WO2010090956A2 - Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors - Google Patents

Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors Download PDF

Info

Publication number
WO2010090956A2
WO2010090956A2 PCT/US2010/022597 US2010022597W WO2010090956A2 WO 2010090956 A2 WO2010090956 A2 WO 2010090956A2 US 2010022597 W US2010022597 W US 2010022597W WO 2010090956 A2 WO2010090956 A2 WO 2010090956A2
Authority
WO
WIPO (PCT)
Prior art keywords
copper
substrate
chamber
tin
porous
Prior art date
Application number
PCT/US2010/022597
Other languages
English (en)
French (fr)
Other versions
WO2010090956A3 (en
Inventor
Sergey D. Lopatin
Dmitri A. Brevnov
Robert Z. Bachrach
Original Assignee
Applied Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/459,313 external-priority patent/US8486562B2/en
Application filed by Applied Materials, Inc. filed Critical Applied Materials, Inc.
Priority to EP10738991A priority Critical patent/EP2394322A2/en
Priority to KR1020117020743A priority patent/KR101733134B1/ko
Priority to JP2011548343A priority patent/JP2012516941A/ja
Priority to CN201080014859.8A priority patent/CN102379050B/zh
Publication of WO2010090956A2 publication Critical patent/WO2010090956A2/en
Publication of WO2010090956A3 publication Critical patent/WO2010090956A3/en

Links

Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • H01G11/26—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, 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
    • 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
    • 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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • 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
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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
    • H01M2004/025—Electrodes composed of, or comprising, active material with shapes other than plane or cylindrical
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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

