EP3857700A1 - Thermionic capacitor chargeable by soret-effect using a gradient temperature - Google Patents

Thermionic capacitor chargeable by soret-effect using a gradient temperature

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Publication number
EP3857700A1
EP3857700A1 EP19787450.6A EP19787450A EP3857700A1 EP 3857700 A1 EP3857700 A1 EP 3857700A1 EP 19787450 A EP19787450 A EP 19787450A EP 3857700 A1 EP3857700 A1 EP 3857700A1
Authority
EP
European Patent Office
Prior art keywords
thermionic
capacitor according
electrolyte
electrodes
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19787450.6A
Other languages
German (de)
French (fr)
Inventor
André Miguel TRINDADE PEREIRA
Clara Isabel BARBOSA RODRIGUES PEREIRA
Ana Lúcia MOTA PIRES
Rui SANTOS COSTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidade do Porto
Original Assignee
Universidade do Porto
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Filing date
Publication date
Application filed by Universidade do Porto filed Critical Universidade do Porto
Publication of EP3857700A1 publication Critical patent/EP3857700A1/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom

Definitions

  • the present disclosure relates to a thermionic capacitor chargeable by a gradient temperature, comprising nanostructured-carbon electrodes and a polymer solid-gel electrolyte comprising cations and anions thermodiffusable under a gradient temperature between said electrodes by Soret-effect.
  • thermoelectric generator using the Soret effect comprising a composition in a closed container provided with means to prevent convective flow within the container when the mixture is molten while permitting flow of ions and of vapour to maintain a concentration gradient within the composition in the presence of a temperature gradient.
  • the generator operates on the principle that a temperature gradient applied across the solution produces a steady-state concentration gradient which results in a voltage between inert electrodes.
  • thermoelectricity and supercapacitance The thermionic capacitor chargeable by a gradient temperature was produced using cost- effective components, regarding the electrodes, solid-gel electrolyte and design.
  • a thermionic capacitor chargeable by a gradient temperature that integrates two different mechanisms in a single multi-tasking device, such as: Electric double-layer capacitor (EDLC) mechanism and Soret effect.
  • EDLC Electric double-layer capacitor
  • Soret effect belongs to the supercapacitor store charge category, which involves the reversible adsorption/desorption of the electrolyte ions onto the surface of a porous electrode material.
  • the Soret effect or Ludwig-Soret effect or Soret diffusion is a mechanism belonging to the thermoelectric phenomenon; it involves ion thermodiffusion which occurs in a material composed by different species that respond differently to the temperature gradient and in this stage the ions separation will occur.
  • a thermionic capacitor chargeable by a gradient temperature that works when exposed to a temperature gradient.
  • it can be manufactured wherein both electrodes are patterned in-plane, herewith also referred as planar, or in a multilayer sandwich configuration, herewith also referred as layered, and the established temperature gradient can thus be in plane (horizontal) or out-of-plane (vertical), respectively.
  • a thermionic capacitor chargeable by a gradient temperature comprising a first and a second nanostructured-carbon electrodes and a polymer solid- gel electrolyte comprising cations and anions thermodiffusable by Soret-effect under a gradient temperature between said electrodes.
  • a temperature gradient can be defined as a progressive temperature difference between said electrodes.
  • the nanostructured-carbon provides electrical conductivity and also thermal conductivity, which allows to create circuits that are both electrical and thermal - delivering heat and electricity as part of the structure of the electrodes.
  • the thermionic capacitor is planar and the electrodes are arranged along two separate regions of a planar substrate being separated by an intermediate region of said substrate, with the electrolyte being laid over said electrodes and said intermediate region.
  • each of the electrodes has protrusions and recesses for meshing with recesses and protrusions of the other electrode, provided that the electrodes are not in electrical contact.
  • the structured temperature-diffusing electrodes allow the creation of temperature gradient shapes, for example created by meandering-shaped electrodes, which improve efficiency by creating more useful area for the Soret-effect and improve the compactness of the device.
  • the protrusions and recesses for meshing with recesses and protrusions refer to a structure comprising teeth of a gearwheel engaging with another gearwheel, provided that as in the present disclosure the electrodes do not make direct electrical contact.
  • the electrodes are interdigitated.
  • Interdigitated electrodes can be defined as two electrodes that interlock like the fingers of two hands about to clasp, such that each electrode, i.e. the fingers of each hand, do not touch the other electrode as in the context of the present disclosure.
  • the planar substrate is rigid, in particular made of glass, silica, cork, or metal sheet.
  • the planar substrate is flexible, in particular made of polyethylene terephthalate - PET, polyethylene naphthalate - PEN, polyethersulfone - PES, polyimide - PI, Kapton, polytetrafluoroethylene - PTFE, polypropylene - PP,
  • B poly(methyl methacrylate) - PMMA, polyvinyl chloride - PVC, latex, paper, rubber, a flexible sheet of cork, or thin metal foil.
