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WO2015199627A1 - A nano structured electrode production method - Google Patents

A nano structured electrode production method Download PDF

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Publication number
WO2015199627A1
WO2015199627A1 PCT/TR2014/000238 TR2014000238W WO2015199627A1 WO 2015199627 A1 WO2015199627 A1 WO 2015199627A1 TR 2014000238 W TR2014000238 W TR 2014000238W WO 2015199627 A1 WO2015199627 A1 WO 2015199627A1
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Prior art keywords
metal
production method
nano
substrate
nano structured
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PCT/TR2014/000238
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French (fr)
Inventor
Gokhan DEMIRCI
Oguzhan Orkut OKUDUR
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Aselsan Elektronik Sanayi Ve Ticaret Anonim Şirketi
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Publication of WO2015199627A1 publication Critical patent/WO2015199627A1/en

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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • H—ELECTRICITY
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    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
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    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
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    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to production method of nano-structured electrodes allowing fluid transfer in liquid or gas phase for applications of electric energy production and storage.
  • Nano structures offer considerable improvement potential in this area as in many other technological areas and the number of electrode material development studies that are based on nano technology are continuously increasing.
  • Metal oxides, particularly nano structured transition metal oxides attract considerable attention in electrode material researches due to their technical advantages and easy manufacturing in large volumes.
  • the current applications do not include any information about the hybrid electrode structure wherein transition metal oxide structures grown on electrically conductive substrates are first reduced to metallic form and then this metallic surface is modified by adding desired electrode materials, or any information about the electrode designs which are obtained by growing these hybrid electrode surface structures on porous substrates and which will allow fluid transfer.
  • An objective of the present invention is to provide a production method for electrodes having a high surface area and high electrical conductivity which are formed by attaching high electrical conductivity nano structures on high electrical conductivity metallic substrates directly with a metallic junction. This method eliminates the need for the usage of additional electrically conductive materials which are used to make nano structured metal oxide structures more suitable for use as an electrode by enhancing electrical conductivity and which cause additional volume, weight and cost.
  • An electrode structure having a high performance in terms of electrical conductivity is obtained by means of the metallic junction provided between the nano structures and the substrate.
  • Another objective of the present invention is to provide a production method for nano structured electrodes with a high mechanical strength without having to use binder materials that cause additional volume, weight and cost.
  • brittle transition metal oxide structures are converted to more flexible metal/oxide hybrid structures.
  • These hybrid structures that preserve transition metal oxide structures to a great extent also have a high porosity level. These properties help to minimize the high level stresses induced by effects like volume changes occurring due to electro deposition/dissolution on the cathode in lithium-oxygen batteries.
  • an electrode structure that allows fluid transfer, as required for the gas transfer in lithium-oxygen battery cathodes can be obtained by using substrates that have openings formed by various methods (perforated, foam, electroform, sieve, carbon fiber weave, etc.).
  • a further objective of the present invention is to provide a nano structured electrode design which increases electrochemical performance due to its morphology suitable for electrical charge and mass transfer. High electrode area and effective electrolyte access to a large portion of the nano structures decrease diffusion path. Electrical charge transfer in hybrid nano structures bound to the substrate by a direct metallic junction is easier when compared to the structure composed of only metal oxide.
  • the electrode structure of the present invention is low cost and suitable for mass production.
  • Figure 1 is the view of the steps of the nano structured electrode production method.
  • Figure 2 is the schematic view of the metal oxide grown on metallic substrate.
  • Figure 3 is the schematic view of the metal oxide converted to metal under reducing atmosphere.
  • Figure 4 is the schematic view of the 3 Dimensional metallic nano structure whose surface is modified and which is connected to the substrate with metallic junctions.
  • Figure 5 is the schematic view of the electrode having nano structures directly connected to the substrate with openings for an electrode design that allows fluid transfer.
  • a nano structured electrode production method (100) which enables to produce nano structured (N) electrodes (E) on a substrate (S) allowing fluid transfer for applications of electrical energy production and storage, basically comprises the steps of
  • protrusions that nucleate and protrude outwards on the nano structure (N) converted to metal ( 104).
