WO2014191529A1 - Supercapacitor-like electronic battery - Google Patents

Supercapacitor-like electronic battery Download PDF

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Publication number
WO2014191529A1
WO2014191529A1 PCT/EP2014/061191 EP2014061191W WO2014191529A1 WO 2014191529 A1 WO2014191529 A1 WO 2014191529A1 EP 2014061191 W EP2014061191 W EP 2014061191W WO 2014191529 A1 WO2014191529 A1 WO 2014191529A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
active material
supercapacitor
electrolyte
nanosheets
Prior art date
Application number
PCT/EP2014/061191
Other languages
French (fr)
Inventor
Emmanuel LHUILLIER
Benoît DUBERTRET
Original Assignee
Solarwell
Fonds De L'espci - Georges Charpak
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Filing date
Publication date
Application filed by Solarwell, Fonds De L'espci - Georges Charpak filed Critical Solarwell
Publication of WO2014191529A1 publication Critical patent/WO2014191529A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates generally to a supercapacitor-like electronic battery. More particularly, this invention relates to a supercapacitor-like electronic battery using nanostructured materials. This invention also relates to the manufacturing process and the use of said supercapacitor-like electronic battery.
  • Li ion batteries comprise an anode, a separator material with an electrolyte medium, and a cathode.
  • the anode electrode of most commercially available Li ion batteries is a copper foil coated with a mixture of graphite powder and a polymer blend such as polyvinylidene difluoride (PVDF).
  • PVDF polyvinylidene difluoride
  • the cathode generally comprises a mixture of lithium transition metal oxides, PVDF and carbon black coated onto an aluminum foil.
  • the electrodes in electrochemical batteries undergo chemical changes, structural changes and/or volume changes, all of which can severely degrade the integrity of the electrodes over time and reduce the capacity of the battery.
  • the charging and discharging processes in the latest generation lithium-ion battery must be carefully controlled - overcharging or over-discharging can limit the performance and cause premature failure of the battery.
  • capacitors store their energy as electrical charge on the electrodes; No chemical changes are involved and most capacitors have cycle lives of a million cycles or more, to 100% depth-of-charge. Capacitors can also be charged and discharged orders of magnitude faster than electrochemical batteries. The emergence of electrochemical capacitors has now provided a viable alternative to traditional electrochemical batteries.
  • Capacitors based on aqueous electrolytes are usually limited to maximum operating cell voltages of slightly over IV - higher voltages lead to unwanted electrolysis of the electrolyte. Liquid electrolytes remain poorly integrable due to the size of the electrochemical cell and possible leakages are poorly compatible with industrial production.
  • Electrochemical capacitors or supercapacitors are intermediate device between battery and dielectric capacitor. They have a stronger energy density compared to regular capacitor and a faster ability to deliver energy than battery. So they look well suited for application where a pulse of energy is required.
  • electrochemical capacitors can be distinguished, depending on the charge storage mechanism as well as the active material.
  • the charging process relies either on the formation of a double ionic layer at the interface between the electrolyte and the active material or through redox process at the surface of the active material.
  • electrochemical capacitors use reversible redox reactions at the surface of active material. Some electrochemical capacitors make also use of the very large capacitance that is generated at the interface between an electrolyte and an active material. This allows them to store more than ten times as much energy as electrostatic capacitors. This phenomenon is exploited in today's commercially available electrochemical double layer (EDL) supercapacitors (sometimes referred to as "ultracapacitors").
  • EDL electrochemical double layer
  • cations from the electrolyte will densely accumulate at the surface (but still in the electrolyte) and will face a negatively charged layer of semiconductor. Moreover in the electrolyte a layer of anions comes on the top of the cations layer to screen them and lead to a null electric field in the bulk of the electrolyte.
  • the charging of the semiconductor occurs through the injection by the source electrodes of electrons.
  • WO2011/063539 discloses the use of a novel device containing one or more electrodes whose structure is comprised of an electrolyte into which is dispersed conductive nanoparticles, such as for instance core- shell nanoparticles.
  • the Applicant uses an active material comprising nanoparticles, which is simply covered by an electrolyte.
  • the Applicant has discovered that, in the supercapacitor-like electronic battery of the present invention, ions from the electrolyte migrate within the active material, i.e. within the bulk of the nanoparticles. Therefore the present invention differs from the solutions of the prior art.
  • the Applicant does not need to disperse the nanoparticles within the electrolyte.
  • the charge density is lower.
  • the supercapacitor-like electronic battery of the present invention bulk doping of the nanoparticles is achieved. It is therefore an object of the present invention to elaborate a supercapacitor-like electronic battery having an ultra large capacitance and allowing bulk doping or charging of the nanoparticles.
  • the present invention relies on two main observations. The first is the fact that a film of 2D nanoparticles can incorporate more charge than a film of 0D nanoparticle with the same composition, see figure 6, and the second is the fact that improved charging can be achieved by using short ligand, see figure 8. We have noticed an increase by a factor 5 to 10 of the charge while using S " ligand instead of organic ligand such as butylamine.
  • the invention is also based on the implementation of the right pair of nanoparticles surface chemistry /electrolyte. It is therefore another object of the present invention to elaborate a supercapacitor-like electronic battery which takes full advantage of the optimized surface chemistry of the active material and which coupled the surface chemistry with a chosen electrolyte.
  • the advantages of the present invention are to be used for battery, supercapacitors and/or pseudocapacitors applications, especially applications in which a substantial pulse of energy is required.
  • the present invention relates to a supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of non-carbon based nanosheets and at least one electrolyte.
  • the supercapacitor-like electronic battery comprises at least two electrodes, at least one active material comprising a plurality of nanoparticles, preferably nanosheets and at least one electrolyte, wherein the electrolyte matrix is not mixed with the active material comprising a plurality of nanoparticles.
  • the present invention also relates to a supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of nanoparticles and at least one electrolyte, wherein said supercapacitor-like electronic battery has a power density of at least 25W/kg and an energy density of at leastlWh/kg.
  • the active material comprises at least 50% by weight of non-carbon based nanosheets.
  • said active material further comprises silicon or conductive polymer such as polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly (b- propiolactone), styrene butadiene rubber, carboxymethyl cellulose salt, sulfonated fluoropolymers, polyimide, poly(acrylic acid); or carbon-based material such as carbon black, graphene, carbon nanotube, boron nitride nanotube, boron nitride nanosheet, graphene oxide, reduced graphene oxide, or mixture thereof.
  • silicon or conductive polymer such as polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly (b- propiolactone), styrene butadiene rubber
  • said non-carbon based nanosheets are semiconductor.
  • said non-carbon based nanosheets are inorganic semiconductor.
  • said nanoparticles are nanocrystals, nanosheets, nanorods, nanoplatelets, nanoparticles, nanowires, nanopowders, nanotubes, nanotetrapods, nanoribbons, nanocubes, quantum dots and/or combinations thereof, preferably nanosheets.
  • said electrolyte is a liquid, a gel or a solid.
  • bulk charging is achieved within said at least one active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nano sheets.
  • said at least one active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets, has a thickness from 10 nanometers to 100 centimeters, preferably from 10 nanometers to 1 millimeter, more preferably from 100 nanometers to 100 micrometers.
  • the present invention also relates to a method for producing a supercapacitor-like electronic battery according to the present invention, the method comprising:
  • step b') if step b') is not implemented, nanoparticle's ligand exchange step on the active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets,
  • the deposition of the active material comprising a plurality of nanoparticles preferably a plurality of non-carbon based nanosheets is achieved by drop casting or spin coating, dip coating, spray casting, screen printing, inkjet printing, sputtering techniques, evaporation techniques, electrophoretic deposition, or vacuum methods.
  • the present invention also relates to a supercapacitor-like electronic battery obtainable by said process.
  • the present invention also relates to a product comprising at least one supercapacitor- like electronic battery.
  • the present invention also relates to a cathode active material for a supercapacitor-like electronic battery comprising an anode and an electrolyte, wherein the active material comprises a plurality of non-carbon based nanosheets.
  • the present invention also relates to the use of the supercapacitor-like electronic battery in any systems or devices which require a substantial pulse of energy below 1 minute.
  • Double layer refers to a structure which describes the variation of electric potential near an interface. If a material is in contact with an electrolyte, a single layer of negative or positive ions from the electrolyte will form in close proximity to the material and a second layer with a preponderance of respectively positive or negative ions will form proximate the aforementioned respectively negative or positive ions forming the so-called double layer.
  • Active material refers to the material (usually a semiconductor) which carrier density and or electronic state will be tuned by the application of a bias over the electrodes.
  • Charge in volume refers to a process by which the capacity of the plurality of nanoparticles forming the active material increases linearly with the film thickness, even if the electrolyte matrix is limited at the interface of the top of the nanoparticles' film, and does not permeate into the film.
  • a film refers to a single or multiple layers or coating of thin-or thick-material.
  • a film is a porous or not, ordered or not, assembly of nanoparticles, which may be flat or rough.
  • Nanoparticle refers to refers to a particle of any shape having at least one dimension in the 0.1 to 100 nanometers range.
  • Nanoplatelet or nanosheet or nanoplate refers to refers to a nanoparticle having one dimension in the 0.1 to 100 nanometers range.
  • This invention relates to a supercapacitor-like electronic battery combining the high power density of current supercapacitors with the high energy density of current batteries.
  • the general approach to describe the active material charging process through an electrolyte relies either on the formation of a double ionic layer at the interface between the electrolyte and the active material, or through redox processes at the surface of the active material.
  • porous materials such as the nanoparticle films are good candidate to obtain a real bulk ions injection.
  • the capacitance enhancement occurs into the pore of the carbon electrodes which role is to dissociate the cations from the anions through a size selection process.
  • the charging process of the bulk of the film by the ions occurs through a different mechanism: under a gate potential one kind of ions from the double layer start penetrating the active material (i.e. the nanoparticles film). Their counterions from the electrolyte remain in the electrolyte.
  • the active material i.e.
  • the penetrating ions start filling the void between the nanoparticles, as seen in Figure IB.
  • the electrical screening of these ions is ensured by the injection at the electrodes of charges into the nanoparticles themselves. With this process there is consequently no need to build a double layer around a nanoparticle in the active material, as seen in Figure 1A.
  • the semiconductor remains electrically neutral, but the charging strongly affects the active material conductance which is increased by decades.
  • This process also differs from the one existing in conventional battery where the ions can penetrate into the material at the atomic scale, as seen in Figure 1C.
  • the nanostructured aspect of the film described in this invention is a key feature to achieve such a charging process.
  • the charging process is reminiscent of the redox processes that can take place at the surface of the active material, when an ion can reversibly give one or more electrons to the active material as in redox based reactions.
  • Such redox process can take place when the right couple (ion/active material surface chemistry) is used.
  • the ion can diffuse in the active material when it is porous, but can also be trapped in the active material when the active material is formed.
  • the present invention provides a supercapacitor-like electronic battery which comprises at least a first and a second electrode, at least a first active material comprising a plurality of nanoparticles and at least one electrolyte.
  • the at least one active material comprising a plurality of nanoparticles is implemented as a film of nanoparticles.
  • the supercapacitor-like electronic battery of the present invention comprises at least two active materials comprising a plurality of nanoparticles.
  • the at least one active material comprises a plurality of non- nanoplatelets, preferably non-carbon based nanoplatelets, and may be implemented as a film of nanoplatelets.
  • the supercapacitor-like electronic battery is implemented within a container and/or on a substrate.
  • the substrate or container may be formed from silicon, silicon dioxide, aluminum oxide, sapphire, germanium, gallium arsenide, an alloy of silicon and germanium, indium phosphide, indium tin oxide, fluorine doped tin oxide, graphene, glass and its derivative, plastic materials or any material that a person skilled in the art would find suitable.
  • the substrate is made of a plastic substrate coated with a conducting material, such as indium tin oxide coating on polyethylene terephthalate.
  • the substrate or container may be form from ZnS, ZnSe InP, CdZnTe, ZnTe, GaSb, or mixture thereof.
  • the substrate or container may comprise an oxide layer acting as an electronic insulator.
  • the substrate or container may comprise several layers with an oxide layer on the top, such as for example a Si0 2 layer on a Si layer.
  • the thickness of the oxide layer is from 10 nanometers to 100 micrometers, preferably from 30 nanometers to 1 micrometer, more preferably from 100 nanometers to 1 micrometer.
  • the substrate or container may be rigid or non-rigid. According to a preferred embodiment, the substrate is rigid. According to another embodiment, the substrate is flexible and/or stretchable.
  • the supercapacitor-like electronic battery does not comprise an actuating substrate configured to undergo reversible deformation during actuation.
  • the supercapacitor-like electronic battery of the present invention comprises 2 electrodes. In one embodiment, the supercapacitor-like electronic battery of the present invention comprises 3 electrodes. In one embodiment, the supercapacitor- like electronic battery of the present invention comprises 4 electrodes.
  • At least one of the electrodes is digitized. In one embodiment, at least a first and a second electrode are interdigitated. In one embodiment, at least one of the electrodes is in contact with the at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In a preferred embodiment, the cathode is in contact with the at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In one embodiment, at least the first and the second electrodes are in contact with a first and a second active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
  • the plurality of nanoparticles may comprise the same or various nanoparticles.
  • At least one of the electrodes of the supercapacitor-like electronic battery of the present invention has a thickness from 10 nm to 1 m, preferably from 100 nm to 1 cm, preferably from lOOnm to 1 mm, more preferably from 100 nm to 1 ⁇ , even more preferably from 10 nm to lOOnm.
  • at least one of the electrodes is not transparent.
  • at least one of the electrodes is formed form transparent conducting layer made for example from transparent conducting oxides such as indium tin oxide, fluorine doped tin oxide, zinc oxide, doped zinc oxide.
  • At least one of the electrodes of the supercapacitor-like electronic battery of the present invention comprises an electrochemically inert material such as for example gold, platinum, palladium, silver.
  • at least one of the electrodes is made up of a metallic collector.
  • the electrodes are made up of a metallic collector.
  • At least one of the electrodes of the supercapacitor-like electronic battery of the present invention comprises any suitable conductive material such as for example gold, silver, copper, chromium, titanium, aluminum, lithium fluoride, silicon, magnesium, indium and conductive alloys.
  • At least one of the electrodes of the supercapacitor-like electronic battery of the present invention is a doped semiconductor.
  • At least one of the electrodes of the supercapacitor-like electronic battery comprises nanoparticles of the same nature as the nanoparticles of the at least first active material comprising a plurality of nanoparticles.
  • At least one of the electrodes is a carbon based electrode, a graphite electrode, a graphene electrode, an electrode comprising carbon nanotube, an electrode comprising graphene oxide, an electrode comprising reduced graphene oxide, an electrode comprising carbon flurry or a metal electrode coated with carbon. In one embodiment, at least one of the electrodes is not a carbon based electrode.
  • At least one of the electrodes is a metal foil or any material that has been metalized previously.
  • the active material comprises a plurality of nanoparticles, preferably a plurality of nanosheets. In a preferred embodiment, the active material comprises a plurality of non-carbon based nanosheets.
  • the active material comprises a plurality of various nanoparticles.
  • the at least one active material comprising a plurality of nanoparticles comprises semiconductor particles.
  • the nanoparticles of the invention are inorganic.
  • the nanoparticles of the invention are colloidal.
  • the nanoparticles of the invention are crystalline.
  • the at least one active material comprising a plurality of nanoparticles comprises oriented nanoparticles.
  • the at least one active material does not comprise randomly arranged nanoparticles. In one embodiment, the at least one active material comprises randomly arranged nanoparticles.
  • the at least one active material comprising a plurality of nanoparticles covers partially or totally the electrode.
  • At least one of the electrodes covers partially or totally the at least one active material comprising a plurality of nanoparticles.
  • the nanoparticles of the invention are 0D, ID, and 2D nanoparticles.
  • the nanoparticles of the invention are for example nanocrystals, nanosheets, nanorods, nanoplatelets, nanoplates, nanoprisms, nanowalls, nanodisks, nanoparticles, nanowires, nanopowders, nanotubes, nanotetrapods, nanoribbons, nanobelts, nanoneedles, nanowires, nanocubes, nanoballs, nanocoils, nanocones, nanopillers, nanoflowers, quantum dots or combination thereof.
  • the nanoparticles of the invention have the shape of a sphere, a cube, a tetrahedron, a rod, a wire, a platelet, a tube, a cube, a ribbon or mixture thereof.
  • the 0D nanoparticle is their very sparse density of state only made of dirac comb which can typically include 2 electrons per state.
  • 2D systems are much more promising due to their larger density of state. They are consequently better candidate than the 0D, ID system to sustain large density charging.
  • the nanoparticles of the invention are nanosheets and the plurality of nanosheets presents an optimum porosity with efficient trade-off between the porosity and the charge density.
  • the active material comprising a plurality of nanosheets comprises pores size inferior to 100 nm, or inferior to 50 nm, or inferior to 10 nm, or inferior to 5 nm, or inferior to lnm, or inferior to 0.5 nm, or mixture thereof.
  • said nanoparticles are used in the manufacture of a film of nanoparticles. In one embodiment, said nanoparticles are used in the manufacture of a colloidal quantum dot film. In one embodiment, said nanoparticles are used in the manufacture of a colloidal nanoplatelets film.