  • the thermionic capacitor is layered and each electrode is a nanostructured-carbon coated layer, and comprises an intermediate layer of electrolyte between the electrode layers, wherein said layers form a stack.
  • the layered thermionic capacitor comprises a textile layer which is:
  • the layered thermionic capacitor comprises two textile layers and an electrolyte embedded in said textile layers, wherein a first textile layer is coated on a side by nanostructured-carbon forming a first electrode and a second textile layer is coated on a side by nanostructured-carbon forming a second electrode, the two textile layers being stacked onto each other such that the two sides having electrodes of the textile layers are facing outwards.
  • the electrolyte is embedded from in-between the two textile layers.
  • the textile is a woven or knitted fabric comprising cotton, polyester, silk, polyamide, or combinations thereof.
  • the textile is a non-woven fabric.
  • the electrode nanostructured-carbon comprises carbon nanotubes, graphene, carbon black, carbon fibres, carbon aerogel, or combinations thereof.
  • either or both electrodes comprise nanostructured-carbon metal oxide, metal nitride, metal sulfide, MXene - 2D transition metal carbide, TMD - transition metal dichalcogenide, MOF - Metal-organic framework, black phosphorus, lithium based material, organic conducting polymer, or combinations thereof.
  • either or both electrodes are obtained by layer-by-layer deposition, screen printing, lithography, spray painting, inkjet printing, sputtering deposition, ion beam deposition, electron beam deposition, chemical vapour deposition, dip-pad-dry process, chemical etching, or optical and mechanical patterning.
  • the electrolyte comprises a polymer and an ion donor of thermodiffusable cations and anions by Soret-effect.
  • the electrolyte comprises a mixture of:
  • phosphoric acid - H3P04 sulphuric acid - H2S04, potassium hydroxide - KOH, potassium sulfate - K2S04, potassium chloride - KCI, sodium sulfate - Na2S04, lithium hydroxide - LiOH, lithium sulfate - U2S04, or combinations thereof.
  • the electrolyte comprises poly(vinyl alcohol, PVA.
  • the electrolyte polymer comprises phosphoric acid - H3P04.
  • the electrolyte is an organic electrolyte comprising: tetraethylammonium tetrafluoroborate - TEABF4, tetraethylammonium difluoro(oxalato)borate - TEAODFB, spiro-(l,10)-bipyrrolidinium tetrafluoroborate - SBPBF4, tetrabutylammonium tetrafluoroborate - Bu4NBF4, or combinations thereof, dissolved in:
  • acetonitrile - ACN propylene carbonate - PC, adiponitrile - ADN or 1, 1,1, 3,3,3- hexafluoropropan-2-ol - HFIP, or combinations thereof.
  • the electrolyte is a ionic liquid comprising l-ethyl-3- methylimidazolium tetrafluoroborate - [EMIM][BF4], l-ethyl-3-methyl-imidazolium- thiocyanate - [EMIM][SCN], l-butyl-3-methylimidazolium tetrafluoroborate [BMIM] [BF4], l-ethyl-3-methylimidazolium tetracyanoborate - [EMIM] [TCB], 1-ethyl- 3-methylimidazolium difluorophosphate - [EMIM][P02F2], or combinations thereof.
  • An embodiment comprises two metallic current collectors each electrically connected to each said electrode.
  • the metallic current collectors are made of deposited metallic layers, in particular deposited metallic layers comprising aluminium, gold, silver, copper, platinum, in particular deposited by layer-by-layer deposition, ion beam deposition, sputtering deposition, chemical vapour deposition, screen printing, lithography, spray painting, inkjet printing, or combinations thereof, further in particular aluminium.
  • said cations and anions are selected such that said cations move towards the first electrode and said anions move towards the second electrode under thermophoretic force caused by the gradient temperature in the direction between said electrodes.
  • the disclosure also includes an electronic device comprising the thermionic capacitor according to any of the disclosed embodiments, in particular the electronic device being a wearable electronic device.
  • the electronic device comprising the thermionic capacitor also comprises a complementary electric power source, in particular a photovoltaic panel, a triboelectric generator, a piezoelectric generator or a magnetic induction generator.
  • a complementary electric power source in particular a photovoltaic panel, a triboelectric generator, a piezoelectric generator or a magnetic induction generator.
  • Figure 1 Shows a (a) schematic 2D representation of an embodiment of a thermionic capacitor chargeable by a gradient temperature with a 2D planar configuration on a flexible substrate, PET, and (b) schematic 3D representation of an embodiment of a thermionic capacitor chargeable by a gradient temperature with a planar configuration on a flexible substrate.
  • Figure 2 Schematic 2D representation of an embodiment of a self-charge thermionic with a sandwich-type configuration on a textile substrate, cotton.
