WO2025133673A2 - Revêtement d'une électrode - Google Patents

Revêtement d'une électrode Download PDF

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Publication number
WO2025133673A2
WO2025133673A2 PCT/IB2023/062856 IB2023062856W WO2025133673A2 WO 2025133673 A2 WO2025133673 A2 WO 2025133673A2 IB 2023062856 W IB2023062856 W IB 2023062856W WO 2025133673 A2 WO2025133673 A2 WO 2025133673A2
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active coating
battery
exemplary embodiment
supercapacitor
electrodes
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WO2025133673A3 (fr
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Worawat MEEVASANA
Unchista WONGPRATAT
Supansa MUSIKAJAROEN
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Eq Tech Energy Co Ltd
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Eq Tech Energy Co Ltd
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Publication of WO2025133673A3 publication Critical patent/WO2025133673A3/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Definitions

  • US 2019/0207202 Al proposes a positive electrode, a method for preparing the positive electrode and an electrochemical device.
  • the present inventors have found that, by applying the active coating according to the embodiments described herein, the resulting electrode active material exhibits a surprising extent of negative electronic compressibility: the negative rate of // over n between 0 and -5.39 x 10' 8 millielectronvolt per electron per cm 2 .
  • said transition metal oxide is doped with at least one metal dopant.
  • said metal dopant is a transition metal element or a post-transition metal element.
  • the transition metal oxide is selected from a group of bismuth ferrite (BiFeCL, BFO), nickel (II) oxide (NiO), and barium titanate (BaTiO3).
  • the transition metal oxide that is doped with at least one metal dopant is Bio.95 Cuo.o5 FeCh.
  • the doping is carried out in order to optimize the negative rate of // over n, such that said negative rate of // over n corresponds to a host energy storage where the active coating is applied.
  • the active coating is applied to the electrode active material by physical vapor deposition.
  • the electrode active material upon which the active coating in accordance with any of the above embodiments is applied, may be used as a component of any known energy storage device that is part of a capacitor (in particular a supercapacitor and the like), or a battery (in particular a lithium-ion battery and the like).
  • Said energy storage device may take the form of a coin cell or a cylindrical cell of a capacitor or a battery.
  • an embodiment is the energy storage device that is part of a capacitor (in particular a supercapacitor and the like), or a battery (in particular a lithium-ion battery and the like) that comprises an electrode active material upon which the active coating in accordance with any of the above embodiments of the first aspect is deposited.
  • a capacitor in particular a supercapacitor and the like
  • a battery in particular a lithium-ion battery and the like
  • said energy storage device takes the form of a coin cell and a cylindrical cell of a capacitor or a battery.
  • Fig. 1 shows a schematic diagram of a supercapacitor having a coin cell configuration according to an exemplary embodiment (not to scale).
  • Fig. 2 shows a schematic diagram of a supercapacitor having a cylindrical cell configuration according to an exemplary embodiment (not to scale).
  • Fig. 3 shows a schematic diagram of a battery having a coin cell configuration according to an exemplary embodiment (not to scale).
  • Fig. 4 shows a schematic diagram of a battery having a cylindrical cell configuration according to an exemplary embodiment (not to scale).
  • Fig. 5 shows the change of voltage (V) over time (minutes) of an NMC electrode coated with an active coating comprising Cu-doped BiFeC according to Exemplary Embodiment No. 1.
  • Fig. 6A shows the change of the chemical potential // as a function of the electron density n 2D of an electrode active material coated with an active coating comprising BiFeCE according to Exemplary Embodiment No. 2.
  • Fig. 6B shows the rate of change of the chemical potential over the electron density (d/z dw) as a function of the electron density n2D of an electrode active material coated with an active coating comprising BiFeCE according to Exemplary Embodiment No. 2.
  • Fig. 7 shows the percentage of energy density increase (%) as a function of active coating thickness in a Li-ion battery-based lithium-nickel-manganese-cobalt oxide (LiNiMnCoCE, NMC) electrode coated with Cu-doped BiFeC thin film according to Exemplary Embodiment No. 3.