  • the electrode structure can also be used as it is after each of the steps 101-102-103-104 without requiring the remaining processes in the other steps.
  • nano structured electrode production method (100) of the present invention first of all the metal oxides are produced attached on the electrically conductive metal substrates (S) (101).
  • hollow, nano rod, flower- like, plate-like, leaf-like, sea urchin-like metal oxides having a high surface area can be produced using various methods such as thermal oxidation, hydrothermal synthetic methods, solution based chemical precipitation methods, solid state thermal change of precursors, electrochemical methods, sonochemical synthesis, microwave synthesis, template assisted methods, sol-gel methods, micro-emulsion methods, electrospinning methods, synthesis methods that are combined with physical methods like spray pyrolysis, thermal based chemical vapor deposition.
  • Figure 2 schematically shows the metal oxide grown on a metallic substrate (S).
  • copper oxide in a sea urchin-like or flower-like form can be grown on a copper substrate (S). Even if the substrates (S) are not metal, they can be used for growing metal oxides thereon by being coated with a metal coating.
  • FIG. 1 shows a schematic view of the metal oxide converted to metal under reducing atmosphere.
  • a copper oxide structure is converted to a structure composed of metallic copper.
  • the metal oxides preserve their original morphologies to a great extent and remain attached to the electrically conductive substrate (S).
  • Figure 4 shows the schematic view of the three dimensional metallic nano structure (N) whose surface is modified and which is connected to the substrate (S) with metallic junctions.
  • the outer surface may be composed of the oxide of the metal as it is in the example of copper oxide on copper.
  • the surface of the transition metal can be formed by metals, alloys or compounds such that it is completely or partially coated.
  • protrusions that nucleate and protrude outwards can also be formed on the nano structure (N) (104).
  • the techniques disclosed in step (101) can be used for the said protruding structures formed in this step.
  • Figure 5 shows the schematic view of the nano structures (N) directly connected to the substrate (S) with openings (A) for an electrode (E) design that allows fluid transfer. Geometry and number of the openings (A) may be changed according to needs.
  • an opening (A) on the electrically conductive substrate (S) will not be needed in applications such as supercapacitor applications, wherein fluid transfer through the electrode (E) is not required; metal oxide growing process (101) and other process steps can be applied on substrates (S) such as imperforated foils or plates which are electrically conductive or the surfaces of which are made conductive.
  • substrates (S) such as imperforated foils or plates which are electrically conductive or the surfaces of which are made conductive.
  • various substrates (S) which are perforated, electroform, metal foam, sintered, sieve, carbon fiber weave, etc. can be used.
  • the substrates (S) may be electrically conductive or their surfaces may be made conductive.
  • the said substrates (S) are masked or cleaned partially to obtain a surface on which electrical connections (C) will be made.
  • the said electrical connection (C) can be at any suitable part of the electrode that connection can be made.
  • the said electrical connection (C) can be in the form of a partial area on the electrode (E), a protrusion protruding outwards from the electrode (E) or a frame that surrounds the entire electrode (E).

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a nano structured electrode production method (100) for applications of electric energy production and storage comprising the steps of growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101), converting metal oxide to metal under reducing atmosphere (102), modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103) and forming protrusions that nucleate and protrude outwards on the nano structure (N) converted to metal (104).

Description

DESCRIPTION
A NANO STRUCTURED ELECTRODE PRODUCTION METHOD Field of the Invention
The present invention relates to production method of nano-structured electrodes allowing fluid transfer in liquid or gas phase for applications of electric energy production and storage.
Background of the Invention
In systems used for producing and storing electric energy (battery, supercapacitor, fuel cell, photovoltaic batteries, etc.); energy density, service life and weight issues are getting more and more important. Nano structures offer considerable improvement potential in this area as in many other technological areas and the number of electrode material development studies that are based on nano technology are continuously increasing. Metal oxides, particularly nano structured transition metal oxides attract considerable attention in electrode material researches due to their technical advantages and easy manufacturing in large volumes.
