WO2014072877A2 - Encre d'impression par sérigraphie à base de graphène et son utilisation dans les supercondensateurs - Google Patents

Encre d'impression par sérigraphie à base de graphène et son utilisation dans les supercondensateurs Download PDF

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WO2014072877A2
WO2014072877A2 PCT/IB2013/059738 IB2013059738W WO2014072877A2 WO 2014072877 A2 WO2014072877 A2 WO 2014072877A2 IB 2013059738 W IB2013059738 W IB 2013059738W WO 2014072877 A2 WO2014072877 A2 WO 2014072877A2
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Prior art keywords
screen
printable ink
solvent
electrode
substrate
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PCT/IB2013/059738
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English (en)
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WO2014072877A3 (fr
Inventor
Yanfei Xu
Matthias Georg SCHWAB
Ingolf Hennig
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Basf Se
Basf (China) Company Limited
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Publication of WO2014072877A2 publication Critical patent/WO2014072877A2/fr
Publication of WO2014072877A3 publication Critical patent/WO2014072877A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to a graphene based printable ink, an electrode comprising such inks and a supercapacitor comprising such electrode.
  • Supercapacitors store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). It is an important energy- storage device due to their high power density, reversibility, long cycle life.
  • Graphene is an ideal electrode material for supercapacitors due to its high conductivity, high surface area, and good mechanical properties. Graphene electrodes can store energy using ion adsorption.
  • Langmuir 2012, 28, 12637-12646 discloses a layer-by-layer self-assembled multilayer desposition of graphene oxide and polyaniline. The graphene oxide in the layers is then reduced to graphene to receive a graphene/polyaniline multilayer structure. Its application in supercapacitors was assessed.
  • ACS Nano Vol. 3, No. 7, 1745-1752, 2009 discloses the preparation of a graphene/polyaniline composite paper by in situ anodic electropolymerization of aniline monomers into a PAni film on graphene paper.
  • ACS Nano 2010, 4 (4), 1963-1970 discloses a method for preparing stable aqueous dispersions of chemically converted graphene ("CCG")/polyaniline-nanofiber composites.
  • CCG chemically converted graphene
  • the dispersion was prepared by mixing the purified polyaniline-nanofiber dispersion with a controlled amount of CCG colloid at pH 10 under sonication. The dispersion was then filtrated to receive the graphene/PANI composite film. Due to the low concentrations (low viscosity) of the CCG/polyaniline dispersion the composition cannot be screen printed.
  • Nanoscale 2010, 2, 2164-2170 discloses a graphene/polyaniline hybrid material for
  • US 2012/0028127 A1 discloses a graphene based ink for forming electrodes of printable batteries or supercapacitors.
  • the in comprises titanium dioxide and a binder.
  • the binder may be selected from polyaniline.
  • US 2010/0239871 A1 discloses polysiloxane inks which contain a pigment, a radical polymerization initiator and optionally an electrically conductive polymers like polyaniline.
  • Graphene sheets may be used as the pigment.
  • Printed electronics is a technology aimed at unconventional electronic device manufacture on plastic/paper foils by printing techniques.
  • screen printing technology is promising because it enables the large-scale production of low-cost, reproducible thin film electrode.
  • formulating printable inks comprising nano graphene platelets (NGPs) and Polyaniline to fabricate a screen-printable supercapacitor electrode has never been explored until now.
  • the electrode materials are coated on Pt or Al foils, Pt or Al foils are used as current collectors.
  • the metal current collectors are expensive and heavy.
  • the film fabrication speed can be enhanced to realize very short timescales of just about 0.1 seconds.
  • a further embodiment of the present invention provides an electrode comprising a printable ink as defined herein.
  • Yet another embodiment of the present invention provides a process for preparing an electrode comprising:
  • This screen-printed electrode on the conductive carbon substrate is a technology aimed at unconventional supercapacitor device manufacture, which is inexpensive, rapid, and capable of mass production.
  • Yet another embodiment of the present invention provides a supercapacitor comprising an electrode as described herein.
