AU2021105896A4 - Honeycomb structured ionic polymer metal nanocomposites using direct bonded of acidic ionic liquid - Google Patents
Honeycomb structured ionic polymer metal nanocomposites using direct bonded of acidic ionic liquid Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 11
- 229920000831 ionic polymer Polymers 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims abstract description 121
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 98
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 98
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- 239000012528 membrane Substances 0.000 claims abstract description 84
- 239000002608 ionic liquid Substances 0.000 claims abstract description 83
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005452 bending Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 8
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- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 2
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- ZPTRYWVRCNOTAS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.[O-]S(=O)(=O)C(F)(F)F ZPTRYWVRCNOTAS-UHFFFAOYSA-M 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
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- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
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- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- RCNFOZUBFOFJKZ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-hexyl-3-methylimidazol-3-ium Chemical compound CCCCCC[N+]=1C=CN(C)C=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F RCNFOZUBFOFJKZ-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
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- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
The present Invention relates to a honeycomb structured ionic polymer-metal nano-composite
(IPMNC) sensor using the direct attachment of an acidic ionic liquid (1-butyl-3
methylimidazoliumhydrogen sulfate) in a poly(vinylidene fluoride-trifluoroethylene
chlorotrifluoroethylene) P(VDF-TrFE-CTFE) and polyvinylpyrrolidone (PVP) blend.
Additionally, for the fabrication of IPMNC sensors, electroless plating process is used for
making the Platinum (Pt) electrode by embedding the Platinum (Pt) nanoparticles (NPs)on the
ionic liquid. Sodium borohydride (NaBH4) and Polyvinylpyrrolidone (PVP) are used as
reducing agent for the composite process and Lithium chloride (LiCl) is used as a reducing
agent for the surface electrode process. The IPMNC sensors of the present invention generate
high sensing voltages up to 380 mV and 300 mV with a bending strain of 0.009 and a stress of
80 MPa, respectively. The honeycomb structure of the present invention, provides uniform
porosity in a P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membrane, improving the proton
conductivity (3.4 times) and Young's modulus (52 times) of the blend membrane.
1/7
P(VDF-TrFE.CTFE) PVP Ionicliquid
P(DF-TrFE-CTFE)PVPflonic liquid basedIPMNC
P(V F-TrFFE E)1PVPlonicliquid PtNPs P(F-TrFE-CTFE)/PYPIlonicliquid
Fig.1
Description
1/7
P(VDF-TrFE.CTFE) PVP Ionicliquid
P(DF-TrFE-CTFE)PVPflonic liquid basedIPMNC
P(V F-TrFFE E)1PVPlonicliquid PtNPs P(F-TrFE-CTFE)/PYPIlonicliquid
Fig.1
Field of the Invention
[0001] The present Invention is in the field of ionic polymer metal nanocomposites sensor for energy harvesting and touch sensing application. Particularly, the Invention provides honeycomb structured ionic polymer metal nanocomposites using direct bonded of acidic ionic liquid in hydrophobic-hydrophilic blend and its method of preparation thereof.
Background of the Invention
[0002] Flexible, stable, and reliable energy harvesting materials are required that are independent of the environmental condition for charging portable devices and touch sensors. The flexible ionic polymer metal nano-composites (IPMNCs) have grabbed the immense interest of the scientific community because of its large actuation at low voltages (I to 5 V) and sensing properties with the bending force. The existing literature reveals that IPMNCs are developed by coating metal particles on an ion polymer membrane. The actuation properties of IPMNC are utilized for swimming robots, biomedical catheters, biomimetic sensory actuators, and drug delivery micro-pumps. The sensing properties of IPMNCs can be utilized for sensors application, energy harvesting application, wearable impact sensor application, flexible impact sensor application, and in the measurement of blood pressure, pulse rate, and rhythm measurement using IPMNC sensors. IPMNC actuators have been utilized extensively in the past, however, exploring the idea of the energy harvesting on IPMNC is the need of the art.
[0003] In order to design an efficient IPMNC energy harvester, metal particle coated ionic membranes were fabricated. The perfluorinated polymer membrane, e.g. the Nafion copolymer consisting of hydrophobic and hydrophilic parts (a commercially available membrane from DuPont) is a commonly used ionic polymer membrane. Due to the high cost, low water uptake, and low ion exchange capacity of the Nafion membrane, researchers have proposed various ionic blend membranes using hydrophobic and hydrophilic acidic and basic polyelectrolytes. However, hydrophilic polyelectrolyte blended ionic membranes show brittleness and irregular porosity, which may cause internal short-circuit and degrade the energy harvesting performance of IPMNCs.
[0004] Polyelectrolyte based ionic polymer-metal nanocomposites are widely being used for the actuator and sensor applications due to the flexibility. However, the polyelectrolyte based IPMNC has the limitation of a low sensing voltage and mechanical strength, which is mainly due to the irregular porosity that hinders its commercial applications.