  • Figure 3 Schematic representation of the working mechanism an embodiment of a thermionic capacitor chargeable by a gradient temperature in: a) planar and b) sandwich (layered) configuration.
  • Figure 4 Summary of the heat flow influence when it is using the two different embodiments with configurations of the disclosure, of a ionic thermoelectric micro supercapacitor with a solid-gel electrolyte that creates an embodiment of an assembled thermionic capacitor chargeable by a gradient temperature.
  • the open- circuit voltage vs. time for the device in a) planar and b) sandwich configuration was studied.
  • Figure 5 Photographic reproduction of infra-red emissions from a planar embodiment according to the disclosure.
  • FIG. 1 The configuration of the planar Thermionic capacitor chargeable by a gradient temperature is shown in Figure 1.
  • Figure 2 The configuration of the planar Thermionic capacitor chargeable by a gradient temperature is shown in Figure 2.
  • the present disclosure is eco-friendly and easy scalable, for example with the screen-printing and dip-pad-dry manufacturing processes, contributing to the reduction of the manufacturing costs.
  • the devices of the present disclosure are able to avoid electrolyte leakages and can also be made to be adapted and/or adaptable to different shapes and forms.
  • the ability to harvest energy and store it simultaneously using a wide range of sources, allows the disclosed sturdy and robust devices to be used in diversified areas.
  • planar Thermionic capacitor chargeable by a gradient temperature is schematically represented.
  • the planar Thermionic capacitor chargeable by a gradient temperature ( Figures la and lb) is fabricated in flexible substrate, such as PET (Al) with 18 cm 2 (4.5 cm x 4 cm) and thickness of ⁇ 0.076 mm.
  • the electrical contact of this device is optimized with the aim to promote the conduction of the charges in the ionic thermoelectric device to the external circuit.
  • Two reversed Au electrical contacts (A2) separated between each other by 1.6 cm, and shaped with 1.49 cm 2 and 50 nm of height were produced using the sputtering technique.
  • the second mask was produced by photolithography process and filled with multiwalled carbon nanotubes (MWCNTs).
  • MWCNTs solution concentration of 10 mg/mL
  • A3 was used to produce interdigitated electrodes constituted by four stripes interconnected between them (1.52 cm 2 ) and shaped with 2 cm of length, 0.2 cm of width and 8 pm of height.
  • the electrolyte solution up to 400 pL (A4) was overspread making a coating- top on the electrodes with an area of 7.5 cm 2 .
  • the textile thermionic capacitor chargeable by a gradient temperature is schematically represented.
  • the textile thermionic capacitor chargeable by a gradient temperature is fabricated using cotton fabric (warp: 3726, weft: 52 threads) with 10 cm 2 (2 cm x 5 cm).
  • the dip-pad-dry process was used to coat the commercial cotton fabric.
  • the cotton substrate (Bl) was dipped into the MWCNTs dispersion and then submitted to a padding process to remove the excess of MWCNTs.
  • the assembly MWCNT-coated fabric (B2) was dried.
  • two MWCNTs-coated fabrics were coated with the electrolyte solution (B3) and then stacked together face- to-face. (B4) represents the assembly between the electrodes and the electrolyte.
  • Figure 5 shows a photographic reproduction of infra-red emissions from a planar embodiment according to the disclosure, clearly showing the thermal circuit provided by the shape-structured electrodes, which allows shaping the thermal gradient between electrodes as desired.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Thermionic capacitor chargeable by a gradient temperature, comprising nanostructured-carbon electrodes and a polymer solid-gel electrolyte comprising cations and anions thermodiffusable under a gradient temperature between said electrodes by Soret-effect. The capacitor may be planar wherein the electrodes are arranged along two separate regions of a planar substrate being separated by an intermediate region of said substrate, with the electrolyte being laid over said electrodes and said intermediate region. The capacitor may be layered, each electrode being a nanostructured-carbon coated layer, comprising an intermediate layer of electrolyte between the electrode layers, wherein said layers form a stack, in particular said layers being comprised in a textile layer or being textile layers.

Description

TH ERMION IC CAPACITOR CHARG EABLE BY SORET-EFFECT
USI NG A G RADI ENT TEM PERATU RE
TECH NICAL FIELD
[0001] The present disclosure relates to a thermionic capacitor chargeable by a gradient temperature, comprising nanostructured-carbon electrodes and a polymer solid-gel electrolyte comprising cations and anions thermodiffusable under a gradient temperature between said electrodes by Soret-effect.
BACKGROUND
[0002] Document GB1162589A discloses a thermoelectric generator using the Soret effect comprising a composition in a closed container provided with means to prevent convective flow within the container when the mixture is molten while permitting flow of ions and of vapour to maintain a concentration gradient within the composition in the presence of a temperature gradient. The generator operates on the principle that a temperature gradient applied across the solution produces a steady-state concentration gradient which results in a voltage between inert electrodes.