  • the film of nanoparticles is obtained from colloidal nanoparticles. In one embodiment, the film of nanoplatelets is obtained from colloidal nanoplatelets.
  • said nanoparticles are used in the manufacture of a quantum dot solid.
  • the nanoparticles, preferably nanoplatelets, of the invention comprise a semi-conductor from group IV, group IIIA-VA, group IIA-VIA, group IIIA- VIA, group IA-IIIA-VIA, group IIA-VA, group IVA-VIA, group VIB-VIA, group VB- VIA, or group IVB-VIA.
  • the nanoparticles, preferably nanoplatelets, of the invention comprise a material MxEy, wherein:
  • M is Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • E is O, S, Se, Te, N, P, As or a mixture thereof;
  • x and y are independently a decimal number from 0 to 5, at the condition that when x is 0, y is not 0 and inversely.
  • the material MxEy comprises cationic elements M and anionic elements E in stoichiometric ratio, said stoichiometric ratio being characterized by values of x and y corresponding to absolute values of mean oxidation number of elements E and M respectively.
  • the nanoparticles, preferably nanoplatelets, of the invention comprises a material MxNyEz, wherein:
  • M is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • N is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • E is selected from O, S, Se, Te, N, P, As or a mixture thereof;
  • x, y and z are independently a decimal number from 0 to 5, at the condition that when x is 0, y and z are not 0, when y is 0, x and z are not 0 and when z is 0, x and y are not 0.
  • the nanoparticles, preferably nanoplatelets, of the invention are made of a quaternary compound such as InAlGaAs, ZnAglnSe or GalnAsSb.
  • the nanoparticles, preferably nanoplatelets, of the invention comprise a material from Si, Ge, Sn, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, CuInS 2 , CuInSe 2 , AgInS 2 , AgInSe 2 , CuS, Cu 2 S, Ag 2 S, Ag 2 Se, Ag 2 Te, InN, InP, InAs, InSb, In 2 S 3 , Cd 3 P 2 , Zn 3 P 2 , Cd 3 As 2 , Zn 3 As 2 , ZnO, A1N, A1P, AlAs, AlSb
  • the nanoparticles, preferably nanoplatelets, of the invention comprise oxygen atoms. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise sulfur atoms. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise atoms of the column VI.
  • the nanoparticles, preferably nanoplatelets, of the invention are made of the following material: Si, SiC, Si0 2 , SiS 2 , Si2Te , Ge, Ge0 2 or GeS 2 .
  • the nanoparticles, preferably nanoplatelets, of the invention comprise lithium or sodium based material.
  • the nanoparticles, preferably nanoplatelets, of the invention comprise a material from LiCo0 2 , LiMn 2 0 4 , LiFeP0 4 , V 2 0 5 , LiT0 2 , LiNiV0 4 , Ti0 2 , Mn0 2 , TiS 2 , MnS 2 , Mo0 2 , MoS 2 , LiNiCoMn0 2 , CuGe03, LiCoP0 4 , Li 4 Ti 5 0 12 , CoSb, Mn 0 .75Nio. 2 5C0 3 , LiNio. 33 Mn 0 . Co 0 . 33 0 2 , Li.
  • the nanoparticles, preferably nanoplatelets, of the invention comprise Li x Ni 1 _ y M y 0 2+a wherein M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr, 0.9 ⁇ x ⁇ l.l, 0 ⁇ y ⁇ 0.7, and 0.05 ⁇ a ⁇ 0.2.
  • the nanoparticles, preferably nanoplatelets, of the invention present a heterostructure, which means that the nanoparticles of the invention are partially coated by at least one layer of inorganic material.
  • the nanoparticles, preferably nanoplatelets, of the invention present a core/shell structure, i.e. the nanoparticles comprise a core and a shell of semiconducting material.
  • the nanoparticles, preferably nanoplatelets, of the invention have a core/shell structure, i.e. the core is totally coated by at least one layer of inorganic material.
  • the nanoparticles, preferably nanoplatelets, of the invention comprises a core totally coated by a first layer of inorganic material, said first layer being partially or totally surrounded by at least one further layer of inorganic material.
  • the core and the at least one layer of inorganic material are composed of the same material or are composed of different material.
  • the core and the at least one layer of inorganic material may be a semi-conductor from group IV, group IIIA-VA, group IIA-VIA, group IDA- VIA, group IA-IIIA-VIA, group IIA-VA, group IVA-VIA, group VIB-VIA, group VB-VIA, or group IVB-VIA.
  • the core and the at least one layer of inorganic material may comprise a material MxEy, wherein:
  • M is Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • E is O, S, Se, Te, N, P, As or a mixture thereof;
  • the core and the at least one layer of inorganic material comprise a material MxNyEz, wherein:
  • M is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • N is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
  • E is selected from O, S, Se, Te, N, P, As or a mixture thereof;
  • x, y and z are independently a decimal number from 0 to 5, at the condition that when x is 0, y and z are not 0, when y is 0, x and z are not 0 and when z is 0, x and y are not 0.
  • the core and the at least one layer of inorganic material are made of a quaternary compound such as InAlGaAs, ZnAglnSe or GalnAsSb.
  • the core and the at least one layer of inorganic material may be composed of a material from Si, Ge, Sn, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, CuInS 2 , CuInSe 2 , AgInS 2 , AgInSe 2 , CuS, Cu 2 S, Ag 2 S, Ag 2 Se, Ag 2 Te, InN, InP, InAs, InSb, In 2 S 3 , Cd 3 P 2 , Zn 3 P 2 , Cd 3 As 2 , Zn 3 As 2 , ZnO, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, FeS 2 , Ti0 2 , Bi 2 S 3 , Bi 2 Se 3 , Bi 2 Te 3 , MoS 2 , WS 2 , V0
  • the nanoparticles, preferably nanoplatelets, of the present invention comprise metallic materials such as gold, silver, copper, aluminum, iron, platinum, lead, or palladium.
  • the nanoparticles, preferably nanoplatelets, of the present invention present a heterostructure comprising metallic materials and semiconductor materials.
  • the nanoparticle, preferably nanoplatelets, of the invention may be further surrounded by a "coat" of an organic capping agent.
  • the organic capping agent may be any number of materials, but has an affinity for the semiconductor surface.
  • the capping agent can be an isolated organic molecule, a polymer (or a monomer for a polymerization reaction).
  • organic capping agents are selected from trioctylphosphine oxide, organic thiols, amines, phosphines, carboxylic acids, phosphonic acids, sulfonic acids, trialkoxysilanes, alkyl and aryl halides; and mixtures thereof.
  • the nanoparticle, preferably nanoplatelets, of the invention may be further surrounded by a "coat" of an inorganic capping agent.
  • the inorganic capping agent comprises an inorganic complex, an extended crystalline structure, metals selected from transition metals, lanthanides, actinides, main group metals, metalloids, and mixture thereof.
  • the inorganic capping agent comprises ionic salts.
  • the nanoparticles, preferably nanoplatelets, of the invention may be surrounded by a mixture of inorganic and organic capping agent.
  • the nanoparticles, preferably nanoplatelets, of the invention for use in a supercapacitor-like electronic battery are selected in the group comprising: CdSe, CdTe, CdS, and the core/shell structures such as CdSe/CdS, CdSe/CdZnS, CdTe/CdS/CdZnS, CdS/ZnS, HgTe, PbS, PbS/CdS, PbSe, PbSe/CdS, PbTe.
  • the nanoparticles are not selected from PbS. In one embodiment, the nanoparticles are not selected from carbon based nanoparticles such as carbon nanowires, carbon nanotubes (multi-walled or single- walled), graphene or combination thereof. In one embodiment, the nanoparticles are not selected from silicon nanoparticles such as silicon quantum dots or silicon nanowires.
  • the nanoparticles are not selected from silver nanowire mesh.
  • the nanoparticles are not selected from metal oxide such as titanium dioxide.
  • the nanoparticles are not selected from lithium based nanoparticles such as LiMn 2 0 4 nanorods or Li 4 Tis0 12 nanopowder.
  • the nanoparticles are not selected from materials that can undergo an intercalation/de-intercalation reaction with lithium ions. In one embodiment, the nanoparticles are not selected from perovskite nanoparticles.
  • the nanoparticles are not obtained by exfoliation of the corresponding layered bulk crystals. In one embodiment the nanoparticle are obtained by exfoliation.
  • the nanoparticles are not obtained by chemical vapor deposition. In one embodiment the nanoparticles are obtained by chemical vapor deposition.
  • the nanoparticles are not obtained by molecular beam epitaxy. In one embodiment the nanoparticles are obtained by molecular beam epitaxy.
  • the nanoparticles are not obtained by solvothermal method. In one embodiment the nanoparticles are obtained by solvothermal method. In one embodiment the nanoparticles are not metal dichalcogenures such as MoS 2 , WS 2 , MoSe 2 , MoTe 2 , WSe 2 , WTe 2 . In one embodiment the nanoparticles are metal dichalcogenures such as MoS 2 , WS 2 , MoSe 2 , MoTe 2 , WSe 2 , WTe 2 .
  • the nanoparticles contain Li atoms. In one embodiment the nanoparticles do not contains Li atoms. In one embodiment, the nanoparticles of the present invention have at least one dimension having a size of about 0.3 nm to less than 1 ⁇ , about 0.5 nm to about 700 nm, about 1 nm to about 500 nm, about 1.5 nm to about 200 nm, about 2 nm to about 100 nm. In one embodiment, the nanoparticles are thicker than 3, 4, 5, 6, 7, 8, 9, 10, 15 lattice parameters.
  • the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 100 centimeters. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 1 centimeter. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 100 micrometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 10 micrometers.
  • the at least one active material comprising a plurality of nanoparticles, preferably nanosheets has a thickness from 10 nanometers to 1 micrometer. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 900 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 800 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 700 nanometers.
  • the at least one active material comprising a plurality of nanoparticles, preferably nanosheets has a thickness from 10 nanometers to 600 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 500 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 400 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 300 nanometers.
  • the at least one active material comprising a plurality of nanoparticles, preferably nanosheets has a thickness from 10 nanometers to 200 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 100 nanometers.
  • the nanosheets of the present invention have a thickness of about 0.3 nm to about 10 mm, about 0.3 nm to about 1 mm, about 0.3 nm to about 100 ⁇ nm, about 0.3 nm to about 10 ⁇ , about 0.3 nm to about 1 ⁇ , about 0.3 nm to about 500 nm, about 0.3 nm to about 250 nm, about 0.3 nm to about 150 nm, about 0.3 nm to about 100 nm, about 0.3 nm to about 50 nm, about 0.3 nm to about 25 nm, about 0.3 nm to about 20 nm, about 0.3 nm to about 15 nm, about 0.3 nm to about 10 nm, about 0.3 nm to about 5 nm.
  • the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 1.5 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 2 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 3 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 10 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 25 times its thickness.
  • the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 50 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 100 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 1000 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 10 4 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 10 5 times its thickness. In another embodiment, the lateral dimensions of the nanosheets are at least 2, 2.5, 3, 3.5, 4, 4.5, 5 times larger than its thickness.
  • the lateral dimensions of the nanosheets are at least 2, 2.5, 3, 3.5, 4.5, 5 times larger than the thickness. In one embodiment, the lateral dimensions of the nanosheets are from at least 0.45 nm to at least 50 mm.
  • the lateral dimensions of the nanosheets are from at least 2 nm to less than 1 m, from 2 nm to 100 mm, from 2 nm to 10 mm, from 2 nm to 1 mm, from 2 nm to 100 ⁇ , from 2 nm to 10 ⁇ , from 2 nm to 1 ⁇ , from 2 nm to 100 nm, from 2 nm to 10 nm.
  • the nanosheet comprised in the nanoparticle of the invention has a quasi-2D structure.
  • the at least two pluralities of nanoparticles comprise the same nanoparticles. In one embodiment, the at least two pluralities of nanoparticles comprise different nanoparticles.
  • the nanoparticles are coupled to a high mobility material.
  • the nanoparticles is mixed or blended with a high mobility material.
  • the active material comprises at least 50% by weight of nanoparticles, preferably at least 70% by weight, more preferably at least 80 % by weight, even more preferably at least 90% by weight.
  • the active material comprises at least 50% by weight of nanoplatelets, preferably at least 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% by weight.
  • the active material comprises nanoparticles, preferably nanoplatelets, mixed with an additive.
  • said additive is a polymer, preferably an electrochemically active polymer.
  • the additive is a carbon-based material such as carbon black, graphene, carbon nanotube, boron nitride nanotube, boron nitride nanosheet, graphene oxide, reduced graphene oxide.
  • the additive is selected from fluorinated polymers (e.g. polyvinylidene fluoride (PVdF)), polypyrrole, polythiaphene, polyethylene oxide, polypropylene oxide, polyacrylonitrile, poly(ethylene succinate), poly (b- propiolactone), styrene butadiene rubber (SBR), carboxymethyl cellulose salt (CMC), sulfonated fluoropolymers, polyimide, poly(acrylic acid), polysiloxanes, polyimides, polyphosphazenes, polyethers, sulfonated polyimides, perfluorinated polymers, polydivinyl polyethylene glycols, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, polyarylsulfones, mixtures and derivatives of said polymers, and copolymers that include repeating units of said polymers.
  • fluorinated polymers e.g. polyvinylidene fluoride (PVdF)
  • the additive is selected from a metal orthophosphate, a metal metaphosphate, a metal polyphosphate, fluorophosphates, a metal polyfluorophosphate, a metal carbonate, a metal borate, a metal polyborate, a metal fluoroborate, a metal polyfluoroborate, a metal sulfate, a metal fluorosulfate, an oxide compound, a fluoroxide compound, an electrically conducting oxide (e.g.
  • fluorine doped tin oxide Sn02:F or indium tin oxide ⁇ ) a titanate, a metal aluminate, a metal fluoroaluminate, a metal silicate, a metal fluorosilicate, a metal borosilicate, a metal fluoroborosilicate, a metal phosphosilicate, fluorophosphosilicate, a metal borophosphosilicate, a metal fluoroborophosphosilicate, a metal fluoroborophosphosilicate, a metal aluminosilicate, a metal fluoroaluminosilicate, a metal aluminophosphosilicate, a metal fluoroaluminophosphosilicate or a mixture thereof.
  • the additive is selected from a lithium, sodium, potassium, ammonium, calcium, magnesium or aluminum phosphate or a mixture thereof. In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium or magnesium carbonate or a mixture thereof. In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium, magnesium or aluminum borate, polyborate, fluoroborate or polyfluoroborate or a mixture thereof.
  • the additive is selected from a lithium, sodium, potassium calcium, magnesium or aluminum sulfate or fluorosulfate (e.g. Li 2 S0 4 , Na 2 S0 4 , K 2 S0 4 , CaS0 4 , MgS0 4 , A1 2 (S0 4 ) 3 ) or a mixture thereof.
  • a lithium, sodium, potassium calcium, magnesium or aluminum sulfate or fluorosulfate e.g. Li 2 S0 4 , Na 2 S0 4 , K 2 S0 4 , CaS0 4 , MgS0 4 , A1 2 (S0 4 ) 3
  • the additive is selected from a lithium, sodium, potassium, boron, calcium, magnesium, aluminum, silicon, tin, titanium or zirconium oxide or fluoroxide (e.g. A1 2 0 3 , B 2 0 3 , CaO, K 2 0, Li 2 0, MgO, Na 2 0, Si0 2 , Sn0 2 , SnO y F z , Ti0 2 , Zr0 2 ) or a mixture thereof.
  • a lithium, sodium, potassium, boron, calcium, magnesium, aluminum, silicon, tin, titanium or zirconium oxide or fluoroxide e.g. A1 2 0 3 , B 2 0 3 , CaO, K 2 0, Li 2 0, MgO, Na 2 0, Si0 2 , Sn0 2 , SnO y F z , Ti0 2 , Zr0 2
  • fluoroxide e.g. A1 2 0 3 , B 2 0 3 , CaO, K 2 0, Li 2 0,
  • the additive is selected from a lithium, sodium, potassium, calcium or magnesium aluminate or fluoroaluminate, or mixture thereof.
  • the additive is selected from a lithium, sodium, potassium, calcium or, magnesium silicate, borosilicate, fluorosilicate, fluoroborosilicate, phosphosilicate, fluorophosphosilicate, borophosphosilicate, fluoroborophosphosilicate, aluminosilicate, fluoroaluminosilicate, aluminophosphosilicate or fluoroaluminophosphosilicate, or mixture thereof.
  • the additive is selected from transition metal oxide, transition metal fluoroxide, transition metal phosphate or transition metal fluorophosphates or mixture thereof.
  • the at least one electrolyte has at least one common interface with each of the at least two active materials comprising a plurality of nanoparticles.
  • the at least one electrolyte has at least one common interface with the at least one active material comprising a plurality of nanoparticles. In one embodiment, the matrix of the electrolyte is not mixed with the at least one active material comprising a plurality of nanoparticles. In one embodiment, the matrix of the electrolyte is not mixed with the pluralities of nanoparticles forming any active material.
  • the matrix of the electrolyte is not mixed with the film of nanoparticles.