  • the industrial NGP/PANI two-electrode supercapacor exhibited high performance up to 305 F/g, when comparing with other supercapacitors using graphene/PAni composite electrode. Futhermore, the supercapacor as described herein shows a good cycling stability.
  • the printable NGP/PAni ink composition comprises nano graphene platelets (also referred to as "NGP"), a polymer comprising aniline monomeric units, at least one solvent, optionally a binder and optionally futher additives.
  • the viscosity of the printable ink generally depends on the printing method. For the preferred screen printing method, viscosites of from 10 mPa s to 50 000 mPa s are preferred. Particularly preferred are viscosities of from 500 mPa s to 50000 mPa s.
  • the shear rate dependency of the ink viscosity is shown in Fig. 4. It can be seen that the inks exhibit a shear-thinning effect.
  • the printable ink consists of nano graphene platelets, polyaniline, a solvent and optionally a binder.
  • Graphene is a monolayer of carbon atoms arranged in a two-dimensional honeycomb network.
  • "Nano graphene platelets” in the terms of the present invention is however not restricted to a material consisting exclusively of single-layer graphene (i.e. graphene in the proper sense and according to the lUPAC definition), but, like in many publications and as used by most commercial providers, rather denotes a bulk material, which is generally a mixture of a single- layer material, a bi-layer material and a material containing 3 to 10 layers and sometimes even more than 20 layers (“few layer graphene").
  • the ratio of the different materials depends on the production process and provider.
  • the material termed "nano graphene platelets” is characterized by the absence of the graphite peak in the XRD:
  • the degree of exfoliation of the graphene material being related to the layer thickness can be monitored by XRD (X-ray diffraction).
  • the graphene of the invention does not reveal a graphite peak related to the stacking and thus unexfoliated material.
  • nano graphene platelets in terms of the present invention are further characterized by a low bulk density of preferably at most 0.2 g/cm 3 , e.g. from 0.001 to 0.2 g/cm 3 or from 0.003 to 0.2 g/cm 3 , more preferably at most 0.15 g/cm 3 , e.g. from 0.001 to 0.15 g/cm 3 or from 0.003 to 0.15 g/cm 3 , even more preferably at most 0.1 g/cm 3 , e.g.
  • “Nano graphene platelets” in terms of the present invention are moreover characterized by a high BET (Brunauer-Emmett-Teller) surface are.
  • the BET area is at least 200 m 2 /g, e.g. from 200 to 2600 or from 200 to 2000 or from 200 to 1500 m 2 /g or from 200 to 700 m 2 /g; more preferably at least 300 m 2 /g, e.g. from 300 to 2600 or from 300 to 2000 or from 300 to 1500 or from 300 to 700 m 2 /g.
  • “Nano graphene platelets” are preferably characterized by a high ratio of carbon to oxygen atoms (C/O ratio):
  • the elemental composition as expressed by the ratio of carbon to oxygen atoms (C/O ratio) is related to the degree of chemical reduction of the graphene material.
  • the C/O ratio is preferably at least 3:1 , more preferably at least 5:1 , even more preferably at least 50:1 , particularly preferably at least 100:1 and in particular at least 500:1 , as determined e. g. from the atomic percentages (at%) of the elements via X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • Nano graphene platelets employed within the inks according to the present invention as such are known to a person skilled in the art.
  • Several methods for producings such NGPs are known, such as but not limited to the exfoliation and wet-chemical reduction of graphite oxide prepared by a modified Hummer's or Staudenmeier's method (ACS Nano 2008, 2 (3), 463-470; Nano Letters 2010, 10 (12), 4863-4868), the thermal shock exposure exfoliation method for graphite oxide (J. Phys. Chem. B, 2006, 1 10 (17), 8535-8539 and McAllister, M. J. et al.; Chem. Mater.
  • the NGP are prepared by reduction of graphene graphite oxide by athermal shock exposure exfoliation method as described in US 2010/0056819 A1 and US 2010/055025 A1 that leads to a simultaneous exfoliation and reduction of the graphite oxide feedstock.
  • the thermal reduction of graphite oxide is much more environment-friendly and offers the possibility for large scale production. This is for example illustrated in Nature Nanotechnology 4, 612 - 614 (2009).