Definitions

  • Embodiments of the present invention generally relate to methods of forming an energy storage device. More particularly, embodiments described herein relate to methods of forming electric batteries and electrochemical capacitors.
  • the current collector is made of an electric conductor.
  • materials for the positive current collector include aluminum, stainless steel, and nickel.
  • materials for the negative current collector include copper (Cu) 1 stainless steel, and nickel (Ni).
  • Such collectors can be in the form of a foil, a film, or a thin plate, having a thickness that generally ranges from about 6 to 50 ⁇ m.
  • the active electrode material in the positive electrode of a Li-ion battery is typically selected from lithium transition metal oxides, such as LiM ⁇ O 4 , LiCo ⁇ 2, and combinations of Ni or Li oxides and includes electroconductive particles, such as carbon or graphite, and binder material.
  • Such positive electrode material is considered to be a lithium-intercalation compound, in which the quantity of conductive material is in the range from 0.1% to 15% by weight.
  • Graphite is usually used as the active electrode material of the negative electrode and can be in the form of a lithium-intercalation meso-carbon micro beads (MCMB) powder made up of MCMBs having a diameter of approximately 10 ⁇ m.
  • the lithium-intercalation MCMB powder is dispersed in a polymeric binder matrix.
  • the polymers for the binder matrix are made of thermoplastic polymers including polymers with rubber elasticity.
  • the polymeric binder serves to bind together the MCMB material powders to preclude crack formation and prevent disintegration of the MCMB powder on the surface of the current collector.
  • the quantity of polymeric binder is in the range of 2% to 30% by weight.
  • the separator of Li-ion batteries is typically made from micro-porous polyethylene and polyolefine, and is applied in a separate manufacturing step.
  • Embodiments described herein generally relate to methods of forming an energy storage device. More particularly, embodiments described herein relate to methods of forming electric batteries and electrochemical capacitors.
  • a method for forming a porous electrode for an electrochemical cell is provided. The method comprises depositing a columnar metal layer over a substrate at a first current density by a diffusion limited deposition process and depositing three dimensional metal porous dendritic structures over the columnar metal layer at a second current density greater than the first current density.
  • a method of forming a porous three dimensional electrode microstructure for an electrochemical cell is provided.
  • a substrate processing system for processing a vertically oriented flexible substrate.
  • the substrate processing system comprises a first plating chamber configured to plate a conductive microstructure comprising a first conductive material over a portion of the vertically oriented conductive substrate, a first rinse chamber disposed adjacent to the first plating chamber configured to rinse and remove any residual plating solution from the portion of the vertically oriented conductive substrate with a rinsing fluid, a second plating chamber disposed adjacent to the first rinse chamber configured to deposit a second conductive material over the conductive microstructure, a second rinse chamber disposed adjacent to the second plating chamber configured to rinse and remove any residual plating solution from the portion of the vertically oriented conductive substrate, a substrate transfer mechanism configured to transfer the vertically oriented flexible substrate among the chambers, wherein each of the chambers comprises a processing volume, a feed roll disposed outside the processing volume and configured to retain a portion of the vertically oriented flexible base, and a take up roll disposed out side the processing volume and
  • FIG. 2A is a flow diagram of a method for forming an anode according to embodiments described herein;
  • FIG. 4B schematically illustrates one embodiment of a vertical processing system according to embodiments described herein;
  • FIG. 5 is a representation of a scanning electron microscope (SEM) image of a three dimensionally plated electrode deposited according to embodiments described herein;
  • FIG. 6 is a representation of a SEM image of a three dimensionally plated electrode deposited according to embodiments described herein;
  • FIGS. 7A-7D are representations of SEM images of three dimensionally plated electrodes deposited according to embodiments described herein;
  • FIG. 8 is X-ray diffraction (XRD) spectra of plated copper-tin and a copper-tin phase diagram.
  • Embodiments described herein generally relate to an electrode structure useful in a battery or an electrochemical capacitor and the methods of creating such an electrode structure that has an improved lifetime, lower production costs, and improved process performance.
  • Embodiments described herein generally include a porous 3-dimensional electrode structure with increased surface area.
  • the electrode structure comprises a columnar metal layer and three dimensional metal porous conductive dendritic structures formed over the columnar metal layer.
  • Anode structures 122a, 122b and cathode structures 123a, 123b each serve as a half-cell of Li-ion battery cell 120, and together form a complete working bi-layer cell of Li-ion battery 120.
  • Anode structures 122a, 122b each include a metal current collector 131a, 131b and a first electrolyte containing material 134a, 134b.
  • cathode structures 123a, 123b include a current collector 133a and 133b respectively and a second electrolyte containing material 132a, 132b, such as a metal oxide, for retaining lithium ions.
  • the electrolyte containing porous material on the cathode side of the Li- ion battery 100, or positive electrode may comprise a lithium-containing metal oxide, such as lithium cobalt dioxide (LiCoO 2 ) or lithium manganese dioxide (LiMnO 2 ).
  • the electrolyte containing porous material may be made from a layered oxide, such as lithium cobalt oxide, an olivine, such as lithium iron phosphate, or a spinel, such as lithium manganese oxide.
  • an exemplary cathode may be made from TiS 2 (titanium disulfide).
  • Li 2 FeSiO 4 Li 2 MnSiO 4 , or Li 2 VOSiO 4 .
  • An exemplary non-lithium compound is Na 5 V 2 (PO 4 J 2 F 3 .
  • FIG. 2A is a flow diagram according to one embodiment described herein of a process 200 for forming a porous three dimensional conductive electrode in accordance with embodiments described herein.
  • FIGS. 3A-3F are schematic cross- sectional views of a porous three dimensional conductive electrode formed according to embodiments described herein.
  • the process 200 includes process steps 202-212, wherein a porous electrode is formed on a substrate 300.
  • the process 200 may be performed as a roll-to-roll manufacturing process.
  • the first process step 202 includes providing the substrate 300.
  • the substrate 300 may comprise a material selected from the group comprising or consisting of copper, aluminum, nickel, zinc, tin, titanium, flexible materials, stainless steel, and combinations thereof.
  • the substrate 300 is a flexible substrate comprising a material selected from the group comprising or consisting of copper, aluminum, nickel, zinc, tin, stainless steel, and combinations thereof.
  • the substrate is a copper foil substrate.
  • the substrate 300 has layers deposited thereon. In one embodiment, the layers are selected from the group comprising or consisting of copper, titanium, chromium, alloys thereof, and combinations thereof.
  • the substrate may be roughened by chemically treating the surface of the substrate to increase the surface area.
  • the second process step 204 includes optionally depositing a barrier layer and/or adhesion layer 302 over the substrate.
  • the barrier layer 302 may be deposited to prevent or inhibit diffusion of subsequently deposited materials over the barrier layer into the underlying substrate.
  • the barrier layer comprises multiple layers such as a barrier-adhesion layer or an adhesion-release layer.
  • barrier layer materials include refractory metals and refractory metal nitrides such as chromium, tantalum (Ta), tantalum nitride (TaN x ), titanium (Ti), titanium nitride (TiN x ), tungsten (W), tungsten nitride (WN x ), alloys thereof, and combinations thereof.
  • barrier layer materials include PVD titanium stuffed with nitrogen, doped silicon, aluminum, aluminum oxides, titanium silicon nitride, tungsten silicon nitride, and combinations thereof.
  • Exemplary barrier layers and barrier layer deposition techniques are further described in U.S. Patent Application Publication 2003/0143837 entitled “Method of Depositing A Catalytic Seed Layer,” filed on January 28, 2002, which is incorporated herein by reference to the extent not inconsistent with the embodiments described herein.
  • the barrier layer may be deposited by CVD techniques, PVD techniques, electroless deposition techniques, evaporation, or molecular beam epitaxy.
  • the barrier layer may also be a multi-layered film deposited individually or sequentially by the same or by a combination of techniques.
  • Physical vapor deposition techniques suitable for the deposition of the barrier layer include techniques such as high density plasma physical vapor deposition (HDP PVD) or collimated or long throw sputtering.
  • HDP PVD high density plasma physical vapor deposition
  • IMP PVD ionized metal plasma physical vapor deposition
  • An example of a chamber capable of IMP PVD of a barrier layer is an IMP VECTRATM chamber. The chamber and process regime are available from Applied Materials, Inc. of Santa Clara, California.
  • IMP PVD involves ionizing a significant fraction of material sputtered from a metal target to deposit a layer of the sputtered material on a substrate. Power supplied to a coil in the chamber enhances the ionization of the sputtered material.
  • An example of a chamber capable of chemical vapor deposition of a barrier layer is a CVD TxZTM chamber.
  • the chamber and the process regime are available from Applied Materials, Inc. of Santa Clara, California.
  • chemical vapor deposition involves flowing a metal precursor into the chamber.
  • the metal precursor chemically reacts to deposit a metal film on the substrate surface.
  • Chemical vapor deposition may further include utilizing a plasma to aid in the deposition of the metal film on the substrate surface.
  • Exemplary processes for the deposition of barrier layers from metal precursors are more fully described in co- pending U.S. Patent Application Serial No.
  • PVD chamber and/or the CVD chamber can be integrated into a processing platform, such as an ENDURATM platform, also available from Applied Materials, Inc. of Santa Clara, California.