[0003] These facts are disclosed in order to illustrate the technical problem addressed by the present disclosure.
GENERAL DESCRIPTION
[0004] It is disclosed a thermionic capacitor chargeable by a gradient temperature that can produce and store energy at the same time, with the aim to be used in energy harvesting and storage. The device has the capability to produce a potential voltage through a heat flow change and to be self-charged simultaneously due to the combination of two phenomena: thermoelectricity and supercapacitance. The thermionic capacitor chargeable by a gradient temperature was produced using cost- effective components, regarding the electrodes, solid-gel electrolyte and design. Through the combination of both phenomena allied with the advantages of the design, low-cost production, possibility to scale up and flexibility, it is possible, by small changes in the structure, to place the device in any environment that has a heat flow change.
[0005] It is disclosed a thermionic capacitor chargeable by a gradient temperature that integrates two different mechanisms in a single multi-tasking device, such as: Electric double-layer capacitor (EDLC) mechanism and Soret effect. The EDLC mechanism belongs to the supercapacitor store charge category, which involves the reversible adsorption/desorption of the electrolyte ions onto the surface of a porous electrode material. The Soret effect or Ludwig-Soret effect or Soret diffusion is a mechanism belonging to the thermoelectric phenomenon; it involves ion thermodiffusion which occurs in a material composed by different species that respond differently to the temperature gradient and in this stage the ions separation will occur. Therefore, when the ions migrate from the hot to the cold side, a positive Soret coefficient is achieved. So, these ions migration (from the solid-gel electrolyte) allows generating a thermovoltage than can be stored in an EDLC (the electrodes).
[0006] It is disclosed a thermionic capacitor chargeable by a gradient temperature that works when exposed to a temperature gradient. For instance, it can be manufactured wherein both electrodes are patterned in-plane, herewith also referred as planar, or in a multilayer sandwich configuration, herewith also referred as layered, and the established temperature gradient can thus be in plane (horizontal) or out-of-plane (vertical), respectively.
[0007] It is disclosed a thermionic capacitor chargeable by a gradient temperature, comprising a first and a second nanostructured-carbon electrodes and a polymer solid- gel electrolyte comprising cations and anions thermodiffusable by Soret-effect under a gradient temperature between said electrodes.
[0008] A temperature gradient can be defined as a progressive temperature difference between said electrodes. [0009] The nanostructured-carbon provides electrical conductivity and also thermal conductivity, which allows to create circuits that are both electrical and thermal - delivering heat and electricity as part of the structure of the electrodes.
[0010] In an embodiment, the thermionic capacitor is planar and the electrodes are arranged along two separate regions of a planar substrate being separated by an intermediate region of said substrate, with the electrolyte being laid over said electrodes and said intermediate region.
[0011] In an embodiment, each of the electrodes has protrusions and recesses for meshing with recesses and protrusions of the other electrode, provided that the electrodes are not in electrical contact.
[0012] The structured temperature-diffusing electrodes allow the creation of temperature gradient shapes, for example created by meandering-shaped electrodes, which improve efficiency by creating more useful area for the Soret-effect and improve the compactness of the device.
[0013] The protrusions and recesses for meshing with recesses and protrusions refer to a structure comprising teeth of a gearwheel engaging with another gearwheel, provided that as in the present disclosure the electrodes do not make direct electrical contact.
[0014] In an embodiment, the electrodes are interdigitated.
[0015] Interdigitated electrodes can be defined as two electrodes that interlock like the fingers of two hands about to clasp, such that each electrode, i.e. the fingers of each hand, do not touch the other electrode as in the context of the present disclosure.
[0016] In an embodiment, the planar substrate is rigid, in particular made of glass, silica, cork, or metal sheet.
[0017] In an embodiment, the planar substrate is flexible, in particular made of polyethylene terephthalate - PET, polyethylene naphthalate - PEN, polyethersulfone - PES, polyimide - PI, Kapton, polytetrafluoroethylene - PTFE, polypropylene - PP,
B poly(methyl methacrylate) - PMMA, polyvinyl chloride - PVC, latex, paper, rubber, a flexible sheet of cork, or thin metal foil.
[0018] In an embodiment, the thermionic capacitor is layered and each electrode is a nanostructured-carbon coated layer, and comprises an intermediate layer of electrolyte between the electrode layers, wherein said layers form a stack.
[0019] In an embodiment, the layered thermionic capacitor comprises a textile layer which is:
coated on a first side by nanostructured-carbon forming a first electrode, coated on a second side by nanostructured-carbon forming a second electrode, and embedded with the electrolyte.