[0005] There exists various IPMNCs for actuation purposes using polymer blends based on polyvinylidene fluoride (PVDF)/polyvinyl pyrrolidone (PVP)/polystyrene sulfonic acid (PSSA). The main drawback of the PVDF/PVP/PSSA ionic polymer was its lower ionic conductivity and lower flexibility in the air than the Nafion membrane. P(VDF TrFE)/PVP/PSSA was utilized for actuator applications, however, it has the limitation of actuation in the air. Therefore, the PVDF/PVP/PSSA and P(VDF-TrFE)/PVP/PSSA based IPMNCs are not suitable for wearable energy harvesting material applications. The fabrication of P(VDF-TrFE-CTFE)/PVP/PSSA and carboxylic graphene (COG) attached P(VDF-TrFE-CTFE)/PVP/PSSA IPMNC sensors was time consuming and expensive because of the addition of the carboxylic graphene. The PSSA based ionic polymer membrane showed an irregular pore size (large and small sizes of pores). To avoid the polyelectrolyte blended membrane and Nafion membrane for energy harvesting applications, an ionic liquid embedded blend membrane can be an alternative material for the development of IPMNCs to control the brittleness and pore structure.
[0006] The literature reveals that previously, ionic liquid embedded hydrophobic membranes were utilized for actuator applications and to control of the morphology in the hydrophobic based membrane. For actuator application, previous researchers deposited electrode using metal leaf by heat pressing method and PEDOT:PSS conducting polymer. The P(VDF-CTFE) and P(VDF-CTFE)/poly(methyl methacrylate) (PMMA) cross-linked blends were exploited as ionic electroactive polymer actuators. They immersed the (P(VDF-CTFE)) and P(VDF-CTFE))/PMMA membrane into 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [C2mim][TfO] ionic liquid to develop the ionic blend membrane and attach separate gold leaf for actuator application. The PVDF and PVDF/ionic liquid blend with 10, 25 and 40% 1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]) and 1-hexyl-3 methylimidazolium bis-(trifluoromethylsulfonyl)imide ([C6mim][NTf2]) ionic liquid blend were prepared via blending method and employed for actuator application without attaching metal electrode. The PEDOT:PSS/PVDF/ionic liquid actuators were fabricated using a solvent casting method with PEDOT:PSS electrode.
[0007] Literature also reveals development of an ionic liquid blend actuator using 10 to 40% 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid attached to different PVDF, PVDF-HFP, and PVDF-CTFE blend membranes. The electrical and actuation properties of the composite membrane depend on the percentage of the ionic content. The ionic liquid/PVDF-CTFE composite showed the best actuation.
[0008] All the previous research on the ionic liquid-based membranes, interfacial bonding of electrode with the liquid-based membrane was not strong and actuation occurred at high voltages. Till date, no research development was realized on the ionic liquid bonded polymer blend with a metal electrode for energy harvesting application. In addition, ionic liquid blended P(VDF-HFP) was used for controlling the morphology in membranes and developed uniform honeycomb structure. The honeycomb structure of blend membrane shows outstanding properties, such as large space area, good structural stability, high mechanical strength, low density, buffering humidity fluctuations, together with thermal and acoustic insulation. In addition, the honeycomb structure enhances the ionic conduction of the blend membrane due to the connected pores inside the membrane.
[0009] Hence, there is a need of an efficient ionic polymer metal nanocomposites sensor and its method of preparation.
Object(s) of the Invention
[0010] A primary object of the present invention is to overcome the drawbacks associated with the prior art.
[0011] Yet another object of the present invention is to provide a honeycomb structured ionic polymer metal nanocomposites sensor.
[0012] Yet another object of the present invention is to provide a method of preparation of a honeycomb structured ionic polymer metal nanocomposites sensor. Another objective of the present invention is to provide a honeycomb structured ionic polymer metal nanocomposites membrane useful for energy harvesting application
[0013] Another objective of the present invention is to provide a honeycomb structured ionic polymer metal nanocomposites membrane prepared by using ionic liquid bonded hydrophobic polymer membrane with metal electrode. Yet another object of the present invention is to provide a cost effective and efficient ionic polymer metal nanocomposite sensor.
Brief Description of the Drawings
[0014] To clarify advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof, which is illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail with the accompanying drawings in which:
[0015] Fig.1 illustrates a schematic diagram of the ionic polymer metal nanocomposites based on a Pt-coated P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membrane of the present invention.
[0016] Fig. 2 illustrates a digital image of the measurement setup to check the sensing voltage after applying force.
[0017] Fig. 3 illustrates FTIR spectra of (a) P(VDF-TrFE-CTFE), the ionic liquid, and the35/15/50, 30/15/55 and 25/15/60 blends. DSC spectra of (b) P(VDF-TrFECTFE),and the /15/50, 30/15/55 and 25/15/60 blends.