  • the matrix of the electrolyte remains outside of the active material. In one embodiment, ions from the matrix of the electrolyte percolate through the active material (i.e. though the void of the film of nanoparticles) while the matrix remains outside, in contact with the active material.
  • the active material is not saturated by the electrolyte.
  • the at least one electrolyte has a thickness from 10 nanometers to 1 centimeter, preferably from 500 nanometers to 2 millimeters, more preferably from 1 micrometer to 10 micrometers.
  • solid, polymer, gel, ion-gel or liquid electrolytes may be implemented, preferably a gel or solid electrolyte.
  • contact between the at least one electrolyte and the first or second electrodes is prevented by the active material comprising a plurality of nanoparticles.
  • contact between the at least one electrolyte and the first and second electrodes is prevented by the active material comprising a plurality of nanoparticles.
  • the supercapacitor-like electronic battery comprises at least two different electrolytes, each of them having one common interface with the at least two active materials comprising a plurality of nanoparticles.
  • the supercapacitor-like electronic battery comprises at least two different electrolytes, one of them having a common interface with the at least one active material comprising a plurality of nanoparticles.
  • the at least one electrolyte can be in the form of an aqueous solution of a dissolved ionic chemical compound (or compounds), a non-aqueous solution of a dissolved ionic chemical compound (or compounds), a polymer electrolyte, a gel electrolyte, a solid electrolyte or a molten salt electrolyte.
  • the at least one electrolyte can be a non-aqueous organic solvent comprising carbonate-based solvent such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like; or ester-based solvent such as methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate, and the like; or mixture thereof.
  • the at least one electrolyte comprises a matrix and ions.
  • the at least one electrolyte comprises a polymer matrix.
  • the polymer matrix of the electrolyte comprises polystyrene, poly(N-isopropyl acrylamide), polyethylene glycol, polyethylene, polybutadiene, polyisoprene, polyethylene oxide, polyethyleneimine, polymethylmethacrylate, polyethylacrylate, polyvinylpyrrolidone, polypropylene glycol, polydimethylsiloxane, polyisobutylene, or a blend/multiblocks polymer thereof.
  • the at least one electrolyte comprises ions salts.
  • the polymer matrix is doped with ions salts.
  • the ions salts is LiCl, LiBr, Lil, LiSCN, LiC10 4 , KC10 4 , NaC10 4 , ZnCl 3 ⁇ , ZnCl 4 2" , ZnBr 2 , LiCF 3 S0 3 , NaCl, Nal, NaBr, NaSCN, Na 2 S0 4 , KC1, KBr, KI, KSCN, LIN(CF 3 S0 2 ) 2 , LiPF 6 , LiAsF 6 , LiN(S0 2 CF 3 ) 2 , LiC(S0 2 CF 3 ) 2 , LiBF , NaBPh 4 , LiAsF 6 , C 2 BF 2 Li0 4 , LiH 2 P0 4 , LiGaCl 4 or mixture thereof.
  • the at least one electrolyte comprises material that contains mobile ions of lithium, sodium, potassium, hydrogen, copper, silver or mixture thereof.
  • the at least one electrolyte comprises polymers and glasses, including but not limited to PEG, PEO, PVDF, PET, PTFE, FEP, FPA, PVC, polyurethane, polyester, polyglycol, silicone, some epoxies, polypropylene, polyimide, polycarbonate, polyphenylene oxide, polysulfone, calcium magnesium aluminosilicate glasses, E-glass, alumino-borosilicate glass, D-glass, borosilicate glass, silicon dioxide, quartz, fused quartz, silicon nitride, silicon oxynitride, or mixture thereof.
  • the at least one electrolyte comprises a carbonate-based, alcohol- based, ester-based, ether-based, ketone -based, or aprotic solvent.
  • the at least one electrolyte comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, butylene carbonate, methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate and the mixture of thereof.
  • the at least one electrolyte comprises ionic liquid.
  • the polymer matrix and the ions are replaced by a polymerizable ionic liquid.
  • the electrolyte is thick enough to act as a separator.
  • the nanoparticle surface chemistry is chosen to be a counterion of one of the ions of the electrolyte.
  • the nanoparticle surface chemistry is chosen so that the nanoparticles and the electrolyte can form a redox reaction. In one embodiment, at least one ion from the electrolyte can reversibly give one or more electron(s) to the active material as in redox based reactions.
  • pairs of nanoparticle surface chemistry/ion include but is not limited to: OH7Li + , OH7Na + , OH7K + , OH 7NH 4 + , OH /any ammonium ion, OH /any ionic liquid, 0 2 7Li + , O 2 7Na + , O 2 7K + , O 2 7NH 4 + , O 2 7any ammonium ion, O 2 7any ionic liquid, HS " /Li + , HS7Na + , HS7K + , HS7NH 4 + , HSVany ammonium ion, HSVany ionic liquid, SCN /Li + , SCN7Na + , SCN7K + , SCN7NH 4 + , SCNVany ammonium ion, SCNVany ionic liquid, NH 2 7Li + , NH 2 7Na + , NH 2 7K + , NH 2
  • the ligand for the nanop article's ligand exchange step is S
  • the pairs of nanoparticle surface chemistry/ion comprise S 2- 7Li + , S 2- " /Na + , S 2 7K + , S 2 7NH 4 + , S 2 7any ammonium ion, S /any ionic liquid.
  • the supercapacitor-like electronic battery comprises a separator, which partitions the at least one electrolyte in two.
  • the supercapacitor-like electronic battery comprises a separator between the at least two electrolytes.
  • the separator partitions the two electrodes, and the electrolyte, while allowing the passage of ions through the separator.
  • the separator provides electronic insulation between the electrode of opposite polarization and support the ionic conduction.
  • the separator is made from polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly ([beta]-propiolactone), and sulfonated fluoropolymers, as well as others known in the art.
  • the separator may be an electrolyte as defined in the present invention.
  • the separator may be composed of paper, glass fiber, ceramic, polymer or mixture thereof.
  • the supercapacitor-like electronic battery of the present invention presents at least one current collector connected to one electrode.
  • the supercapacitor-like electronic battery of the invention presents at least two current collectors connected to the at least two electrodes.
  • the supercapacitor-like electronic battery of the present invention presents good cycling properties between 1 to 1 million cycles, preferably between 10 to 10 6 cycles, more preferably between 10 2 to 10 5 cycles.
  • the supercapacitor-like electronic battery has a gate capacitance per unit of surface of active material ranging from 1 to 10 5 ⁇ .c -2 , preferably from 10 to 50 000 ⁇ . ⁇ 2 , more preferably from 20 to 15 000 ⁇ . ⁇ 2 .
  • the supercapacitor-like electronic battery has a gate capacitance per mass unit ranging from 10 - “ 3 to 103 Fg- " 1 , preferably from 1 to 100 Fg - " 1.
  • the supercapacitor-like electronic battery of the present invention has an energy density ranging from O.lWh/Kg to lOOOWh/kg, preferably from lWh/kg to 500Wh/kg, more preferably from lOWh/kg to lOOWh/kg, even more preferably from lOWh/kg to 500Wh/kg.
  • the supercapacitor-like electronic battery of the present invention has an energy density of at least O. lWh/kg, or at least IWh/kg, or at least lOWh/kg, or at least lOOWh/kg, or at least 200Wh/kg, or at least 300Wh/kg, or at least 400Wh/kg, or at least 500Wh/kg, or at least 600Wh/kg, or at least 700Wh/kg, or at least 800Wh/kg, or at least 900Wh/kg, or at least lOOOWh/kg, or at least 5000Wh/kg, or at least lOkWh/kg.
  • the supercapacitor-like electronic battery of the present invention has a power density ranging from 1 to 10 6 W/Kg, preferably from 1 to 5xl0 5 W/Kg, more preferably from 25 to 10 5 W/Kg, even more preferably from 100 to 10 4 W/Kg.
  • the supercapacitor-like electronic battery of the present invention has a power density of at least IW/kg, or at least 25 W/Kg, or at least 100 W/Kg, or at least 10 3 W/Kg, or at least 10 4 W/Kg, or at least 5xl0 4 W/Kg, or at least 10 5 W/Kg, or at least 5xl0 5 W/Kg, or at least 10 6 W/Kg, or at least 10 7 W/Kg.
  • the pore density is in the 10 1U to 10" 1 cm “ range, preferably in 10 to 10 cm “ range.
  • the density of state of the 2D system is from 10 eVcm “ to 10 eVcm “ ' preferably from 5xl0 12 eVcm “2 to 4xl0 14 eVcm “2 .
  • At least one dimension of the nanoparticles is of the same order of magnitude as the Bohr radius (a B ) of the material, meaning that at least one dimension of the nanoparticles is ranging from 0.1a B and 10 a B .
  • the specific surface of the nanoparticles of the active material is
  • ions from the at least one electrolyte migrate at the interface between the at least one electrolyte and at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In one embodiment, ions from the at least one electrolyte migrate within at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
  • counterions from the at least one electrolyte remain within the electrolyte.
  • bulk doping or bulk charging is achieved within at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
  • bulk doping or bulk charging is achieved within at least one film of nanoparticles, preferably nanoplatelets.
  • charges are injected in the active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets; the introduction of the ions induces indeed a charging of the quantum states of the nanoparticles.
  • the continuity of at least one active material comprising a plurality of nanoparticle, preferably a plurality of nanoplatelets, prevents direct contact between the at least one electrolyte and the first and/or second electrodes therefore preventing leakage through the dielectric.
  • nanoparticles refer preferably to non-carbon based nanosheets.
  • the manufacturing process for preparing the supercapacitor-like electronic battery of the present invention comprises three main steps:
  • the method for producing a supercapacitor-like electronic battery comprises:
  • step b') if step b') is not implemented, nanoparticle' s ligand exchange step on the active material comprising a plurality of nanoparticles,
  • a second solution of nanoparticles may be deposited between the electrolyte and the second electrode, said solution of nanoparticle being the same or different from the solution of step b).
  • step b) reads as the preparation of one solution of nanoparticles mixed with additives.
  • the at least first and second electrodes are fabricated using a lift-off procedure.
  • the at least first and second electrodes may be deposited using conventional deposition techniques, including for example, drop casting, inkjet printing, screen printing, gravure printing, flexographic printing or any other means that a person skilled in the art would find appropriate.
  • the at least first and second electrodes are onto the substrate or within the container.
  • the nanoparticles of the invention are dispersed in a solvent, such as for example a mixture of hexane and octane with a volume ratio of 9: 1, in order to obtain the solution of nanoparticles.
  • the solution of nanoparticles of step b) is partially deposited during step c) onto a substrate.
  • the solution of nanoparticles of step b) is deposited during step c) onto a substrate and on at least one electrode.
  • the solution of nanoparticles deposited during step c) comprises various nanoparticles.
  • steps b), b'), c), c') may implemented more than once with various nanoparticles.
  • the electrodes are processed with a gas treatment before step c).
  • the electrodes are treated with molecules such as short- chain alkane thiols to improve the adhesion of the nanoparticles before step c). According to one embodiment, the electrodes are treated with a coating for passivating the surface of the at least two electrodes before step c).
  • the electrodes are annealed before step c) at a temperature ranging from 100°C to 1000°C.
  • the deposition of nanoparticles is achieved during step c) by sputtering techniques, evaporation techniques, electrophoretic deposition, vacuum methods, lithography process, spray pyrolysis, hot and cold plasma, inert gas phase condensation techniques or any other means that a person skilled in the art would find suitable.
  • the deposition of nanoparticles is achieved during step c) by drop casting, spin coating, dip coating, spray coating, screen printing, inkjet printing or any other means that a person skilled in the art would find appropriate.
  • the nanoparticles prepared in solution at step b) presents wide or narrow band gap.
  • nanoparticle's ligand exchange is performed in the active material comprising a plurality of nanoparticles after deposition or on the nanoparticles in solution prior to the deposition, preferably in the active material comprising a plurality of nanoparticles after deposition.
  • nanoparticle's ligand exchange is performed in the active material comprising a plurality of nanoparticles after deposition or on the nanoparticles in solution prior to the deposition, preferably on the nanoparticles in solution prior to the deposition.
  • nanoparticle's ligand exchange is performed on the active material comprising a plurality of nanoparticles during step c'), for example by dipping the nanoparticles in a solution.
  • the nanoparticle's ligand exchange is performed directly in solution prior to the deposition of nanoparticles as in step b').
  • the component in progress is annealed before step d) at low temperature, typically below 400°C, or below 300°C or below 200°C, or below 100°C.
  • the electrolyte is brushed on the active material comprising a plurality of nanoparticles.
  • the electrolyte is deposited using any printing methods that a person skilled in the art would find suitable, such as for example spin coating or dip coating, or drop casting.
  • the electrolyte is onto the active material comprising a plurality of nanoparticles; or within the container and in contact with the active material comprising a plurality of nanoparticles.
  • the electrolyte is prepared by dissolving an ion salt and a polymer matrix in a polar solvent.
  • the electrolyte is prepared by melting ion salt in the polymer matrix at moderate temperature, typically 150°C.
  • the second electrode is deposited by any methods that a person skilled in the art would find suitable.
  • step d) is performed after the deposition of the second electrode (step e)).
  • the supercapacitor-like electronic battery of the invention are particularly useful as power source.
  • the supercapacitor-like electronic battery is operated between - 50°C and 100°C, preferably between -20°C and 80°C, more preferably between 0°C and 60°C.
  • At least two supercapacitor-like electronic battery of the present invention are associated together.
  • the invention can find applications as power source for many household and industrial applications.
  • the invention can find applications as starter for bringing fast power for vehicles or engines at start.
  • the invention can find applications in renewable energy production. In one embodiment, the invention can find applications in aerospace systems.
  • the invention can find application in elevators, pallet trucks or any applications in the electric transportation domain (cars, trucks, trams, trains, buses).
  • the present invention may be used for applications in electrical wireless device, in eolian applications, in energy regulation devices, in the military domain or in the health area, etc.
  • the present invention can find application in any systems or devices which require a substantial pulse of energy having duration below 1 minute, preferably below 30 seconds, more preferably below 10 seconds.
  • the present invention can find application in any device which required high power application.
  • the present invention can find application in any device which required low power application but where the batteries are at the origin of maintenance problems or of insufficient lifetime performance.
  • Figure 1A illustrates a nanoparticle surface charged through (A) a ionic layer process, (B) through the proposed mechanism of the invention, (C) through direct injection of the ions into the material at the atomic scale.
  • Figure IB illustrates the three different regimes of operation of the nanoparticle based supercapacitor: a) on left the ion injection regime (low frequency regime), b) on middle the double electrostatic layer (intermediate frequency regime) and c) on right the high frequency mode where the electrolyte is used as a dielectric.
  • Figure 2 is a sectional view of a supercapacitor-like electronic battery according to one embodiment of the present invention.
  • Figure 3 is a sectional view of a supercapacitor-like electronic battery according to another embodiment of the present invention.
  • Figure 4 is a sectional view of a supercapacitor-like electronic battery according to one embodiment of the present invention.
  • Figure 5 shows the plot of power against energy density also called a Ragone plot for different technology of energy storage device, the current invention has an operation range highlighted with some dashed lines.
  • Figure 7 illustrates the cycling properties of the supercapacitor-like electronic battery of the present invention.
  • Figure 8 illustrates the difference of charge which can be injected in a film of CdSe/CdS nanoplatelets depending of the used surface chemistry.
  • TMSS Bis(trimethylsilyl)sulfide
  • ODE octadecene
  • the solution is quickly cooled to room temperature.
  • the solution is precipitated by adding ethanol and centrifuged for 5min at 3000rpm.
  • the solid is redispersed in toluene.
  • the cleaning step is repeated a second time. At the third cleaning, selective precipitation is performed to separate the different size.
  • 0.44g of lead oxide are mixed in a three-neck flask with 2mL of oleic acid and lOmL of phenyl ether at 150°C under Argon for thirty minutes.
  • 32mg of sulfur flake are sonicated with 2mL of filtered oleylamine.
  • the obtained mixture is red- orange.
  • the flask is heated up to 190°C and the sulfur in oleylamine quickly injected.
  • the reaction is then conducted at 180°C for 5 minutes.
  • the cleaning process is done three times by adding ethanol/methanol as non-solvent and toluene as non-polar solvent.
  • trioctylphosphine selenide (TOPSe) is prepared by stirring Se powder in trioctylphosphine (TOP) at room temperature.
  • TOP trioctylphosphine
  • a three-neck flask 650mg of trihydrate lead(II) acetate Pb(Oac) 2 (H 2 0)3 are introduced with 2mL of phenyl ether, 1.5mL of oleic acid and 8mL of TOP.
  • the solution is degased, as well as a second flask only filled with lOmL of pure phenyl ether, for lhour at 85°C.
  • the one containing the lead precursor is cooled to 45°C and 1.7mL of the TOPSe solution is added.
  • trioctylphosphine telluride (TOPTe) is prepared by a slow stirring of Te powder in trioctylphosphine (TOP).
  • TOP trioctylphosphine
  • 135mg of HgCl 2 and 7.4g of octadecylamine are degased under vacuum for lhour at 120°C.
  • the atmosphere is then switch to Argon and the solution heated at 80°C.