[0020] In an embodiment, the layered thermionic capacitor comprises two textile layers and an electrolyte embedded in said textile layers, wherein a first textile layer is coated on a side by nanostructured-carbon forming a first electrode and a second textile layer is coated on a side by nanostructured-carbon forming a second electrode, the two textile layers being stacked onto each other such that the two sides having electrodes of the textile layers are facing outwards.
[0021] In an embodiment, the electrolyte is embedded from in-between the two textile layers.
[0022] In an embodiment, the textile is a woven or knitted fabric comprising cotton, polyester, silk, polyamide, or combinations thereof.
[0023] In an embodiment, the textile is a non-woven fabric.
[0024] In an embodiment, the electrode nanostructured-carbon comprises carbon nanotubes, graphene, carbon black, carbon fibres, carbon aerogel, or combinations thereof.
[0025] In an embodiment, either or both electrodes comprise nanostructured-carbon metal oxide, metal nitride, metal sulfide, MXene - 2D transition metal carbide, TMD - transition metal dichalcogenide, MOF - Metal-organic framework, black phosphorus, lithium based material, organic conducting polymer, or combinations thereof. [0026] In an embodiment, either or both electrodes are obtained by layer-by-layer deposition, screen printing, lithography, spray painting, inkjet printing, sputtering deposition, ion beam deposition, electron beam deposition, chemical vapour deposition, dip-pad-dry process, chemical etching, or optical and mechanical patterning.
[0027] In an embodiment, the electrolyte comprises a polymer and an ion donor of thermodiffusable cations and anions by Soret-effect.
[0028] In an embodiment, the electrolyte comprises a mixture of:
poly(vinyl alcohol) - PVA, poly(methylmethacrylate) - PMMA, poly(polycrylate) - PAA, poly(amineester) - PAE, poly(ethylene-oxide) - PEO, polya(crylonitrile) - PAN, poly(vinylidene fluoride) - PVDF, or combinations thereof, with:
phosphoric acid - H3P04, sulphuric acid - H2S04, potassium hydroxide - KOH, potassium sulfate - K2S04, potassium chloride - KCI, sodium sulfate - Na2S04, lithium hydroxide - LiOH, lithium sulfate - U2S04, or combinations thereof.
[0029] In an embodiment, the electrolyte comprises poly(vinyl alcohol, PVA.
[0030] In an embodiment, the electrolyte polymer comprises phosphoric acid - H3P04.
[0031] In an embodiment, the electrolyte is an organic electrolyte comprising: tetraethylammonium tetrafluoroborate - TEABF4, tetraethylammonium difluoro(oxalato)borate - TEAODFB, spiro-(l,10)-bipyrrolidinium tetrafluoroborate - SBPBF4, tetrabutylammonium tetrafluoroborate - Bu4NBF4, or combinations thereof, dissolved in:
acetonitrile - ACN, propylene carbonate - PC, adiponitrile - ADN or 1, 1,1, 3,3,3- hexafluoropropan-2-ol - HFIP, or combinations thereof.
[0032] In an embodiment, the electrolyte is a ionic liquid comprising l-ethyl-3- methylimidazolium tetrafluoroborate - [EMIM][BF4], l-ethyl-3-methyl-imidazolium- thiocyanate - [EMIM][SCN], l-butyl-3-methylimidazolium tetrafluoroborate [BMIM] [BF4], l-ethyl-3-methylimidazolium tetracyanoborate - [EMIM] [TCB], 1-ethyl- 3-methylimidazolium difluorophosphate - [EMIM][P02F2], or combinations thereof. [0033] An embodiment comprises two metallic current collectors each electrically connected to each said electrode.
[0034] In an embodiment, the metallic current collectors are made of deposited metallic layers, in particular deposited metallic layers comprising aluminium, gold, silver, copper, platinum, in particular deposited by layer-by-layer deposition, ion beam deposition, sputtering deposition, chemical vapour deposition, screen printing, lithography, spray painting, inkjet printing, or combinations thereof, further in particular aluminium.
[0035] In an embodiment, said cations and anions are selected such that said cations move towards the first electrode and said anions move towards the second electrode under thermophoretic force caused by the gradient temperature in the direction between said electrodes.
[0036] The disclosure also includes an electronic device comprising the thermionic capacitor according to any of the disclosed embodiments, in particular the electronic device being a wearable electronic device.
[0037] In an embodiment, the electronic device comprising the thermionic capacitor also comprises a complementary electric power source, in particular a photovoltaic panel, a triboelectric generator, a piezoelectric generator or a magnetic induction generator.
BRI EF DESCRI PTION OF THE DRAWI NGS
[00B8] The following figures provide preferred embodiments for illustrating the disclosure and should not be seen as limiting the scope of invention.