  • An example of a processing tool capable of roll-to-roll evaporation of a barrier layer is the SMARTWEBTM vacuum web coater available from Applied Materials, Inc. of Santa Clara, California.
  • evaporation involves placing the material to be deposited or source material in a chamber or crucible and heating in a vacuum environment until the material vaporizes.
  • One method of heating involves using an electron beam to heat the material.
  • the use of a high vacuum environment increases the mean free path of the vapor molecules allowing the vapor to travel in a straight path with minimal collisions until the vapor strikes a surface and condenses to form a film.
  • the rate of removal from the source material varies with vapor pressure which correspondingly varies with temperature.
  • Films which may be deposited using evaporation methods include films containing Copper (Cu), Chromium (Cr), Titanium (Ti), alloys thereof, combinations thereof, and Titanium Nitride (TiN).
  • the third process step 206 includes optionally depositing a seed layer 304 over the substrate 300.
  • the seed layer 304 comprises a conductive metal that aids in subsequent deposition of materials thereover.
  • the seed layer 304 preferably comprises a copper seed layer or alloys thereof. Other metals, particularly noble metals, may also be used for the seed layer.
  • the seed layer 304 may be deposited over the barrier layer by techniques conventionally known in the art including physical vapor deposition techniques, chemical vapor deposition techniques, and electroless deposition techniques.
  • Physical vapor deposition techniques suitable for the deposition of the seed layer include techniques such as high density plasma physical vapor deposition (HDP PVD) or collimated or long throw sputtering.
  • HDP PVD high density plasma physical vapor deposition
  • IMP PVD ionized metal plasma physical vapor deposition
  • An example of a chamber capable of ionized metal plasma physical vapor deposition of a seed layer is an IMP VectraTM chamber. The chamber and process regime are available from Applied Materials, Inc. of Santa Clara, California.
  • An exemplary process for the deposition of a seed layer utilizing PVD techniques is more fully described in co- pending U.S. Patent Application Serial No.
  • the fourth process step 208 includes forming a columnar metal layer 306 over the seed layer 304.
  • the columnar metal layer 306 is formed directly on a surface of the substrate 300.
  • Formation of the columnar metal layer 306 includes establishing process conditions under which evolution of hydrogen results in the formation of a porous metal film. In one embodiment, such process conditions are achieved by performing at least one of: increasing the concentration of metal ions near the cathode (e.g., seed layer surface) by reducing the diffusion boundary layer, and by increasing the metal ion concentration in the electrolyte bath. It should be noted that the diffusion boundary layer is strongly related to the hydrodynamic boundary layer.
  • the limiting current JL
  • the diffusion limited plating process created when the limiting current is reached prevents the increase in plating rate by the application of more power (e.g., voltage) to the cathode (e.g., metalized substrate surface).
  • the cathode e.g., metalized substrate surface.
  • Formation of the columnar metal layer 306 generally takes place in a processing chamber.
  • a processing chamber that may be adapted to perform one or more of the process steps described herein may include an electroplating chamber, such as the SLIMCELL® electroplating chamber available from Applied Materials, Inc. of Santa Clara, California. Other processing chambers and systems, including those available from other manufactures may also be used to practice the embodiments described herein.
  • One exemplary processing system includes a roll- to-roll processing system described herein.
  • the processing chamber includes a suitable plating solution. Suitable plating solutions that may be used with the processes described herein include electrolyte solutions containing a metal ion source, an acid solution, and optional additives.
  • the plating solution used in step 208 contains at least one or more acid solutions.
  • Suitable acid solutions include, for example, inorganic acids such as sulfuric acid, phosphoric acid, pyrophosphoric acid, perchloric acid, acetic acid, citric acid, combinations thereof, as well as acid electrolyte derivatives, including ammonium and potassium salts thereof.
  • the plating solution may include one or more additive compounds.
  • Additive compounds include electrolyte additives including, but not limited to, suppressors, enhancers, levelers, brighteners and stabilizers to improve the effectiveness of the plating solution for depositing metal, namely copper to the substrate surface.
  • certain additives may be used to control the mechanism of bubble formation.
  • Certain additives may decrease the ionization rate of the metal atoms, thereby inhibiting the dissolution process, whereas other additives may provide a finished, shiny substrate surface.
  • the additives may be present in the plating solution in concentrations up to about 15% by weight or volume, and may vary based upon the desired result after plating.
  • Optional additives include polyethylene glycol (PEG), polyethylene glycol derivatives, polyamides, polyimides including polyethyleneimide, polyglycine, 2-amino-1- napthalenesulfonic acid, 3-amino-1-propane-sulfnoic acid, 4-aminotoluene-2-sulfonic acid, polyacrylamide, polyacrylic acid polymers, polycarboxylate copolymers, coconut diethanolamide, oleic diethanolamide, ethanolamide derivatives, sulfur containing compounds such as sulfite or di-sulfite, and combinations thereof.
  • PEG polyethylene glycol
  • polyamides polyimides including polyethyleneimide, polyglycine, 2-amino-1- napthalenesulfonic acid, 3-amino-1-propane-sulfnoic acid, 4-aminotoluene-2-sulfonic acid
  • polyacrylamide polyacrylic acid polymers
  • polycarboxylate copolymers coconut diethanolamide, o
  • the metal ion source within the plating solution used in step 208 is a copper ion source.
  • the concentration of copper ions in the electrolyte may range from about 0.1 M to about 1.1 M, preferably from about 0.4 M to about 0.9 M.
  • Useful copper sources include copper sulfate (CuSO 4 ), copper chloride (CuCI 2 ), copper acetate (Cu(CO 2 CHs) 2 ), copper pyrophosphate (Cu 2 P 2 O 7 ), copper fluoroborate (Cu(BF 4 ) 2 ), derivatives thereof, hydrates thereof or combinations thereof.
  • the electrolyte composition can also be based on the alkaline copper plating baths (e.g., cyanide, glycerin, ammonia, etc) as well.
  • the electrolyte is an aqueous solution that contains between about 200 and 250 g/l of copper sulfate pentahydrate (CuSO4 # 5(H 2 O)), between about 40 and about 70 g/l of sulfuric acid (H 2 SO 4 ), and about 0.04 g/l of hydrochloric acid (HCI).
  • a low cost pH adjusting agent such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) to form an inexpensive electrolyte that has a desirable pH to reduce the cost of ownership required to form a metal contact structure for a solar cell.
  • TMAH tetramethylammonium hydroxide
  • the electrolyte is an aqueous solution that contains between about 220 and 250 g/l of copper fluoroborate (Cu(BF 4 ) 2 ), between about 2 and about 15 g/l of tetrafluoroboric acid (HBF 4 ), and about 15 and about 16 g/l of boric acid (H 3 BO 3 ).
  • a pH adjusting agent such as potassium hydroxide (KOH), or sodium hydroxide (NaOH) to form an inexpensive electrolyte that has a desirable pH to reduce the cost of ownership required to form a metal contact structure for a solar cell.
  • TMAH tetramethylammonium hydroxide
  • the electrolyte is an aqueous solution that contains between about 60 and about 90 g/l of copper sulfate pentahydrate (CuSO 4 » 5(H 2 O)), between about 300 and about 330 g/l of potassium pyrophosphate (K 4 P 2 O 7 ), and about 10 to about 35 g/l of 5-sulfosalicylic acid dehydrate sodium salt (C 7 H 5 O 6 SNa « 2H 2 O).
  • the electrolyte is an aqueous solution that contains between about 30 and about 50 g/l of copper sulfate pentahydrate (CuSO 4 « 5(H 2 O)), and between about 120 and about 180 g/l of sodium pyrophosphate decahydrate (Na 4 P 2 O 7 *10(H 2 O)).
  • a pH adjusting agent such as potassium hydroxide (KOH), or sodium hydroxide (NaOH) to form an inexpensive electrolyte that has a desirable pH to reduce the cost of ownership required to form a metal contact structure for a solar cell.
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • TMAH tetramethylammonium hydroxide
  • a second metal ion to the primary metal ion containing electrolyte bath (e.g., copper ion containing bath) that will plate out or be incorporated in the growing electrochemically deposited layer or on the grain boundaries of the electrochemically deposited layer.
  • the formation of a metal layer that contains a percentage of a second element can be useful to reduce the intrinsic stress of the formed layer and/or improve its electrical and electromigration properties.
  • a silver (Ag), nickel (Ni), zinc (Zn), tin (Sn), or lithium (Li) metal ion source to a copper plating bath to form a copper alloy that has between about 1 % and about 4% of the second metal in the deposited layer.
  • the metal ion source within the electrolyte solution used in step 208 is a silver, tin, zinc or nickel ion source.
  • the concentration of silver, tin, zinc or nickel ions in the electrolyte may range from about 0.1 M to about 0.4M.
  • Useful nickel sources include nickel sulfate, nickel chloride, nickel acetate, nickel phosphate, derivatives thereof, hydrates thereof or combinations thereof.
  • Suitable tin sources include soluble tin compounds.
  • a soluble tin compound can be a stannic or stannous salt.
  • the stannic or stannous salt can be a sulfate, an alkane sulfonate, or an alkanol sulfonate.
  • the bath soluble tin compound can be one or more stannous alkane sulfonates of the formula: (RSO 3 ⁇ Sn where R is an alkyl group that includes from one to twelve carbon atoms.
  • the stannous alkane sulfonate can be stannous methane sulfonate with the formula:
  • the bath soluble tin compound can also be stannous sulfate of the formula: SnSO 4
  • Examples of the soluble tin compound can also include tin(ll) salts of organic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, 2- propanolsulfonic acid, p-phenolsulfonic acid and like, tin(ll) borofluoride, tin(ll) sulfosuccinate, tin(ll) sulfate, tin(ll) oxide, tin(ll) chloride and the like.
  • tin(ll) salts of organic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, 2- propanolsulfonic acid, p-phenolsulfonic acid and like
  • tin(ll) borofluoride tin(ll) sulfosuccinate, tin(ll) sulfate, tin(ll) oxide, tin(ll) chloride and the like.