  • 0,5ml of the 1M TOPTe are quickly injected and the reaction is performed at the same temperature for 5min.
  • the solution is quenched by a quick addition of dodecanthiol. Finally the flask is cooled down to room temperature.
  • the flask After 5min the flask is cooled to 300°C, every two minutes 0.4ml of the TOPS mixture is injected. The color of the solution turn yellowish after 30minutes and this color will increase up to the end. Once all the TOPS has been injected the heating mantle is removed and the flask quickly cooled down. Around 70°C some toluene is added to avoid the TOPO solidification. The cleaning process is repeating three times by precipitating the rods by adding ethanol and redispersing them in toluene.
  • Cadmium myristate (Cd(Myr) 2 ) is prepared.
  • Cd(Myr) 2 25mg Se powder are mixed in 30ml of ODE, the solution degased under vacuum for 20min at room temperature. Then the atmosphere is switch to Argon and the temperature is set to 240°C.
  • 204°C 40mg of Cd(OAc) 2 are quickly added.
  • the reaction is performed 12min at 240°C. 1ml of oleic acid is quickly injected to quench the reaction and the solution is cooled down.
  • the precipitation of the nanoplatelets is done by adding ethanol. After centrifugation the obtained solid is redispersed in hexane. The cleaning procedure is repeated three times.
  • a solution of tetrakis (acetonitrile) copper(I) hexafluorophosphate in methanol is prepared with a concentration of at 50 mmol/L.
  • CdSe NPL are mixed with this solution Cu + solution with a 10 time excess of Cu + compared to Cd 2+ .
  • the solution is then washed twice air free using methanol as polar solvent and toluene as non-polar solvent.
  • a stock solution made of 125 mg of ZnC12, 4 mL of oleylamine and 6 mL of octadecene is degased for 30 min at room temperature.
  • the mixture is heated under Ar at 250°C.
  • Some Cu 2 Se NPL dispersed in trioctylphosphine are quickly injected onto the Zinc mixture.
  • the reaction is conducted for 5 minutes.
  • the solution is then washed twice using methanol as polar solvent and toluene as non-polar solvent.
  • a stock solution made of Pb(OAc)2.3 H20 is prepared by dissolving 56 mg of solid in 1 mL methanol and 100 ⁇ ⁇ tributylphosphine. This solution is added to the solution of Cu 2 Se NPL with a ratio of Pb 2+ /Cu + of 50. The reaction is performed for 1 hour. Then lead oleate is added to stop the reaction. The solution is then washed twice using methanol as polar solvent and toluene as non-polar solvent. ZnS nanoplatelets
  • Cadmium propanoate (Cd(Prop) 2 ) is prepared by mixing 1.036g of CdO in 10ml of propionic acid under Argon for 1 hour. Then the flask is open to air and the temperature risen to 140°C up to the point the volume get divided by a factor two. The whitish solution is precipitated by addition of acetone. After centrifugation the solid is dried under vacuum for 24 hours.
  • TOPTe is prepared by stirring 2.55g of Te pellets in 20ml of TOP for four days at room temperature.
  • the electrolyte is a mixture of polyethylene glycol (PEG) or polyethylene oxide (PEO) with a given molar weight and ions.
  • PEG polyethylene glycol
  • PEO polyethylene oxide
  • the molar ratio between the cation and the oxygen is taken equal to 16.
  • PEG/PEO molar weight the mixture is heated at 200°C. Processing the electrolyte in air has not lead to any noticeable change.
  • Electrodes are fabricated using a regular lift-off procedure onto a Si/Si0 2 wafer with an oxide thickness of 500nm. A thermal evaporation of Cr (2.5nm) and gold (17.5nm) is used for the contact. Electrodes are composed of 25 interdigitated pairs which are 2.5mm long. Two sets of electrodes have been designed with a spacing of 10 and 20 ⁇ . The W/L ratio is 6250 for the ⁇ spaced electrodes and 3125 for the 20 ⁇ spaced electrodes. In another embodiment a Cu sheet is used as a support for the electrodes.
  • the nanoparticles are dispersed in a mixture of hexane and octane (9: 1 as volume ratio).
  • the electrodes are warmed at 125°C on a hot plate for two minutes and then thermalized at room temperature.
  • the solution is dropcasted onto the interdigitated electrodes.
  • the typical thickness for a film is 30nm.
  • the film is then rinsed in pure ethanol.
  • the film is annealed at 80°C for one minute.
  • This solution is dropcasted on the electrodes on a hot plate at 100°C.
  • the heating is performed 10 minutes more than requested to dry the film.
  • the typical thickness for a film is 40nm.
  • the nanoparticles capped with S " ligands and dispersed in NMFA are dropcasted on a substrate of Si/Si0 2 where a metallic contact has been deposited by thermal evaporation of Cr and Au.
  • the drying of the solution is made by warming the substrate on a hot plate at 100°C. This step is repeated several times to obtain a film with the right thickness.
  • the electrolyte as described previously is also warm on the hot plate up to the point where the material is soften and can be more easily brushed directly on the nanoparticles film.
  • a metallic contact is deposited on the top of the electrolyte. Alternatively the top contact can be obtained by metal evaporation though an adapted shadow mask.
  • a metallic electrodes with an adapted shape (it can be a tube, a porous tube, or any system maximizing the surface of the electrodes) is warmed at a temperature between 80°C and 100°C using a heat gun.
  • the electrode is dipped in the solution of nanoparticles capped with S " ligands and dispersed in NMFA. The dipping process is repeated several times, up to the point where the nanoparticles coating of the electrodes reached the desired thickness.
  • a recipient containing some of the electrolyte is warmed on a hot plate at a temperature between 60°C and 100°C to soften the electrolyte.
  • the electrode coated with the nanoparticles is immerged in the electrolyte as well as a second metallic uncoated electrode.
  • the whole device is used as a supercapacitor.
  • the nanoparticle capped with organic ligand are electrophoretically deposited on a conductive substrate.
  • the latter can be metallic or an ITO coated glass slide.
  • the typical biases for the deposition are in the 0V-2000V range and the deposition is performed during between 10s and several hours depending of the solution concentration and the amount of polar solvent.
  • a recipient containing some of the electrolyte is warmed on a hot plate at a temperature between 60°C and 100°C to soften the electrolyte.
  • the electrode coated with the nanoparticles is immerged in the electrolyte as well as a second metallic uncoated electrode.
  • the whole device is used as a supercapacitor.
  • the nanoparticles (CdSe/CdS nanoplatelets) are capped with S " ligands using the procedure described in example 4' .
  • the nanoparticles in solution are mixed with carbon black in a weight ratio of 3: 1.
  • the blend is dried in an oven at 100°C for lh.
  • the obtained powder is deposited on a Cu substrate.
  • LiC10 4 in ethylene carbonate is used as electrolyte.
  • a Li foil is used as counter electrodes to form a half electrochemical cell.
  • the supercapacitor as disclosed hereabove presents an energy density of 77Wh/kg, a power density of 54 kW/kg, a capacitance of 55 F/g and a discharge time between 10 and 100 seconds.

Abstract

The present invention relates to a supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of nanoparticles and at least one electrolyte, wherein the electrolyte matrix is not mixed with the active material comprising a plurality of nanoparticles. The present invention also relates to a supercapacitor-like electronic battery having a power density above 25k W/kg and an energy density above 1Wh/Kg. An aspect of the invention is also to provide a manufacturing process and the use of said supercapacitor-like electronic battery.

Description

SUPERCAPACITOR-LIKE ELECTRONIC BATTERY
FIELD OF INVENTION
The present invention relates generally to a supercapacitor-like electronic battery. More particularly, this invention relates to a supercapacitor-like electronic battery using nanostructured materials. This invention also relates to the manufacturing process and the use of said supercapacitor-like electronic battery.
BACKGROUND OF INVENTION Nowadays the field of energy conversion and storage generates increased research activity. Recently, a lot of attention has been focused on improving current energy storage technology, especially as rechargeable lithium-ion batteries find new uses in addition to the mobile electronics applications for which they were developed originally. While lithium-ion batteries offer a good combination of specific energy and power density, some applications require faster recharge times, higher cycle lives and even higher power densities.
Traditional batteries, including lithium (Li) ion batteries, comprise an anode, a separator material with an electrolyte medium, and a cathode. The anode electrode of most commercially available Li ion batteries is a copper foil coated with a mixture of graphite powder and a polymer blend such as polyvinylidene difluoride (PVDF). The cathode generally comprises a mixture of lithium transition metal oxides, PVDF and carbon black coated onto an aluminum foil.
By their very nature, the electrodes in electrochemical batteries undergo chemical changes, structural changes and/or volume changes, all of which can severely degrade the integrity of the electrodes over time and reduce the capacity of the battery. Indeed the charging and discharging processes in the latest generation lithium-ion battery must be carefully controlled - overcharging or over-discharging can limit the performance and cause premature failure of the battery.
In contrast, capacitors store their energy as electrical charge on the electrodes; No chemical changes are involved and most capacitors have cycle lives of a million cycles or more, to 100% depth-of-charge. Capacitors can also be charged and discharged orders of magnitude faster than electrochemical batteries. The emergence of electrochemical capacitors has now provided a viable alternative to traditional electrochemical batteries.
Capacitors based on aqueous electrolytes are usually limited to maximum operating cell voltages of slightly over IV - higher voltages lead to unwanted electrolysis of the electrolyte. Liquid electrolytes remain poorly integrable due to the size of the electrochemical cell and possible leakages are poorly compatible with industrial production.
Electrochemical capacitors or supercapacitors are intermediate device between battery and dielectric capacitor. They have a stronger energy density compared to regular capacitor and a faster ability to deliver energy than battery. So they look well suited for application where a pulse of energy is required.
Several types of electrochemical capacitors can be distinguished, depending on the charge storage mechanism as well as the active material. The charging process relies either on the formation of a double ionic layer at the interface between the electrolyte and the active material or through redox process at the surface of the active material.
Some electrochemical capacitors use reversible redox reactions at the surface of active material. Some electrochemical capacitors make also use of the very large capacitance that is generated at the interface between an electrolyte and an active material. This allows them to store more than ten times as much energy as electrostatic capacitors. This phenomenon is exploited in today's commercially available electrochemical double layer (EDL) supercapacitors (sometimes referred to as "ultracapacitors"). The general approach to describe the semiconductor charging process through an electrolyte relies on the formation of a double ionic layer at the interface between the electrolyte and the semiconductor as proposed by von Helmholtz in 1853. For example in a n-type material, cations from the electrolyte will densely accumulate at the surface (but still in the electrolyte) and will face a negatively charged layer of semiconductor. Moreover in the electrolyte a layer of anions comes on the top of the cations layer to screen them and lead to a null electric field in the bulk of the electrolyte. The charging of the semiconductor occurs through the injection by the source electrodes of electrons.
Sn far this process leads to a limited interface capacitance which value is a°L wherein 0 is the vacuum permittivity, r is the electrolyte dielectric constant and DL is the width of the double layer. Because the Helmholtz double layer forms only at the interface between electrode and electrolyte, it is necessary to create a structure that maximizes this interfacial region.
It will be of great interests to be able to inject ions within the bulk of the semiconductor to obtain larger capacitance. In battery for example large specific surface material with fractal aspect are used and the charging occurs a very large interface between the electrolyte and the semiconductor.
In order to maximize this interfacial region, WO2011/063539 discloses the use of a novel device containing one or more electrodes whose structure is comprised of an electrolyte into which is dispersed conductive nanoparticles, such as for instance core- shell nanoparticles. In the present invention, the Applicant uses an active material comprising nanoparticles, which is simply covered by an electrolyte. On the contrary to the prior art the Applicant has discovered that, in the supercapacitor-like electronic battery of the present invention, ions from the electrolyte migrate within the active material, i.e. within the bulk of the nanoparticles. Therefore the present invention differs from the solutions of the prior art. The Applicant does not need to disperse the nanoparticles within the electrolyte. In WO 2011/063539 the charge density is lower. In the supercapacitor-like electronic battery of the present invention bulk doping of the nanoparticles is achieved. It is therefore an object of the present invention to elaborate a supercapacitor-like electronic battery having an ultra large capacitance and allowing bulk doping or charging of the nanoparticles.
In US 2010/0297502, the authors used various nanostructures for implementing a battery. It discloses a battery slurry and/or battery electrodes comprising one or more of a carbon-comprising Si-based nanostructures. It relates to a mixture of nanostructures with a conductive polymer and a carbon-based material to form a slurry, which is not the case in the present invention. Accordingly, higher capacitance is achieved in the present invention thanks to bulk doping of the nanoparticles within the assembly of nanoparticles while the electrolyte only covers the assembly. Maximizing the interfacial surface, if desirable, is not any more the main issue. Therefore the present invention differs from the solutions of the prior art.
The present invention relies on two main observations. The first is the fact that a film of 2D nanoparticles can incorporate more charge than a film of 0D nanoparticle with the same composition, see figure 6, and the second is the fact that improved charging can be achieved by using short ligand, see figure 8. We have noticed an increase by a factor 5 to 10 of the charge while using S " ligand instead of organic ligand such as butylamine.
It is an object of the present invention to elaborate a supercapacitor-like electronic battery which takes full advantage of the large capacitance induced by the bulk doping or charging of the active material. The invention is also based on the implementation of the right pair of nanoparticles surface chemistry /electrolyte. It is therefore another object of the present invention to elaborate a supercapacitor-like electronic battery which takes full advantage of the optimized surface chemistry of the active material and which coupled the surface chemistry with a chosen electrolyte. The advantages of the present invention are to be used for battery, supercapacitors and/or pseudocapacitors applications, especially applications in which a substantial pulse of energy is required. SUMMARY
The present invention relates to a supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of non-carbon based nanosheets and at least one electrolyte. In one embodiment, the supercapacitor-like electronic battery comprises at least two electrodes, at least one active material comprising a plurality of nanoparticles, preferably nanosheets and at least one electrolyte, wherein the electrolyte matrix is not mixed with the active material comprising a plurality of nanoparticles.
The present invention also relates to a supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of nanoparticles and at least one electrolyte, wherein said supercapacitor-like electronic battery has a power density of at least 25W/kg and an energy density of at leastlWh/kg.
In one embodiment, the active material comprises at least 50% by weight of non-carbon based nanosheets. In one embodiment, said active material further comprises silicon or conductive polymer such as polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly (b- propiolactone), styrene butadiene rubber, carboxymethyl cellulose salt, sulfonated fluoropolymers, polyimide, poly(acrylic acid); or carbon-based material such as carbon black, graphene, carbon nanotube, boron nitride nanotube, boron nitride nanosheet, graphene oxide, reduced graphene oxide, or mixture thereof.
In one embodiment, said non-carbon based nanosheets are semiconductor.
In one embodiment, said non-carbon based nanosheets are inorganic semiconductor.
In one embodiment, said nanoparticles are nanocrystals, nanosheets, nanorods, nanoplatelets, nanoparticles, nanowires, nanopowders, nanotubes, nanotetrapods, nanoribbons, nanocubes, quantum dots and/or combinations thereof, preferably nanosheets. In one embodiment, said electrolyte is a liquid, a gel or a solid.
In one embodiment, bulk charging is achieved within said at least one active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nano sheets.
In one embodiment, said at least one active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets, has a thickness from 10 nanometers to 100 centimeters, preferably from 10 nanometers to 1 millimeter, more preferably from 100 nanometers to 100 micrometers.
The present invention also relates to a method for producing a supercapacitor-like electronic battery according to the present invention, the method comprising:
a) deposition of the first electrode onto a substrate or within a container, b) the preparation of one solution of nanoparticles,
b') a nanoparticle's ligand exchange step in solution,
c) deposition of the previous solution onto the first electrode,
c') if step b') is not implemented, nanoparticle's ligand exchange step on the active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets,
d) electrolyte deposition onto the active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets, or within the container and in contact with the active material comprising a plurality of nanoparticles, preferably a plurality of non-carbon based nanosheets,
e) deposition of the second electrode in contact with the electrolyte.
In one embodiment, the deposition of the active material comprising a plurality of nanoparticles preferably a plurality of non-carbon based nanosheets, is achieved by drop casting or spin coating, dip coating, spray casting, screen printing, inkjet printing, sputtering techniques, evaporation techniques, electrophoretic deposition, or vacuum methods.
The present invention also relates to a supercapacitor-like electronic battery obtainable by said process. The present invention also relates to a product comprising at least one supercapacitor- like electronic battery.
The present invention also relates to a cathode active material for a supercapacitor-like electronic battery comprising an anode and an electrolyte, wherein the active material comprises a plurality of non-carbon based nanosheets.
The present invention also relates to the use of the supercapacitor-like electronic battery in any systems or devices which require a substantial pulse of energy below 1 minute.
DEFINITIONS In the present invention, the following terms have the following meanings:
- "Double layer" refers to a structure which describes the variation of electric potential near an interface. If a material is in contact with an electrolyte, a single layer of negative or positive ions from the electrolyte will form in close proximity to the material and a second layer with a preponderance of respectively positive or negative ions will form proximate the aforementioned respectively negative or positive ions forming the so-called double layer.