  • Fig. 8A shows the change of voltage (V) over time (minutes) of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 4.
  • Fig. 8B shows the change of energy density (Wh/kg) over cycles of charge/discharge of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 4.
  • Fig. 9A shows the change of voltage (V) over time (minutes) of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 5.
  • Fig. 9B shows the change of energy density (Wh/kg) over cycles of charge/discharge of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 5.
  • Fig. 10A shows the change of voltage (V) over time (minutes) of a super capacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 6.
  • Fig. 10B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 6.
  • Fig. 11A shows the change of voltage (V) over time (minutes) of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 7.
  • Fig. 11B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 7.
  • Fig. 12A shows the change of voltage (V) over time (minutes) of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 8.
  • Fig. 12B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 8.
  • Fig. 13 A shows the change of voltage (V) over time (minutes) of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 9.
  • Fig. 13B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 9.
  • Fig. 14B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 10.
  • Fig. 15A shows the change of voltage (V) over time (minutes) of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 11.
  • Fig. 15B shows the change of energy density (Wh/kg) over cycles of charge/dis charge of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 11.
  • compositions and methods include the recited elements, but not excluding others.
  • Consisting essentially of when used to define compositions and methods, shall mean excluding other elements of any essential significance to the combination for the stated purpose. Thus, a device or method consisting essentially of the elements as defined herein would not exclude other materials or steps that do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • Consisting of shall mean excluding more than trace elements of other ingredients and substantial method steps. Embodiments defined by each of these transition terms are within the scope of this invention.
  • Electron density refers to the number of electrons per unit area.
  • an active coating modifies the electrode active material’s rate of u over n (i.e., the chemical shift).
  • exemplary materials for the active coating include copper-doped bismuth ferrite (Cu-doped BFO).
  • the active coating is preferably applied to the electrode active material before the protective coating.
  • the protective coating protects the active coating from chemical attacks during the charge and discharge.
  • the protective coating is a conductive metal, preferably copper (Cu), nickel (Ni), or aluminum (Al) or their alloy, which helps reduce the electrode active material’s electrical resistance. The reduction of electrode active material’s electrical resistance is favorable to its performance according to the concept of the present invention.
  • the protective coating may be coated preferably on the active coating that is coated upon either the anode or cathode active material (see also description on cathode and anode active materials in the next section).
  • the coating according to any of the embodiments may be applied to the electrode active material by any known process.
  • Physical vapor deposition is one of the preferred coating processes.
  • the coatings were applied to the electrode active materials by sputtering process, which is a variant of physical vapor deposition. Specifically, in the Exemplary Embodiments, each of the sputtering processes that were carried out in order to apply the coatings to the electrode active materials was divided into two phases: the sputtering for forming an active coating, and the sputtering for forming a protective coating.
  • the sputtering for forming the active coating was applied by radio frequency (RF) magnetron sputtering.
  • the electrode active materials used in the Exemplary Embodiments had the area of 100 cm 2 , for which the power was set to be in the range of 80 - 200 Watts (W) and the deposition time was set to be within 30 seconds to 30 minutes.
  • the reactive gas was a mixture consisting essentially of argon (Ar) and oxygen (O2). The process was run at the room temperature (RT) under the pressure in the range of 1 - 5 Pascal (Pa).
  • the sputtering for forming the protective coating was then applied by direct current (DC) sputtering.
  • the protective coatings were formed by sputtering conductive metal materials which were preferably copper (Cu), nickel (Ni), and aluminum (Al).
  • the power was set to be in the range of 20 - 50 Watts (W) and the deposition time was set to be within 1 - 5 minutes.
  • the reactive gas was a mixture consisting essentially of argon (Ar). The process was run under the pressure in the range of 0.5 - 2.0 Pascal (Pa), and at the room temperature (RT).
