber, thereby producing 1.0 parts by weight of molybdenum sulfide.

[0168]

[0169] Cathode Example 11 (EC1.5): A triboelectric cathode layer was manufactured in the same manner as Cathode Example 8, except that 0.15 g of molybdenum sulfide was added to 100 parts by weight of silicone rubber, and 1.5 parts by weight of molybdenum sulfide was manufactured.

[0170]

[0171] Negative Electrode Example 12: A triboelectric negative electrode layer was manufactured in the same manner as in Negative Electrode Example 8, except that 0.20 g of molybdenum sulfide was added to 100 parts by weight of silicone rubber, and 2.0 parts by weight of molybdenum sulfide was manufactured. The example manufactured in this manner did not harden.

[0172]

[0173] Cathode Comparative Example 3 (EC0): Manufactured in the same manner as Cathode Example 8, except that molybdenum sulfide was not added.

[0174]

[0175] Example: Fabrication of a triboelectric nanogenerator

[0176] A triboelectric nanogenerator was manufactured by combining the previously manufactured examples and comparative examples. First, the triboelectric anode layers of the cathode examples and the cathode comparative examples were cut to a size of 5 cm x 5 cm in length x width, and one side was bonded to one side of an Al electrode of the same size. The triboelectric anode layers of the anode examples and the cathode comparative examples were also cut to a size of 5 cm x 5 cm in length x width, and one side was bonded to one side of an Al electrode of the same size. An 8 mm spacer was placed between the other surfaces of the triboelectric cathode layers and the other surfaces of the triboelectric anode layers, and then the other surfaces of each were arranged to face the spacer, and two acrylic plates, each measuring 5 cm x 5 cm in length x width, were attached to the other surfaces of the Al electrodes. The overall shape is as shown in Fig. 1. When pressure was applied to the acrylic plates, the triboelectric anode layers and the triboelectric cathode layers came into contact with each other.

[0177]

[0178] Experimental example: Visual observation

[0179] Negative examples 1 to 4 and negative comparative example 1 were observed with the naked eye. In the case of negative example 4, the content of fluorine-functionalized graphite was excessive, so that curing did not occur properly, making it impossible to use it as a triboelectric negative electrode layer.

[0180]

[0181] Experimental Example: SEM Analysis

[0182] This analysis was performed using a scanning electron microscope (SEM, JEOL Ltd. JSM-6510) at 15 kV. Fig. 2 shows SEM images of reduced graphene oxide functionalized with tetraethylene pentamine, positive electrode comparative example 1, and positive electrode examples 1 to 4, Fig. 4 shows SEM images of negative electrode example 3, Figs. 9(a) and (b) show SEM images of negative electrode examples 5 and 7, respectively, and Figs. 12(a) and (b) show SEM images of negative electrode example 11 and negative electrode comparative example 3, respectively.

[0183] Referring to FIG. 2, it can be seen that lumps were observed on the surface of the positive electrode examples 3 (PUAFG05) and 4 (PUAFGO10) in which the content of reduced graphene oxide functionalized with tetraethylene pentamine was 5 parts by weight or more.

[0184]

[0185] Experimental Example: EDS Analysis

[0186] The surface elements of the examples and comparative examples were analyzed using an EDS device.

[0187] Table 1 shows the analysis results of reduced graphene oxide functionalized with tetraethylene pentamine, anode examples, and anode comparative examples. According to Table 1, it can be seen that the measured value of the N element increases as the content of reduced graphene oxide functionalized with tetraethylene pentamine increases.

[0188] Classification C (wt%) N (wt%) O (wt%) rGO-TEPA powder 73.6 12.4 14.0 Anode Example 1 76.9 2.8 20.2 Anode Example 2 76.23 220.4 Anode Example 3 74.23 22.4 Anode Example 4 75.23 24.4 Anode Comparative Example 177.6 2.2 20.1

[0189] Figure 5 shows the analysis results for cathode example 3, and Table 2 shows the analysis results for fluorine-functionalized graphite and cathode examples 1 to 4. From Figure 5, it can be seen that Si, O, C, and F elements are observed. In addition, according to Table 2, it can be seen that the measured value of F element increases significantly as the content of fluorine-functionalized graphite increases.

[0190] Classification C (wt%) O (wt%) F (wt%) Si (wt%) Fluorine functionalized graphite 62.26.831.3-Cathode Example 1 30.325.80.843.3Cathode Example 2 31.324.21.143.4Cathode Example 3 28.317.82.151.8Cathode Example 4-31.9-68.1

[0191]

[0192] Experimental example: XRD analysis

[0193] XRD analysis was performed using CuK α under conditions of 40 kV and 3 mA.