  • the NGPs obtainable by the thermal shock exposure exfoliation method reveal a crumpled, sheet-like morphology as shown in Figs. 5 and 6 that is in contrast to NGPs obtained from the wet-chemical exfoliation and reduction of graphite oxide and which are typically of a fully planar nature.
  • the electron microscopy analysis reveals that the overall atomically thin and transclucent sheets display large wrinkles and folds that are distributed over the surface of the individual NGPs.
  • the formation of these characteristic wrinkles has been ascribed to the fast thermal reduction of adjacent epoxy sites that are present within the graphite oxide raw material leaving no time for the NGPs to readopt a fully planar conformation (J. Phys.
  • a useful side-effect of the wrinkled nature of the NGPs prepared by the thermal shock exposure exfoliation method is that it prevents the re-stacking and reaggregation of the NGPs.
  • NGPs prepared by the thermal shock exposure exfoliation method can also be easily identified from morphological analysis studies.
  • supercapacitors can be divided into two classes: 1 ) electrochemical double-layer capacitors (EDLCs) which store energy using the adsorption of both anions and cations, And 2) pseudo-capacitors that store energy through fast surface redox reactions.
  • EDLCs electrochemical double-layer capacitors
  • pseudo-capacitors that store energy through fast surface redox reactions.
  • the capacitance in graphene based EDLC devices is stored as a build-up of ion charge in the layers of the electrical double-layer formed at the interface between a high-surface area electrode and an electrolyte.
  • the larger graphene surface area, the larger ion can be adsorpted on the graphene surface.
  • the platelets generally have dimensions in the nanometer scale, preferably of from about 50 nm x 50 nm to about 10000 nm *10000 nm.
  • the electrical conductivity of the graphene composites should generally be of from about 1 ⁇ 10 2 S/cm to about 5 x 10 "1 S/cm (powder conductivity measured at 500 bar on compressed pellets).
  • the concentration of the nano graphene platelets in the printable ink may generally be of from about 0.05% by weight to about 10 % by weight, preferably of from about 0.1 % by weight to about 5% by weight, most preferably of from about 0.5 % by weight to about 2.5% by weight.
  • the printable in comprises a polymer comprising an aniline monomer unit.
  • Such polymers may be homopolymers of aniline or copolymers of aniline with other monomeric units, in the following both also referred to as "Polyanilines”.
  • the polymer consists of aniline homopolymers.
  • Polyanilines are polymerized from the inexpensive aniline monomer.
  • Aniline homopolymers can be described by the formula I:
  • the emeraldine base (EB) is neutral and, if doped (protonated) it is called emeraldine salt (ES), with the amine nitrogens protonated by an acid. Protonation is necessary to delocalize the otherwise trapped
  • the production of aniline homopolymers is well known in the art and available from serveral sources in the market.
  • the emeraldine salt aniline homopolymer is used.
  • the molecular weight Mw of polyaniline may be of from about 1000 g/mol to about 200000 g/mol, preferably of from about 2000 g/mol to about 100000 g/mol, most preferably of from about 5000 g/mol to about 50000 g/mol.
  • copolymers of aniline may be used.
  • Such copolymers may be but are not limited to copolymers of aniline and N ⁇ pheny1glycine, copolymers of aniline and alkyianiline, copolymers of aniline and N-4(sulfophenyl)aniline and any other electrically conducting copolymer.
  • the concentration of the polyaniline in the printable ink may generally of from about 0.1 % by weight to about 20 % by weight, preferably of from about 0.2 % by weight to about 10 % by weight, most preferably of from about 0.5 % by weight to about 5.0 % by weight.
  • the weight ratio between the NGPs and the polyaniline may generally be from 1 : 10 to 10: 1 , preferably from 1 :5 to 5: 1 , more preferably from 1 :3 to 1 : 1 , most preferably 1 :2 to 1 : 1 .5.
  • the printable ink further comprises at least one solvent.
  • the solvent should be cabable of solving the polyaniline and optionally the binder. Furthermore the solvent should be capable of forming a stable dispersion of graphene in the presence of the polyaniline. Last not least the solvents need to be vaporizable in order to be removed from the deposited ink to form the electrode layer.