  • the enclosure 410 was constructed of an aluminum foil with a thickness of 1 mm.
  • the anode 420 was constructed essentially of graphite.
  • the separator 430 was constructed of polypropylene (PP) with a length of 100 cm for cylindrical cell assembly.
  • the cathode 440 was constructed of the electrode active material as specified in the respective exemplary embodiment and may be coated with a coating material and by the process parameters as specified in the respective exemplary embodiment.
  • the core 450 was constructed of stainless steel with a dimension of 18 (OD) mm x 17.5 mm (ID) x 67 mm (height).
  • two systems of supercapacitor or battery of same electrode configuration were constructed.
  • the two systems differed in their electrodes.
  • the first system was built of the electrode active material as specified in Table 1 or 2 below without any coating (the “reference electrode”); whereas the second system was built similarly to the first system, except that the said electrode active material was coated according to Table 1 or 2 below (the “exemplary electrode”).
  • the said carbon-based electrode on nickel foam substrate was prepared from a mixture of activated carbon, acetylene black, and poly vinylidene difluoride (PVDF), at the respective weight ratio of 8: 8: 1.
  • the said mixture solution of the 8: 1:1 ratio of activated carbon, acetylene black, and PVDF, of approximately 75 pL was dropped on a nickel foam substrate with an area of 1 cm 2 .
  • a nickel foam substrate was baked at 80 °C for 8 hours to remove moisture and allow the dry carbon solution to adhere on the substrate.
  • the nickel foam substrate was then compressed with a pressure of 5 MPa for 1 minute and then weighed to determine the mass of carbon attached on the nickel foam substrate.
  • a lithium-nickel-manganese-cobalt oxide LiNiMnCoO2, NMC
  • the said NMC had the respective molecular weight ratio of 5 : 3 : 2.
  • the NMCs in Exemplary Embodiment No. 1 and 7 were purchased from GELON LIB Group; the NMCs in Exemplary Embodiment Nos. 8 - 11 were purchased from MTI Corporation.
  • the sputtering source for applying all active coatings was radio frequency (RF) magnetron.
  • the sputtering source for applying all protective coatings was direct current (DC) (if applicable).
  • the galvanostatic charge/discharge was measured in an electrolyte comprising IM of tetraethylammonium tetrafluoroborate (Et4NBF4) in propylene carbonate (PC) with a separator constructed of a cellulose-based paper.
  • Et4NBF4 tetraethylammonium tetrafluoroborate
  • PC propylene carbonate
  • the measurement was carried out by the Field Emission Scanning Electron Microscopy (FESEM), operating at 5 kV, using a Hitachi S-4700 and Zeiss AURIGA equipped with an X-ray energy-dispersive spectroscopy (EDS) analyzer.
  • FESEM Field Emission Scanning Electron Microscopy
  • Table 2 below sets out the specifics of Exemplary Embodiment Nos. 4 - 7 in addition to the preceding general description.
  • Table 3 further below sets out the specifics of Exemplary Embodiment Nos. 8 - 11 in addition to the preceding general description.
  • Fig. 5 shows the change of voltage (V) over time (minutes) of an NMC electrode coated with an active coating comprising Cu-doped BiFeCh according to Exemplary Embodiment No. 1.
  • V voltage
  • the exemplary electrode exhibited a negative slope representing the rate of -0.006 V/min.
  • the electric current was kept constant at 0.98 mA throughout the charge/discharge cycle, including the time in which the negative rate was observed (110 - 145 minutes of the charging phase).
  • the reference electrode showed a positive slope through the charging phase at the rate of 0.004 V/min.
  • the change of slope was determined to be 0.068 V/Coulomb.
  • the negative rate of // over n as observed from the said negative slope, promoted the electrode’s energy density and thus electrical capacity, as will be shown and discussed with respect to later exemplary embodiments.
