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WO2024123062A1 - Gel polymère pour nanogénérateur triboélectrique comprenant un liquide ionique, et nanogénérateur triboélectrique le comprenant - Google Patents

Gel polymère pour nanogénérateur triboélectrique comprenant un liquide ionique, et nanogénérateur triboélectrique le comprenant Download PDF

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Publication number
WO2024123062A1
WO2024123062A1 PCT/KR2023/019952 KR2023019952W WO2024123062A1 WO 2024123062 A1 WO2024123062 A1 WO 2024123062A1 KR 2023019952 W KR2023019952 W KR 2023019952W WO 2024123062 A1 WO2024123062 A1 WO 2024123062A1
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WO
WIPO (PCT)
Prior art keywords
triboelectric nanogenerator
polymer gel
ionic liquid
imide
methylimidazolium
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Ceased
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PCT/KR2023/019952
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English (en)
Korean (ko)
Inventor
배진우
우인선
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Industry Academy Collaboration Foundation of Korea University
Industry University Cooperation Foundation of Korea University of Technology and Education
Original Assignee
Industry Academy Collaboration Foundation of Korea University
Industry University Cooperation Foundation of Korea University of Technology and Education
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Publication of WO2024123062A1 publication Critical patent/WO2024123062A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04—Friction generators
    • 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
    • H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
    • 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
    • H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
    • H02N2/186—Vibration harvesters