  • the boiling point (at atmospheric pressure) of the solvent is below about 200 °C, preferably from about 50 °C to about 150 °C, most preferably from about 70 °C to about 120 °C.
  • the solvent may be a protic or aprotic polar organic solvents or water.
  • Protic polar solvents may be selected from Ci to Ce alkanols, preferably methanol, ethanol or propanol.
  • the protic organic solvents have a low water content and are most preferably essentially water-free.
  • a low water contentent as used herein means that the water content of the solvent is below 5 %, preferably below 3 %.
  • Aprotic polar solvents may be selected from
  • Nitrogen containing solvents such as but not limited to N-methyl-2-pyrrolidone, N-ethyl-2- pyrrolidone dimethylformamide, and dimethylacetamide (DMAC),
  • Aromatic solvents such as but not limited to 3-methylphenol (m-cresol),
  • sulfoxides such as but not limited to dimethyl sulfoxide (DMSO).
  • the solvent is selected from ethanol, N-methyl-2-pyrrolidone,
  • combinations of the said solvents may be used as long as they form a one phase solution. Preferable only one solvent is used.
  • the amount of the solvent in the printable ink may generally be of from about 1 % by weight to about 99 % by weight, preferably of from about 50 % by weight to about 99 % by weight, most preferably of from about 95 % by weight to about 99 % by weight.
  • the printable ink may preferably comprise a binder in order to adjust the viscosity of the ink and to improve the adhesion interaction between the ink and the substrate.
  • Suitable binders are selected from organic polymers, including water-soluble and water- insoluble organic polymers, whereby the expression polymers does also encompass copolymers.
  • Preferred water-insoluble polymers are fluorinated polymers such as
  • tetrafluoroethylene and hexafluoro propylene copolymers from vinylidene fluoride and hexafluoro propylene or copolymers from vinylidene fluoride and tetrafluoroethylene.
  • vinylidene fluoride can also be referred to as vinylidene difluoride
  • polyvinylidene fluoride can also be referred to as polyvinylidene difluoride.
  • a particularly preferred water-soluble binder is polytetrafluoroethylene (PTFE).
  • the concentration of the binder in the printable ink may generally be of from about 0 % by weight to about 10 % by weight.
  • the concentration of the binder is about 0 % by weight. In another embodiment the concentration of the binder is from about 0.01 % by weight to about 5 % by weight, most preferably of from about 0.1 % by weight to about 2.5 % by weight.
  • additives may be present in the printable ink.
  • Such additives may be, but are not limited to surfactants and conducting additives, such as but not limited to carbon black.
  • the ink if free from carbon black, most preferably free from any carbon material except the NGP.
  • Useful surfactants may be anionic, cationic nonionic or amphoteric surfatants. Particularly preferred are anionic surfactants, such as but not limited to sodium dodecylbenzenesulfonate (SDBS).
  • SDBS sodium dodecylbenzenesulfonate
  • Another embodiment of the present invention is a composite material comprising nano graphene platelets, polyaniline, optionally a binder, and optionally a surfactant as described herein.
  • the capacitance is an important parameter of an electrode and a supercapacitor comprising such composite material. Generally, the higher the capacitance the better is the performace.
  • the composite material preferably has a capacitance of 100 F g _1 or more, more preferably of 200 F g- 1 or more, most preferably of from 300 F g _1 or more.
  • the capacitance can be determined, e. g. according to J. R. Miller and A. F. Burke, Electric Vehicle Capacitor Test, Procedures Manual, Idaho National Engineering Laboratory, Report No. DOE/I D-10491 , 1994, and/or according to R. B. Wright and C. Motloch, Freedom CAR Ultracapacitor Test, Manual, Idaho National Engineering Laboratory, Report No. DOE/NE ID-1 1 173, 2004.
  • Another subject of the present invention is an electrode comprising at least one composite material as described above and at least one binder.
  • the concentration of the NGPs in the electrode may generally be of from about 10 % by weight to about 95 % by weight, preferably of from about 20 % by weight to about 80% by weight, most preferably of from about 30 % by weight to about 60% by weight.