[0018] Fig. 4 illustrates (a-c) Cross-section view SEM images of (a) P(VDF-TrFE-CTFE), (b)the 35/15/50 blend, (c) the 30/15/55 blend and (d) the 25/15/60 blend. PtEDX profiles of the upper (e) and lower (f) part of the P(VDF-TrFE)/PVP/PSSA 30/15/55 IPMNC. Surface view of the 30/15/55 IPMNC at low (g) and high (h) magnification.
[0019] Fig. 5 illustrates load with strain spectra of the 35/15/50, 30/15/55 and 25/15/60 blends.
[0020] Fig. 6 illustrates Sensing voltage of (a) the 30/15/55 and 25/15/60 IPMNCs with time, (b) sensing current of the 30/15/55 and 25/15/60 IPMNCs with time, (c) sensing voltage of the 30/15/55 and 25/15/60 IPMNCs with the number of cycles, (d) sensing voltage of the /15/55 IPMNC with different frequencies, (e) sensing voltage of the 30/15/55 and 25/15/60 IPMNCs with time at 80 MPa, and (f) sensing voltage of various IPMNCs with applied stress.
[0021] Fig. 7 The current density of the 30/15/15 and 25/15/60 IPMNCs with voltage.
Summary of the Invention
[0022] The present disclosure discloses a honeycomb structured ionic polymer-metal nanocomposite (IPMNC) sensor and its method of preparation thereof.
[0023] In an aspect of the Invention, there is provided a honeycomb structured ionic polymer-metal nanocomposite (IPMNC) sensor, comprising (1-butyl-3-methylimidazolium hydrogen sulfate) as acidic ionic liquid, Poly (vinylidene fluoride-trifluoroethylene chlorotrifluoroethylene) P(VDF-TrFE-CTFE) and Polyvinylpyrrolidone (PVP):
[0024] In an another aspect of the Invention, there is provided a method of preparation of honeycomb structured ionic polymer-metal nanocomposite (IPMNC) sensor, comprising the steps of: a. dissolving of (1-butyl-3-methylimidazolium-hydrogen sulfate) as acidic ionic liquid, Poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) P(VDF-TrFE-CTFE) and Polyvinylpyrrolidone (PVP) in N,N-dimethyl formamide (DMF) to form a blend solution; b. stirring of the blend solution for 12 hours with a magnetic stirrer; c. casting of the blend solution onto a glass petri dish; d. keeping the glass petri dish in a vacuum at 800C for 24 hours and at 1000C for 12 hours for evaporation of the solvent; e. after cooling of the glass Petri dish, stripping off the membrane from the glass Petri dish; f. immersing the membrane in water for 24 h for saturating the matrix with water; g. drying and sand-blasting the membrane for surface roughening; h. making of Pt electrode by embedding the Platinum (Pt) nanoparticles (NPs) in the membrane.
Detailed description
[0025] For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.
[0026] It will be understood by those skilled in the art that the foregoing general description and the following detailed description are exemplary and explanatory of the invention and are not intended to be restrictive thereof. Throughout the patent specification, a convention employed is that in the appended drawings, like numerals denote like components.
[0027] The present Invention provides anionic polymer metal nanocomposites sensor for energy harvesting and touch sensing application. Particularly, the Invention provides honeycomb structured ionic polymer metal nanocomposites using direct bonded of acidic ionic liquid in hydrophobic-hydrophilic blend and its method of preparation thereof.
[0028] Therefore the present invention provides a honeycomb structured ionic polymer metal nanocomposite (IPMNC) sensorand its method of preparation thereof.
[0029] In an embodiment, a honeycomb structured ionic polymer-metal nanocomposite (IPMNC) sensor, comprises: (1-butyl-3-methylimidazolium-hydrogen sulfate) as acidic ionic liquid, Poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) P(VDF-TrFE CTFE) and Polyvinylpyrrolidone (PVP).
[0030] In one embodiment of present invention, Platinum (Pt) metal nanoparticles (NPs) are used for the synthesis of ionic polymer-metal nanocomposite.
[0031] In another aspect of the invention, the method of preparation of honeycomb structured ionic polymer-metal nanocomposite (IPMNC) sensoris provided. The method comprising the following steps: a. dissolving of (1-butyl-3-methylimidazolium-hydrogen sulfate) as acidic ionic liquid, Poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) P(VDF-TrFE-CTFE) and Polyvinylpyrrolidone (PVP) in N,N-dimethyl formamide (DMF) to form a blend solution; b. stirring of the blend solution for 12 hours with a magnetic stirrer; c. casting of the blend solution onto a glass petri dish; d. keeping the glass petri dish in a vacuum at 800 C for 24 hours and at 100°C for 12 hours for evaporation of the solvent; e. after cooling of the glass Petri dish, stripping off the membrane from the glass Petri dish; f. immersing the membrane in water for 24 h for saturating the matrix with water;
g. drying and sand-blasting the membrane for surface roughening; h. making of Pt electrode by embedding the Platinum (Pt) nanoparticles (NPs) in the membrane.