  • Example of suitable cobalt source may include cobalt salt selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt bromide, cobalt carbonate, cobalt acetate, ethylene diamine tetraacetic acid cobalt, cobalt (II) acetyl acetonate, cobalt (III) acetyl acetonate, glycine cobalt (III), and cobalt pyrophosphate, or combinations thereof.
  • cobalt salt selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt bromide, cobalt carbonate, cobalt acetate, ethylene diamine tetraacetic acid cobalt, cobalt (II) acetyl acetonate, cobalt (III) acetyl acetonate, glycine cobalt (III), and cobalt pyrophosphate, or
  • the plating solution contains free copper ions in place of copper source compounds and complexed copper ions.
  • the columnar metal layer 306 is formed using a diffusion limited deposition process.
  • the current densities of the deposition bias are selected such that the current densities are above the limiting current (i L ).
  • the limiting current When the limiting current is reached the columnar metal film is formed due to the evolution of hydrogen gas and resulting dendritic type film growth that occurs due to the mass transport limited process.
  • the deposition bias generally has a current density of about 10 A/cm 2 or less, preferably about 5 A/cm 2 or less, more preferably at about 3 A/cm 2 or less. In one embodiment, the deposition bias has a current density in the range from about 0.05 A/cm 2 to about 3.0 A/cm 2 .
  • the deposition bias has a current density between about 0.1 A/cm 2 and about 0.5 A/cm 2 . In yet another embodiment, the deposition bias has a current density between about 0.05 A/cm 2 and about 0.3 A/cm 2 . In yet another embodiment, the deposition bias has a current density between about 0.05 A/cm 2 and about 0.2 A/cm 2 . In one embodiment, this results in the formation of a columnar metal layer between about 1 micron and about 300 microns thick on the copper seed layer. In another embodiment, this results in the formation of a columnar metal layer between about 10 microns and about 30 microns.
  • the columnar metal layer 306 may be deposited using a multi-step plating process.
  • the multi-step plating process may use different current densities for each step.
  • the fifth process step 210 includes forming porous conductive dendritic structure 308 on the columnar metal layer 306.
  • the porous conductive dendritic structure 308 may be formed on the columnar metal layer 306 by increasing the voltage and corresponding current density from the deposition of the columnar metal layer.
  • the deposition bias generally has a current density of about 10 A/cm 2 or less, preferably about 5 A/cm 2 or less, more preferably at about 3 A/cm 2 or less. In one embodiment, the deposition bias has a current density in the range from about 0.3 A/cm 2 to about 3.0 A/cm 2 . In another embodiment, the deposition bias has a current density in the range of about 1 A/cm 2 and about 2 A/cm 2 .
  • the deposition bias has a current density in the range of about 0.5 A/cm 2 and about 2 A/cm 2 . In yet another embodiment, the deposition bias has a current density in the range of about 0.3 A/cm 2 and about 1 A/cm 2 . In yet another embodiment, the deposition bias has a current density in the range of about 0.3 A/cm 2 and about 2 A/cm 2 . In one embodiment, the porous conductive dendritic structure 308 has a porosity of between 30% and 70%, for example, about 50%, of the total surface area.
  • the porous conductive dendritic structure 308 may comprise one or more of various forms of porosities.
  • the porous conductive dendritic structure 308 comprises a macro-porous dendritic structure having pores of about 100 microns or less, wherein the non-porous portion of the macro-porous dendritic structure has pores of between about 2nm to about 50nm in diameter (meso-porosity).
  • the porous dendritic structure 308 comprises a macro-porous dendritic structure having pores of about 30 microns.
  • surfaces of the porous dendritic structure 308 may comprise nano-structures. The combination of micro-porosity, meso-porosity, and nano structure yields a significant increase in the surface area of the porous dendritic structure 308.
  • the porous dendritic structure 308 may be formed from a single material, such as copper, zinc, nickel, cobalt, palladium, platinum, tin, ruthenium, lithium, and other suitable material.
  • the porous dendritic structure 308 may comprise alloys of copper, zinc, nickel, cobalt, palladium, platinum, tin, ruthenium, lithium, combinations thereof, or other suitable materials.
  • the porous dendritic structure 308 comprises a copper-tin alloy.
  • a sixth processing step 212 can be performed to form an additional layer or passivation layer 310 on the porous dendritic structure 308, as shown in Figure 3F.
  • the passivation layer 310 has a thickness between about 1 nm and about 1000 nm. In another embodiment, the passivation layer 310 has a thickness between about 200 nm and about 800 nm. In yet another embodiment, the passivation layer 310 has a thickness between about 400 nm and about 600 nm.
  • the passivation layer 310 is a copper containing layer selected from the group comprising copper oxides (Cu 2 O, CuO, Cu 2 O-CuO), copper-chlorides (CuCI), copper-sulfides (Cu 2 S, CuS, Cu 2 S-CuS), copper-nitriles, copper-carbonates, copper-phosphides, copper-tin oxides, copper-cobalt-tin oxides, copper-cobalt-tin-titanium oxides, copper-silicon oxides, copper-nickel oxides, copper-cobalt oxides, copper-cobalt-tin-titanium oxides, copper-cobalt-nickel- aluminum oxides, copper-titanium oxides, copper-manganese oxides, and copper- iron phosphates.
  • copper oxides Cu 2 O, CuO, Cu 2 O-CuO
  • CuCI copper-chlorides
  • Cu 2 S, CuS, Cu 2 S-CuS copper-nitriles
  • copper-carbonates
  • the passivation layer 310 is an aluminum containing layer such as an aluminum-silicon layer.
  • the passivation layer 310 is a lithium containing layer selected from the group comprising lithium-copper-phosphorous-oxynitride (P-O-N), lithium-copper-boron- oxynitride (B-O-N), lithium-copper-oxides, lithium-copper-silicon oxides, lithium- copper-nickel oxides, lithium-copper-tin oxides, lithium-copper-cobalt oxides, lithium- copper-cobalt-tin-titanium oxides, lithium-copper-cobalt-nickel-aluminum oxides, lithium-copper-titanium oxides, lithium-aluminum-silicon, lithium-copper-manganese oxides, and lithium-copper-iron-phosphides.
  • lithium is inserted into the lithium containing layers after the first charge.
  • lithium is inserted into the passivation layer by exposing the passivation layer to a lithium containing solution.
  • lithium is deposited using a plasma spraying process.
  • the additional structures or layers 310 may comprise a metal or metal alloy layer.
  • the layer 310 may comprise a material selected from the group consisting of tin, cobalt, and combinations thereof.
  • the layer 310 can be formed by an electrochemical plating process.
  • the layer 310 provides high capacity and long cycle life for the electrode to be formed.
  • the porous structure 308 comprises copper and tin alloy and the layer 310 comprises a tin layer.
  • the porous structure 308 comprises cobalt and a tin alloy.
  • the layer 310 may be formed by immersing the substrate 300 in a new plating bath configured to plate the layer 310 after a rinsing step.
  • the electrode structure can be of any shape (e.g., circular, square, rectangle, polygonal, etc.) and size.
  • the type of electrode material is not limiting and can be made of any material that is conductive or that can be made conductive, such as a metal, plastic, graphite, polymers, carbon-containing polymer, composite, or other suitable materials. More specifically, the electrode material may comprise, for example, copper, zinc, nickel, cobalt, palladium, platinum, tin, ruthenium, stainless steel, alloys thereof, and combinations thereof.
  • a seventh processing step can be performed to anneal the substrate.
  • the substrate may be heated to a temperature in a range from about 100 0 C to about 250 0 C, for example, between about 150 0 C and about 190°C.
  • the substrate may be annealed in an atmosphere containing at least one anneal gas, such as O 2 , N 2 , NH 3 , N 2 H 4 , NO,
  • the substrate may be annealed in ambient atmosphere.
  • the substrate may be annealed at a pressure from about 5 Torr to about 100 Torr, for example, at about 50 Torr.
  • the annealing process serves to drive out moisture from the pore structure.
  • the annealing process serves to diffuse atoms into the copper base, for example, annealing the substrate allows tin atoms to diffuse into the copper base, making a much stronger copper-tin layer bond.
  • FIG. 2B is a flow diagram of a method 220 of forming an anode according to embodiments described herein.
  • FIG. 3G is a schematic cross-sectional view of an electrode 320 similar to electrode formed according to the embodiments described in FIG. 2B.
  • a columnar metal layer 326 similar to columnar metal layer 306 is formed over a copper foil substrate 324.
  • a three- dimensional porous dendritic structure 328 similar to three dimensional porous dendritic structure 308 is formed over the copper foil substrate 324.
  • Certain embodiments described herein further include lithiated electrodes and processes for forming lithiated electrodes by the application of a pre-lithiation process to the electrodes described herein.
  • the pre-lithiation process may be performed by adding a lithium source to the aforementioned plating solutions. Suitable lithium sources include but are not limited to LiH 2 PO 4 , LiOH, LiNO 3 , LiCH 3 COO, LiCI 1 Li 2 SO 4 , Li 3 PO 4 , Li(C 5 H 8 O 2 ), lithium surface stabilized particles (e.g. carbon coated lithium particles), and combinations thereof.
  • the pre- lithiation process may further comprise adding a complexing agent, for example, citric acid and salts thereof to the plating solution.
  • the pre- lithiation process results in an electrode comprising about 1-40 atomic percent lithium.
  • the pre-lithiation process results in an electrode comprising about 10-25 atomic percent lithium.
  • the pre-lithiation process may be performed by applying lithium to the electrode in a particle form using powder application techniques including but not limited to sifting techniques, electrostatic spraying techniques, thermal or flame spraying techniques, fluidized bed coating techniques, slit coating techniques, roll coating techniques, and combinations thereof, all of which are known to those skilled in the art.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 3 cm 2 .
  • a three dimensional porous copper electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, and 200 ppm of citric acid.
  • a columnar copper structure was deposited at a current density of about 0.4 A/cm 2 .