  • the concentration of the polyaniline in the electrode may generally of from about 10 % by weight to about 95 % by weight, preferably of from about 20 % by weight to about 80 % by weight, most preferably of from about 60 % by weight to about 30 % by weight.
  • the concentration of the binder in the electrode may generally be of from about 0 % by weight to about 30 % by weight, preferably of from about 0 % by weight to about 20 % by weight, most preferably of from about 5 % by weight to about 10 % by weight.
  • the electrode comprises
  • the printed electrode has a thickness of from about 1 ⁇ to about 100 ⁇ , preferably from about 3 ⁇ to about 50 ⁇ ⁇ , most preferably from 5 to 15 ⁇ .
  • the electrodes may be connected through one or more current collectors to at least one other component of the capacitor.
  • said current collector will not be considered as component of the electrode according to the present invention.
  • the electrodes may further comprise a backbone, such as a metal foil or a metal gauze.
  • Suitable metal foils can be made from, e. g., nickel.
  • Suitable metal gauze can be made from steel, in particular from stainless steel.
  • said current backbone will not be considered as component of the electrode according to the present invention.
  • the electrode according to the present invention may further comprise an electrolyte which is preferably a PVA H2SO4 gel (a gel made of polyvinyl alcohol and H2SO4), a PVA H3PO4 gel, a PVA KOH gel, a PVA NaOH gel, a PVA Na 2 S0 4 gel, a ionic liquid polymer gel or any other organic polymer based electrolyte.
  • an electrolyte which is preferably a PVA H2SO4 gel (a gel made of polyvinyl alcohol and H2SO4), a PVA H3PO4 gel, a PVA KOH gel, a PVA NaOH gel, a PVA Na 2 S0 4 gel, a ionic liquid polymer gel or any other organic polymer based electrolyte.
  • PVA H2SO4 gel a gel made of polyvinyl alcohol and H2SO4
  • PVA H3PO4 gel a PVA KOH gel
  • PVA NaOH gel a PVA NaOH gel
  • an ionic liquid polymer gel it is preferred to employ at least one ionic liquid of the formula 1 -alkyl-3-methylimidazolium halide, wherein alkyl is preferably C3 to Cg-alkyl and/or halide is preferably iodide.
  • a low molecular weight polymer such as poly(vinylidinefluoride-co-hexafluoropropylene).
  • the electrolyte is a PVA H2SO4 gel. It is also preferred that the electrode according to the present invention is obtained by cutting the aerogel into slices having a thickness of 0.5 to 1 .5 mm and/or having a diameter of 5 to 15 mm. According to a further embodiment of the present invention the electrode if free of any electrolyte.
  • a further embodiment of the present invention is a process for preparing a conducting ink, comprising
  • Step (a) may be performed by any method in which shearing forces are applied to the NGPs in order to exfoliate and disperse the NGPs in the solvent.
  • shearing forces are applied to the NGPs in order to exfoliate and disperse the NGPs in the solvent.
  • ball milling of NGPs in the solvent may be used for a time sufficient to at least partly, preferably essentially, most preferably completly exfoliate the nano graphenen platelets (i.e. to produce singly layered graphene sheets).
  • the polyaniline in step (b) may be provided in pure form or as a solution in a solvent.
  • the polyaniline is provided as a solution in the solvent as used in step (a).
  • the binder in step (c) may be provided in pure form or as a solution in a solvent.
  • the binder is provided as a solution in the solvent as used in step (a).
  • Yet another embodiment of the present invention is a process for preparing an electrode, comprising
  • step (ii) may be selcted from a metal foil, conductive cloth;
  • conductive carbon fabrics and a flexible conductive fabric.
  • carbon fabrics may be made from cotton yarns coated with a solution based on carbon black.
  • a conductive fabric or cloth consist of a non-conductive or less conductive substrate, which is either coated or embedded with electrically conductive elements, often carbon, nickel, copper, gold, silver, or titanium.
  • Substrates typically include cotton, polyester, nylon, and stainless steel as well as high performance fibers such as aramids.