- "Active material" refers to the material (usually a semiconductor) which carrier density and or electronic state will be tuned by the application of a bias over the electrodes. - "Charged in volume" refers to a process by which the capacity of the plurality of nanoparticles forming the active material increases linearly with the film thickness, even if the electrolyte matrix is limited at the interface of the top of the nanoparticles' film, and does not permeate into the film.
- "Film" refers to a single or multiple layers or coating of thin-or thick-material. In the present invention, a film is a porous or not, ordered or not, assembly of nanoparticles, which may be flat or rough.
- "Nanoparticle" refers to refers to a particle of any shape having at least one dimension in the 0.1 to 100 nanometers range. - "Nanoplatelet or nanosheet or nanoplate" refers to refers to a nanoparticle having one dimension in the 0.1 to 100 nanometers range.
DETAILED DESCRIPTION This invention relates to a supercapacitor-like electronic battery combining the high power density of current supercapacitors with the high energy density of current batteries.
Without willing to be bound by any theory, the general approach to describe the active material charging process through an electrolyte relies either on the formation of a double ionic layer at the interface between the electrolyte and the active material, or through redox processes at the surface of the active material. To achieve ions injection in the bulk of the active material, porous materials such as the nanoparticle films are good candidate to obtain a real bulk ions injection. Once the double electrostatic layer is formed ions from the electrolyte start to permeate in the semiconductor. This kind of process has been described in carbon porous system used as supercapacitor in On the molecular origin of supercapacitance in nanoporous carbon electrodes, Nature Materials 11, 306 (2012) by C. Merlet, B. Rotenberg, P. A. Madden, P.-L. Taberna, P. Simon, Y. Gogotsi, M. Salanne. Nevertheless in their case the capacitance enhancement occurs into the pore of the carbon electrodes which role is to dissociate the cations from the anions through a size selection process. In the present invention it is understood that the charging process of the bulk of the film by the ions occurs through a different mechanism: under a gate potential one kind of ions from the double layer start penetrating the active material (i.e. the nanoparticles film). Their counterions from the electrolyte remain in the electrolyte. In the active material (i.e. the nanoparticle film), the penetrating ions start filling the void between the nanoparticles, as seen in Figure IB. The electrical screening of these ions is ensured by the injection at the electrodes of charges into the nanoparticles themselves. With this process there is consequently no need to build a double layer around a nanoparticle in the active material, as seen in Figure 1A. The semiconductor remains electrically neutral, but the charging strongly affects the active material conductance which is increased by decades. This process also differs from the one existing in conventional battery where the ions can penetrate into the material at the atomic scale, as seen in Figure 1C. The nanostructured aspect of the film described in this invention is a key feature to achieve such a charging process.
Moreover it should be understood that this process, where one type only of ions is penetrating the nanoparticle film, strongly relies on the affinity of the ions for the nanoparticles surface chemistry. Indeed the authors noticed that a change of the surface chemistry may avoid the charging process. In this sense, without willing to be bound by any theory, the proposed mechanism can be seen as a new path to store energy, intermediate between the process involved in battery (energy is stored in chemical bonds) and double layer capacitor (energy is stored in a ionic double layer). In the described system the energy is still stored electrostatically but the chemical affinity of the ions for the nanoparticle surface is also involved.
The charging process is reminiscent of the redox processes that can take place at the surface of the active material, when an ion can reversibly give one or more electrons to the active material as in redox based reactions. Such redox process can take place when the right couple (ion/active material surface chemistry) is used. The ion can diffuse in the active material when it is porous, but can also be trapped in the active material when the active material is formed.
According to a first embodiment, the present invention provides a supercapacitor-like electronic battery which comprises at least a first and a second electrode, at least a first active material comprising a plurality of nanoparticles and at least one electrolyte.
In one embodiment, the at least one active material comprising a plurality of nanoparticles is implemented as a film of nanoparticles.
In one embodiment, the supercapacitor-like electronic battery of the present invention comprises at least two active materials comprising a plurality of nanoparticles.
In a preferred embodiment, the at least one active material comprises a plurality of non- nanoplatelets, preferably non-carbon based nanoplatelets, and may be implemented as a film of nanoplatelets. In one embodiment, the supercapacitor-like electronic battery is implemented within a container and/or on a substrate.
In one embodiment, the substrate or container may be formed from silicon, silicon dioxide, aluminum oxide, sapphire, germanium, gallium arsenide, an alloy of silicon and germanium, indium phosphide, indium tin oxide, fluorine doped tin oxide, graphene, glass and its derivative, plastic materials or any material that a person skilled in the art would find suitable.
In another embodiment, the substrate is made of a plastic substrate coated with a conducting material, such as indium tin oxide coating on polyethylene terephthalate. In another embodiment, the substrate or container may be form from ZnS, ZnSe InP, CdZnTe, ZnTe, GaSb, or mixture thereof.
In one embodiment, the substrate or container may comprise an oxide layer acting as an electronic insulator.
In one embodiment, the substrate or container may comprise several layers with an oxide layer on the top, such as for example a Si02 layer on a Si layer.
In one embodiment, the thickness of the oxide layer is from 10 nanometers to 100 micrometers, preferably from 30 nanometers to 1 micrometer, more preferably from 100 nanometers to 1 micrometer.
In one embodiment, the substrate or container may be rigid or non-rigid. According to a preferred embodiment, the substrate is rigid. According to another embodiment, the substrate is flexible and/or stretchable.
In one embodiment, the supercapacitor-like electronic battery does not comprise an actuating substrate configured to undergo reversible deformation during actuation.
In one embodiment, the supercapacitor-like electronic battery of the present invention comprises 2 electrodes. In one embodiment, the supercapacitor-like electronic battery of the present invention comprises 3 electrodes. In one embodiment, the supercapacitor- like electronic battery of the present invention comprises 4 electrodes.
In one embodiment, at least one of the electrodes is digitized. In one embodiment, at least a first and a second electrode are interdigitated. In one embodiment, at least one of the electrodes is in contact with the at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In a preferred embodiment, the cathode is in contact with the at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In one embodiment, at least the first and the second electrodes are in contact with a first and a second active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
In an embodiment wherein more than one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets, is implemented, the plurality of nanoparticles may comprise the same or various nanoparticles.
In one embodiment, at least one of the electrodes of the supercapacitor-like electronic battery of the present invention has a thickness from 10 nm to 1 m, preferably from 100 nm to 1 cm, preferably from lOOnm to 1 mm, more preferably from 100 nm to 1 μιη, even more preferably from 10 nm to lOOnm. In one embodiment, at least one of the electrodes is not transparent. In one embodiment, at least one of the electrodes is formed form transparent conducting layer made for example from transparent conducting oxides such as indium tin oxide, fluorine doped tin oxide, zinc oxide, doped zinc oxide.
In one embodiment, at least one of the electrodes of the supercapacitor-like electronic battery of the present invention comprises an electrochemically inert material such as for example gold, platinum, palladium, silver. In an embodiment, at least one of the electrodes is made up of a metallic collector. In an embodiment, the electrodes are made up of a metallic collector.
In one embodiment, at least one of the electrodes of the supercapacitor-like electronic battery of the present invention comprises any suitable conductive material such as for example gold, silver, copper, chromium, titanium, aluminum, lithium fluoride, silicon, magnesium, indium and conductive alloys.
In one embodiment, at least one of the electrodes of the supercapacitor-like electronic battery of the present invention is a doped semiconductor.
In one embodiment, at least one of the electrodes of the supercapacitor-like electronic battery comprises nanoparticles of the same nature as the nanoparticles of the at least first active material comprising a plurality of nanoparticles.
In one embodiment, at least one of the electrodes is a carbon based electrode, a graphite electrode, a graphene electrode, an electrode comprising carbon nanotube, an electrode comprising graphene oxide, an electrode comprising reduced graphene oxide, an electrode comprising carbon flurry or a metal electrode coated with carbon. In one embodiment, at least one of the electrodes is not a carbon based electrode.
In one embodiment, at least one of the electrodes is a metal foil or any material that has been metalized previously.
In one embodiment, the active material comprises a plurality of nanoparticles, preferably a plurality of nanosheets. In a preferred embodiment, the active material comprises a plurality of non-carbon based nanosheets.
In one embodiment, the active material comprises a plurality of various nanoparticles.
In one embodiment, the at least one active material comprising a plurality of nanoparticles comprises semiconductor particles. In one embodiment, the nanoparticles of the invention are inorganic. In one embodiment, the nanoparticles of the invention are colloidal. In one embodiment, the nanoparticles of the invention are crystalline.
In one embodiment, the at least one active material comprising a plurality of nanoparticles comprises oriented nanoparticles.
In one embodiment, the at least one active material does not comprise randomly arranged nanoparticles. In one embodiment, the at least one active material comprises randomly arranged nanoparticles.
In one embodiment, the at least one active material comprising a plurality of nanoparticles covers partially or totally the electrode.
In one embodiment, at least one of the electrodes covers partially or totally the at least one active material comprising a plurality of nanoparticles.
In one embodiment, the nanoparticles of the invention are 0D, ID, and 2D nanoparticles. In one embodiment, the nanoparticles of the invention are for example nanocrystals, nanosheets, nanorods, nanoplatelets, nanoplates, nanoprisms, nanowalls, nanodisks, nanoparticles, nanowires, nanopowders, nanotubes, nanotetrapods, nanoribbons, nanobelts, nanoneedles, nanowires, nanocubes, nanoballs, nanocoils, nanocones, nanopillers, nanoflowers, quantum dots or combination thereof. In one embodiment, the nanoparticles of the invention have the shape of a sphere, a cube, a tetrahedron, a rod, a wire, a platelet, a tube, a cube, a ribbon or mixture thereof.
One of the drawbacks of the 0D nanoparticle is their very sparse density of state only made of dirac comb which can typically include 2 electrons per state. On the other hand 2D systems are much more promising due to their larger density of state. They are consequently better candidate than the 0D, ID system to sustain large density charging. It is one aim of the present invention to provide a large density of state and a large porosity. In one embodiment, the nanoparticles of the invention are nanosheets and the plurality of nanosheets presents an optimum porosity with efficient trade-off between the porosity and the charge density. In this embodiment, the active material comprising a plurality of nanosheets comprises pores size inferior to 100 nm, or inferior to 50 nm, or inferior to 10 nm, or inferior to 5 nm, or inferior to lnm, or inferior to 0.5 nm, or mixture thereof.
In one embodiment, said nanoparticles are used in the manufacture of a film of nanoparticles. In one embodiment, said nanoparticles are used in the manufacture of a colloidal quantum dot film. In one embodiment, said nanoparticles are used in the manufacture of a colloidal nanoplatelets film.
In one embodiment, the film of nanoparticles is obtained from colloidal nanoparticles. In one embodiment, the film of nanoplatelets is obtained from colloidal nanoplatelets.
In one embodiment, said nanoparticles are used in the manufacture of a quantum dot solid.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise a semi-conductor from group IV, group IIIA-VA, group IIA-VIA, group IIIA- VIA, group IA-IIIA-VIA, group IIA-VA, group IVA-VIA, group VIB-VIA, group VB- VIA, or group IVB-VIA. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise a material MxEy, wherein:
M is Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
E is O, S, Se, Te, N, P, As or a mixture thereof; and
x and y are independently a decimal number from 0 to 5, at the condition that when x is 0, y is not 0 and inversely.
In one embodiment, the material MxEy comprises cationic elements M and anionic elements E in stoichiometric ratio, said stoichiometric ratio being characterized by values of x and y corresponding to absolute values of mean oxidation number of elements E and M respectively.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprises a material MxNyEz, wherein:
M is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
N is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
E is selected from O, S, Se, Te, N, P, As or a mixture thereof; and
x, y and z are independently a decimal number from 0 to 5, at the condition that when x is 0, y and z are not 0, when y is 0, x and z are not 0 and when z is 0, x and y are not 0.
According to one embodiment, the nanoparticles, preferably nanoplatelets, of the invention are made of a quaternary compound such as InAlGaAs, ZnAglnSe or GalnAsSb. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise a material from Si, Ge, Sn, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, CuInS2, CuInSe2, AgInS2, AgInSe2, CuS, Cu2S, Ag2S, Ag2Se, Ag2Te, InN, InP, InAs, InSb, In2S3, Cd3P2, Zn3P2, Cd3As2, Zn3As2, ZnO, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, FeS2, Ti02, Bi2S3, Bi2Se3, Bi2Te3, MoS2, WS2, V02,and alloys and mixtures thereof.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise oxygen atoms. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise sulfur atoms. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise atoms of the column VI.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention are made of the following material: Si, SiC, Si02, SiS2, Si2Te , Ge, Ge02 or GeS2. In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise lithium or sodium based material.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise a material from LiCo02, LiMn204, LiFeP04, V205, LiT02, LiNiV04, Ti02, Mn02, TiS2, MnS2, Mo02, MoS2, LiNiCoMn02, CuGe03, LiCoP04, Li4Ti5012, CoSb, Mn0.75Nio.25C03, LiNio.33Mn0. Co0.3302, Li.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprise LixNi1_yMy02+a wherein M is one or more selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr, 0.9<x<l.l, 0<y<0.7, and 0.05<a<0.2.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention present a heterostructure, which means that the nanoparticles of the invention are partially coated by at least one layer of inorganic material.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention present a core/shell structure, i.e. the nanoparticles comprise a core and a shell of semiconducting material.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the invention have a core/shell structure, i.e. the core is totally coated by at least one layer of inorganic material.
In another embodiment, the nanoparticles, preferably nanoplatelets, of the invention comprises a core totally coated by a first layer of inorganic material, said first layer being partially or totally surrounded by at least one further layer of inorganic material.
In one embodiment, the core and the at least one layer of inorganic material are composed of the same material or are composed of different material.
In one embodiment, the core and the at least one layer of inorganic material may be a semi-conductor from group IV, group IIIA-VA, group IIA-VIA, group IDA- VIA, group IA-IIIA-VIA, group IIA-VA, group IVA-VIA, group VIB-VIA, group VB-VIA, or group IVB-VIA.
In another embodiment, the core and the at least one layer of inorganic material may comprise a material MxEy, wherein:
M is Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
E is O, S, Se, Te, N, P, As or a mixture thereof; and
x and y are independently a decimal number from 0 to 5, at the condition that when x is 0, y is not 0 and inversely. In one embodiment, the core and the at least one layer of inorganic material comprise a material MxNyEz, wherein:
M is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
N is selected from Zn, Cd, Hg, Cu, Ag, Al, Ga, In, Si, Sn, Ge, Pb, Sb, Sn, Pd, Fe, Au, Ti, Bi, W, Mo, V or a mixture thereof;
E is selected from O, S, Se, Te, N, P, As or a mixture thereof; and
x, y and z are independently a decimal number from 0 to 5, at the condition that when x is 0, y and z are not 0, when y is 0, x and z are not 0 and when z is 0, x and y are not 0.
In one embodiment the core and the at least one layer of inorganic material are made of a quaternary compound such as InAlGaAs, ZnAglnSe or GalnAsSb.
In another embodiment, the core and the at least one layer of inorganic material may be composed of a material from Si, Ge, Sn, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, CuInS2, CuInSe2, AgInS2, AgInSe2, CuS, Cu2S, Ag2S, Ag2Se, Ag2Te, InN, InP, InAs, InSb, In2S3, Cd3P2, Zn3P2, Cd3As2, Zn3As2, ZnO, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, FeS2, Ti02, Bi2S3, Bi2Se3, Bi2Te3, MoS2, WS2, V02,and alloys and mixtures thereof.
In one embodiment, the nanoparticles, preferably nanoplatelets, of the present invention comprise metallic materials such as gold, silver, copper, aluminum, iron, platinum, lead, or palladium. In another embodiment, the nanoparticles, preferably nanoplatelets, of the present invention present a heterostructure comprising metallic materials and semiconductor materials.
In an embodiment of the invention, the nanoparticle, preferably nanoplatelets, of the invention may be further surrounded by a "coat" of an organic capping agent. The organic capping agent may be any number of materials, but has an affinity for the semiconductor surface. In general, the capping agent can be an isolated organic molecule, a polymer (or a monomer for a polymerization reaction).
In one embodiment, organic capping agents are selected from trioctylphosphine oxide, organic thiols, amines, phosphines, carboxylic acids, phosphonic acids, sulfonic acids, trialkoxysilanes, alkyl and aryl halides; and mixtures thereof.
In another embodiment of the invention, the nanoparticle, preferably nanoplatelets, of the invention may be further surrounded by a "coat" of an inorganic capping agent. In one embodiment, the inorganic capping agent comprises an inorganic complex, an extended crystalline structure, metals selected from transition metals, lanthanides, actinides, main group metals, metalloids, and mixture thereof.
In one embodiment, the inorganic capping agent comprises ionic salts.
In another embodiment, the nanoparticles, preferably nanoplatelets, of the invention may be surrounded by a mixture of inorganic and organic capping agent. Preferably, the nanoparticles, preferably nanoplatelets, of the invention for use in a supercapacitor-like electronic battery are selected in the group comprising: CdSe, CdTe, CdS, and the core/shell structures such as CdSe/CdS, CdSe/CdZnS, CdTe/CdS/CdZnS, CdS/ZnS, HgTe, PbS, PbS/CdS, PbSe, PbSe/CdS, PbTe.