[0039] Figure 1: Shows a (a) schematic 2D representation of an embodiment of a thermionic capacitor chargeable by a gradient temperature with a 2D planar configuration on a flexible substrate, PET, and (b) schematic 3D representation of an embodiment of a thermionic capacitor chargeable by a gradient temperature with a planar configuration on a flexible substrate. [0040] Figure 2: Schematic 2D representation of an embodiment of a self-charge thermionic with a sandwich-type configuration on a textile substrate, cotton. Schematic SD representation of an embodiment of a thermionic capacitor chargeable by a gradient temperature with a sandwich-type configuration on a textile substrate.
[0041] Figure 3: Schematic representation of the working mechanism an embodiment of a thermionic capacitor chargeable by a gradient temperature in: a) planar and b) sandwich (layered) configuration.
[0042] Figure 4: Summary of the heat flow influence when it is using the two different embodiments with configurations of the disclosure, of a ionic thermoelectric micro supercapacitor with a solid-gel electrolyte that creates an embodiment of an assembled thermionic capacitor chargeable by a gradient temperature. The open- circuit voltage vs. time for the device in a) planar and b) sandwich configuration was studied.
[0043] Figure 5: Photographic reproduction of infra-red emissions from a planar embodiment according to the disclosure.
DETAILED DESCRI PTION
[0044] In the embodiments of the present disclosure, there are included two different configurations, which have the same working operation build up in different substrates, such as: a) 2D planar configuration using flexible substrates, for example PET and b) a sandwich-type configuration using, for example textile as substrate, also flexible. However, many possibilities of substrates can be used.
[0045] The configuration of the planar Thermionic capacitor chargeable by a gradient temperature is shown in Figure 1. On the other hand, a sandwich-type configuration that is used in a textile Thermionic capacitor chargeable by a gradient temperature is shown in Figure 2.
[0046] In the embodiments of the present disclosure, different types of materials can be used in the three principal components of the Thermionic capacitor chargeable by a gradient temperature, such as: 1) the electrodes, 2) the electrolyte and 3) the substrate.
[0047] With a simple, flexible, light-weight design and low-cost material, the present disclosure is eco-friendly and easy scalable, for example with the screen-printing and dip-pad-dry manufacturing processes, contributing to the reduction of the manufacturing costs. The devices of the present disclosure are able to avoid electrolyte leakages and can also be made to be adapted and/or adaptable to different shapes and forms. The ability to harvest energy and store it simultaneously using a wide range of sources, allows the disclosed sturdy and robust devices to be used in diversified areas.
[0048] With the reference to the drawings and more specifically to Figure la) and b), the planar Thermionic capacitor chargeable by a gradient temperature is schematically represented. The planar Thermionic capacitor chargeable by a gradient temperature (Figures la and lb) is fabricated in flexible substrate, such as PET (Al) with 18 cm2 (4.5 cm x 4 cm) and thickness of ~0.076 mm.
[0049] Two photolithography processes, using mask align, were performed with the aim to build the final planar thermionic capacitor chargeable by a gradient temperature with the chosen pattern/masks. The first mask was used to produce the electrical contacts on the device and the second mask was used to produce the electrodes in the thermionic capacitor chargeable by a gradient temperature.
[0050] The electrical contact of this device is optimized with the aim to promote the conduction of the charges in the ionic thermoelectric device to the external circuit. Two reversed Au electrical contacts (A2) separated between each other by 1.6 cm, and shaped with 1.49 cm2 and 50 nm of height were produced using the sputtering technique.
[0051] The second mask was produced by photolithography process and filled with multiwalled carbon nanotubes (MWCNTs). The MWCNTs solution (concentration of 10 mg/mL) (A3) was used to produce interdigitated electrodes constituted by four stripes interconnected between them (1.52 cm2) and shaped with 2 cm of length, 0.2 cm of width and 8 pm of height. [0052] The electrolyte solution (up to 400 pL) (A4) was overspread making a coating- top on the electrodes with an area of 7.5 cm2.
[0053] With the reference to the drawings and more specifically to Figure 2, the textile thermionic capacitor chargeable by a gradient temperature is schematically represented. The textile thermionic capacitor chargeable by a gradient temperature is fabricated using cotton fabric (warp: 3726, weft: 52 threads) with 10 cm2 (2 cm x 5 cm).
[0054] The dip-pad-dry process was used to coat the commercial cotton fabric. In this process, the cotton substrate (Bl) was dipped into the MWCNTs dispersion and then submitted to a padding process to remove the excess of MWCNTs. Then, the assembly MWCNT-coated fabric (B2) was dried. To produce the thermionic capacitor chargeable by a gradient temperature in sandwich-type configuration, two MWCNTs-coated fabrics were coated with the electrolyte solution (B3) and then stacked together face- to-face. (B4) represents the assembly between the electrodes and the electrolyte.