[0032] In an embodiment, the ratio of said P(VDF-TrFE-CTFE), PVP and acidic ionic, is selected from group consisting of 25/15/60, 35/15/50 or 30/15/55. In an embodiment, the electroless plating process is used for making the Pt electrode.
[0033] In an another embodiment, the Sodium borohydride (NaBH4) and Polyvinylpyrrolidone (PVP) are used as reducing agent for the composite process. In an embodiment, the Lithium chloride (LiCL) is used as reducing agent for the surface electrode process.
[0034] In an embodiment, a sensing voltage and sensing current of the PVDF-TrFE CTFE/PVP/ionic liquid IPMNC are generated with applied stress due to the separation of the cations and anions.
[0035] The schematic diagram of P(VDF-TrFE-CTFE)/PVP/ionic liquid/Pt IPMNC is presented in Fig. 1. In the composite structure, the ionic liquid is attached to the chains of P(VDFTrFE-CTFE) via the cation of 1-butyl-3-methylimidazolium and the anion of hydrogen sulfate via hydrogen bonding. PVP molecules interact with P(VDF-TrFE-CTFE) and the ionic liquid via the oxygen atom. The spherical bubbles of a white smoke color show the P(VDF TrFE-CTFE)/PVP/ionic liquid blend membrane and the peach color bubbles on both sides of the blend membrane showthe Pt NPs.
[0036] For the energy harvesting application (sensing voltage and sensing current), the IPMNC sample (polyethylene terephthalate (PET) as a base substrate for the IPMNC) was clamped to a bending machine as shown in Fig. 2. The sensing signal was measured using a Keithley source meter. The speed of the bending machine was5mms 1 and the bending radius of the sensor was around 10 mm. The bending strain was calculated using the following formula L/2r, where L is the thickness of the sample and r is the bending radius. To check the sensing signals with various pressures, the IPMNC sample with a PET substrate was clamped in a different bending machine and a hardnesstester was used to apply pressure as shown in Fig. 2.
[0037] In an embodiment of the present invention, there is provided a honeycomb structured ionic liquid embedded P(VDF-TrFE-CTFE) and PVP based ionic polymer-metal nanocomposite sensor with an enhanced sensing voltage and mechanical strength in comparison with the polyelectrolyte attached P(VDF-TrFE-CTFE) membrane, Nafion and Flemnion based ionic polymer-metal nanocomposite sensors. The ionic liquid embedded P(VDF-TrFE-CTFE) via PVP blend membrane displayed a honeycomb structure that enhanced the ion exchange capacity and mechanical strength compared to that of the polyelectrolyte (PSSA) attached P(VDF-TrFE-CTFE)/PVP membrane.
[0038] In an another preferred embodiment of the present invention, a P(VDF-TrFE CTFE)/PVP/ionic liquid (30/15/55) blend membrane demonstrates a proton conductivity increase of up to 2.1 times and a Young's modulus increase of up to51 times compared to those of the P(VDF-TrFE-CTFE)/PVP/PSSA(30/15/55) blend membrane. The ionic polymer membrane nanocomposite (IPMNC) sensors based on the P(VDF-TrFECTFE)/PVP/ionic liquid blend membrane showed sensing voltages enhanced by up to 12, 5.4, 75 and 50 times in comparison with the P(VDF-TrFE-CTFE)/PVP/PSSA, P(VDF-TrFE CTFE)/PVP/PSSA/COG, Nafion, and Flemion IPMNCs, respectively. TheP(VDF-TrFE CTFE)/PVP/ionic liquid IPMNC showed constant sensing voltage signals up to 6000 cycles.
[0039] In an another aspect of the present invention, the flexible energy harvester sensor based on ionic liquid embedded P(VDF-TrFE-CTFE) with Pt-coated ionic polymer-metal nanocomposites with enhanced sensing voltage will be useful in energy harvesting and touch sensor technology applications, where highly efficient flexible energy harvester materials for portable devices are required.
[0040] In an another preferred embodiment of the present invention, electroless deposition of Pt nanoparticles (NPs) on ionic liquid embedded P(VDF-TrFE-CTFE) using LiCl as a reducing agent, which is a novel strategy to fabricate IPMNC sensors. In an embodiment, the deposition of electro-less deposition of Pt NPs can be extended to other polymer composite based IPMNC sensors.
[0041] The Invention is further described with the help of non-limiting examples.
Example 1:
[0042] To estimate the optimum composition of the P(VDF-TrFECTFE)/PVP/ionic liquid blend membrane, various ratios of P(VDF-TrFE-CTFE)/PVP/ionic liquid were fabricated. After optimization, the blending ratio of 30/15/55 of P(VDF-TrFE-CTFE)/PVP/ionic liquid exhibited the maximum proton conductivity and IEC with optimal values of the WUP, as compared to the other blending ratios of 35/15/50 and 25/15/60. The samples were sand blasted for surface roughening before Pt NP penetration to improve the surface area.