Definitions

  • the present invention relates to a polymer gel for a triboelectric nanogenerator containing an ionic liquid and a triboelectric nanogenerator containing the same. More specifically, the polymer gel contains an ionic liquid, so that a triboelectric nanogenerator containing the same is provided. It is characterized by excellent performance.
  • This invention is the result of research conducted with the support of the 'Piezoelectric fluorine-based copolymer resin manufacturing and utilization technology development' project of the Korea Institute of Industrial Technology Evaluation and Planning funded by the government (Ministry of Trade, Industry and Energy) from 2021.04.01 to 2024.12.31 (No. 1415185197).
  • TENG Triboelectric nanogenerator
  • the present inventors While researching to improve the performance of the TENG, the present inventors discovered an appropriate type of polymer resin and mixed the ionic liquid with the polymer resin to use it as a triboelectric (triboelectric) nanogenerator.
  • the present invention was completed by discovering that the triboelectric nanogenerator can have excellent performance when used as a charged polymer layer.
  • Republic of Korea Patent Publication No. 10-2021-0040342 discloses an energy harvester and a method of manufacturing the same.
  • the present invention provides a polymer gel for triboelectric nanogenerators containing an ionic liquid.
  • the present invention provides a triboelectric nanogenerator comprising the polymer gel.
  • the present invention provides a method for producing the polymer gel for the triboelectric nanogenerator.
  • one aspect of the present invention is,
  • a polymer gel for triboelectric nanogenerators containing a polymer resin and an ionic liquid.
  • the polymer resin is polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-trifluoroethylene (PVDF-TrFE), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polyurethane (PU), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyimide (PI), polyethylene terephthalate It may contain a polymer resin selected from the group consisting of (PET) and combinations thereof.
  • PVDF polyvinylidene fluoride
  • PVDF-TrFE polyvinyl chloride
  • PTFE polytetrafluoroethylene
  • PU polyurethane
  • PU polymethyl methacrylate
  • PDMS polydimethylsiloxane
  • PVA polyvinyl alcohol
  • PVP polyvinylpyrroli
  • the ionic liquid may include an ionic liquid selected from the group consisting of a neutral liquid, anionic liquid, cationic liquid, and combinations thereof.
  • the neutral liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Emim TFSI), 1-butyl-3-methyl Imidazolium bis(trifluoromethylsulfonyl)imide (1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, Bmim TFSI), 1-Butyl-3-methylimidazolium hexafluorophosphate (1-Butyl -3-methylimidazolium hexafluorophosphate, Bmim PF 6 ), 1-Ethyl-3-methylimidazolium tetrafluoroborate, Emim BF 4 ), 1-methyl-3-propylimidazolium Iodide (1-methyl-3-propylimidazolium iodide, PMII), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ),
  • the anionic liquid includes trifluoroacetate ([tfa] - ), trifluoromethanesulfonate ([CF 3 SO 3 ] - ), and bis (fluorosulfonyl)imide (bis ( fluorosulfonyl)imide)([N(SO 2 F) 2 ] - ), bis(trifluoromethanesulfonyl)imide)([N(SO 2 CF 3 ) 2 ] - ), DC Dicyanamide ([N(CN) 2 ] - ), tetracyanoborate ([B(CN) 4 ] - ), dihydrogenphosphate ([H 2 PO 4 ] - ) , hydrogen sulfate ([HSO 4 ] - ), and combinations thereof.
  • the cationic liquid may include a cationic liquid selected from the group consisting of imidazolium, pyrrolidinium, piperidinium alkylmethylimidazolium, and combinations thereof. there is.
  • the content of the ionic liquid may be 1 to 100 parts by weight based on 100 parts by weight of the polymer resin.
  • the content of the ionic liquid may be 10 to 50 parts by weight based on 100 parts by weight of the polymer resin.
  • First electrodes spaced apart from each other; and a second electrode and a charged polymer layer containing the polymer gel bonded to one surface of the first electrode.
  • the first electrode and the second electrode are each made of aluminum (Al), copper (Cu), titanium (Ti), gold (Au), silver (Ag), platinum (Pt), nickel (Ni), zinc (Zn), It may contain a metal selected from the group consisting of iron (Fe), cobalt (Co), and combinations thereof.
  • the triboelectric nanogenerator may further include a friction layer bonded to one surface of the second electrode.
  • a method for producing a polymer gel for a triboelectric nanogenerator is provided.
  • the drying may be performed at a temperature of 50°C to 100°C for 1 hour to 3 hours.
  • the annealing may be performed at a temperature of 80°C to 200°C for 1 hour to 5 hours.
  • the polymer gel for triboelectric nanogenerator according to the present invention as described above may have transparent properties by containing an ionic liquid.
  • the triboelectric nanogenerator containing the polymer gel has an excellent dielectric constant and a small leakage current value, and thus may have an excellent output voltage value.
  • Figure 1 is a schematic diagram showing a method of manufacturing a polymer gel for a triboelectric nanogenerator according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram showing a triboelectric nanogenerator according to an embodiment of the present invention.
  • Figure 3 is a photograph showing the appearance of a polymer gel for a triboelectric nanogenerator according to an embodiment of the present invention.
  • Figure 4 is a graph showing the output voltage of the triboelectric nanogenerator according to an embodiment of the present invention.
  • Figure 5 is a graph showing the dielectric constant of a triboelectric nanogenerator according to an embodiment of the present invention.
  • Figure 6 is a graph showing the leakage current of the triboelectric nanogenerator according to an embodiment of the present invention.
  • the first aspect of the present application is,
  • a polymer gel for triboelectric nanogenerators containing a polymer resin and an ionic liquid.
  • the polymer gel for a triboelectric nanogenerator may include a polymer resin.
  • the polymer resin may be a non-aqueous based polymer, and accordingly, the polymer gel for the triboelectric nanogenerator may have long-term stability without changes in weight and volume.
  • the polymer resin can be plasticized without a solvent, such as polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-trifluoroethylene (PVDF-TrFE), polyvinyl Chloride (PVC), polytetrafluoroethylene (PTFE), polyurethane (PU), polymethyl methacrylate (PMMA), polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) ), polyethylene oxide (PEO), polyimide (PI), polyethylene terephthalate (PET), and combinations thereof, preferably polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • PVDF-TrFE polyvinyl Chloride
  • PTFE polytetrafluoroethylene
  • PU polyurethane
  • PMMA polymethyl methacrylate
  • PDMS polydimethylsiloxane
  • PVA poly
  • PVDF-TrFE polyvinylidene fluoride-co-trifluoroethylene
  • PVDF-TrFE polyvinylidene fluoride-co-trifluoroethylene
  • PVDF-TrFE polyvinylidene fluoride-co-trifluoroethylene
  • the ionic liquid refers to a liquid containing ions, and may include, for example, a neutral liquid, anionic liquid, or cationic liquid.
  • the neutral liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Emim TFSI).
  • Emim TFSI 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • Bmim TFSI 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • Bmim TFSI 1-Butyl-3-methylimidazolium Hexafluorophosphate (1-Butyl-3-methylimidazolium hexafluorophosphate, Bmim PF 6 ), 1-Ethyl-3-methylimidazolium tetrafluoroborate (Emim BF 4 ), 1- Methyl-3-propylimidazolium iodide (PMII), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 )
  • Emim TFSI -3-Methylimidazolium bis(trifluoromethylsulfonyl)imide
