WO2005124901A1 - Hybrid superelastic metal-metal sulfide materials for current collector and anode of battery - Google Patents

Hybrid superelastic metal-metal sulfide materials for current collector and anode of battery Download PDF

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WO2005124901A1
WO2005124901A1 PCT/KR2004/001763 KR2004001763W WO2005124901A1 WO 2005124901 A1 WO2005124901 A1 WO 2005124901A1 KR 2004001763 W KR2004001763 W KR 2004001763W WO 2005124901 A1 WO2005124901 A1 WO 2005124901A1
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Prior art keywords
current collector
atom
anode
metal
battery
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PCT/KR2004/001763
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French (fr)
Inventor
Tae-Hyun Nam
Hyo-Jun Ahn
Ki-Won Kim
Kwon-Koo Cho
Jou-Hyeon Ahn
Su-Mun Park
Hwi-Beom Shin
Hyun-Chil Choi
Jong-Uk Kim
Gyu-Bong Cho
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Industry-Academic Cooperation Foundation Gyeongsang National University
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Priority to US11/629,465 priority Critical patent/US20080066832A1/en
Priority to JP2007516374A priority patent/JP4744515B2/en
Publication of WO2005124901A1 publication Critical patent/WO2005124901A1/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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • 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
    • H01M4/04—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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • 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
    • H01M4/70—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

Definitions

  • the present invention relates to a hybrid superelastic metal-metal sulfide materials for current collector and anode of battery, more precisely a hybrid sulfide materials for current collector and anode which use a plate materials and wire materials of Ti-Ni superelastic alloy as current collector, and produce a Ti, Ni sulfide at a surface of current collector to allow to use as an active materials of positive electrode, and perform a role of current collector and anode of battery with one material by endowing all materials with superelastic characteristic, and have a thin plate and fine wire shape.
  • the present invention is proposed under consideration of the above-described drawback for conventional current collector, and is achieved by producing a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.
  • DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM The object of the present invention is to provide a hybrid superelastic metal-metal sulfide material for current collector and anode of battery.
  • the above-mentioned object of the present invention can be achieved by providing a hybrid superelastic metal- metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.
  • Figure 1 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of thin plate shape according to the present invention.
  • Figure 2 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of fine wire shape according to the present invention ' .
  • Figure 3 is a graph showing superelastic characteristic of Ti-Ni alloy.
  • Figure 4 is a schematic view showing a producing apparatus of hybrid materials for current collector and anode.
  • Figure 5 is X-ray diffraction pattern of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Mo current collector and anode.
  • Figure 6 is a graph showing superelastic characteristic of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Cu current collector and anode.
  • Figure 7 is a graph showing battery characteristic of hybrid superelastic metal-metal sulfide materials for Ti- Ni-Cr current collector and anode.
  • the present invention is characterized in that it provide a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.
  • a hybrid superelastic metal- metal sulfide material for current collector and anode for battery can be produced with a thin plate or fine wire shape according to its usage.
  • Figure 1 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of thin plate shape according to the present invention.
  • a superelastic alloy of Ti-Ni is used as current collector (1) , and a Ti and Ni sulfide (2) is produced at one side of current collector.
  • Figure 2 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of fine wire shape.
  • a superelastic alloy of Ti-Ni is used as current collector (1) , and a Ti and Ni sulfide (2) is produced around current collector.
  • a superelastic effect means phenomenon that stress is added to material at mother phase state of high temperature to produce stress organic martensite so that material is deformed, and then it is returned to original shape with removing stress.
  • Figure 3 is a graph showing superelastic characteristic of Ti-Ni alloy. A deformity of about 3% is formed by metamorphosis of stress organic martensite provided that an alloy is heated to produce mother phase, and then added stress (Fig. 3a) . And when removing stress, its deformity is totally restored with changing martensite to mother phase (Fig. 3b) .
  • the above-described superelastic effect is obtained at two phase alloy of Ti-Ni as well as three phase alloy of
  • Ti-Ni-X In two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %. In three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, molybdenum (Mo) of 0.1 - 2.5 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5
  • FIG. 4 is a schematic view showing a producing apparatus of hybrid materials for current collector and anode.
  • two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X as current collector (1) is introduced into furnace for heat treatment (3) under vacuum state, and sulfur (4) of solid state is also introduced simultaneously and then it is heated at 400 - 700 ° Cfor 1 - 30 hours. If heating temperature is low than 400 ° C or heating time is below 1 hour, formation of sulfide is imperfect. Also, if heating temperature is higher than 700 °Q oxidation is generated. Also, heating time exceed 30 hours, there is no change of amount of sulfide formation.
  • Figure 5 is X-ray diffraction pattern of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Mo current collector and anode. There is shown that Ti sulfide and Ni sulfide is produced at a surface of materials. A similar result is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %.
  • concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %.
  • FIG. 6 is a graph showing superelastic characteristic of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Cu current collector and anode. There is shown that superelastic characteristic present similar to before of sulfide formation. A similar superelastic characteristic is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %.
  • concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %.
  • FIG. 7 is a graph showing battery characteristic of hybrid superelastic metal-metal sulfide materials for Ti- Ni-Cr current collector and anode.
  • a similar battery characteristic is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %.
  • concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %. If concentration of each atom is departed from the above range, there is no superelastic effect.
  • the present invention relates to a hybrid superelastic metal-metal sulfide materials for current collector and anode of battery, and is very useful in electric and electronic industry since it is provide a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape which use .
  • two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.