[0043] The water uptake (WUP), ion exchange capacity (IEC), and ionicconductivity of the blend membrane are shown in Table 1.The water uptake of the blend membrane provides indications of the water content in the blend membrane. An optimized amount of the WUP of the blend membrane is required for ion movement. The ion exchange capacity (IEC) provides an indication of the ion-exchangeable groups present in a blended group. Ion exchange groups are responsible for the conduction of protons and anions that control the ionic conductivity. The ionic conductivity of the blend membrane indicates the speed of the free ions in the blend membrane. The WUP of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membrane increased with increasing ionic liquid content dueto the free SO 3 H ions (shown in Table 1).
[0044] The blend 25/15/60showed the highest WUP as compared to the other blends. However, the P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membranes showed a lower WUP as compared to P(VDF-TrFECTFE)/PVP/PSSA because the P(VDF-TrFE CTFE)/PVP/PSSAblend showed large and irregular pores that stored more water. The porosities of P(VDF-TrFE-CTFE)/PVP/ionic liquid are shownin Fig. 4.
35/15/50 (this work) 0.52 1.8 0.0016 30/15/55 (this work) 0.62 2.7 0.0021 25/15/60 (this work) 0.84 2.1 0.0019 P(VDF-TrFE- 1.25 2.35 0.001 CTFE)/PVP/PSSA (30/15/55)
Table 1: Electrochemical properties of various blend membranes
[0045] The IECs of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membrane are shown in Table 1. The 30/15/55 ionic blend showed the highest IEC as compared to that of the other blends of 35/15/50 and 25/15/60. This might be due to the strong intermolecular interactions of the 30/15/55 blend as compared to the other blends. The enhanced intermolecular interactions occur via hydrogen bonding between the N cation and the SO3Hanion of the ionic liquid, the CO group of PVP, and the CH2group of P(VDF-TrFE-CTFE), improving the proton conduction, IEC, and mechanical properties of the blend membrane. The IEC of the ionic liquid embedded blend membrane helps in the deposition of Pt electrodes on both sides of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blend surface via interaction of Pt salt ions with CO sites, 1-butyl-3-methylimidazoliumand hydrogen sulfate ion sites of the P(VDF-TrFE CTFE)/PVP/ionic liquid blend using reducing agents (sodium borohydride and LiCl). The proton conductivity of the 30/15/55 P(VDF-TrFE-CTFE)/PVP/ionic liquid blend shows the best conductivity as compared to the other blends due to the uniform distribution of the ion exchange sites in the backbone of P(VDF-TrFE-CTFE) (shown in Table 1). The ionic liquid embedded P(VDF-TrFE-CTFE) showed a higher proton conductivity than that of the polyelectrolyte embedded P(VDF-TrFE-CTFE) due to the large numbers of cations and anions.
[0046] The electrochemical and mechanical properties of theP(VDF-TrFE CTFE)/PVP/ionic liquid blend membrane occur via intermolecular interactions (hydrogen bonding) between CH 2 , CO, an amide group, and the SO 3 H groups of P(VDF PTrFECTFE)/PVP/ionic liquid, which are analyzed via FTIR and DSC. To check the intermolecular interactions of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blend for miscibility, the DSC and FTIR spectra of P(VDF-TrFE-CTFE), PVP, the ionic liquid, and the /15/50,30/15/55, and 25/15/60 blends are shown in Fig. 3(a) and (b), respectively. From the FTIR analysis (Fig. 3(a)), the OH peak, amide (I)peak, and amide (II) peak of the ionic liquid were found at 3444 cm- 1, 1550 cm- 1, and 1686 cm-1. The CO peak of PVP was found at 1674 cm- 1. The CH 2 , CC, and CF 2 peaks of *pure P(VDF-TrFE-CTFE) were at 1397 cm- 1, 1264 cm 1 , and 887.9 cm 1 . The OH of the ionic liquid in 30/15/55 was broadened and shifted to higher frequency ranges and the OH bond of the other blends did not show any large change in the other blends of 35/15/50 and 25/15/60. The amide (I) peak and amide (II) of the ionic liquid broadened without changing intensity in all blends. In the case of 30/15/55, the CO peak of PVP broadened with shifting behavior, however, the35/15/50 and 25/15/60 blends did not indicate any change, which implies that weaker intermolecular interactions exist in the /15/50 and 25/15/60 blends than in the 30/15/55blend. In addition, the CH2 , CC, and CF 2 peaks of pure P(VDF-TrFE-CTFE) were broadened and shifted more to higher frequency in the case of the 30/15/55 blend as compared to those of the 35/15/50 and 25/15/60 blends. This indicates that the 30/15/55 blend shows perfect miscible behavior of the ionic liquid with the hydrophobic polymers due to the strong hydrogen bonding (intermolecular bonding). The strong hydrogen bonding of the 30/15/55 blend is also confirmed by a single glass transition in DSC analysis and uniform honeycomb morphology in SEM analysis. The perfect miscibility of the ionic liquid in the blend membrane increases the proton conductivity and IEC (shown in Table 1).