  • Three dimensional porous copper structures were deposited on the columnar metal layer at a current density of about 1.3 A/cm 2 . The process was performed at room temperature.
  • Example #2
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 25 cm 2 .
  • a three dimensional porous copper electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, and 200 ppm of citric acid.
  • a columnar copper structure was deposited at a current density of about 0.5 A/cm 2 .
  • Three dimensional copper porous dendritic structures were deposited on the columnar copper structure at a current density of about 1.5 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 1 m 2 .
  • a three dimensional copper porous electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, and 200 ppm of citric acid.
  • a columnar copper structure was deposited at a current density of about 0.5 A/cm 2 .
  • Three dimensional porous dendritic structures were deposited on the columnar copper structure at a current density of about 1.7 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 1 m 2 .
  • a three dimensional porous copper electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, and 200 ppm of citric acid.
  • a columnar copper structure was deposited at a current density of about 0.1 A/cm 2 .
  • Three dimensional porous copper dendritic structures were deposited on the columnar copper structure at a current density of about 1.5 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 25 cm 2 .
  • a three dimensional porous copper electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, and 200 ppm of citric acid.
  • a columnar copper structure was deposited at a current density of about 0.4 A/cm 2 .
  • Three dimensional copper porous dendritic structures were deposited on the columnar porous dendritic structure at a current density of about 2 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 25 cm 2 .
  • a three dimensional porous electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.25 M stannous sulfate, and 200 ppm of citric acid.
  • a columnar tin structure was deposited at a current density of about 0.05 A/cm 2 .
  • Three dimensional porous tin structures were deposited on the columnar tin structure at a current density of about 2 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 1 m 2 .
  • a three dimensional porous tin electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.25 M stannous sulfate, and 200 ppm of citric acid.
  • a columnar tin structure was deposited at a current density of about 0.3 A/cm 2 .
  • Three dimensional porous tin structures were deposited on the columnar tin structure at a current density of about 1.5 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 25 cm 2 .
  • a three dimensional porous copper-tin electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, 0.15 M stannous sulfate, and 200 ppm of citric acid.
  • a columnar copper-tin alloy structure was deposited at a current density of about 0.1 A/cm 2 .
  • Three dimensional copper-tin alloy porous dendritic structures were deposited on the columnar copper-tin alloy structure at a current density of about 1.0 A/cm 2 . The process was performed at room temperature.
  • a substrate was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 3 cm 2 .
  • a three dimensional copper-tin porous electrode structure was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, 0.23 M stannous sulfate, and 200 ppm of citric acid.
  • a columnar copper-tin structure was deposited at a current density of about 0.2 A/cm 2 .
  • Three dimensional porous copper-tin structures were deposited on the columnar copper-tin structure at a current density of about 1.0 A/cm 2 . The process was performed at room temperature.
  • a substrate comprising a titanium layer was placed in an electroplating chamber comprising a Pt(Ti) anode with a surface area of about 1 m 2 .
  • a three dimensional copper-tin-cobalt porous electrode was formed in a plating solution initially comprising 1.0 M sulfuric acid, 0.28 M copper sulfate, 0.23 M stannous sulfate, 0.20 cobalt sulfate, and 200 ppm of citric acid.
  • a columnar copper-tin-cobalt structure was deposited at a current density of about 0.30 A/cm 2 .
  • FIG. 4A schematically illustrates a plating system 400 using on which the embodiments described herein may be practiced.
  • the plating system 400 generally comprises a plurality of processing chambers arranged in a line, each configured to perform one processing step to a substrate formed on one portion of a continuous flexible base 410.
  • the processing chambers 401-406 are generally arranged along a line so that portions of the flexible base 410 can be streamlined through each chamber through feed rolls 407i -6 and take up rolls 408i -6 of each chamber.
  • the feed rolls 407i -6 and take up rolls 408i -6 may be activated simultaneously during substrate transferring step to move each portion of the flexible base 410 one chamber forward.
  • Other details of the plating system are disclosed in United States Serial No. 61/117,535, titled APPARATUS AND METHOD FOR FORMING 3D NANOSTRUCTURE ELECTRODE OF AN ELECTROCHEMICAL BATTERY AND CAPACITOR, to Lopatin et al., filed November 18, 2009, of which FIGS. 5A-5C, 6A-6E, 7A-7C, and 8A-8D and text corresponding to the aforementioned figures are incorporated by reference.
  • the processing system 420 comprises a first plating chamber 432 configured to perform a first plating process, for a example, a copper plating process, on at least a portion of the flexible conductive substrate 430.
  • the first plating chamber 432 is adapted to plate a copper conductive microstructure over the vertically oriented conductive flexible substrate 430.
  • the copper conductive microstructure comprises a columnar metal layer with a porous conductive dendritic structure deposited thereon.
  • the processing system 420 further comprises a first rinse chamber 434 configured to rinse and remove any residual plating solution from the portion of the vertically oriented conductive flexible substrate 430 with a rinsing fluid, for example, de-ionized water, after the first plating process.
  • a rinsing fluid for example, de-ionized water
  • the processing system 420 further comprises a second plating chamber 436 disposed next to the first rinse chamber 434.
  • the second plating chamber 436 is configured to perform a second plating process.
  • the second plating chamber 436 is adapted to deposit a second conductive material, for example, tin, over the vertically oriented conductive flexible substrate 430.
  • the processing system 420 further comprises a first drying chamber 448 disposed adjacent to the second spray coating chamber 446 configured to expose the vertically oriented conductive substrate 430 to a drying process.
  • the first drying chamber 448 is configured to perform a drying process such as an air drying process, an infrared drying process, or a marangoni drying process.
  • the processing system 420 further comprises a compression chamber 450 disposed adjacent to the first drying chamber 448 configured to expose the vertically oriented conductive substrate 430 to a calendaring process to compress the deposited powder into the conductive microstructure.
  • the processing system 420 further comprises a second drying chamber 454 disposed adjacent to the third spray coating chamber 452 configured to expose the vertically oriented conductive substrate 430 to a drying process.
  • the second drying chamber 454 is configured to perform a drying process such as an air drying process, an infrared drying process, or a marangoni drying process.
  • the processing system 420 further comprises additional processing chambers.
  • the additional modular processing chambers may comprise one or more processing chambers selected from the group of processing chambers comprising an electrochemical plating chamber, an electroless deposition chamber, a chemical vapor deposition chamber, a plasma enhanced chemical vapor deposition chamber, an atomic layer deposition chamber, a rinse chamber, an anneal chamber, a drying chamber, a spray coating chamber, and combinations thereof. It should also be understood that additional chambers or fewer chambers may be included in the in-line processing system.
  • the processing chambers 432-454 are generally arranged along a line so that portions of the vertically oriented conductive substrate 430 can be streamlined through each chamber through feed roll 460 and take up roll 462.
  • chamber 432 may be replaced with a chamber configured to perform aluminum oxide removal and chamber 436 may be replaced with an aluminum electro-etch chamber.
  • FIG. 6 is a representation of a SEM image of a three dimensionally plated electrode deposited according to embodiments described herein.
  • FIG. 6 depicts a schematic representation of tin nano-rod arrays.
  • the SEM image was taken at 201 X at a 36 degree tilt with respect to the lens, trigonometric tilt correction applied.
  • the nano-rods are connected to each other and to the substrate thus offering very low resistance.
  • FIGS. 7A-7D are schematic representations of SEM images of three dimensionally plated electrodes deposited according to embodiments described herein.
  • FIG. 7A is a representation of three dimensional copper-tin plated on copper foil. The SEM image was taken at 23X at a 36 degree tilt with respect to the lens, trigonometric tilt correction applied.
  • FIG. 7B is another representation of three dimensional copper-tin plated on copper foil. The SEM image was taken at 38X at a 36 degree tilt with respect to the lens, trigonometric tilt correction applied.
  • FIG. 7C is another representation of three dimensional copper-tin plated on copper foil. The SEM image was taken at 100X at a 36 degree tilt angle with respect to the lens, trigonometric tilt correction applied.
  • FIG. 7D is yet another representation of copper- tin plated on copper foil. The SEM image was taken at 37X at a 36 degree tilt angle with respect to the lens, trigonometric tilt correction applied.
  • FIG. 8 is an XRD spectra of plated copper-tin plated according to embodiments described herein and a copper-tin phase diagram.
  • the XRD spectra indicate the presence of Cu 6 Sn 5 which is the preferred medium for lithium ion absorbing medium.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
PCT/US2010/022597 2009-02-04 2010-01-29 Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors WO2010090956A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP10738991A EP2394322A2 (en) 2009-02-04 2010-01-29 Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors
KR1020117020743A KR101733134B1 (ko) 2009-02-04 2010-01-29 배터리 및 울트라 캐패시터용의 다공성 삼차원 구리, 주석, 구리―주석, 구리―주석―코발트 및 구리―주석―코발트―티타늄 전극
JP2011548343A JP2012516941A (ja) 2009-02-04 2010-01-29 電池およびウルトラキャパシタ用の銅、スズ、銅スズ、銅スズコバルト、および銅スズコバルトチタンの三次元多孔質電極
CN201080014859.8A CN102379050B (zh) 2009-02-04 2010-01-29 用于电池和超电容器的多孔三维铜、锡、铜锡、铜锡钴、及铜锡钴钛电极