  • conductive carbon substrates may be derived from polyacrylonitrile (PAN) precursor. It combines electrically conductivity, high strength, low modulus of elasticity and low density for maximum performance.
  • PAN polyacrylonitrile
  • the conductive carbon substrate is flexible.
  • “Flexible” as used herein means that the modulus of elasticity of the substrate is below 5 kN/mm 2 , preferably below 2 kN/mm 2 .
  • the substrate is selected from a conductive carbon fabric and a flexible carbon substrate, most preferably the substrate is a flexible carbon substrate.
  • the deposition in step (iii) may be performed by any common liquid deposition method, perferably by printing, most preferably by screen-printing.
  • the screen is generally placed a few millimeters above the surface of the substrate.
  • a rubber "squeegee” is swept across the surface of the screen thus bringing it into close contact with the substrate.
  • the ink flows from the screen to the surface of the substrate.
  • the screen separates from the substrate, leaving behind ink that dries to yield a continuous film.
  • the solvent has to be at least partly removed in step (iv). This can simply be done by evaporation at room temperature or supported by increased temperature or reduced pressure.
  • the residual solvent should not exceed 3 % by weight, preferably, 1 % by weight, most preferably 0.1 % by weight.
  • the composite material prepared by using the inks according to the invention may be any suitable material prepared by using the inks according to the invention.
  • capacitors particularly supercapacitors.
  • a further embodiment of the present invention is a supercapacitor, also called electric double-layer capacitor comprising a composite material prepared by using the printable ink or an electrode as described above.
  • supercapacitors as such are well known in the art. They are useful for the energy storage and power delivery solutions for automotive, heavy transportation, uninterruptible power system.
  • a conductive substrate is used as the current collector directly, it is easier and more efficient compared to the conventional supercapacitor electrode fabrication where the active electrode material is pressed on a Ni foam current electrode.
  • the carbon substrate may be used as the current collector, the NGP/PAni based thin film supercapacitor is more flexible and light-weight comparing with conventional supercapacitor device in which Pt or Ni is used as current collectors.
  • the composite material and the electrodes as described herein may also advantageously be used in gas sensor applications.
  • Fig. 1 a shows the double electrode capacitor setup according to example 2.
  • Fig. 1 b shows the flexible double electrode capacitor setup according to example 3.
  • Fig. 2 shows the capacitance of the respective electrodes according to example 2.
  • Fig. 3 shows the cycling stability of NGP and NGP/PAni supercapacitor device over 1000 cycles, cycling stability measured at a constant current 5 mA, with 1 M H2SO4 electrolyte according to example 2.
  • Inset Galvanostatic charge-discharge curves of
  • Fig. 4 shows the dependency of the ink viscosity as a function of shear rate for NGP, PAni and various weight ratios between the NGP and PAni.
  • Fig. 5 shows a SEM study of the carbon fabric substrate (A, B); NGP (C,D) and NGP/PAni
  • Fig. 6 shows a TEM picture of an individual NGP flake.
  • Graphene N002-PDR (average thickness 1 -10 nm) was purchased from Angstron Materials Inc. (Dayton, OH, United Stated of America), Polyaniline (emeraldine base, average M w ⁇ 5,000 g/mol) was purchased from Sigma-Aldrich. PTFE (60% in water) was purchased from DuPont. The carbon fabric (34BA) was purchased from SGL Carbon. The flexible carbon substrate (H2315 IX 1 1 ) was purchased from Freudenberg & Co.
  • Ball milling experiments were carried out using a Dispermat ball miller from Vma-Getzmann GmbH.
  • the milling ball material was ZrC"2 68% (SAZ-Zirkonmischoxid ER 120 S).
  • the printing experiments were carried out using a fully automated Screen Printer (Alrauntechnik, AT 701 M) with Sefar sreen mesh (32-1 OOW PW).
  • the viscosity was measured by HAAKE analytical instruments, using a 60 mm 0, 0.5o cone and plate.
  • Scanning electron microscope (SEM) measurements were carried out with a Zeiss Ultra 55 (FE-SEM), operated at 5 kV. Nitrogen adsorption and desorption isotherm measurements were carried out at 77 K with a
  • NGP and NGP/PAni inks were prepared by ball milling method.