[0047] The DSC spectrum of P(VDF-TrFE-CTFE) is shown in Fig. 3(a).P(VDF-TrFE CTFE) showed a crystalline as well as ferroelectricnature because the melting temperature of P(VDF-TrFE-CTFE) is found at 129 0C. In the DSC spectra of the blend membrane, no endothermic peak was observed, except for the 35/15/50 blend, which showed small endothermic behavior at 97 0C and 143 0C.The small endothermic peaks were linked to the relaxation of the amorphous phase of the P(VDF-TrFE-CTFE) polymer and ascribed to the folded-chain segment of P(VDF-TrFE-CTFE) on the surfaceof the crystalline phase.
[0048] In the DSC spectra of the ionic polymer blends, broader peaks were observed at 110.61, 108.44, and 105.53 for 35/15/50,30/15/55 and 25/15/60, respectively, which are related to the glass transition temperature (Tg) of the ionic polymer blends. The Tg of the ionic polymer blends was calculated at the mid point of the area where specific heat (ACp) change was occurred. The Tg was calculated using a previously reported method. The calculation of Tg of the 35/15/50, 30/15/55 and 25/15/60blends using the DSC spectra is shown in Fig. 4(a), (b) and (c), respectively. A single Tg of the 30/15/55 and the 25/15/60blend was obtained as compared to 35/15/50 due to the amorphous nature, large porous structure (see Fig. 4(c) and (d)), high Young's modulus (Table 2), and strong hydrogen bonding of the 30/15/55 and /15/60 blends.15 In the case of the 35/15/50blend, it showed a high Tg and small endothermic peaks, which are ascribed to the immiscibility of the blend, which deteriorates the hydrogen bonding of this blend and reduces the stiffness compared to that of the 30/15/55 and 25/15/60 blends (Table 2).From the DSC analysis, the 30/15/55 and 25/15/60 blends showed perfect miscible behavior with a single Tg compared to the 35/15/50blend. Previous ionic liquid/hydrophobic polymer blends showed endothermic peaks because they contained a lower amount of ionic liquid. From this study, it has been found that our proposed P(VDF TrFE-CTFE)/PVP/ionic liquid blends are temperature sensitive and the physical properties of the materialare changed during heating.
35/15/50this work) 153 4.5 131 30/15/55 (this work) 163 15 3.95 25/15/60 (this work) 360 7 0.031 P(VDF-TrFE- 3.2 8 1.5 CTFE)/PVP/PSSA (30/15/55)
Table 2: Tensile properties of various compositions of 35/15/50, 30/15/55and 25/15/60 blends
[0049] The blend membranes and IPMNCs were characterized by SEM analysis to check the morphology of the samples. The SEM image of P(VDF-TrFE-CTFE) is shown in Fig. 4(a) and a fibers structure of P(VDF-TrFE-CTFE) was found. Fig. 4(b)-(d) show the cross-section images of the 35/15/50, 30/15/55, and 25/15/60blends, respectively. The ionic liquid embedded blends show a connected porous structure. The 35/15/50 blend shows a regular, small, and uniform pore structure due to the low amount of ionic liquid, high amount of polymer content, and weak hydrogen bonding of the polymer blend with the ionic liquid (DSC showed Tg and endothermic peaks). The cross section images of the 30/15/55 and /15/60 blends showed honeycomb structures of pores due to the addition of the ionic liquid. The 30/15/55 blend showed a connected and uniform honeycomb structure and showed a single Tg with strong hydrogen bonding between the polymers and the ionic liquid. The honeycomb structure of 30/15/55 showed high tensile strength and tensile strain properties (see Fig. 5 and Table 2). The 25/15/60 blend showed irregular pores due to the high content of the ionic liquid. The30/15/55 blend shows a honeycomb structure of pores, which shows the strong compatibility of the 30/15/55 blend compared to that of the blends 35/15/50 and /15/60. This implies that the 30/15/55 blend shows strong intermolecular bonding between P(VDF-TrFE-CTFE) and the ionic liquid via PVP. The honeycomb structure of the blend membrane implies the controllable pores in large area, good structural stability, high mechanical strength, and enhanced ionic conduction of the blend membrane. The penetration depth of the metal particles in the blend membrane confirms the formation of the electrode and IEC. The deeper penetration of metal particles enhances the sensing and electrical properties.