  • Emim TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • the anionic liquid is trifluoroacetate ([tfa] - ), trifluoromethanesulfonate ([CF 3 SO 3 ] - ), bis (fluoro Sulfonyl)imide (bis(fluorosulfonyl)imide)([N(SO 2 F) 2 ] - ), bis(trifluoromethanesulfonyl)imide)([N(SO 2 CF 3 ) 2 ] - ), Dicyanamide ([N(CN) 2 ] - ), tetracyanoborate ([B(CN) 4 ] - ), dihydrogenphosphate ( It may include an anionic liquid selected from the group consisting of [H 2 PO 4 ] - ), hydrogen sulfate ([HSO 4 ] - ), and combinations thereof.
  • the cationic liquid is selected from the group consisting of imidazolium, pyrrolidinium, piperidinium alkylmethylimidazolium, and combinations thereof. It may contain a cationic liquid.
  • the ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, Emim TFSI), which may be represented by the following formula (2).
  • the polymer gel for a triboelectric nanogenerator may further include a solvent in addition to the polymer resin and ionic liquid.
  • the polymer resin and ionic liquid are dissolved in the solvent. It may be there.
  • the type of solvent is not greatly limited, but according to an embodiment of the present invention, methyl ethyl ketone (MEK) may be used, which may be represented by the following formula (3).
  • the content of the ionic liquid may be 1 part by weight to 100 parts by weight based on 100 parts by weight of the polymer resin, preferably 10 parts by weight to 50 parts by weight based on 100 parts by weight of the polymer resin. It could be. If the content of the ionic liquid is less than 1 part by weight compared to 100 parts by weight of the polymer resin, the content of the ionic liquid may be too small and the polymer gel may be opaque or have a low dielectric constant, and if it exceeds 100 parts by weight, the ionic liquid may be opaque or have a low dielectric constant. The content of is too high, resulting in a high leakage current value, which may deteriorate the performance of the triboelectric nanogenerator containing it.
  • the second aspect of the present application is,
  • First electrodes spaced apart from each other; and a second electrode and a charged polymer layer including the polymer gel according to the first aspect of the present application bonded to one surface of the first electrode.
  • the triboelectric nanogenerator may include a first electrode and a second electrode, and as shown in FIG. 2, one surface of the first electrode has a surface according to the first aspect of the present application.
  • a charged polymer layer containing a polymer gel may be bonded. At this time, the bonding may be used without limitation as long as a conventional bonding method is used.
  • the second electrode may be positioned to be spaced apart from the first electrode, and the first electrode and the second electrode may be made of aluminum (Al), copper (Cu), and titanium (Ti), respectively. , gold (Au), silver (Ag), platinum (Pt), nickel (Ni), zinc (Zn), iron (Fe), cobalt (Co), and combinations thereof. It may be, and according to an embodiment of the present invention, aluminum (Al) may be used.
  • the triboelectric nanogenerator may further include a friction layer bonded to one surface of the second electrode.
  • the friction layer may be any material commonly used in triboelectric nanogenerators without limitation, and according to an embodiment of the present invention, polytetrafluoroethylene (PTFE) may be used.
  • PTFE polytetrafluoroethylene
  • the triboelectric nanogenerator may include a polymer gel bonded to one surface of the first electrode and a friction layer bonded to the second electrode, and the polymer gel and friction layer are bonded to each other. It may be located in a facing direction. That is, as shown in Figure 2, the first electrode, the polymer gel, the friction layer, and the second electrode may be located sequentially, the polymer gel and the friction layer are installed to be spaced apart from each other, and the first electrode and the second electrode Each electrode may have a wire connected to it.
  • the triboelectric nanogenerator may have excellent output voltage by including the polymer gel according to the first aspect of the present application as a charged polymer layer.
  • the third aspect of the present application is,
  • a method for producing a polymer gel for a triboelectric nanogenerator is provided.
  • the method for producing a polymer gel for a triboelectric nanogenerator may include preparing a solution by dissolving a polymer resin and an ionic liquid in a solvent.
  • the method for producing the polymer gel for a triboelectric nanogenerator may include the step of drying the solution.
  • the drying may be performed at a temperature of 50°C to 100°C for 1 hour to 3 hours, and according to an embodiment of the present invention, it may be performed at a temperature of about 80°C for about 2 hours. It may be.
  • the method for manufacturing the polymer gel for a triboelectric nanogenerator may include the step of annealing the dried solution.
  • the annealing may be performed at a temperature of 80°C to 200°C for 1 hour to 5 hours, and according to an embodiment of the present invention, the annealing may be performed at a temperature of about 120°C for about 3 hours. It may be.
  • PVDF-TrFE polyvinylidene fluoride-co-trifluoroethylene
  • 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
  • MEK methyl ethyl ketone
  • the weight mixing ratio of the PVDF-TrFE and IL was 1:0.1.
  • the polymer gel prepared in step 1 above is bonded to the aluminum (Al) electrode, and polytetrafluoroethylene (PTFE) is bonded to the opposite electrode, aluminum (Al), as a friction material, Both electrodes were separately connected to wires.
  • PTFE polytetrafluoroethylene
  • the size of both electrodes was 5 x 5 cm, and the thickness of the gel was 0.1 mm.
  • a triboelectric nanogenerator was manufactured in the same manner as in Example 1, except that the weight mixing ratio of PVDF-TrFE and IL (Emim TFSI) was changed to 1:0.3.
  • a triboelectric nanogenerator was manufactured in the same manner as in Example 1, except that the weight mixing ratio of PVDF-TrFE and IL (Emim TFSI) was changed to 1:0.5.
  • Example 1 the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Emim TFSI) was not used.
  • a triboelectric nanogenerator was manufactured in the same manner except that it was not used.
  • the output voltage was measured using pushing machines (Pushing Machine, SnM), an oscilloscope (TBS 2204B, Tektronix Co.), and a high-voltage passive probe (P5100A, Tektronix Co.), under the conditions of contact separation mode, 3N, 5Hz. It was measured.
  • the dielectric constant was measured using an impedance/gain-phase analyzer (SI 1260, Solartron) and a dielectric interface (SI 1296, Solartron), with an electrode diameter of 10 mm, 1 Hz to 1 MHz, 2V, and room temperature.
  • the leakage current was measured using a potentiostat/galvanostat (Biologic Science Instruments, SP300) at 80V/mm and room temperature.
  • the triboelectric nanogenerator is a capacitive type nanogenerator, and as the dielectric constant increases, more charges and storage are possible. Therefore, it was confirmed that the performance of the triboelectric nanogenerator also increases as the content of ionic liquid increases.
  • Example 3 where the content of the ionic liquid is 0.5, the effect is due to the increase in leakage current rather than the effect due to the increase in dielectric constant. It was confirmed that the effect was more dominant and the performance of the triboelectric nanogenerator was actually reduced.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne un gel polymère pour un nanogénérateur triboélectrique et un nanogénérateur triboélectrique le comprenant, le gel polymère comprenant un liquide ionique. Plus spécifiquement, étant donné que le gel polymère comprend le liquide ionique, le nanogénérateur triboélectrique comprenant le gel polymère présente d'excellentes performances.
PCT/KR2023/019952 2022-12-07 2023-12-06 Gel polymère pour nanogénérateur triboélectrique comprenant un liquide ionique, et nanogénérateur triboélectrique le comprenant Ceased WO2024123062A1 (fr)