In one embodiment, the nanoparticles are not selected from PbS. In one embodiment, the nanoparticles are not selected from carbon based nanoparticles such as carbon nanowires, carbon nanotubes (multi-walled or single- walled), graphene or combination thereof. In one embodiment, the nanoparticles are not selected from silicon nanoparticles such as silicon quantum dots or silicon nanowires.
In one embodiment, the nanoparticles are not selected from silver nanowire mesh.
In one embodiment, the nanoparticles are not selected from metal oxide such as titanium dioxide.
In one embodiment, the nanoparticles are not selected from lithium based nanoparticles such as LiMn204 nanorods or Li4Tis012 nanopowder.
In one embodiment, the nanoparticles are not selected from materials that can undergo an intercalation/de-intercalation reaction with lithium ions. In one embodiment, the nanoparticles are not selected from perovskite nanoparticles.
In one embodiment, the nanoparticles are not obtained by exfoliation of the corresponding layered bulk crystals. In one embodiment the nanoparticle are obtained by exfoliation.
In one embodiment the nanoparticles are not obtained by chemical vapor deposition. In one embodiment the nanoparticles are obtained by chemical vapor deposition.
In one embodiment the nanoparticles are not obtained by molecular beam epitaxy. In one embodiment the nanoparticles are obtained by molecular beam epitaxy.
In one embodiment the nanoparticles are not obtained by solvothermal method. In one embodiment the nanoparticles are obtained by solvothermal method. In one embodiment the nanoparticles are not metal dichalcogenures such as MoS2, WS2, MoSe2, MoTe2, WSe2, WTe2. In one embodiment the nanoparticles are metal dichalcogenures such as MoS2, WS2, MoSe2, MoTe2, WSe2, WTe2.
In one embodiment the nanoparticles contain Li atoms. In one embodiment the nanoparticles do not contains Li atoms. In one embodiment, the nanoparticles of the present invention have at least one dimension having a size of about 0.3 nm to less than 1 μιη, about 0.5 nm to about 700 nm, about 1 nm to about 500 nm, about 1.5 nm to about 200 nm, about 2 nm to about 100 nm. In one embodiment, the nanoparticles are thicker than 3, 4, 5, 6, 7, 8, 9, 10, 15 lattice parameters.
In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 100 centimeters. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 1 centimeter. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, of the present invention has a thickness from 10 nanometers to 100 micrometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 10 micrometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 1 micrometer. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 900 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 800 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 700 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 600 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 500 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 400 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 300 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 200 nanometers. In one embodiment, the at least one active material comprising a plurality of nanoparticles, preferably nanosheets, has a thickness from 10 nanometers to 100 nanometers.
In one embodiment, the nanosheets of the present invention have a thickness of about 0.3 nm to about 10 mm, about 0.3 nm to about 1 mm, about 0.3 nm to about 100 μιη nm, about 0.3 nm to about 10 μιη, about 0.3 nm to about 1 μιη, about 0.3 nm to about 500 nm, about 0.3 nm to about 250 nm, about 0.3 nm to about 150 nm, about 0.3 nm to about 100 nm, about 0.3 nm to about 50 nm, about 0.3 nm to about 25 nm, about 0.3 nm to about 20 nm, about 0.3 nm to about 15 nm, about 0.3 nm to about 10 nm, about 0.3 nm to about 5 nm.
In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 1.5 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 2 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 3 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 10 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 25 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 50 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 100 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 1000 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 104 times its thickness. In one embodiment, the nanosheets of the present invention have a lateral dimensions (length and/or width) of at least 105 times its thickness. In another embodiment, the lateral dimensions of the nanosheets are at least 2, 2.5, 3, 3.5, 4, 4.5, 5 times larger than its thickness.
In another embodiment of the invention, the lateral dimensions of the nanosheets are at least 2, 2.5, 3, 3.5, 4.5, 5 times larger than the thickness. In one embodiment, the lateral dimensions of the nanosheets are from at least 0.45 nm to at least 50 mm.
In one embodiment, the lateral dimensions of the nanosheets are from at least 2 nm to less than 1 m, from 2 nm to 100 mm, from 2 nm to 10 mm, from 2 nm to 1 mm, from 2 nm to 100 μηηι, from 2 nm to 10 μηηι, from 2 nm to 1 μηηι, from 2 nm to 100 nm, from 2 nm to 10 nm.
In one embodiment, the nanosheet comprised in the nanoparticle of the invention has a quasi-2D structure.
In one embodiment, the at least two pluralities of nanoparticles comprise the same nanoparticles. In one embodiment, the at least two pluralities of nanoparticles comprise different nanoparticles.
In one embodiment, the nanoparticles are coupled to a high mobility material.
In one embodiment, the nanoparticles is mixed or blended with a high mobility material.
In one embodiment, the active material comprises at least 50% by weight of nanoparticles, preferably at least 70% by weight, more preferably at least 80 % by weight, even more preferably at least 90% by weight.
In one embodiment, the active material comprises at least 50% by weight of nanoplatelets, preferably at least 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% by weight.
In one embodiment, the active material comprises nanoparticles, preferably nanoplatelets, mixed with an additive. In one embodiment, said additive is a polymer, preferably an electrochemically active polymer. In one embodiment the additive is a carbon-based material such as carbon black, graphene, carbon nanotube, boron nitride nanotube, boron nitride nanosheet, graphene oxide, reduced graphene oxide.
In one embodiment, the additive is selected from fluorinated polymers (e.g. polyvinylidene fluoride (PVdF)), polypyrrole, polythiaphene, polyethylene oxide, polypropylene oxide, polyacrylonitrile, poly(ethylene succinate), poly (b- propiolactone), styrene butadiene rubber (SBR), carboxymethyl cellulose salt (CMC), sulfonated fluoropolymers, polyimide, poly(acrylic acid), polysiloxanes, polyimides, polyphosphazenes, polyethers, sulfonated polyimides, perfluorinated polymers, polydivinyl polyethylene glycols, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, polyarylsulfones, mixtures and derivatives of said polymers, and copolymers that include repeating units of said polymers.
In one embodiment, the additive is selected from a metal orthophosphate, a metal metaphosphate, a metal polyphosphate, fluorophosphates, a metal polyfluorophosphate, a metal carbonate, a metal borate, a metal polyborate, a metal fluoroborate, a metal polyfluoroborate, a metal sulfate, a metal fluorosulfate, an oxide compound, a fluoroxide compound, an electrically conducting oxide (e.g. fluorine doped tin oxide Sn02:F or indium tin oxide ΓΓΟ), a titanate, a metal aluminate, a metal fluoroaluminate, a metal silicate, a metal fluorosilicate, a metal borosilicate, a metal fluoroborosilicate, a metal phosphosilicate, fluorophosphosilicate, a metal borophosphosilicate, a metal fluoroborophosphosilicate, a metal aluminosilicate, a metal fluoroaluminosilicate, a metal aluminophosphosilicate, a metal fluoroaluminophosphosilicate or a mixture thereof.
In one embodiment, the additive is selected from a lithium, sodium, potassium, ammonium, calcium, magnesium or aluminum phosphate or a mixture thereof. In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium or magnesium carbonate or a mixture thereof. In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium, magnesium or aluminum borate, polyborate, fluoroborate or polyfluoroborate or a mixture thereof.
In one embodiment, the additive is selected from a lithium, sodium, potassium calcium, magnesium or aluminum sulfate or fluorosulfate (e.g. Li2S04, Na2S04, K2S04, CaS04, MgS04, A12(S04)3) or a mixture thereof.
In one embodiment, the additive is selected from a lithium, sodium, potassium, boron, calcium, magnesium, aluminum, silicon, tin, titanium or zirconium oxide or fluoroxide (e.g. A1203, B203, CaO, K20, Li20, MgO, Na20, Si02, Sn02, SnOyFz, Ti02, Zr02) or a mixture thereof.
In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium or magnesium aluminate or fluoroaluminate, or mixture thereof.
In one embodiment, the additive is selected from a lithium, sodium, potassium, calcium or, magnesium silicate, borosilicate, fluorosilicate, fluoroborosilicate, phosphosilicate, fluorophosphosilicate, borophosphosilicate, fluoroborophosphosilicate, aluminosilicate, fluoroaluminosilicate, aluminophosphosilicate or fluoroaluminophosphosilicate, or mixture thereof.
In one embodiment, the additive is selected from transition metal oxide, transition metal fluoroxide, transition metal phosphate or transition metal fluorophosphates or mixture thereof.
In one embodiment, the at least one electrolyte has at least one common interface with each of the at least two active materials comprising a plurality of nanoparticles.
In one embodiment, the at least one electrolyte has at least one common interface with the at least one active material comprising a plurality of nanoparticles. In one embodiment, the matrix of the electrolyte is not mixed with the at least one active material comprising a plurality of nanoparticles. In one embodiment, the matrix of the electrolyte is not mixed with the pluralities of nanoparticles forming any active material.
In one embodiment, the matrix of the electrolyte is not mixed with the film of nanoparticles.
In one embodiment, the matrix of the electrolyte remains outside of the active material. In one embodiment, ions from the matrix of the electrolyte percolate through the active material (i.e. though the void of the film of nanoparticles) while the matrix remains outside, in contact with the active material.
In one embodiment, the active material is not saturated by the electrolyte.
In one embodiment, the at least one electrolyte has a thickness from 10 nanometers to 1 centimeter, preferably from 500 nanometers to 2 millimeters, more preferably from 1 micrometer to 10 micrometers.
In one embodiment, solid, polymer, gel, ion-gel or liquid electrolytes may be implemented, preferably a gel or solid electrolyte.
In one embodiment, contact between the at least one electrolyte and the first or second electrodes is prevented by the active material comprising a plurality of nanoparticles.
In one embodiment, contact between the at least one electrolyte and the first and second electrodes is prevented by the active material comprising a plurality of nanoparticles.
In another embodiment, the supercapacitor-like electronic battery comprises at least two different electrolytes, each of them having one common interface with the at least two active materials comprising a plurality of nanoparticles.
In another embodiment, the supercapacitor-like electronic battery comprises at least two different electrolytes, one of them having a common interface with the at least one active material comprising a plurality of nanoparticles.
In an embodiment, the at least one electrolyte can be in the form of an aqueous solution of a dissolved ionic chemical compound (or compounds), a non-aqueous solution of a dissolved ionic chemical compound (or compounds), a polymer electrolyte, a gel electrolyte, a solid electrolyte or a molten salt electrolyte.
In an embodiment, the at least one electrolyte can be a non-aqueous organic solvent comprising carbonate-based solvent such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like; or ester-based solvent such as methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate, and the like; or mixture thereof. In one embodiment, the at least one electrolyte comprises a matrix and ions.
In one embodiment, the at least one electrolyte comprises a polymer matrix.
In one embodiment, the polymer matrix of the electrolyte comprises polystyrene, poly(N-isopropyl acrylamide), polyethylene glycol, polyethylene, polybutadiene, polyisoprene, polyethylene oxide, polyethyleneimine, polymethylmethacrylate, polyethylacrylate, polyvinylpyrrolidone, polypropylene glycol, polydimethylsiloxane, polyisobutylene, or a blend/multiblocks polymer thereof.
In one embodiment, the at least one electrolyte comprises ions salts.
In one embodiment, the polymer matrix is doped with ions salts.
In one embodiment, the ions salts is LiCl, LiBr, Lil, LiSCN, LiC104, KC104, NaC104, ZnCl3 ~, ZnCl4 2", ZnBr2, LiCF3S03, NaCl, Nal, NaBr, NaSCN, Na2S04, KC1, KBr, KI, KSCN, LIN(CF3S02)2, LiPF6, LiAsF6, LiN(S02CF3)2, LiC(S02CF3)2, LiBF , NaBPh4, LiAsF6, C2BF2Li04, LiH2P04, LiGaCl4 or mixture thereof.
In one embodiment, the at least one electrolyte comprises material that contains mobile ions of lithium, sodium, potassium, hydrogen, copper, silver or mixture thereof. In one embodiment, the at least one electrolyte comprises polymers and glasses, including but not limited to PEG, PEO, PVDF, PET, PTFE, FEP, FPA, PVC, polyurethane, polyester, polyglycol, silicone, some epoxies, polypropylene, polyimide, polycarbonate, polyphenylene oxide, polysulfone, calcium magnesium aluminosilicate glasses, E-glass, alumino-borosilicate glass, D-glass, borosilicate glass, silicon dioxide, quartz, fused quartz, silicon nitride, silicon oxynitride, or mixture thereof. In one embodiment, the at least one electrolyte comprises a carbonate-based, alcohol- based, ester-based, ether-based, ketone -based, or aprotic solvent.
In one embodiment, the at least one electrolyte comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, butylene carbonate, methyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethylpropionate and the mixture of thereof.
In one embodiment, the at least one electrolyte comprises ionic liquid.
In one embodiment, the polymer matrix and the ions are replaced by a polymerizable ionic liquid. In one embodiment, the electrolyte is thick enough to act as a separator.
In one embodiment, the nanoparticle surface chemistry is chosen to be a counterion of one of the ions of the electrolyte.
In one embodiment, the nanoparticle surface chemistry is chosen so that the nanoparticles and the electrolyte can form a redox reaction. In one embodiment, at least one ion from the electrolyte can reversibly give one or more electron(s) to the active material as in redox based reactions.
Examples of pairs of nanoparticle surface chemistry/ion include but is not limited to: OH7Li+, OH7Na+, OH7K+, OH 7NH4 +, OH /any ammonium ion, OH /any ionic liquid, 027Li+, O 27Na+, O 27K+, O 27NH4 +, O 27any ammonium ion, O 27any ionic liquid, HS" /Li+, HS7Na+, HS7K+, HS7NH4 +, HSVany ammonium ion, HSVany ionic liquid, SCN /Li+, SCN7Na+, SCN7K+, SCN7NH4 +, SCNVany ammonium ion, SCNVany ionic liquid, NH27Li+, NH27Na+, NH27K+, NH27NH4 +, NH27any ammonium ion, NH27any ionic liquid, S27Li+, S27Na+, S27K+, S27NH4 +, S27any ammonium ion, S27any ionic liquid, Se27Li+, Se27Na+, Se27K+, Se27NH4 +, Se27any ammonium ion, Se2 /any ionic liquid, Te27Li+, Te27Na+, Te27K+, Te27NH4 +, Te27any ammonium ion, Te27any ionic liquid, C17Li+, C17Na+, C17K+, C17NH4 +, C17any ammonium ion, C17any ionic liquid, Br7Li+, Br 7Na+, Br 7K+, Br 7NH4 +, Br /any ammonium ion, Br /any ionic liquid, T/Li+, 17Na+, 17K+, 17NH4 +, I /any ammonium ion, I /any ionic liquid, Any metal-chalcogenide/ Li+, Any metal-chalcogenide /Na+, Any metal-chalcogenide /K+, Any metal-chalcogenide /NH4 +, Any metal-chalcogenide /any ammonium ion, Any metal-chalcogenide /any ionic liquid, Cd2+/Cl", Cd2+/Br", Cd2+/I~, Cd2+/S042", Cd2+/C104 ", Cd2+/BF4 ", Cd2+/N03 ~, Cd2+/ any ionic liquid, Pb2+/Cl", Pb2+/Br", Pb2+/T, Pb2+/S042", Pb2+/C104 ", Pb2+/BF4 ", Pb2+/N03 ", Pb2+/ any ionic liquid, Zn2+/Cl", Zn2+/Br", Zn2+/I", Zn2+/S042", Zn2+/C104 ", Zn2+/BF4 ", Zn2+/N03 ", Zn2+/ any ionic liquid, Hg2+/Cl", Hg 2+/Br", Hg 2+/I", Hg 2+/S042", Hg 2+/C104 ", Hg 2+/BF4 ", Hg2+/N03 ", Hg2+/ any ionic liquid, NH3 +/C1", NH +/Br", NH3 +/I", NH3 +/S042", NH3 +/C104 ", NH3 +/BF4 ", NH3 +/N03 ", NH3 +/ any ionic liquid.
In one embodiment, the ligand for the nanop article's ligand exchange step is S
In one embodiment, the pairs of nanoparticle surface chemistry/ion comprise S 2- 7Li + , S 2-" /Na+, S27K+, S27NH4 +, S27any ammonium ion, S /any ionic liquid.
In one embodiment, the supercapacitor-like electronic battery comprises a separator, which partitions the at least one electrolyte in two.
In one embodiment, the supercapacitor-like electronic battery comprises a separator between the at least two electrolytes.
The separator partitions the two electrodes, and the electrolyte, while allowing the passage of ions through the separator. The separator provides electronic insulation between the electrode of opposite polarization and support the ionic conduction.
In one embodiment, the separator is made from polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly ([beta]-propiolactone), and sulfonated fluoropolymers, as well as others known in the art.
In another embodiment, the separator may be an electrolyte as defined in the present invention. In an embodiment, the separator may be composed of paper, glass fiber, ceramic, polymer or mixture thereof.
In one embodiment, the supercapacitor-like electronic battery of the present invention presents at least one current collector connected to one electrode.