[0050] The Pt electrode thickness of the blend membranes was investigated via thickness profiles of energy dispersive X-ray spectroscopy for the Pt-coated blend membranes, as shown in Fig. 4(e) and (f). The yellow dotted lines on both sides of the cross-section images of the IPMNC show the depth of the Pt NP penetration inside the blend membranes. It was observed that the Pt NPs penetrate deeply into the 30/15/55 blends up to 150 mm from the top and bottom surfaces. Fig. 4(g) and (h) show the surface structure of the Pt penetration at lower and higher magnification. Fig. 4(g) shows the cracked structure of the Pt electrode. The magnified form of the Pt electrode is shown in Fig. 4(h) and showed a coral structure of the NPs which was developed after combing the nanoparticles.
[0051] The tensile properties were investigated to confirm the mechanical behavior of the blend membranes. The stress-strain spectra of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blends with various component ratios 35/15/50, 30/15/55, and 25/15/60 are shown in Fig. 5 and Table 2. In addition, the mechanical strength of the P(VDF-TrFE-CTFE)/PVP/ionic liquid blends was compared with the PSSA blended P(VDF-TrFE-CTFE)/PVP membrane. From the stress-strain curve, we can observe that the Young's modulus of the P(VDF-TrFE CTFE)/PVP/ionic liquid blend increased with an increasing amount of ionic liquid. The30/15/55 and 25/15/60 blends showed a higher Young's modulus than the 35/15/50 blend due to the single Tg with strong hydrogen bonding of the miscible 30/15/55 and 25/15/60 blends as discussed in the DSC analysis. The 30/15/55 P(VDF-TrFECTFE)/PVP/ionic liquid blend membrane showed the high tensile strength and tensile strain as compared to the other blends of P(VDF-TrFE-CTFE)/PVP/ionic liquid due to the honeycomb structure of the /15/55 blend. The P(VDF-TrFECTFE)/PVP/ionic liquid blend showed high mechanical strength as compared to that of PSSA blended P(VDF-TrFE-CTFE)/PVP due to the honeycomb structure of P(VDF-TrFE-CTFE)/PVP/ionic liquid, which improves the mechanical strength with structural stability.
[0052] For energy harvesting applications in dry conditions, we designed an ionic liquid embedded P(VDF-TrFE-CTFE) via PVP IPMNC with a composition of 30/15/55 and /15/60 to check the sensing voltage and current signals. Fig. 6(a) and (b) show the voltage and sensing signals with a bending strain of the P(VDF-TrFE-CTFE)/PVP/ionic liquid-based IPMNC, respectively. The sensing voltage and current of the IPMNC sensors were evaluated using a bending machine (shown in Fig. 2) with a bending strain of 0.009 and a speed of the bending machine of 5 mm s-.
[0053] The sensing voltage and current of the 30/15/55 IPMNC were higher than that of the /15/55 IPMNC. To check the durability, the sensing voltage of the IPMNCs was analyzed over6000 cycles as shown in Fig. 6(c). The sensing voltage of the IPMNCs displayed steady behaviour over 6000 bending cycles. The sensing current of the IPMNC with 30/15/55 and /15/60 over 6000 cycles is shown in Fig.4. For comparison of the sensing voltage of ionic liquid embedded (VDF-TrFE-CTFE) with previous work of polyelectrolyte and carboxylic grapheme attached P(VDF-TrFE-CTFE) for energy harvesting, the sensing voltage of P(VDF TrFE-CTFE)/PVP/PSSA and P(VDF-TrFE-CTFE)/PVP/PSSA/carboxylic graphene is shown in Fig. 5. The sensing voltage of P(VDF-TrFE-CTFE)/PVP/PSSA and P(VDF-
TrFECTFE)/PVP/PSSA/carboxylic graphene was lower than that of P(VDF-TrFE CTFE)/PVP/ionic liquid. This might be due to the low IEC and low electrical current with voltage of P(VDF-TrFECTFE)/PVP/ionic liquid compared to that of P(VDF-TrFE CTFE)/PVP/PSSA and P(VDF-TrFE-CTFE)/PVP/PSSA/carboxylic graphene. To check the effect of frequency on the sensing voltage, the sensing voltage of the 30/15/55 IPMNC with a bending frequency of 0.2, 0.1 and 0.04 Hz is evaluated and the corresponding sensing voltage-frequency plot is shown in Fig. 6(d). It was found that the value of the sensing voltage of the IPMNC was not affected by the change in bending frequency. All the IPMNC samples showed similar behavior.
[0054] For touch sensing applications, the variation of the sensing voltage of the IPMNCs with time at a pressure of 80 MPa is shown in Fig. 6(e). IPMNC 30/15/55 displayed a high sensing voltage of 0.3 V with a fast response time. In addition, the variation of the sensing voltage of IPMNC 30/15/55 with time is shown in Fig. 6 at different pressures of 4 MPa, 40 MPa, and 80 MPa. The sensing voltage of the various IPMNCs with increasing applied stress is shown in Fig. 6(f). The sensing voltage of the IPMNCs increased with increasing pressure and showed linear behavior. With a mild force of 4 MPa, the IPMNC with 30/15/55 produced 0.025 V, which could be beneficial for soft touch sensing applications. The generation of a sensing voltage and sensing current of P(VDF-TrFE-CTFE)/PVP/ionic liquid using a bending strain and applied force can charge a battery and it can be used for energy harvesting.