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Abstract

The present invention relates to a hybrid superelastic metal-metal sulfide materials for current collector and anode of battery, which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X as current collector, and produce a Ti, Ni sulfide at a surface of current collector with an inside sulfide method to allow to use as an active materials of positive electrode, and perform a role of current collector and anode of battery with one material by endowing all materials with superelastic characteristic, and it have an excellent effect providing a hybrid superelastic metal-metal sulfide materials for current collector and anode having thin plate and fine wire shape.

Description

DESCRIPTION HYBRID SUPERELASTIC METAL-METAL SULFIDE MATERIALS FOR CURRENT COLLECTOR AND ANODE OF BATTERY
TECHNICAL FIELD The present invention relates to a hybrid superelastic metal-metal sulfide materials for current collector and anode of battery, more precisely a hybrid sulfide materials for current collector and anode which use a plate materials and wire materials of Ti-Ni superelastic alloy as current collector, and produce a Ti, Ni sulfide at a surface of current collector to allow to use as an active materials of positive electrode, and perform a role of current collector and anode of battery with one material by endowing all materials with superelastic characteristic, and have a thin plate and fine wire shape.
BACKGROUND ART Conventional battery is generally consisted of cathode, anode, electrolyte, and current collector. Current collector plays role collecting electricity produced from battery during discharging. Reducing reaction is generated at anode by an electron produced from cathode. Cupper (Cu) , stainless steel and the like are used as current collector, and metal oxide, sulfide, hydroxide and the like are used as anode by now. At conventional battery, current collector is generated a plasticity change according to change of battery pattern. There is characteristic that a flexible battery whose use spectrum is expanded in recent is able to exchange its form according to a purpose of use. However, when using conventional current collector, processing hardening is occurred by generating a plasticity change according to repeated change of form so that hardening and breakage of current collector are generated. Therefore, the present invention is proposed under consideration of the above-described drawback for conventional current collector, and is achieved by producing a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form. DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM The object of the present invention is to provide a hybrid superelastic metal-metal sulfide material for current collector and anode of battery.
TECHNICAL SOLUTION The above-mentioned object of the present invention can be achieved by providing a hybrid superelastic metal- metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.
DESCRIPTION OF DRAWINGS Other objects and aspects of the present invention will become apparent from the following description of embodiments with reference to the accompanying drawing in which: Figure 1 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of thin plate shape according to the present invention. Figure 2 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of fine wire shape according to the present invention'. Figure 3 is a graph showing superelastic characteristic of Ti-Ni alloy. Figure 4 is a schematic view showing a producing apparatus of hybrid materials for current collector and anode. Figure 5 is X-ray diffraction pattern of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Mo current collector and anode. Figure 6 is a graph showing superelastic characteristic of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Cu current collector and anode. Figure 7 is a graph showing battery characteristic of hybrid superelastic metal-metal sulfide materials for Ti- Ni-Cr current collector and anode.
BEST MODE The present invention will be described in detail by preferable embodiments with reference to the accompanying drawing as the following description. The present invention is characterized in that it provide a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery having superelastic characteristic which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form. In the present invention, a hybrid superelastic metal- metal sulfide material for current collector and anode for battery can be produced with a thin plate or fine wire shape according to its usage. Concrete structure and effects of the present invention will be described in detail with reference to the accompanying drawing. Figure 1 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of thin plate shape according to the present invention. A superelastic alloy of Ti-Ni is used as current collector (1) , and a Ti and Ni sulfide (2) is produced at one side of current collector. Figure 2 is a constructing view showing hybrid superelastic metal-metal sulfide materials for current collector and anode of fine wire shape. A superelastic alloy of Ti-Ni is used as current collector (1) , and a Ti and Ni sulfide (2) is produced around current collector. A superelastic effect means phenomenon that stress is added to material at mother phase state of high temperature to produce stress organic martensite so that material is deformed, and then it is returned to original shape with removing stress. Figure 3 is a graph showing superelastic characteristic of Ti-Ni alloy. A deformity of about 3% is formed by metamorphosis of stress organic martensite provided that an alloy is heated to produce mother phase, and then added stress (Fig. 3a) . And when removing stress, its deformity is totally restored with changing martensite to mother phase (Fig. 3b) . The above-described superelastic effect is obtained at two phase alloy of Ti-Ni as well as three phase alloy of
Ti-Ni-X. In two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %. In three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, molybdenum (Mo) of 0.1 - 2.5 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %. If concentration of each atom is departed from the above range, there is no superelastic effect. Figure 4 is a schematic view showing a producing apparatus of hybrid materials for current collector and anode. First, two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X as current collector (1) is introduced into furnace for heat treatment (3) under vacuum state, and sulfur (4) of solid state is also introduced simultaneously and then it is heated at 400 - 700°Cfor 1 - 30 hours. If heating temperature is low than 400 °C or heating time is below 1 hour, formation of sulfide is imperfect. Also, if heating temperature is higher than 700 °Q oxidation is generated. Also, heating time exceed 30 hours, there is no change of amount of sulfide formation. Figure 5 is X-ray diffraction pattern of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Mo current collector and anode. There is shown that Ti sulfide and Ni sulfide is produced at a surface of materials. A similar result is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %. In the above three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %. If concentration of each atom is departed from the above range, there is no superelastic effect. Figure 6 is a graph showing superelastic characteristic of hybrid superelastic metal-metal sulfide materials for Ti-Ni-Cu current collector and anode. There is shown that superelastic characteristic present similar to before of sulfide formation. A similar superelastic characteristic is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %. In the above three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %. If concentration of each atom is departed from the above range, there is no superelastic effect. Figure 7 is a graph showing battery characteristic of hybrid superelastic metal-metal sulfide materials for Ti- Ni-Cr current collector and anode. A similar battery characteristic is also obtained from two phase alloy of Ti- Ni and Ti-Ni-X alloy. In the above two phase alloy of Ti-Ni, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 48.0 - 52.0 atom %. In the above three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, cobalt (Co) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom %. If concentration of each atom is departed from the above range, there is no superelastic effect.
ADVANTAGEOUS EFFECTS The present invention relates to a hybrid superelastic metal-metal sulfide materials for current collector and anode of battery, and is very useful in electric and electronic industry since it is provide a hybrid superelastic metal-metal sulfide materials for current collector and anode for battery of a thin plate and fine wire shape which use .two phase alloy of Ti-Ni or three phase alloy of Ti-Ni-X having superelastic characteristic as current collector, thereby producing a Ti and Ni sulfide at a surface of current collector to allow to remove stress after deformity of current collector and anode and return to its initial form.