In order to use transition metal oxides that are synthesized without using a substrate as electrodes; binders and electrical conductivity enhancing materials which cause additional volume, weight and cost are required to be used. On the other hand, there are problems observed due to inherent characteristics of the oxide materials such as poor electrical conductivity and low mechanical strength for nano structured metal oxide structures that can be grown on electrically conductive substrates. The article Nano Energy (2014) 6, J 9-26, Jiexi Wang et al. "Three-dimensional hierarchical Co^O^CuO nanowire heterostructure arrays on nickel foam for high-performance lithium ion batteries" in the state of the art, discloses a metal oxide application on a porous metal substrate.
The article J. Phys. Chem. C 2010, 114, 14368-14376, Khadga M. Shrestha et al, "Synthesis of CuO Nanorods, Reduction of CuO into Cu Nanorods, and Diffuse Reflectance Measurements of CuO and Cu Nanomaterials in the Near Infrared Region " in the state of the art discloses reduction of copper oxides into copper metal for an application other than electrochemical.
The article Electrochimica Acta 53 (2007) 951-956, Qimin Pan et al, "Flower- like CuO film-electrode for lithium ion batteries and the effect of surface morphology on electrochemical performance" in the state of the art discloses CuO coated electrodes in Li-ion batteries.
The current applications do not include any information about the hybrid electrode structure wherein transition metal oxide structures grown on electrically conductive substrates are first reduced to metallic form and then this metallic surface is modified by adding desired electrode materials, or any information about the electrode designs which are obtained by growing these hybrid electrode surface structures on porous substrates and which will allow fluid transfer.
Summary of the Invention
An objective of the present invention is to provide a production method for electrodes having a high surface area and high electrical conductivity which are formed by attaching high electrical conductivity nano structures on high electrical conductivity metallic substrates directly with a metallic junction. This method eliminates the need for the usage of additional electrically conductive materials which are used to make nano structured metal oxide structures more suitable for use as an electrode by enhancing electrical conductivity and which cause additional volume, weight and cost. An electrode structure having a high performance in terms of electrical conductivity is obtained by means of the metallic junction provided between the nano structures and the substrate.
Another objective of the present invention is to provide a production method for nano structured electrodes with a high mechanical strength without having to use binder materials that cause additional volume, weight and cost. With this method, brittle transition metal oxide structures are converted to more flexible metal/oxide hybrid structures. These hybrid structures that preserve transition metal oxide structures to a great extent also have a high porosity level. These properties help to minimize the high level stresses induced by effects like volume changes occurring due to electro deposition/dissolution on the cathode in lithium-oxygen batteries. Additionally, an electrode structure that allows fluid transfer, as required for the gas transfer in lithium-oxygen battery cathodes, can be obtained by using substrates that have openings formed by various methods (perforated, foam, electroform, sieve, carbon fiber weave, etc.).
A further objective of the present invention is to provide a nano structured electrode design which increases electrochemical performance due to its morphology suitable for electrical charge and mass transfer. High electrode area and effective electrolyte access to a large portion of the nano structures decrease diffusion path. Electrical charge transfer in hybrid nano structures bound to the substrate by a direct metallic junction is easier when compared to the structure composed of only metal oxide.
A large number of material combinations can be produced by using electrical, mechanical and electrochemical advantages provided by these electrodes based on hybrid nanostructures Furthermore, the electrode structure of the present invention is low cost and suitable for mass production.
Detailed Description of the Invention
Nano structured electrode production method developed to fulfill the objective of the present invention is illustrated in the accompanying figures, in which;
Figure 1 is the view of the steps of the nano structured electrode production method.
Figure 2 is the schematic view of the metal oxide grown on metallic substrate. Figure 3 is the schematic view of the metal oxide converted to metal under reducing atmosphere.
Figure 4 is the schematic view of the 3 Dimensional metallic nano structure whose surface is modified and which is connected to the substrate with metallic junctions.