[0055] The operations principle of the thermionic capacitor chargeable by a gradient temperature can be explained by the generation of voltage through the device in response to an applied temperature gradient that promotes the migration of the ions towards the cold electrode combined with the ability to storage simultaneously, following 4 processes as show in Figure 3. When there is no temperature gradient, the ions that belong to the electrolyte are stationary and randomly spread on the electrolyte Figure 3 (al) and (bl)); consequently, no voltage is generated. This corresponds to the initial state. Immediately after the applied temperature gradient, the migration of the ions towards the cold electrode occurs and an electromotive force is generated, leading to a voltage generation thus moving the charges on the outer circuit to and accumulated at the electrode to compensate the electromotive force generate at the electrolyte (charged state - Figure 3 (a2) and (b2)). When the temperature gradient is removed, the system open circuit remains in equilibrium and storage this energy on the device working as a supercapacitor (storage state - Figure 3 (a3) and (b3)). When a load is connected to the device, a disequilibrium of the ions starts to appear (Discharged state - Figure 3 (a4) and (b4)) and the generated potential difference can be externally loaded, thus generating a current on the outer circuit. The charge process and consequently the external load are directly dependent of the temperature gradient that is created and the ions amount.
[0056] For the two configurations of the thermionic capacitor chargeable by a gradient temperature disclosed in the scope of the invention, different temperature gradients were studied as well as their influence in open-circuit voltage (Voc), with the aim of studying the effective energy harvesting (Figure 4 (a) and (b)). The Voc linearly increases with the increase of the temperature gradient. For example, the thermionic capacitor chargeable by a gradient temperature in-plane configuration led to 40 mV for a temperature gradient of 20 K. In the case of the sandwich-type configuration, for
DT =30 K it was obtained 140 mV.
[0057] The following results were obtained for the planar interdigitated embodiment:
[0058] The following results were obtained for the layered textile embodiment:
[0059] Figure 5 shows a photographic reproduction of infra-red emissions from a planar embodiment according to the disclosure, clearly showing the thermal circuit provided by the shape-structured electrodes, which allows shaping the thermal gradient between electrodes as desired.
[0060] The term "comprising" whenever used in this document is intended to indicate the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. The disclosure should not be seen in any way restricted to the embodiments described and a person with ordinary skill in the art will foreknow many possibilities to modifications thereof. The above described embodiments are combinable. The following claims further set out particular embodiments of the disclosure.

Claims

C L A I M S
1. Thermionic capacitor chargeable by a gradient temperature, comprising a first and a second nanostructured-carbon electrodes and a polymer solid-gel electrolyte comprising cations and anions thermodiffusable by Soret-effect under a gradient temperature between said electrodes.
2. Planar thermionic capacitor according to claim 1 wherein the electrodes are arranged along two separate regions of a planar substrate being separated by an intermediate region of said substrate, with the electrolyte being laid over said electrodes and said intermediate region.
3. Planar thermionic capacitor according the previous claim wherein each of the electrodes has protrusions and recesses for meshing with recesses and protrusions of the other electrode, provided that the electrodes are not in electrical contact.
4. Planar thermionic capacitor according the previous claim wherein the electrodes are interdigitated.
5. Planar thermionic capacitor according any of the claims 2 - 4 wherein the planar substrate is rigid, in particular made of glass, silica, cork, or metal sheet.
6. Planar thermionic capacitor according any of the claims 2 - 5 wherein the planar substrate is flexible, in particular made of polyethylene terephthalate - PET, polyethylene naphthalate - PEN, polyethersulfone - PES, polyimide - PI, Kapton, polytetrafluoroethylene - PTFE, polypropylene - PP, poly(methyl methacrylate) - PMMA, polyvinyl chloride - PVC, latex, paper, rubber, a flexible sheet of cork, or thin metal foil.
7. Layered thermionic capacitor according to claim 1, each electrode being a layer coated with nanostructured-carbon, comprising an intermediate electrolyte layer between the electrode layers, wherein said layers form a stack.
8. Layered thermionic capacitor according to the previous claim wherein said electrode layers and electrolyte layers are comprised in a textile layer which is: coated on a first side by nanostructured-carbon forming a first electrode, coated on a second side by nanostructured-carbon forming a second electrode, and embedded with the electrolyte forming the electrolyte layer.
9. Layered thermionic capacitor according to claim 7 comprising two textile layers and an electrolyte embedded in said textile layers, wherein a first textile layer is coated on a side by nanostructured-carbon forming a first electrode and a second textile layer is coated on a side by nanostructured-carbon forming a second electrode, the two textile layers being stacked onto each other such that the two sides having electrodes of the textile layers are facing outwards.
10. Layered thermionic capacitor according to the previous claim wherein the electrolyte is embedded from in-between the two textile layers.
11. Layered thermionic capacitor according any of the claims 7-10 wherein the textile is a woven or knitted fabric comprising cotton, polyester, silk, polyamide, or combinations thereof.