In one embodiment, the supercapacitor-like electronic battery of the invention presents at least two current collectors connected to the at least two electrodes.
In one embodiment, the gate capacitance per unit of surface of active material is higher than that expected to be formed at the electrolyte channel interface of standard ionic c L = £ r£
double layer: 0 ; wherein £ is the vacuum permittivity, £r is the electrolyte aDL
dielectric constant and aDL is the width of the double layer. In one embodiment, the supercapacitor-like electronic battery of the present invention presents good cycling properties between 1 to 1 million cycles, preferably between 10 to 106 cycles, more preferably between 102 to 105 cycles.
In one embodiment, the supercapacitor-like electronic battery has a gate capacitance per unit of surface of active material ranging from 1 to 10 5 ^¥.c -2 , preferably from 10 to 50 000 μΡ.αη 2, more preferably from 20 to 15 000 μΡ.αη 2.
In one embodiment, the supercapacitor-like electronic battery has a gate capacitance per mass unit ranging from 10 -"3 to 103 Fg-"1 , preferably from 1 to 100 Fg -"1.
In one embodiment, the supercapacitor-like electronic battery of the present invention has an energy density ranging from O.lWh/Kg to lOOOWh/kg, preferably from lWh/kg to 500Wh/kg, more preferably from lOWh/kg to lOOWh/kg, even more preferably from lOWh/kg to 500Wh/kg.
In one embodiment, the supercapacitor-like electronic battery of the present invention has an energy density of at least O. lWh/kg, or at least IWh/kg, or at least lOWh/kg, or at least lOOWh/kg, or at least 200Wh/kg, or at least 300Wh/kg, or at least 400Wh/kg, or at least 500Wh/kg, or at least 600Wh/kg, or at least 700Wh/kg, or at least 800Wh/kg, or at least 900Wh/kg, or at least lOOOWh/kg, or at least 5000Wh/kg, or at least lOkWh/kg.
In one embodiment, the supercapacitor-like electronic battery of the present invention has a power density ranging from 1 to 106 W/Kg, preferably from 1 to 5xl05 W/Kg, more preferably from 25 to 105W/Kg, even more preferably from 100 to 104W/Kg.
In one embodiment, the supercapacitor-like electronic battery of the present invention has a power density of at least IW/kg, or at least 25 W/Kg, or at least 100 W/Kg, or at least 103 W/Kg, or at least 104 W/Kg, or at least 5xl04 W/Kg, or at least 105 W/Kg, or at least 5xl05 W/Kg, or at least 106 W/Kg, or at least 107 W/Kg.
16 21 -3 18 20 -3
The pore density is in the 101U to 10"1 cm" range, preferably in 10 to 10 cm" range.
12 -2 15 -2
The density of state of the 2D system is from 10 eVcm" to 10 eVcm" ' preferably from 5xl012eVcm"2 to 4xl014 eVcm"2.
In one embodiment, at least one dimension of the nanoparticles, preferably the nanosheets, is of the same order of magnitude as the Bohr radius (aB) of the material, meaning that at least one dimension of the nanoparticles is ranging from 0.1aB and 10 aB.
In one embodiment, the specific surface of the nanoparticles of the active material is
2 -1 2 -1
higher than 10 m g" , preferably higher than 20 m g" , and even more preferably above 100 m2g In one embodiment, ions from the at least one electrolyte migrate at the interface between the at least one electrolyte and at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets. In one embodiment, ions from the at least one electrolyte migrate within at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
In one embodiment, counterions from the at least one electrolyte remain within the electrolyte.
In on embodiment, bulk doping or bulk charging is achieved within at least one active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets.
In on embodiment, bulk doping or bulk charging is achieved within at least one film of nanoparticles, preferably nanoplatelets. In one embodiment, charges are injected in the active material comprising a plurality of nanoparticles, preferably a plurality of nanoplatelets; the introduction of the ions induces indeed a charging of the quantum states of the nanoparticles.
In one embodiment, the continuity of at least one active material comprising a plurality of nanoparticle, preferably a plurality of nanoplatelets, prevents direct contact between the at least one electrolyte and the first and/or second electrodes therefore preventing leakage through the dielectric.
It should be understood that the spatial descriptions (e.g., "above", "below", "up", "down", "top", "bottom", "on", "under", etc.) made herein are for purposes of illustration only, and that devices of the present invention can be spatially arranged in any orientation or manner.
In the following descriptions of the method for producing a supercapacitor-like electronic battery, nanoparticles refer preferably to non-carbon based nanosheets.
In one embodiment, the manufacturing process for preparing the supercapacitor-like electronic battery of the present invention comprises three main steps:
- Electrodes fabrication,
Deposition of the nanoparticles and nanoparticle' s ligand exchange after or before deposition on a first electrode, Electrolyte deposition,
Deposition of the second electrode.
More precisely, the method for producing a supercapacitor-like electronic battery comprises:
a) the deposition of the first electrode onto a substrate or within a container, b) the preparation of one solution of nanoparticles,
b') a nanoparticle' s ligand exchange step in solution,
c) deposition of the previous solution of nanoparticles, which will form the active material onto the first electrode,
c') if step b') is not implemented, nanoparticle' s ligand exchange step on the active material comprising a plurality of nanoparticles,
d) the electrolyte deposition on the active material comprising a plurality of nanoparticles; or within the container and in contact with the active material comprising a plurality of nanoparticles,
e) deposition of the second electrode in contact with the electrolyte.
In one embodiment, a second solution of nanoparticles may be deposited between the electrolyte and the second electrode, said solution of nanoparticle being the same or different from the solution of step b).
In one embodiment wherein additives are implemented within the active material, step b) reads as the preparation of one solution of nanoparticles mixed with additives.
In one embodiment, the at least first and second electrodes are fabricated using a lift-off procedure.
In one embodiment, the at least first and second electrodes may be deposited using conventional deposition techniques, including for example, drop casting, inkjet printing, screen printing, gravure printing, flexographic printing or any other means that a person skilled in the art would find appropriate.
In another embodiment, the at least first and second electrodes are onto the substrate or within the container. In one embodiment, the nanoparticles of the invention are dispersed in a solvent, such as for example a mixture of hexane and octane with a volume ratio of 9: 1, in order to obtain the solution of nanoparticles. In one embodiment, the solution of nanoparticles of step b) is partially deposited during step c) onto a substrate. In one embodiment, the solution of nanoparticles of step b) is deposited during step c) onto a substrate and on at least one electrode.
In one embodiment, the solution of nanoparticles deposited during step c) comprises various nanoparticles.
In another embodiment, the steps b), b'), c), c') may implemented more than once with various nanoparticles.
According to one embodiment, the electrodes are processed with a gas treatment before step c).
According to one embodiment, the electrodes are treated with molecules such as short- chain alkane thiols to improve the adhesion of the nanoparticles before step c). According to one embodiment, the electrodes are treated with a coating for passivating the surface of the at least two electrodes before step c).
According to an embodiment, the electrodes are annealed before step c) at a temperature ranging from 100°C to 1000°C.
In one embodiment, the deposition of nanoparticles is achieved during step c) by sputtering techniques, evaporation techniques, electrophoretic deposition, vacuum methods, lithography process, spray pyrolysis, hot and cold plasma, inert gas phase condensation techniques or any other means that a person skilled in the art would find suitable.
In one embodiment, the deposition of nanoparticles is achieved during step c) by drop casting, spin coating, dip coating, spray coating, screen printing, inkjet printing or any other means that a person skilled in the art would find appropriate. In one embodiment, the nanoparticles prepared in solution at step b) presents wide or narrow band gap.
In an embodiment, for narrow band gap material, nanoparticle's ligand exchange is performed in the active material comprising a plurality of nanoparticles after deposition or on the nanoparticles in solution prior to the deposition, preferably in the active material comprising a plurality of nanoparticles after deposition.
In an embodiment, for wide band gap material nanoparticle's ligand exchange is performed in the active material comprising a plurality of nanoparticles after deposition or on the nanoparticles in solution prior to the deposition, preferably on the nanoparticles in solution prior to the deposition.
In one embodiment, nanoparticle's ligand exchange is performed on the active material comprising a plurality of nanoparticles during step c'), for example by dipping the nanoparticles in a solution.
In one embodiment, the nanoparticle's ligand exchange is performed directly in solution prior to the deposition of nanoparticles as in step b').
In one embodiment, the component in progress is annealed before step d) at low temperature, typically below 400°C, or below 300°C or below 200°C, or below 100°C.
In one embodiment, during step d) the electrolyte is brushed on the active material comprising a plurality of nanoparticles. In one embodiment, the electrolyte is deposited using any printing methods that a person skilled in the art would find suitable, such as for example spin coating or dip coating, or drop casting.
In one embodiment, the electrolyte is onto the active material comprising a plurality of nanoparticles; or within the container and in contact with the active material comprising a plurality of nanoparticles. In one embodiment, the electrolyte is prepared by dissolving an ion salt and a polymer matrix in a polar solvent. In one embodiment, the electrolyte is prepared by melting ion salt in the polymer matrix at moderate temperature, typically 150°C.
In one embodiment, the second electrode is deposited by any methods that a person skilled in the art would find suitable.
In another embodiment, the step d) is performed after the deposition of the second electrode (step e)).
Due to their properties as mentioned here above, the supercapacitor-like electronic battery of the invention are particularly useful as power source. In one embodiment, the supercapacitor-like electronic battery is operated between - 50°C and 100°C, preferably between -20°C and 80°C, more preferably between 0°C and 60°C.
In one embodiment, at least two supercapacitor-like electronic battery of the present invention are associated together. In one embodiment, the invention can find applications as power source for many household and industrial applications.
In one embodiment, the invention can find applications as starter for bringing fast power for vehicles or engines at start.
In one embodiment, the invention can find applications in renewable energy production. In one embodiment, the invention can find applications in aerospace systems.
In one embodiment, the invention can find application in elevators, pallet trucks or any applications in the electric transportation domain (cars, trucks, trams, trains, buses...).
In another embodiment, the present invention may be used for applications in electrical wireless device, in eolian applications, in energy regulation devices, in the military domain or in the health area, etc. In one embodiment, the present invention can find application in any systems or devices which require a substantial pulse of energy having duration below 1 minute, preferably below 30 seconds, more preferably below 10 seconds.
In one embodiment, the present invention can find application in any device which required high power application.
In another embodiment, the present invention can find application in any device which required low power application but where the batteries are at the origin of maintenance problems or of insufficient lifetime performance.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1A illustrates a nanoparticle surface charged through (A) a ionic layer process, (B) through the proposed mechanism of the invention, (C) through direct injection of the ions into the material at the atomic scale.
Figure IB illustrates the three different regimes of operation of the nanoparticle based supercapacitor: a) on left the ion injection regime (low frequency regime), b) on middle the double electrostatic layer (intermediate frequency regime) and c) on right the high frequency mode where the electrolyte is used as a dielectric.
Figure 2 is a sectional view of a supercapacitor-like electronic battery according to one embodiment of the present invention. Figure 3 is a sectional view of a supercapacitor-like electronic battery according to another embodiment of the present invention.
Figure 4 is a sectional view of a supercapacitor-like electronic battery according to one embodiment of the present invention.
Figure 5 shows the plot of power against energy density also called a Ragone plot for different technology of energy storage device, the current invention has an operation range highlighted with some dashed lines. Adapted from Nano Lett., 12, 1857 (2012). Figure 6 shows the evolution of the gate capacitance per unit area of a film of nanoparticles (NPL=2D nanoplatelets and QD: 0D quantum dot) as a function of its thickness.
Figure 7 illustrates the cycling properties of the supercapacitor-like electronic battery of the present invention.
Figure 8 illustrates the difference of charge which can be injected in a film of CdSe/CdS nanoplatelets depending of the used surface chemistry.
EXAMPLES The present invention is further illustrated by the following examples.
1. Nanoparticles synthesis PbS spherical quantum dots ( QD )
In a three-neck flask, we introduce 0.9g lead oxide and 40mL of oleic acid. The mixture is degased for lh at 100°C under vacuum and then heated under Argon at 150°C for three hours. In the glove box 0.4mL of Bis(trimethylsilyl)sulfide (TMSS) are mixed in 20mL of octadecene (ODE). In a lOOmL three-neck flask, 12ml of the lead oleate Pb(OA) mixture previously prepared are quickly degased at 100°C and then heated at 150°C under Argon. 6mL of the solution of TMSS in ODE are quickly injected to the flask and the reaction performed for 3 minutes. Finally the solution is quickly cooled to room temperature. The solution is precipitated by adding ethanol and centrifuged for 5min at 3000rpm. The solid is redispersed in toluene. The cleaning step is repeated a second time. At the third cleaning, selective precipitation is performed to separate the different size.
QD with a bluer band gap have also been synthetized for electrochromism measurement. In this case 0.45g of lead oxide are stirred in 5ml of oleic acid overnight at 100°C under vacuum. The obtained yellowish solution is dissolved by adding 15ml of ODE. The flask is then switch under Argon and the temperature risen up to 125°C. Then 10ml of a TMMS in ODE solution (0.1M) are quickly injected. The heating mantle is removed and the solution gently cooled down up to room temperature. The three steps cleaning procedure including selective precipitation is done using a mixture of methanol/ethanol as polar solvent and chloroform as non-polar solvent. >· PbS nanocube
0.44g of lead oxide are mixed in a three-neck flask with 2mL of oleic acid and lOmL of phenyl ether at 150°C under Argon for thirty minutes. In the meanwhile 32mg of sulfur flake are sonicated with 2mL of filtered oleylamine. The obtained mixture is red- orange. The flask is heated up to 190°C and the sulfur in oleylamine quickly injected. The reaction is then conducted at 180°C for 5 minutes. The cleaning process is done three times by adding ethanol/methanol as non-solvent and toluene as non-polar solvent. PbSe sphericalQD
In the glove box a 1M solution of trioctylphosphine selenide (TOPSe) is prepared by stirring Se powder in trioctylphosphine (TOP) at room temperature. In a three-neck flask 650mg of trihydrate lead(II) acetate Pb(Oac)2(H20)3 are introduced with 2mL of phenyl ether, 1.5mL of oleic acid and 8mL of TOP. The solution is degased, as well as a second flask only filled with lOmL of pure phenyl ether, for lhour at 85°C. The one containing the lead precursor is cooled to 45°C and 1.7mL of the TOPSe solution is added. The solution is kept under stirring condition for 5 extra minutes. Finally the content of the flask is introduced in a 20mL syringe. The flask filled with just phenyl ether is heated up to 200°C under Argon. The content of the syringe is quickly injected. The Temperature of the flask cooled down to 140°C after the injection. During the next 90s the temperature is set at 120°C to avoid a too fast cooling. After this delay the flask is promptly cooled to room temperature. The cleaning is operated in the first step by addition of methanol and ethanol. After centrifugation the solid is dispersed in toluene. For the second (third) cleaning step ethanol (acetone/ethanol) is used. > HgTe QD
In the glove box a 1M solution of trioctylphosphine telluride (TOPTe) is prepared by a slow stirring of Te powder in trioctylphosphine (TOP). In a three neck flask 135mg of HgCl2 and 7.4g of octadecylamine are degased under vacuum for lhour at 120°C. The atmosphere is then switch to Argon and the solution heated at 80°C. 0,5ml of the 1M TOPTe are quickly injected and the reaction is performed at the same temperature for 5min. The solution is quenched by a quick addition of dodecanthiol. Finally the flask is cooled down to room temperature. The obtained dark solution is then splitted between two centrifuge tubes filled with a 10% in volume mixture of dodecathiol (DDT) in tetrachloroethylene (TCE) and a droplet of TOP. The solution is precipitated by addition of methanol. After centrifugation the solid is dried and redispersed in chloroform. The cleaning step is repeated three times. CdS rods
In the glove box, 0.18g of sulfur powder are stirred in 20ml of TOP up to dissolution and formation of trioctylphosphine sulfide (TOPS). The final solution is reddish. In a 100ml three-neck flask, 0.23g of CdO, 0.83g of n-tetradecylphosphonic acid (nTDPA) and 7g of trioctylphosphine oxyde (TOPO) are degased under vacuum for two hours at 80°C. Then the flask is switch under Argon and the temperature risen up to 340°C. Above 300°C the solution turns colorless. After 5min the flask is cooled to 300°C, every two minutes 0.4ml of the TOPS mixture is injected. The color of the solution turn yellowish after 30minutes and this color will increase up to the end. Once all the TOPS has been injected the heating mantle is removed and the flask quickly cooled down. Around 70°C some toluene is added to avoid the TOPO solidification. The cleaning process is repeating three times by precipitating the rods by adding ethanol and redispersing them in toluene.
> CdSe QD
In a three-neck flask, 8ml of ODE, 1.5g of TOPO and 0.75ml of Cd(OA)2 at 0.5M in oleic acid are degased for 30minutes under vacuum. Then under argon flow, the temperature is set at 280°C and a mixture of 3ml of oleylamine and 4ml of TOPSe at 1M in TOP are quickly injected at 300°C while the temperature is set at 280°C. After 8 minutes, the reaction is stopped and the quantum dots are precipitated twice with ethanol and resuspended in hexane.