[0194] Figures 3(a), (b), and (c) show the XRD analysis results of Anode Comparative Example 1, reduced graphene oxide functionalized with tetraethylene pentamine, and Anode Example 4, respectively. Figure 3(c) is expressed using Gaussian multi-peak fitting of Origin software. Referring to Figure 3, it can be seen that the peaks of the reduced graphene oxide functionalized with polyurethane and tetraethylene pentamine are all observed in Anode Example 4.

[0195] Figures 6(a), (b), and (c) are silicone rubber (Ecoflex) respectively TM -00-30), the XRD analysis results of fluorine-functionalized graphite and cathode example 3. Fig. 6(c) is expressed using Gaussian multi-peak fitting of Origin software. Referring to Fig. 6, it can be seen that the peaks of both silicone rubber and fluorine-functionalized graphite are observed in cathode layer manufacturing example 3.

[0196] Figure 10 shows the XRD analysis results of cathode examples 5 to 7 and cathode comparative example 2. Referring to Figure 10, it can be seen that characteristic peaks of barium strontium titanate are observed in cathode examples 5 to 7.

[0197] Figure 13 shows the XRD analysis results of cathode examples 8 to 11. Referring to Figure 13, it can be seen that characteristic peaks of molybdenum sulfide are observed in cathode examples 8 to 11.

[0198]

[0199] Experimental Example: Measurement of Dielectric Constant and Dielectric Loss

[0200] The permittivity and dielectric loss were measured using an impedance / gain phase analyzer (SI-1260, Solartron Analytical Co., UK) at 25°C and 41% relative humidity.

[0201] Figures 7(a) and (b) show the results of dielectric constant and dielectric loss measurements for cathode examples 1 to 3 and cathode comparative example 1, respectively. Referring to Figure 7, it can be seen that the dielectric constant increased as the content of fluorine-functionalized graphite increased, but the change in dielectric loss was not significant. That is, it was proven that in cathode example 3, where the content of fluorine-functionalized graphite was 15 parts by weight, the dielectric constant could be improved without affecting the dielectric loss.

[0202] Figures 11(a) and (b) show the results of permittivity and dielectric loss measurements for cathode examples 5 to 7 and cathode comparative example 2, respectively. Referring to Figure 11, it can be seen that the permittivity increases as the content of barium strontium titanate increases, but the change in dielectric loss is not significant. This shows that by adding barium strontium titanate, the permittivity can be improved without affecting the dielectric loss.

[0203] Figures 14(a) and (b) show the results of permittivity and dielectric loss measurements for cathode examples 8 to 11 and cathode comparative example 3, respectively. Referring to Figure 14, it can be seen that the permittivity increases as the content of molybdenum sulfide increases, but the change in dielectric loss is not significant. This shows that the addition of molybdenum sulfide improves the permittivity without affecting the dielectric loss.

[0204]

[0205] Experimental example: Surface potential measurement

[0206] The surface potential was measured in non-contact mode using a Kelvin probe force microscope (KPFM; NX10, Park Systems).

[0207] Figure 8 shows the results of surface potential measurements over time for cathode examples 1 to 3 and cathode comparative example 1. Referring to Figure 8, it can be seen that the surface potential significantly decreased for the first 10 hours and then converged to a constant level. After 40 hours, the surface potential of cathode example 4 decreased 19-fold from -848 V to -43 V, but that of cathode example 3 decreased 5-fold from -1813 V to -346 V, indicating that cathode example 3 has superior performance.

[0208]

[0209] Experimental Example: Measurement of Electrical Characteristics of a Triboelectric Nanogenerator

[0210] Using a triboelectric nanogenerator manufactured by combining the previously manufactured triboelectric cathode layer and triboelectric anode layer, V OC , I SC was measured. For this purpose, an oscilloscope (TBS2204B, Tektronix), a low-noise current amplifier (DLPCA-200, Femto), and an electrometer (6514, Keithley) were used.

[0211] Fig. 15(a) shows the measured values ​​of a triboelectric nanogenerator combined with cathode comparative example 1, anode examples 1 to 4, and anode comparative example 1, Fig. 15(b) shows the measured values ​​of a triboelectric nanogenerator combined with cathode example 1, anode examples 1 to 4, and anode comparative example 1, Fig. 15(c) shows the measured values ​​of a triboelectric nanogenerator combined with cathode example 2, anode examples 1 to 4, and anode comparative example 1, and Fig. 15(d) shows the measured values ​​of a triboelectric nanogenerator combined with cathode example 3, anode examples 1 to 4, and anode comparative example 1. Referring to Fig. 15, it can be seen that anode example 2 in which the content of reduced graphene oxide functionalized with tetraethylene pentamine is 2 parts by weight shows the best electrical characteristics, and when the content deviates from this, the electrical characteristics decrease.