  • Fig. 6A shows the change of the chemical potential // as a function of the electron density n2D of the exemplary electrode
  • Fig. 6B shows the rate of change of the chemical potential over the electron density (d/z dw) as a function of the electron density n2D of the exemplary electrode.
  • the negative rate of z over n which was calculated in Exemplary Embodiment No. 1, may be directly measured by ultraviolet photoemission spectroscopy (UPS).
  • UPS ultraviolet photoemission spectroscopy
  • the electronic structure of BiFeCE measured by UPS was performed using Scienta R4000 electron analyzer located at Beamline 10.0.1 Advanced Light Source (USA) and Beamline 3.2a of the Synchrotron Light Research Institute, Thailand.
  • the measurements were performed at room temperature with base pressure better than 5 x 10' 8 mbar and the photon energy was set to be 60 eV.
  • the negative chemical potential shift indicated a counterintuitive lowering of the chemical potential with increasing electron densities, which was a direct spectroscopic signature of the negative electron compressibility (NEC).
  • the negative rate of // over n resulting from the Exemplary Embodiment No. 2 was determined to be in the range of -2.34 x 10' 8 to -5.39 x 10' 8 millielectronvolt per electron per cm 2 .
  • Fig. 7 shows the percentage of energy density increased in Li-ion battery-based lithiumnickel-manganese-cobalt oxide (LiNiMnCoCh, NMC) electrode coated with Cu-doped BiFeO, thin film presented as a function of thickness.
  • LiNiMnCoCh, NMC Li-ion battery-based lithiumnickel-manganese-cobalt oxide
  • the increased energy density was measured relative to the active coating's thicknesses of 3.5 - 34 nm.
  • a remarkably high percentage of the increase of energy density was observed at the active coating’s thicknesses of 3.5 - 14.0 nm. This indicated that within the working thickness range, a thin active coating provides a better energy density than a thick active coating.
  • Figs. 8 A and 8B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 4.
  • the supercapacitor comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 3 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the supercapacitor comprising the exemplary electrodes had a greater energy capacity than the supercapacitor comprising the reference electrodes.
  • the supercapacitor comprising the exemplary electrodes exhibited an energy density that was about 100 % greater than the supercapacitor comprising the reference electrodes.
  • the supercapacitor comprising exemplary electrodes exhibited an energy density of 8 ⁇ 0.1 Wh/kg; the supercapacitor comprising reference electrodes exhibited an energy density of 4 ⁇ 0.1 Wh/kg. This superiority in the energy capacity was retained after the 10 th charge/discharge cycle.
  • Exemplary Embodiment No. 5 Figs. 9A and 9B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 5.
  • the supercapacitor comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 2.5 - 2.6 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the supercapacitor comprising the exemplary electrodes had a greater energy capacity than the supercapacitor comprising the reference electrodes.
  • Figs. 10A and 10B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a supercapacitor comprising reference electrodes and another supercapacitor comprising electrodes according to Exemplary Embodiment No. 6.
  • the supercapacitor comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 2.6 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the supercapacitor comprising the exemplary electrodes had a greater energy capacity than the supercapacitor comprising the reference electrodes.
  • the supercapacitor comprising the exemplary electrodes exhibited an energy density that was about 46 % greater than the supercapacitor comprising the reference electrodes.
  • the supercapacitor comprising exemplary electrodes exhibited an energy density of 13 ⁇ 0.1 Wh/kg; the supercapacitor comprising reference electrodes exhibited an energy density of 9 ⁇ 0.1 Wh/kg. This superiority in the energy capacity was retained after the 10 th charge/discharge cycle.
  • Figs. 11A and 11B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 7.
  • the battery comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 4.2 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the battery comprising the exemplary electrodes had a greater energy capacity than the battery comprising the reference electrodes.
  • the battery comprising the exemplary electrodes exhibited an energy density that was about 22 % greater than the battery comprising the reference electrodes.
  • the battery comprising exemplary electrodes exhibited an energy density of 275 ⁇ 5 Wh/kg; the battery comprising reference electrodes exhibited an energy density of 225 ⁇ 5 Wh/kg. This superiority in the energy capacity was retained after the 10 th charge/discharge cycle.