> CdSe/CdS QD In a first procedure, 30mg of NaSH are mixed in 4 ml of N methyl formamide (NMFA) in a 20mL vial up to dissolution. Then 500μί of the CdSe QD core in solution in hexane are added in the vial. The solution is stirred until a complete transfer of the nanoparticles in the NMFA phase. Then 500μ1 of 0.2M cadmium acetate in NMFA are added in the vial. The reaction is performed for lhour at room temperature under stirring. Precipitation is ensured by addition of ethanol. After centrifugation the obtained solid is dispersed in NMFA. The cleaning step is repeated a second time. CdSe nanoplatelets
In a first step Cadmium myristate (Cd(Myr)2) is prepared. In a typical synthesis 240mg of Cd(Myr)2, 25mg Se powder are mixed in 30ml of ODE, the solution degased under vacuum for 20min at room temperature. Then the atmosphere is switch to Argon and the temperature is set to 240°C. At 204°C 40mg of Cd(OAc)2 are quickly added. The reaction is performed 12min at 240°C. 1ml of oleic acid is quickly injected to quench the reaction and the solution is cooled down. The precipitation of the nanoplatelets is done by adding ethanol. After centrifugation the obtained solid is redispersed in hexane. The cleaning procedure is repeated three times. Cu2Se nanoplatelets
In a glove box a solution of tetrakis (acetonitrile) copper(I) hexafluorophosphate in methanol is prepared with a concentration of at 50 mmol/L. CdSe NPL are mixed with this solution Cu+ solution with a 10 time excess of Cu+ compared to Cd2+. The solution is then washed twice air free using methanol as polar solvent and toluene as non-polar solvent. ZnSe nanoplatelets
A stock solution made of 125 mg of ZnC12, 4 mL of oleylamine and 6 mL of octadecene is degased for 30 min at room temperature. The mixture is heated under Ar at 250°C. Some Cu2Se NPL dispersed in trioctylphosphine are quickly injected onto the Zinc mixture. The reaction is conducted for 5 minutes. The solution is then washed twice using methanol as polar solvent and toluene as non-polar solvent. PbSe nanoplatelets
A stock solution made of Pb(OAc)2.3 H20 is prepared by dissolving 56 mg of solid in 1 mL methanol and 100 μΐ^ tributylphosphine. This solution is added to the solution of Cu2Se NPL with a ratio of Pb2+/Cu+ of 50. The reaction is performed for 1 hour. Then lead oleate is added to stop the reaction. The solution is then washed twice using methanol as polar solvent and toluene as non-polar solvent. ZnS nanoplatelets
65 mg of thioacetamide (0.87 mmol) and 1.08 mL of octylamine (6.5 mmol) were mixed with 4 mL of chloroform in a vial. 500 μΐ^ of a solution of zinc nitrate at 0.2M (0.1 mmol) in ethanol was added. The vial was put in the oven for 3h at 60°C. After 3h, ZnS nanoplatelets were precipitated with ethanol and redispersed in chloroform. This cycle of centrifugation/dispersion was repeated 3 times then the nanoplatelets were dispersed in hexane. CdSe/CdS core/shell nanoplatelets
Two procedures can be performed to obtain a CdS shell on CdSe core.
In a first procedure, 30mg of NaSH are mixed in 4 ml of N methyl formamide (NMFA) in a 20mL vial up to dissolution. Then 500μί of the CdSe core in solution in hexane are added in the vial. The solution is stirred until a complete transfer of the nanoparticles in the NMFA phase. Then 500μ1 of 0.2M cadmium acetate in NMFA are added in the vial. The reaction is performed for lhour at room temperature under stirring. Precipitation is ensured by addition of ethanol. After centrifugation the obtained solid is dispersed in NMFA. The cleaning step is repeated a second time. The performance of this material is tested on figure 6 and 8.
As an alternative procedure to grow the shell it is possible to disolve 30mg of Na2S are mixed in 2 ml of NMFA in a 4mL vial up to dissolution. The core are then precipitated by addition of acetonitrile to remove the excess of sulfide and redispersed in NMFA. Then 500μ1 of 0.2M cadmium acetate in NMFA are added in the vial. After the almost immediate reaction the excess of precursors is removed by precipitation of the nanocrystals with a mixture of toluene and acetonitrile (5 : 1). The solid obtained by centrifugation is redisolved in NMFA. The procedure is repeated 3.5 times. The final nanoparticles are storred in NMFA. CdTe nanoplatelets
In a first step Cadmium propanoate (Cd(Prop)2) is prepared by mixing 1.036g of CdO in 10ml of propionic acid under Argon for 1 hour. Then the flask is open to air and the temperature risen to 140°C up to the point the volume get divided by a factor two. The whitish solution is precipitated by addition of acetone. After centrifugation the solid is dried under vacuum for 24 hours.
In the glove box 1M TOPTe is prepared by stirring 2.55g of Te pellets in 20ml of TOP for four days at room temperature.
In a three-neck flask 0.13g of Cd(Prop)2, 160μιη of oleic acid and 10ml ODE are degased for 90 minutes at 95°C. Then the atmosphere is switched to Argon and the temperature risen to 210°C. 0.2mL of 1M TOPTe is quickly injected in the flask. After 20 minutes the reaction is quenched by adding lmL of oleic acid and cooling down the flask at room temperature. The cleaning process is done by adding Ethanol to precipitate the CdTe nanoplatelets. The solid obtained after centrifugation is redispersed in hexane. This procedure is repeated three times. 2. Electrolyte preparation
The electrolyte is a mixture of polyethylene glycol (PEG) or polyethylene oxide (PEO) with a given molar weight and ions. The molar ratio between the cation and the oxygen is taken equal to 16. For a typical electrolyte 50mg of LiC104 and 230mg of PEG (Mw=6000g.mol"1) are heated together at 150°C on a hot plate in the glove box. For higher PEG/PEO molar weight the mixture is heated at 200°C. Processing the electrolyte in air has not lead to any noticeable change.
3. Electrodes preparation
Electrodes are fabricated using a regular lift-off procedure onto a Si/Si02 wafer with an oxide thickness of 500nm. A thermal evaporation of Cr (2.5nm) and gold (17.5nm) is used for the contact. Electrodes are composed of 25 interdigitated pairs which are 2.5mm long. Two sets of electrodes have been designed with a spacing of 10 and 20μιη. The W/L ratio is 6250 for the ΙΟμιη spaced electrodes and 3125 for the 20μιη spaced electrodes. In another embodiment a Cu sheet is used as a support for the electrodes.
4. Film preparation with ligand exchange on film
The nanoparticles are dispersed in a mixture of hexane and octane (9: 1 as volume ratio). The electrodes are warmed at 125°C on a hot plate for two minutes and then thermalized at room temperature. The solution is dropcasted onto the interdigitated electrodes. The typical thickness for a film is 30nm. Then the film is dipped in a Na2S solution dispersed in ethanol ([Na2S]=l-5g.L_1) for 1 minute for PbS and PbSe and 30 s for HgTe. The film is then rinsed in pure ethanol. Finally the film is annealed at 80°C for one minute.
4' . Film preparation with ligand exchange in solution For a typical ligand exchange 15mg of Na2S are dissolved in 0.5ml of N methyl formamide (NMFA) by sonication. Then 1ml of the solution of nanoparticles in a non- polar solvent is added. The mixture is then stirred up to the point where the nanoparticles get dissolved in the polar phase. Then 2ml of hexane is added, and after sonication the non-polar phase is removed. This step is repeated a second time. Finally the nanoparticles are precipitated by addition of acetonitrile, after the centrifugation the solid is redispersed in NMFA.
This solution is dropcasted on the electrodes on a hot plate at 100°C. The heating is performed 10 minutes more than requested to dry the film. The typical thickness for a film is 40nm.
5. Supercapacitor-like electronic battery preparation In one embodiment the nanoparticles capped with S " ligands and dispersed in NMFA are dropcasted on a substrate of Si/Si02 where a metallic contact has been deposited by thermal evaporation of Cr and Au. The drying of the solution is made by warming the substrate on a hot plate at 100°C. This step is repeated several times to obtain a film with the right thickness. The electrolyte as described previously is also warm on the hot plate up to the point where the material is soften and can be more easily brushed directly on the nanoparticles film. Finally a metallic contact is deposited on the top of the electrolyte. Alternatively the top contact can be obtained by metal evaporation though an adapted shadow mask.
In another embodiment a metallic electrodes with an adapted shape (it can be a tube, a porous tube, or any system maximizing the surface of the electrodes) is warmed at a temperature between 80°C and 100°C using a heat gun. The electrode is dipped in the solution of nanoparticles capped with S " ligands and dispersed in NMFA. The dipping process is repeated several times, up to the point where the nanoparticles coating of the electrodes reached the desired thickness. A recipient containing some of the electrolyte is warmed on a hot plate at a temperature between 60°C and 100°C to soften the electrolyte. The electrode coated with the nanoparticles is immerged in the electrolyte as well as a second metallic uncoated electrode. The whole device is used as a supercapacitor. In another embodiment the nanoparticle capped with organic ligand are electrophoretically deposited on a conductive substrate. The latter can be metallic or an ITO coated glass slide. The typical biases for the deposition are in the 0V-2000V range and the deposition is performed during between 10s and several hours depending of the solution concentration and the amount of polar solvent. A recipient containing some of the electrolyte is warmed on a hot plate at a temperature between 60°C and 100°C to soften the electrolyte. The electrode coated with the nanoparticles is immerged in the electrolyte as well as a second metallic uncoated electrode. The whole device is used as a supercapacitor. In another embodiment the nanoparticles (CdSe/CdS nanoplatelets) are capped with S " ligands using the procedure described in example 4' . The nanoparticles in solution are mixed with carbon black in a weight ratio of 3: 1. The blend is dried in an oven at 100°C for lh. The obtained powder is deposited on a Cu substrate. LiC104 in ethylene carbonate is used as electrolyte. A Li foil is used as counter electrodes to form a half electrochemical cell.
The supercapacitor as disclosed hereabove presents an energy density of 77Wh/kg, a power density of 54 kW/kg, a capacitance of 55 F/g and a discharge time between 10 and 100 seconds.

Claims

A supercapacitor-like electronic battery comprising at least two electrodes, at least one active material comprising a plurality of non-carbon based nanosheets and at least one electrolyte.
A supercapacitor-like electronic battery according to claim 1, wherein the active material comprises at least 50% by weight of non-carbon based nanosheets.
The supercapacitor-like electronic battery according to claim 1 or 2, wherein said non-carbon based nanosheets are semiconductor.
The supercapacitor-like electronic battery according to anyone of claims 1 to 3, wherein said active material further comprises silicon or conductive polymer such as polyvinylidene fluoride, polypyrrole, polythiaphene, polyethylene oxide, polyacrylonitrile, poly(ethylene succinate), polypropylene, poly (b-propiolactone), styrene butadiene rubber, carboxymethyl cellulose salt, sulfonated fluoropolymers, polyimide, poly(acrylic acid); or carbon-based material such as carbon black, graphene, carbon nanotube, boron nitride nanotube, boron nitride nanosheet, graphene oxide, reduced graphene oxide, or mixture thereof.
The supercapacitor-like electronic battery according to anyone of claims 1 to 4, wherein said electrolyte is a liquid, a gel, or a solid.
The supercapacitor-like electronic battery according to anyone of claims 1 to 5, wherein bulk charging is achieved within said at least one active material comprising a plurality of non-carbon based nanosheets.
The supercapacitor-like electronic battery according to anyone of claims 1 to 6, wherein said at least one active material comprising a plurality of nanosheets has a thickness from 10 nanometers to 100 centimeters, preferably from 10 nanometers to 1 millimeter, more preferably from 10 nanometers to 100 micrometers.
8. A method for producing a supercapacitor-like electronic battery according to anyone of claims 1 to 7, the method comprising:
a) deposition of the first electrode onto a substrate or within a container, b) the preparation of one solution of nanosheets,
b') a nanosheets' ligand exchange step in solution,
c) deposition of the previous solution onto the first electrode,
c') if step b') is not implemented, nanosheets' ligand exchange step on the active material comprising a plurality of non-carbon based nanosheets, d) electrolyte deposition onto the active material comprising a plurality of non- carbon based nanosheets, or within the container and in contact with the active material comprising a plurality of non-carbon based nanosheets, e) deposition of the second electrode in contact with the electrolyte.
9. The method according to claim 8, wherein said deposition of the active material comprising a plurality of nanosheets is achieved by drop casting or spin coating, dip coating, spray casting, screen printing, inkjet printing, sputtering techniques, evaporation techniques, electrophoretic deposition, or vacuum methods.
10. A supercapacitor-like electronic battery obtainable by the process according to anyone of claims 8 or 9.
11. A product comprising at least one supercapacitor-like electronic battery according to anyone of claims 1 to 7 and 10.
12. A cathode active material for a supercapacitor-like electronic battery comprising an anode and an electrolyte, wherein the active material comprises a plurality of non-carbon based nanosheets.
13. Use of the supercapacitor-like electronic battery according to any one of claims 1 to 7 and 10 in any systems or devices which require a substantial pulse of energy below 1 minute.
PCT/EP2014/061191 2013-05-31 2014-05-28 Supercapacitor-like electronic battery WO2014191529A1 (en)

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Publication number Priority date Publication date Assignee Title
DE102017217039A1 (en) * 2017-09-26 2019-03-28 Robert Bosch Gmbh Electrochemical solid-state cell comprising boron nitride nanotube membrane
RU2726945C1 (en) * 2019-12-16 2020-07-17 Общество с ограниченной ответственнотью "ИОН" Flat supercapacitor based on carbon-carbon nanocomposite and method of its production
CN112646470A (en) * 2020-12-17 2021-04-13 中国科学院宁波材料技术与工程研究所 Preparation method of electric field assisted cold spraying graphene-based coating
RU2809837C2 (en) * 2021-12-20 2023-12-19 Государственное бюджетное образовательное учреждение высшего образования Московской области "Университет "Дубна" (Государственный университет "Дубна") Flat thin supercapacitor with low resistance and method of its manufacture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1463071A2 (en) * 2003-03-28 2004-09-29 Wataru Sugimoto Ruthenic acid nanosheet and production method thereof
US20100297502A1 (en) 2009-05-19 2010-11-25 Nanosys, Inc. Nanostructured Materials for Battery Applications
WO2011063539A2 (en) 2009-11-30 2011-06-03 Oc Oerlikon Balzers Ag Electronic battery with nano-composite
US20120100424A1 (en) * 2010-10-20 2012-04-26 Samsung Electro-Mechanics Co., Ltd Cathode active material, and cathode and magnesium battery including the same
WO2012112818A2 (en) * 2011-02-16 2012-08-23 The Regents Of The University Of California Interpenetrating networks of crystalline carbon and nano-scale electroactive materials
US20130115453A1 (en) * 2011-11-03 2013-05-09 Nanyang Technological University Hybrid nanostructure, a method for forming the hybrid nanostructure, and an electrode including a plurality of the hybrid nanostructures

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1463071A2 (en) * 2003-03-28 2004-09-29 Wataru Sugimoto Ruthenic acid nanosheet and production method thereof
US20100297502A1 (en) 2009-05-19 2010-11-25 Nanosys, Inc. Nanostructured Materials for Battery Applications
WO2011063539A2 (en) 2009-11-30 2011-06-03 Oc Oerlikon Balzers Ag Electronic battery with nano-composite
US20120100424A1 (en) * 2010-10-20 2012-04-26 Samsung Electro-Mechanics Co., Ltd Cathode active material, and cathode and magnesium battery including the same
WO2012112818A2 (en) * 2011-02-16 2012-08-23 The Regents Of The University Of California Interpenetrating networks of crystalline carbon and nano-scale electroactive materials
US20130115453A1 (en) * 2011-11-03 2013-05-09 Nanyang Technological University Hybrid nanostructure, a method for forming the hybrid nanostructure, and an electrode including a plurality of the hybrid nanostructures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. MERLET; B. ROTENBERG; P. A. MADDEN; P.-L. TABERNA; P. SIMON; Y. GOGOTSI; M. SALANNE, NATURE MATERIALS, vol. 11, 2012, pages 306
KANG J G ET AL: "Superior rate capabilities of SnS nanosheet electrodes for Li ion batteries", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 12, no. 2, 1 February 2010 (2010-02-01), pages 307 - 310, XP026858677, ISSN: 1388-2481, [retrieved on 20100116], DOI: 10.1016/J.ELECOM.2009.12.025 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017217039A1 (en) * 2017-09-26 2019-03-28 Robert Bosch Gmbh Electrochemical solid-state cell comprising boron nitride nanotube membrane
RU2726945C1 (en) * 2019-12-16 2020-07-17 Общество с ограниченной ответственнотью "ИОН" Flat supercapacitor based on carbon-carbon nanocomposite and method of its production
CN112646470A (en) * 2020-12-17 2021-04-13 中国科学院宁波材料技术与工程研究所 Preparation method of electric field assisted cold spraying graphene-based coating
RU2809837C2 (en) * 2021-12-20 2023-12-19 Государственное бюджетное образовательное учреждение высшего образования Московской области "Университет "Дубна" (Государственный университет "Дубна") Flat thin supercapacitor with low resistance and method of its manufacture

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