[0055] The current density of the 30/15/55 and 25/15/60 IPMNCs with voltage is shown in Fig. 7. A large sensing current density of an IPMNC depends on the electrode formation on the blend membrane and storage of a large amount of cations and anions in the near-interface region of the electrode and electrolyte. A high current density with voltage of an IPMNC increases the dissipated electric power density of the IPMNC, which is proportional to the sensing current. The areas of the current density-voltage cycle corresponding to the dissipated electric power density of the 30/15/55 and 25/15/60 IPMNCs are found to be 0.0019 A cm-2 and 0.0013 A cm-2 , respectively. The capacitance of all the samples was also evaluated using the cyclic current density-voltage spectrum (Fig. 7). The capacitance of the 35/15/55 and /15/60 IPMNCs was found to bel.58 mF and 1.2 mF, respectively. The high value of the capacitance of the ionic liquid embedded P(VDF-TrFE-CTFE)IPMNC can also be applicable in super capacitor devices for high charge storing capacity.
[0056] Our P(VDF-TrFE-CTFE)/PVP/ionic liquid attached IPMNC sensors produced a high sensing voltage as compared to the Nafion (8 mV with 6 mm s-1), Flemion IPMNC (12 mV with6 mm s-1), P(VDF-TrFE-CTFE)/PVP/PSSA (50 mV with 5 mm s-1), and COG/P(VDF TrFE-CTFE)/PVP/PSSA (110 mV with mm s-1) based sensors. The comparison of various sensors with the bending speed is shown in Table 3. It is quite evident that our proposed ionic liquid embedded polymer sensor with a metal electrode can be utilized for energy harvesting applications with bending and touch forces.
P(VDF-TrFE-CTFE)/PVP/ionic 600 5 This liquid work
IBM-1(IL) (IPMNC) 50 5 [1]
IBM-1/COG(99.7/0.3)(IL) 110 5 [1] (IPMNC)
Nafion (IPMC) 8 6 [2]
Flemion (IPMNC) 12 6 [2]
Table 3: Comparison of the sensing voltage of various sensors
[0057] This research was financially supported by the Science and Engineering Research Board, File No.-ECR/2016/001113, India.
Claims (5)
1. A honeycomb structured platinum coated ionic polymer-metal nanocomposite (IPMNC) blend membrane comprising an acidic ionic liquid, Poly (vinylidene fluoride trifluoroethylene-chlorotrifluoroethylene) and Polyvinylpyrrolidone (PVP); wherein said acidic ionic liquid comprises (1-butyl-3-methylimidazolium-hydrogen sulfate); wherein said composite comprises direct attachment of said (1-butyl-3 methylimidazolium-hydrogen sulfate) in said P(VDF-TrFE-CTFE)/polyvinylpyrrolidone (PVP) blend; wherein platinum (Pt) metal nanoparticles are embedded on the said honeycomb structured P(VDF-TrFE-CTFE)/PVP/ionic liquid blend membrane.
2. The membrane as claimed in claim 1, wherein the ratio of said P(VDF-TrFE-CTFE), PVP, and (1-butyl-3-methylimidazolium-hydrogen sulfate) ranges 25/15/60, 35/15/50 or /15/55.
3. The membrane as claimed in claim 1, wherein said ionic liquid is embedded into the backbone of said hydrophobic P(VDF-TrFE-CTFE) to produce the ion exchange sites.
4. The membrane as claimed in claim 1, wherein said membrane generates high sensing voltage upto 380 mV and 300mV with a bending strain of 0.009 and stress of 80 MPa.
5. A method of producing a honeycomb structured platinum coated ionic polymer metal nanocomposite (IPMNC) blend membrane as claimed in claim 1, comprising the step/s of: a. dissolving of Poly (vinylidene fluoride-trifluoroethylene chlorotrifluoroethylene), Polyvinylpyrrolidone (PVP), and (1-butyl-3-methylimidazolium hydrogen sulfate) in N,N-dimethyl formamide (DMF) to obtain a blend solution; b. stirring the blend solution obtained from step (a) for 12 hours followed by casting it onto a glass Petri dish; c. Treating the casted Petri dish resulting from step (b)at 80 0C for 24 hours and at 100°C for 12 hours to evaporate the solvent and obtain the membrane comprising Poly
(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene), Polyvinylpyrrolidone (PVP) and 1-butyl-3-methylimidazolium-hydrogen sulfate; d. Stripping the membrane from the glass Petri dish followed by immersing in water for 24 hours to saturate the matrix with water; e. drying and sand-blasting the membrane resulting from step (d) for surface roughening; f. embedding the Platinum (Pt) nanoparticles (NPs) by electroless plating on the membrane resulting into the formation of platinum electrode wherein said deposition is performed in the presence of LiCl as reducing agent;
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