12. Layered thermionic capacitor according any of the claims 7-10 wherein the textile is a non-woven fabric.
13. Thermionic capacitor according to any of the previous claims wherein the electrode nanostructured-carbon comprises carbon nanotubes, graphene, carbon black, carbon fibres, carbon aerogel, or combinations thereof.
IB
14. Thermionic capacitor according to any of the previous claims wherein either or both electrodes comprise nanostructured-carbon metal oxide, metal nitride, metal sulfide, MXene - 2D transition metal carbide, TMD - transition metal dichalcogenide, MOF - Metal-organic framework, black phosphorus, lithium based material, organic conducting polymer, or combinations thereof.
15. Thermionic capacitor according to any of the previous claims wherein either or both electrodes are obtained by layer-by-layer deposition, screen printing, lithography, spray painting, inkjet printing, sputtering deposition, ion beam deposition, electron beam deposition, chemical vapour deposition, dip-pad-dry process, chemical etching, or optical and mechanical patterning.
16. Thermionic capacitor according to any of the previous claims wherein the electrolyte comprises a polymer and an ion donor of thermodiffusable cations and anions by Soret-effect.
17. Thermionic capacitor according to the previous claim wherein the electrolyte comprises a mixture of:
poly(vinyl alcohol) - PVA, poly(methylmethacrylate) - PMMA, poly(polycrylate) - PAA, poly(amineester) - PAE, poly(ethylene-oxide) - PEO, polya(crylonitrile) - PAN, poly(vinylidene fluoride) - PVDF, or combinations thereof, with:
phosphoric acid - H3P04, sulphuric acid - H2S04, potassium hydroxide - KOH, potassium sulfate - K2S04, potassium chloride - KCI, sodium sulfate - Na2S04, lithium hydroxide - LiOH, lithium sulfate - U2S04, or combinations thereof.
18. Thermionic capacitor according to the previous claim wherein the electrolyte comprises poly(vinyl alcohol, PVA.
19. Thermionic capacitor according to claim 17 or 18 wherein the electrolyte polymer comprises phosphoric acid - H3P04.
20. Thermionic capacitor according to any of the claims 1-15 wherein the electrolyte is an organic electrolyte comprising: tetraethylammonium tetrafluoroborate - TEABF4, tetraethylammonium difluoro(oxalato)borate - TEAODFB, spiro-(l,10)- bipyrrolidinium tetrafluoroborate - SBPBF4, tetrabutylammonium tetrafluoroborate - Bu4NBF4, or combinations thereof, dissolved in:
acetonitrile - ACN, propylene carbonate - PC, adiponitrile - ADN or 1, 1,1, 3,3,3- hexafluoropropan-2-ol - HFIP, or combinations thereof.
21. Thermionic capacitor according to any of the claims 1-15 wherein the electrolyte is a ionic liquid comprising l-ethyl-3-methylimidazolium tetrafluoroborate - [EMI M] [BF4], l-ethyl-3-methyl-imidazolium-thiocyanate - [EMIM] [SCN], l-butyl-3- methylimidazolium tetrafluoroborate - [BMI M] [BF4], l-ethyl-3-methylimidazolium tetracyanoborate - [EMIM] [TCB], l-ethyl-3-methylimidazolium difluorophosphate - [EMIM][P02F2], or combinations thereof.
22. Thermionic capacitor according to any of the previous claims further comprising two metallic current collectors each electrically connected to each said electrode.
23. Thermionic capacitor according to the previous claim wherein the metallic current collectors are made of deposited metallic layers, in particular deposited metallic layers comprising aluminium, gold, silver, copper, platinum, in particular deposited by layer-by-layer deposition, ion beam deposition, sputtering deposition, chemical vapour deposition, screen printing, lithography, spray painting, inkjet printing, or combinations thereof, further in particular aluminium.
24. Thermionic capacitor according to any of the previous claims wherein said cations and anions are selected such that said cations move towards the first electrode and said anions move towards the second electrode under thermophoretic force caused by the gradient temperature in the direction between said electrodes.
25. Electronic device comprising the thermionic capacitor according to any of the previous claims, in particular the electronic device being a wearable electronic device.
26. Electronic device comprising the thermionic capacitor according to any of the claims 1-24 comprising a complementary electric power source, in particular a photovoltaic panel, a triboelectric generator, a piezoelectric generator or a magnetic induction generator.
EP19787450.6A 2018-09-24 2019-09-24 Thermionic capacitor chargeable by soret-effect using a gradient temperature Pending EP3857700A1 (en)

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PT115035A PT115035A (en) 2018-09-24 2018-09-24 SORET EFFECT CHARGABLE THERMOIONIC CONDENSER USING A TEMPERATURE GRADIENT
PCT/IB2019/058099 WO2020065533A1 (en) 2018-09-24 2019-09-24 Thermionic capacitor chargeable by soret-effect using a gradient temperature

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