  • the weight ratio of NGP, PAni and PTFE was varied as 90:0:10, 60:30:10, 45:45:10, 36:54:10, 30:60:10.
  • the resulting inks are labelled as NGP, NGP/PAnii :0 .5, NGP/PAn : i, NGP/PAnii : i. 5 , NGP/PAnii:2, respectively.
  • NGP/PAnii i.
  • the NGP/PANI inks used herein all exhibited good shear thinning behavior with a viscosity of around 125 mPa s observed at a shear rate of 10 s -1 . These viscosity results fit to the screen- printing requirements.
  • Two-electrode supercapacitors were fabricated as these devices best represent those commonly produced commercially.
  • the NGP/PAni electrodes (diameter 2 cm) on a hard carbon fabric substrate were assembled in a stainless steel supercapacitor cell with titanium current collectors.
  • the two-electrode supercapacitor was built using a sandwich type construction (electrode/glass microfiber filter separator/electrode, see Fig. 1 a).
  • the ink was printed on the carbon fabric substrate as follows: During screen printing deposition, the screen mask was placed a few millimeters above the surface of the carbon fabric substrate. After loading the NGP/PAni ink onto the screen, a rubber "squeegee" was swept with a velocity of 35 cm/s across the surface of the screen thus bringing it into close contact with the substrate. At this point, the ink flew from the screen to the surface of the substrate. As the squeegee then passed over a region, the screen separated from the substrate, leaving behind ink that dried to yield a continuous film. A thin film with dimensions of 4 cm ⁇ 3 cm could be fabricated in a very short timescale of just 0.1 seconds. The ability to produce thin films of high quality on this short timescale is highly desirable in industrial applications.
  • NGP, NGP/PAnii : o. 5 , NGP/PAn : i , NGP/PAnii : i . 5 and NGP/PAnii :2 deliver specific capacitances of 26, 85, 190, 269, and 177 F g _1 , respectively, based on the active materials mass of two electrodes (including the mass of PTFE binder).
  • Nitrogen adsorption-desorption analysis revealed a typical Brunauer-Emmett-Teller specific surface area of the NGP, NGP/PAnii :0 .5, NGP/PAn : i , NGP/PAnii : i . 5 , NGP/PAnii :2 , are 497, 260, 232, 215, 184 m 2 g -1 , respectively, while the specific surface area for the pure PAni is 34 m 2 g- 1 .
  • the NGP/PAnii:i .5 supercapacitors showed the best specific capacitance of 269 F g- 1 , power density of 454 kW kg -1 and energy density of 9.3 Wh kg -1 , operating in 1 M H2SO4 electrolytes.
  • the supercapacitor showed excellent cyclic stability with no degradation over 1000
  • the ink was printed on the flexible carbon substrate as follows: During screen printing deposition, the screen mask was placed a few millimeters above the surface of the flexible carbon substrate. After loading the NGP/PAni ink onto the screen, a rubber "squeegee" was swept with a velocity of 35 cm/s across the surface of the screen thus bringing it into close contact with the substrate. At this point, the ink flew from the screen to the surface of the substrate. As the squeegee then passed over a region, the screen separated from the substrate, leaving behind ink that dried to yield a continuous film. A thin film with dimensions of 4 cm x 3 cm could be fabricated in a very short timescale of just 0.1 seconds. The ability to produce thin films of high quality on this short timescale is highly desirable in industrial applications.

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Abstract

La présente invention concerne une encre d'impression par sérigraphie contenant (a) des nanoplaquettes de graphène, (b) un polymère contenant des motifs monomères d'aniline, (c) au moins un solvant.
PCT/IB2013/059738 2012-11-08 2013-10-29 Encre d'impression par sérigraphie à base de graphène et son utilisation dans les supercondensateurs WO2014072877A2 (fr)

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CN102324317A (zh) * 2011-09-14 2012-01-18 中国第一汽车股份有限公司 一种用于柔性固态超级电容器的电极及其制备方法

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