Applications Claiming Priority (2)

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KR1020220170022A KR102823986B1 (ko) 2022-12-07 2022-12-07 이온성 액체를 포함하는 마찰대전 나노발전기용 고분자 겔 및 이를 포함하는 마찰대전 나노발전기
KR10-2022-0170022 2022-12-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118984074A (zh) * 2024-08-05 2024-11-19 山东农业大学 一种基于导电离子凝胶的摩擦自供电柔性力感知传感器

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Publication number Priority date Publication date Assignee Title
JP2008228542A (ja) * 2007-03-16 2008-09-25 National Institute Of Advanced Industrial & Technology ポリマーイオンゲルを用いたアクチュエータ素子及びその製造方法
KR20180002267A (ko) * 2016-06-29 2018-01-08 삼성전자주식회사 마찰전기를 이용한 에너지 하베스터 및 이를 포함하는 장치
CN110358002A (zh) * 2019-07-04 2019-10-22 东华大学 一种离子凝胶及离子凝胶基摩擦纳米发电机
KR102307520B1 (ko) * 2020-04-06 2021-09-30 울산과학기술원 마찰전기 발전기-슈퍼 커패시터 복합장치 및 이의 제조방법
WO2022031230A1 (fr) * 2020-08-03 2022-02-10 National University Of Singapore Dispositif triboélectrique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210040342A (ko) 2021-04-02 2021-04-13 연세대학교 산학협력단 에너지 하베스터 및 그 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008228542A (ja) * 2007-03-16 2008-09-25 National Institute Of Advanced Industrial & Technology ポリマーイオンゲルを用いたアクチュエータ素子及びその製造方法
KR20180002267A (ko) * 2016-06-29 2018-01-08 삼성전자주식회사 마찰전기를 이용한 에너지 하베스터 및 이를 포함하는 장치
CN110358002A (zh) * 2019-07-04 2019-10-22 东华大学 一种离子凝胶及离子凝胶基摩擦纳米发电机
KR102307520B1 (ko) * 2020-04-06 2021-09-30 울산과학기술원 마찰전기 발전기-슈퍼 커패시터 복합장치 및 이의 제조방법
WO2022031230A1 (fr) * 2020-08-03 2022-02-10 National University Of Singapore Dispositif triboélectrique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118984074A (zh) * 2024-08-05 2024-11-19 山东农业大学 一种基于导电离子凝胶的摩擦自供电柔性力感知传感器

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