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US14993309P 2009-02-04 2009-02-04
US61/149,933 2009-02-04
US15545409P 2009-02-25 2009-02-25
US61/155,454 2009-02-25
US15686209P 2009-03-02 2009-03-02
US61/156,862 2009-03-02
US12/459,313 US8486562B2 (en) 2009-02-25 2009-06-30 Thin film electrochemical energy storage device with three-dimensional anodic structure
US12/459,313 2009-06-30

Publications (2)

Publication Number Publication Date
WO2010090956A2 true WO2010090956A2 (en) 2010-08-12
WO2010090956A3 WO2010090956A3 (en) 2010-11-11

Family

ID=42542611

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/022597 WO2010090956A2 (en) 2009-02-04 2010-01-29 Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors

Country Status (6)

Country Link
EP (1) EP2394322A2 (zh)
JP (1) JP2012516941A (zh)
KR (1) KR101733134B1 (zh)
CN (1) CN102379050B (zh)
TW (1) TW201035383A (zh)
WO (1) WO2010090956A2 (zh)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102810671A (zh) * 2011-06-03 2012-12-05 株式会社半导体能源研究所 单层和多层石墨烯及其制造方法、具有单层和多层石墨烯的物体或电器设备
JP2013023709A (ja) * 2011-07-19 2013-02-04 Murata Mfg Co Ltd 多孔質金属膜、電極、集電体、電気化学センサ、蓄電デバイス及び摺動部材並びに多孔質金属膜の製造方法
US8822088B2 (en) 2011-09-16 2014-09-02 Semiconductor Energy Laboratory Co., Ltd. Power storage device
DE102015009944A1 (de) * 2015-06-29 2016-12-29 Diehl Metal Applications Gmbh Band aus einer Aluminium-Legierung
US9806331B2 (en) 2012-01-24 2017-10-31 Enovix Corporation Microstructured electrode structures
US10177400B2 (en) 2016-05-13 2019-01-08 Enovix Corporation Dimensional constraints for three-dimensional batteries
US10256507B1 (en) 2017-11-15 2019-04-09 Enovix Corporation Constrained electrode assembly
US10283807B2 (en) 2015-05-14 2019-05-07 Enovix Corporation Longitudinal constraints for energy storage devices
US10648096B2 (en) 2014-12-12 2020-05-12 Infineon Technologies Ag Electrolyte, method of forming a copper layer and method of forming a chip
KR20200056405A (ko) * 2017-09-25 2020-05-22 고쿠리츠 다이가쿠 호우징 지바 다이가쿠 도전성 나노 구조를 갖는 다공질 도전체, 그것을 이용한 축전 디바이스
US10707466B2 (en) 2013-03-15 2020-07-07 Enovix Corporation Separators for three-dimensional batteries
US10749207B2 (en) 2012-08-16 2020-08-18 Enovix Corporation Electrode structures for three-dimensional batteries
US11063299B2 (en) 2016-11-16 2021-07-13 Enovix Corporation Three-dimensional batteries with compressible cathodes
IT202100010658A1 (it) * 2021-04-27 2021-07-27 Novac S R L Metodo per elettrodeposizione in due fasi di materiale capacitivo da applicare nella costruzione di elettrodi per energy storage devices e materiale ottenuto con l'applicazione di tale metodo
IT202100010661A1 (it) * 2021-04-27 2021-07-27 Novac S R L Materiale nanostrutturato per elettrodi positivi di supercondensatori e relativo metodo di costruzione
US11128020B2 (en) 2017-11-15 2021-09-21 Enovix Corporation Electrode assembly, secondary battery, and method of manufacture
US11211639B2 (en) 2018-08-06 2021-12-28 Enovix Corporation Electrode assembly manufacture and device
US11296322B2 (en) 2011-06-03 2022-04-05 Semiconductor Energy Laboratory Co., Ltd. Single-layer and multilayer graphene, method of manufacturing the same, object including the same, and electric device including the same
US11411253B2 (en) 2020-12-09 2022-08-09 Enovix Operations Inc. Apparatus, systems and methods for the production of electrodes, electrode stacks and batteries
WO2022229994A1 (en) * 2021-04-27 2022-11-03 Novac S.R.L. Nanostructured material for positive electrodes of super capacitors and related construction method
US11495784B2 (en) 2020-09-18 2022-11-08 Enovix Operations Inc. Apparatus, systems and methods for the production of electrodes for use in batteries
US11942618B2 (en) 2017-06-20 2024-03-26 Coreshell Technologies, Incorporated Methods, systems, and compositions for the liquid-phase deposition of thin films onto the surface of battery electrodes
US11961991B2 (en) 2017-06-20 2024-04-16 Coreshell Technologies, Incorporated Solution-phase deposition of thin films on solid-state electrolytes
US11990609B2 (en) 2017-06-20 2024-05-21 Coreshell Technologies, Incorporated Solution-deposited electrode coatings for thermal runaway mitigation in rechargeable batteries