Figure 5 is the schematic view of the electrode having nano structures directly connected to the substrate with openings for an electrode design that allows fluid transfer.
The components shown in the figures are each given reference numbers as follows:
100. Nano structured electrode production method
101. Growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer.
102. Converting metal oxide to metal under reducing atmosphere.
103. Modifying the surfaces of the structures converted to metal by applying various material combinations thereon.
104. Forming protrusions that nucleate and protrude outwards on the nano structure converted to metal. A. Opening
C. Electrical connection
E. Electrode
N. Nano structure
S. Substrate
A nano structured electrode production method (100) which enables to produce nano structured (N) electrodes (E) on a substrate (S) allowing fluid transfer for applications of electrical energy production and storage, basically comprises the steps of
growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101),
converting metal oxide to metal under reducing atmosphere (102),
- modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103),
forming protrusions that nucleate and protrude outwards on the nano structure (N) converted to metal ( 104).
According to the embodiment, the electrode structure can also be used as it is after each of the steps 101-102-103-104 without requiring the remaining processes in the other steps.
In the nano structured electrode production method (100) of the present invention, first of all the metal oxides are produced attached on the electrically conductive metal substrates (S) (101). During this production stage; hollow, nano rod, flower- like, plate-like, leaf-like, sea urchin-like metal oxides having a high surface area can be produced using various methods such as thermal oxidation, hydrothermal synthetic methods, solution based chemical precipitation methods, solid state thermal change of precursors, electrochemical methods, sonochemical synthesis, microwave synthesis, template assisted methods, sol-gel methods, micro-emulsion methods, electrospinning methods, synthesis methods that are combined with physical methods like spray pyrolysis, thermal based chemical vapor deposition. Figure 2 schematically shows the metal oxide grown on a metallic substrate (S). For example, copper oxide in a sea urchin-like or flower-like form can be grown on a copper substrate (S). Even if the substrates (S) are not metal, they can be used for growing metal oxides thereon by being coated with a metal coating.
After nano structures with high surface area (N) are obtained, the said nano structures (N) are converted to metal under a reducing gas such as hydrogen, formic acid, etc. (102). Figure 3 shows a schematic view of the metal oxide converted to metal under reducing atmosphere. For example a copper oxide structure is converted to a structure composed of metallic copper. In the process of conversion to metal, the metal oxides preserve their original morphologies to a great extent and remain attached to the electrically conductive substrate (S).
Various material combinations are applied on these metal structures, which are integrated with the electrically conductive substrate (S), by means of chemical, electrochemical or thin film methods (103). This way, various material combinations including precious metals, alloys, metal oxides can be formed on metal nano structure (N) by changing the surfaces of the metallic nano structures (N). As a result of this procedure, electrochemical behaviors of nano structured (N) electrodes ((E) are enabled to be developed. For example, by partial oxidation of the metal structure; a hybrid structure, which has oxidized outer layer and metallic core that is attached well to the metallic substrate (S) with a metallic joint, is obtained. Similarly various material layers in different morphologies can be added on top of this metallic nano structure (N). These hybrid nano structures (N) will enable to produce an electrode (E) comprising various material combinations for high initial reversible capacity and capacity retention over extended cycling.
Figure 4 shows the schematic view of the three dimensional metallic nano structure (N) whose surface is modified and which is connected to the substrate (S) with metallic junctions. The outer surface may be composed of the oxide of the metal as it is in the example of copper oxide on copper. In another embodiment, the surface of the transition metal can be formed by metals, alloys or compounds such that it is completely or partially coated. In another embodiment of the invention, protrusions that nucleate and protrude outwards can also be formed on the nano structure (N) (104). For the said protruding structures formed in this step, the techniques disclosed in step (101) can be used.
Figure 5 shows the schematic view of the nano structures (N) directly connected to the substrate (S) with openings (A) for an electrode (E) design that allows fluid transfer. Geometry and number of the openings (A) may be changed according to needs.