[0212] Figures 17(a) to (c) are the VOC, ISC, and Q measurement results of the triboelectric nanogenerator in which positive electrode examples 1 to 3, positive electrode comparative example 1, negative electrode examples 5 to 7, and negative electrode comparative example 2 are combined, respectively. Referring to Figure 17(a), in combination with positive electrode example 2, while the content of barium strontium titanate increases from 0 to 7.5 parts by weight, V OC increased from 161 V to 257 V, but decreased to 130 V at 10 parts by weight, which exceeded 7.5 parts by weight. In addition, this trend was similar to that of I SC A similar observation was made in (see Fig. 17(b)). This shows that the current density decreases when the content of barium strontium titanate exceeds a certain value.

[0213] Figure 19 shows the VOC and ISC measurement results of a triboelectric nanogenerator combined with anode embodiment 2, cathode embodiments 8 to 11, and cathode comparative example 3. Referring to Figure 19, in combination with anode embodiment 2, while the content of molybdenum sulfide increases from 0 to 1.5 parts by weight, V OC increased from 297.4 V to 451 V, and I SC Likewise, it increased as the content of molybdenum sulfide increased. In particular, high values ​​were observed in cathode examples 10 and 11 in which the content of molybdenum sulfide was 1.0 part by weight or more.

[0214]

[0215] Experimental Example: Measurement of Electrical Characteristics of a Triboelectric Nanogenerator According to Load Pressure

[0216] When a load of 0.3 to 10 N is applied to the triboelectric nanogenerator, V OC , I SC The change was measured.

[0217] Figure 16 shows the results of measuring the electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode embodiment 2 and negative electrode embodiment 3. Referring to Figure 16, it can be seen that the output improves according to load, and in particular, a high output is shown at a pressure of 6 N or more.

[0218] Figure 18 shows the results of measuring the electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode embodiment 2 and negative electrode embodiment 5. Referring to Figure 18, it can be seen that the output improves according to load.

[0219] Figure 20 shows the results of measuring the electrical characteristics according to load in a triboelectric nanogenerator combined with positive electrode embodiment 2 and negative electrode embodiment 11. Referring to Figure 20, it can be seen that the output improves according to load.

Claims

1. Comprising reduced graphene oxide-tetraethylenepentamine (rGO-TEPA) functionalized with tetraethylenepentamine and a first polymer, A triboelectric anode composition for a triboelectric nanogenerator.

2. In paragraph 1, The content of the reduced graphene oxide functionalized with the above tetraethylene pentamine is 1 to 10 parts by weight based on 100 parts by weight of the first polymer. A triboelectric anode composition for a triboelectric nanogenerator.

3. Fluorine-functionalized graphite, perovskite materials and molybdenum sulfide (MoS 2 ) and a second polymer, A triboelectric cathode composition for a triboelectric nanogenerator.

4. In paragraph 3, The content of the above fluorine-functionalized graphite is 5 to 15 parts by weight based on 100 parts by weight of the second polymer, The content of the perovskite material is 5 to 10 parts by weight based on 100 parts by weight of the second polymer, The content of the above molybdenum sulfide is 0.2 to 2.0 parts by weight based on 100 parts by weight of the second polymer. A triboelectric cathode composition for a triboelectric nanogenerator.

5. In paragraph 3, The above perovskite material is barium strontium titanate. A triboelectric cathode composition for a triboelectric nanogenerator.

6. Contains a tribo-positive layer and a tribo-negative layer, The above triboelectric anode layer comprises reduced graphene oxide-tetraethylenepentamine (rGO-TEPA) functionalized with tetraethylenepentamine and a first polymer, The above triboelectric cathode layer comprises fluorine-functionalized graphite, perovskite material and molybdenum sulfide (MoS 2 ) and a second polymer, Triboelectric nanogenerator.

7. In paragraph 6, The above-mentioned triboelectric anode layer is manufactured by electrospinning using a first mixture in which the reduced graphene oxide functionalized with the tetraethylene pentamine and the first polymer are mixed. Triboelectric nanogenerator.

8. In paragraph 6, The above triboelectric cathode layer comprises the fluorine-functionalized graphite, perovskite material and molybdenum sulfide (MoS 2 ) and a second mixture in which a second polymer is mixed, manufactured by a casting method. Triboelectric nanogenerator.

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