  • Figs. 12A and 12B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 8.
  • Figs. 14A and 14B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 10.
  • the battery comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 3.0 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the battery comprising the exemplary electrodes had a greater energy capacity than the battery comprising the reference electrodes.
  • the battery comprising the exemplary electrodes exhibited an energy density that was about 31 % greater than the battery comprising the reference electrodes.
  • the battery comprising exemplary electrodes exhibited an energy density of 21 ⁇ 5 Wh/kg; the battery comprising reference electrodes exhibited an energy density of 16 ⁇ 5 Wh/kg. This superiority in the energy capacity was retained after the 10 th charge/discharge cycle.
  • Figs. 15A and 15B show, respectively, the change of voltage (V) over time (minutes) and the change of energy density (Wh/kg) over cycles of charge/discharge, of a lithium-ion battery comprising reference electrodes and another lithium-ion battery comprising electrodes according to Exemplary Embodiment No. 11.
  • the battery comprising the exemplary electrodes exhibited a significantly longer time to charge to, and discharge from, the discharge/charge voltages of 3.0 V.
  • the area under the curve of voltage over time was positively proportional to energy capacity.
  • the battery comprising the exemplary electrodes had a greater energy capacity than the battery comprising the reference electrodes.
  • the battery comprising the exemplary electrodes exhibited an energy density that was about 44 % greater than the battery comprising the reference electrodes.
  • the battery comprising exemplary electrodes exhibited an energy density of 23 ⁇ 5 Wh/kg; the battery comprising reference electrodes exhibited an energy density of 16 ⁇ 5 Wh/kg. This superiority in the energy capacity was retained after the 10 th charge/discharge cycle.
  • the coating of Cu-doped BFO thin film was applied on the electrodes of supercapacitors and lithium-ion batteries by using sputtering technique.
  • the capacity enhancements were clearly observed on the supercapacitors and lithium-ion batteries with the coated electrodes.
  • the retention performance became better than the original supercapacitors and lithium-ion batteries without the coating of Cu-doped BFO thin film and the protective coating.

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Abstract

Des aspects de la présente invention concernent un revêtement actif d'un matériau actif d'électrode, ledit revêtement actif ayant une épaisseur de 1 nanomètre à 1 micromètre et comprenant un oxyde de métal de transition, ledit revêtement actif conférant, au matériau actif d'électrode sur lequel ledit revêtement actif est déposé, un taux négatif de μ sur n, dans lequel : ladite μ représente un potentiel chimique ; ledit n représente un nombre d'électrons par unité de surface ; et ledit taux négatif est compris entre 0 et -5,39 x 10-8 milliélectronvolt par électron par cm2.
PCT/IB2023/062856 2023-12-18 2023-12-18 Revêtement d'une électrode Pending WO2025133673A2 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2025133673A3 (fr) * 2023-12-18 2025-09-18 Eq Tech Energy Co. Ltd. Revêtement d'une électrode

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KR101556299B1 (ko) * 2013-07-12 2015-10-02 한국과학기술연구원 비정질 리튬전이금속 산화물 코팅층을 포함하는 리튬이차전지용 양극 및 그 제조방법
CN106887460B (zh) * 2017-03-20 2019-06-07 北京大学 负电子压缩率-超陡亚阈斜率场效应晶体管及其制备方法
EP4350800A4 (fr) * 2021-05-31 2025-06-18 Panasonic Intellectual Property Management Co., Ltd. Substance active revêtue, matériau d'électrode positive, électrode positive et batterie
WO2025133673A2 (fr) * 2023-12-18 2025-06-26 Eq Tech Energy Co. Ltd. Revêtement d'une électrode

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025133673A3 (fr) * 2023-12-18 2025-09-18 Eq Tech Energy Co. Ltd. Revêtement d'une électrode

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