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012118840A2 (en) * 2011-02-28 2012-09-07 Applied Materials, Inc. Manufacturing of high capacity prismatic lithium-ion alloy anodes
PT106470A (pt) * 2012-07-27 2014-01-27 Inst Superior Tecnico Processo de eletrodeposição de revestimentos de níquel-cobalto com estrutura dendrítica
RU2658775C2 (ru) * 2012-11-08 2018-06-22 Монэ Руаяль Канадиен / Ройал Канадиан Минт Усовершенствованный способ получения золотой бронзы путем взаимной диффузии олова и меди в контролируемых условиях
KR101511984B1 (ko) * 2012-12-06 2015-04-14 한국표준과학연구원 구리산화물 나노구조체의 제조방법 및 리튬이온 이차전지용 음극의 제조방법
JP2014208395A (ja) * 2013-03-26 2014-11-06 学校法人 関西大学 微小構造体、電子素子、及び微小構造体の製造方法
KR101536432B1 (ko) * 2013-11-08 2015-07-13 주식회사 포스코 박판 주조용 주조롤의 표면 처리 방법 및 장치
KR101561961B1 (ko) 2014-03-19 2015-10-20 고려대학교 산학협력단 전고체상 박막형 수퍼커패시터 및 그 제조 방법
CN104851955A (zh) * 2015-04-09 2015-08-19 苏州晶品新材料股份有限公司 基于二次光学设计的柔性荧光基板及led光源
JP6621169B2 (ja) * 2015-04-28 2019-12-18 オーエム産業株式会社 めっき品の製造方法
TWI625430B (zh) * 2015-06-22 2018-06-01 薛康琳 金屬電極及其製備方法
CN106435665B (zh) * 2016-09-18 2019-04-05 中山大学 一种具有天然多尺度树枝状微针翅铜表面结构及其制备方法
CN106876657A (zh) * 2017-03-16 2017-06-20 盐城工学院 一种锂电池负极及其制备方法
CN107868966B (zh) * 2017-11-16 2019-08-13 中达电子(江苏)有限公司 铜合金多孔吸液芯及其制备方法
KR102176349B1 (ko) * 2018-11-08 2020-11-09 주식회사 포스코 리튬 금속 음극, 이의 제조 방법 및 이를 이용한 리튬 이차 전지
CN110629258A (zh) * 2019-10-16 2019-12-31 东莞领杰金属精密制造科技有限公司 一种多孔铜吸液芯的制备方法
CN111276672B (zh) * 2020-02-14 2021-07-20 苏州大学 含锡阵列结构的电极的制备及应用
CN112342584A (zh) * 2020-09-29 2021-02-09 扬州市景杨表面工程有限公司 一种心脏起搏器电容器件无磁化铜锡电镀工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006134894A (ja) * 2004-05-12 2006-05-25 Mitsui Mining & Smelting Co Ltd 非水電解液二次電池用負極及びその製造方法
JP2008098094A (ja) * 2006-10-16 2008-04-24 Matsushita Electric Ind Co Ltd リチウム二次電池用負極およびその製造方法
US20080261096A1 (en) * 2000-06-29 2008-10-23 Wolfgang Kollmann Method For Producing Cathodes and Anodes for Electrochemical Systems, Metallised Material Used Therein, Method and Device For Production of Said Metallised Material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100524900C (zh) * 2004-05-12 2009-08-05 三井金属矿业株式会社 非水电解液二次电池用负极及其制造方法
JP2008184651A (ja) 2007-01-30 2008-08-14 Dainippon Screen Mfg Co Ltd メッキシステムおよびメッキ方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080261096A1 (en) * 2000-06-29 2008-10-23 Wolfgang Kollmann Method For Producing Cathodes and Anodes for Electrochemical Systems, Metallised Material Used Therein, Method and Device For Production of Said Metallised Material
JP2006134894A (ja) * 2004-05-12 2006-05-25 Mitsui Mining & Smelting Co Ltd 非水電解液二次電池用負極及びその製造方法
JP2008098094A (ja) * 2006-10-16 2008-04-24 Matsushita Electric Ind Co Ltd リチウム二次電池用負極およびその製造方法