Claims

CLAIMS 1. A hybrid superelastic metal-metal sulfide materials for current collector and anode of battery which use two phase alloy of Ti-Ni or three phase alloy of Ti-Ni- X as current collector, and produce a Ti, Ni sulfide at a surface of current collector with an inside sulfide method to allow to use as an active materials of positive electrode, and perform a role of current collector and anode of battery with one material by endowing all materials with superelastic characteristic.
2. A hybrid superelastic metal-metal sulfide materials for current collector and anode of battery of the above claim 1, wherein in the above three phase alloy of Ti-Ni-X, concentration of Ti is in range of 48.0 - 52.0 atom %, and concentration of Ni is in range of 23.0 - 51.95 atom %, and X is any one selected from a group consisted of iron (Fe) of 0.1 - 2.0 atom %, aluminum (Al) of 0.1 - 2.0 atom %, molybdenum (Mo) of 0.1 - 2.5 atom %, cobalt (Co) of 0.05 - 1.5 atom %, chromium (Cr) of 0.05 - 1.5 atom %, vanadium (V) of 0.1 - 2.5 atom %, cupper (Cu) of 1.0 - 25.0 atom %, manganese (Mn) of 0.05 - 1.5 atom %, hafnium (Hf) of 1.0 - 25.0 atom %, and zirconium (Zr) of 1.0 - 25.0 atom % .
3. A hybrid superelastic metal-metal sulfide materials for current collector and anode of battery of the above claim 1, wherein the above materials is produced with a thin plate or fine wire shape.
4. A hybrid superelastic metal-metal sulfide materials for current collector and anode of battery of the above claim 1, wherein the above inside sulfide method is that a vaporized sulfur is contacted to the above surface of current collector and then it is heated at 400 - 700 °C for 1 - 30 hours.
PCT/KR2004/001763 2004-06-16 2004-07-15 Hybrid superelastic metal-metal sulfide materials for current collector and anode of battery WO2005124901A1 (en)

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