Since an opening (A) on the electrically conductive substrate (S) will not be needed in applications such as supercapacitor applications, wherein fluid transfer through the electrode (E) is not required; metal oxide growing process (101) and other process steps can be applied on substrates (S) such as imperforated foils or plates which are electrically conductive or the surfaces of which are made conductive. In applications wherein fluid transfer is necessary between the electrochemical cell and outside of the cell through the electrode (for example the cathode structure in metal-air batteries); various substrates (S) which are perforated, electroform, metal foam, sintered, sieve, carbon fiber weave, etc. can be used. Again in these embodiments, the substrates (S) may be electrically conductive or their surfaces may be made conductive. The said substrates (S) are masked or cleaned partially to obtain a surface on which electrical connections (C) will be made. The said electrical connection (C) can be at any suitable part of the electrode that connection can be made. The said electrical connection (C) can be in the form of a partial area on the electrode (E), a protrusion protruding outwards from the electrode (E) or a frame that surrounds the entire electrode (E).

Claims

A nano structured electrode production method (100) which enables to produce nano structured (N) electrodes (E) on a substrate (S) allowing fluid transfer in gas and liquid phase for electrochemical applications, basically characterized by the steps of
growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101),
converting metal oxide to metal under reducing atmosphere (102),
modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103).
A nano structured electrode production method (100) according to Claim 1, characterized in that the metal oxides are grown on an electrically conductive metal substrate (S) in the step of "growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101)".
A nano structured electrode production method (100) according to Claim 1, characterized in that a non-metal substrate (S) is coated with a metal coating and a metal oxide is grown thereon in the step of "growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101)".
A nano structured electrode production method (100) according to any one of the preceding claims, characterized in that hollow, nano rod, sea urchin-like, flower-like, plate-like, leaf-like metal oxides having a high surface area are grown on a substrate (S) in the step of "growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101)".
A nano structured electrode production method (100) according to any one of the preceding claims, characterized in that in applications wherein fluid transfer is necessary between the electrochemical cell and outside of the cell through the electrode (for example the cathode structure in metal-air batteries); various substrates (S) which are perforated, electroform, metal foam, sintered, sieve, carbon fiber weave, etc. are used in the step of "growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101)".
A nano structured electrode production method (100) according to Claim 1, characterized in that in applications such as supercapacitor applications, wherein fluid transfer through the electrode (E) is not required; metal oxide growing process (101) is performed on substrates (S) such as imperforated foils or plates which do not have an opening (A) and which are electrically conductive or the surfaces of which are made conductive in the step of "growing metal oxides on a substrate (S) having at least one opening (A) allowing fluid transfer (101)".
7. A nano structured electrode production method (100) according to Claim 6, characterized in that a surface; on which electrical connections (C) will be made, and which is in the form of a partial area on the electrode (E), a protrusion protruding from the electrode (E) or a frame that surrounds the entire electrode (E); is obtained by partially masking or cleaning the substrates (S).
8. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that various material combinations including precious metals, alloys, metal oxides are formed on metal nano structure (N) in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
9. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that by partial oxidation of the metal structure; a hybrid structure, which has oxidized outer layer and metallic core that is attached well to the metallic substrate (S) with a metallic joint, is obtained in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
10. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that various material layers in different morphologies are added on top of this metallic nano structure (N) in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
11. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that the outer surface of the metal oxide is composed of its own oxide in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
12. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that the surface of the metal is formed by metals, alloys or compounds such that it is completely coated in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon ( 103)".
13. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that the surface of the metal is formed by metals, alloys or compounds such that it is partially coated in the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
14. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that by the step of "forming protrusions that nucleate on the nano structure (N) converted to metal (104)" carried out after the step of "modifying the surfaces of the structures converted to metal by applying various material combinations thereon (103)".
15. A nano structured electrode production method (100) according to any one of preceding claims, characterized in that the nucleating structures are formed in the form of a protrusion protruding outwards in the step of "forming protrusions that nucleate on the nano structure (N) converted to metal (104)".
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