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102810671A (zh) * 2011-06-03 2012-12-05 株式会社半导体能源研究所 单层和多层石墨烯及其制造方法、具有单层和多层石墨烯的物体或电器设备
US11699790B2 (en) 2011-06-03 2023-07-11 Semiconductor Energy Laboratory Co., Ltd. Single-layer and multilayer graphene, method of manufacturing the same, object including the same, and electric device including the same
US11296322B2 (en) 2011-06-03 2022-04-05 Semiconductor Energy Laboratory Co., Ltd. Single-layer and multilayer graphene, method of manufacturing the same, object including the same, and electric device including the same
US10644315B2 (en) 2011-06-03 2020-05-05 Semiconductor Energy Laboratory Co., Ltd. Single-layer and multilayer graphene, method of manufacturing the same, object including the same, and electric device including the same
JP2013023709A (ja) * 2011-07-19 2013-02-04 Murata Mfg Co Ltd 多孔質金属膜、電極、集電体、電気化学センサ、蓄電デバイス及び摺動部材並びに多孔質金属膜の製造方法
US9911973B2 (en) 2011-09-16 2018-03-06 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US8822088B2 (en) 2011-09-16 2014-09-02 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US10403884B2 (en) 2012-01-24 2019-09-03 Enovix Corporation Electrode structures
US9806331B2 (en) 2012-01-24 2017-10-31 Enovix Corporation Microstructured electrode structures
US12009473B2 (en) 2012-08-16 2024-06-11 Enovix Corporation Electrode structures for three-dimensional batteries
US11600848B2 (en) 2012-08-16 2023-03-07 Enovix Corporation Electrode structures for three-dimensional batteries
US10749207B2 (en) 2012-08-16 2020-08-18 Enovix Corporation Electrode structures for three-dimensional batteries
US10707466B2 (en) 2013-03-15 2020-07-07 Enovix Corporation Separators for three-dimensional batteries
US11355816B2 (en) 2013-03-15 2022-06-07 Enovix Operations Inc. Separators for three-dimensional batteries
US10648096B2 (en) 2014-12-12 2020-05-12 Infineon Technologies Ag Electrolyte, method of forming a copper layer and method of forming a chip
US10283807B2 (en) 2015-05-14 2019-05-07 Enovix Corporation Longitudinal constraints for energy storage devices
US11894512B2 (en) 2015-05-14 2024-02-06 Enovix Corporation Longitudinal constraints for energy storage devices
US11239488B2 (en) 2015-05-14 2022-02-01 Enovix Corporation Longitudinal constraints for energy storage devices
DE102015009944B4 (de) 2015-06-29 2019-03-14 Diehl Metal Applications Gmbh Steckverbinder hergestellt aus einem Band aus einer Aluminium-Legierung
US10851441B2 (en) 2015-06-29 2020-12-01 Diehl Metal Applications Gmbh Plug-in connector and semi-finished product made from an aluminum alloy strip
CN107735846A (zh) * 2015-06-29 2018-02-23 迪尔金属应用有限公司 铝合金带材制成的插接器
DE102015009944A1 (de) * 2015-06-29 2016-12-29 Diehl Metal Applications Gmbh Band aus einer Aluminium-Legierung
US11081718B2 (en) 2016-05-13 2021-08-03 Enovix Corporation Dimensional constraints for three-dimensional batteries
US10177400B2 (en) 2016-05-13 2019-01-08 Enovix Corporation Dimensional constraints for three-dimensional batteries
US11444310B2 (en) 2016-05-13 2022-09-13 Enovix Operations Inc. Dimensional constraints for three-dimensional batteries
US11961952B2 (en) 2016-05-13 2024-04-16 Enovix Corporation Dimensional constraints for three-dimensional batteries
US11901514B2 (en) 2016-11-16 2024-02-13 Enovix Corporation Three-dimensional batteries with compressible cathodes
US11063299B2 (en) 2016-11-16 2021-07-13 Enovix Corporation Three-dimensional batteries with compressible cathodes
US11942618B2 (en) 2017-06-20 2024-03-26 Coreshell Technologies, Incorporated Methods, systems, and compositions for the liquid-phase deposition of thin films onto the surface of battery electrodes
US11990609B2 (en) 2017-06-20 2024-05-21 Coreshell Technologies, Incorporated Solution-deposited electrode coatings for thermal runaway mitigation in rechargeable batteries
US11961991B2 (en) 2017-06-20 2024-04-16 Coreshell Technologies, Incorporated Solution-phase deposition of thin films on solid-state electrolytes
US20200273631A1 (en) * 2017-09-25 2020-08-27 National University Corporation Chiba University Porous conductor having conductive nanostructure and electricity storage device using same
US11948740B2 (en) * 2017-09-25 2024-04-02 National University Corporation Chiba University Porous conductor having conductive nanostructure and electricity storage device using same
KR20200056405A (ko) * 2017-09-25 2020-05-22 고쿠리츠 다이가쿠 호우징 지바 다이가쿠 도전성 나노 구조를 갖는 다공질 도전체, 그것을 이용한 축전 디바이스
US11264680B2 (en) 2017-11-15 2022-03-01 Enovix Corporation Electrode assembly and secondary battery
US11600864B2 (en) 2017-11-15 2023-03-07 Enovix Corporation Constrained electrode assembly
US11128020B2 (en) 2017-11-15 2021-09-21 Enovix Corporation Electrode assembly, secondary battery, and method of manufacture
US10256507B1 (en) 2017-11-15 2019-04-09 Enovix Corporation Constrained electrode assembly
US11205803B2 (en) 2017-11-15 2021-12-21 Enovix Corporation Constrained electrode assembly
US11211639B2 (en) 2018-08-06 2021-12-28 Enovix Corporation Electrode assembly manufacture and device
US11495784B2 (en) 2020-09-18 2022-11-08 Enovix Operations Inc. Apparatus, systems and methods for the production of electrodes for use in batteries
US11811047B2 (en) 2020-09-18 2023-11-07 Enovix Corporation Apparatus, systems and methods for the production of electrodes for use in batteries
US11411253B2 (en) 2020-12-09 2022-08-09 Enovix Operations Inc. Apparatus, systems and methods for the production of electrodes, electrode stacks and batteries
WO2022229994A1 (en) * 2021-04-27 2022-11-03 Novac S.R.L. Nanostructured material for positive electrodes of super capacitors and related construction method
IT202100010658A1 (it) * 2021-04-27 2021-07-27 Novac S R L Metodo per elettrodeposizione in due fasi di materiale capacitivo da applicare nella costruzione di elettrodi per energy storage devices e materiale ottenuto con l'applicazione di tale metodo
IT202100010661A1 (it) * 2021-04-27 2021-07-27 Novac S R L Materiale nanostrutturato per elettrodi positivi di supercondensatori e relativo metodo di costruzione

Also Published As

Publication number Publication date
CN102379050A (zh) 2012-03-14
KR101733134B1 (ko) 2017-05-08
TW201035383A (en) 2010-10-01
CN102379050B (zh) 2014-06-11
JP2012516941A (ja) 2012-07-26
KR20110122177A (ko) 2011-11-09
WO2010090956A3 (en) 2010-11-11
EP2394322A2 (en) 2011-12-14

Similar Documents

Publication Publication Date Title
US8206569B2 (en) Porous three dimensional copper, tin, copper-tin, copper-tin-cobalt, and copper-tin-cobalt-titanium electrodes for batteries and ultra capacitors
KR101733134B1 (ko) 배터리 및 울트라 캐패시터용의 다공성 삼차원 구리, 주석, 구리―주석, 구리―주석―코발트 및 구리―주석―코발트―티타늄 전극
US9761882B2 (en) Manufacturing of high capacity prismatic lithium-ion alloy anodes
US8669011B2 (en) Nucleation and growth of tin particles into three dimensional composite active anode for lithium high capacity energy storage device
CN102405545B (zh) 具有三维阳极结构的薄膜电化学能量存储器件
KR101732608B1 (ko) 에너지 저장 디바이스 내의 3차원 구리 함유 전극의 고체 전해질 인터페이스를 위한 패시베이션 막
JP2019522879A (ja) 改善されたリチウム金属サイクリングのための中間相層
US20110129732A1 (en) Compressed powder 3d battery electrode manufacturing
US9493885B2 (en) Lithium-ion batteries with nanostructured electrodes and associated methods of making
EP2719003A2 (en) Batteries with nanostructured electrodes and associated methods

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080014859.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10738991

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2010738991

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011548343

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20117020743

Country of ref document: KR

Kind code of ref document: A