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WO2013137665A1 - Ensemble électrode négative pour batterie secondaire au lithium, et procédé de fabrication associé - Google Patents

Ensemble électrode négative pour batterie secondaire au lithium, et procédé de fabrication associé Download PDF

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Publication number
WO2013137665A1
WO2013137665A1 PCT/KR2013/002066 KR2013002066W WO2013137665A1 WO 2013137665 A1 WO2013137665 A1 WO 2013137665A1 KR 2013002066 W KR2013002066 W KR 2013002066W WO 2013137665 A1 WO2013137665 A1 WO 2013137665A1
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lithium
network layer
conductive network
conductive
layer
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PCT/KR2013/002066
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English (en)
Korean (ko)
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김철환
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(주)오렌지파워
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • 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
    • 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
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 secondary battery technology, and more particularly, to a negative electrode assembly for a lithium secondary battery and a manufacturing method thereof.
  • a secondary battery is a battery which can be charged and discharged by using an electrode material having excellent reversibility, and is a nickel-hydrogen (Ni-MH) battery, a lithium (Li) battery, a lithium ion (Li-ion) battery, etc. according to a positive electrode and a negative electrode active material. It can be divided into.
  • Such secondary batteries are increasingly being applied as a power source for smart devices such as smart phones, portable computers, and electronic devices such as electronic paper, or vehicles such as bicycles and electric vehicles.
  • Secondary batteries using lithium or a compound thereof as a negative electrode active material have high voltage and high energy density and have been the subject of many studies.
  • chemical reactions due to charging and discharging and natural chemical reactions occur constantly, and thus, lithium dendrite, which is an undesirable crystalline protrusion in the metallic lithium anode, may be formed. have.
  • the pores of the separator may be blocked, and thus the movement of the ionic material may be blocked. As a result, the charging and discharging efficiency of the battery may be reduced, thereby reducing the life of the secondary battery.
  • the dendritic lithium when the dendritic lithium is excessively grown, the dendritic lithium may penetrate the separator to short-circuit the positive and negative electrodes of the secondary battery.
  • the technical problem to be solved by the present invention is to provide a negative electrode assembly with improved charging and discharging efficiency and lifespan.
  • Another technical problem to be solved by the present invention is to provide a method for producing a negative electrode assembly having the above advantages.
  • the negative electrode assembly for solving the above technical problem, extends in at least two different directions to be in contact with each other, the conductive wire to form a three-dimensional solid with pores formed from the surface to the inside And a conductive network layer including the conductive network layer, wherein lithium is electrodeposited on the conductive wires through the pores when the battery is charged, and the lithium electrodeposited on the conductive wires is ionized and detached when the battery is discharged. As the battery is charged and discharged, electrodeposition and detachment of the lithium are repeated.
  • the conductive network layer may have a nonwoven structure. Further, in another embodiment, the conductive network layer may have a lattice structure. In addition, at least a portion of the conductive network layer may have an increased porosity in the direction of the anode facing the cathode assembly in the conductive network layer.
  • the conductive wires may comprise any one or combination of stainless steel, nickel, titanium, tantalum, copper, gold, platinum, ruthenium, silver or alloys thereof.
  • the conductive wires may include a lithium compound.
  • the negative electrode assembly may further comprise a lithium source comprising any one or a combination of lithium and lithium compounds provided in the pores of the conductive network layer or bonded onto the surface of the conductive network layer.
  • a lithium source comprising any one or a combination of lithium and lithium compounds provided in the pores of the conductive network layer or bonded onto the surface of the conductive network layer.
  • the lithium source provided in the pores of the conductive network layer may have a powder form.
  • the lithium source bonded on the surface of the conductive network layer may be a gap containing metal foil.
  • a current collecting tab or lead wire may be coupled to the conductive network layer.
  • the cathode assembly may further include a binder layer on the surface of the conductive network layer for adhesion with an adjacent layer, wherein the binder layer may include linear binders.
  • the adjacent layer may include any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane.
  • the negative electrode assembly may further include linear binders mixed with the conductive wires in the conductive network layer.
  • the negative electrode assembly may further include an adjacent layer adhered to the conductive network layer, and the adjacent layer includes any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane. can do.
  • a method of manufacturing a negative electrode assembly which extends in at least two different directions to be in contact with each other, and has a three-dimensional shape with pores formed therein from a surface thereof.
  • a method of manufacturing a negative electrode assembly which extends in at least two different directions to be in contact with each other, and has three-dimensional shapes with pores formed therein from the surface thereof.
  • the adjacent layer may include any one of a lithium-containing metal foil, a current collector layer, a conductive network layer, a separator, and an electrolyte membrane.
  • the step of heating the binder layer may be further performed.
  • a conductive network layer including conductive wires having conductive pores formed from the surface to form a three-dimensional solid, and the charging and discharging of the battery causes the pores on the conductive wires.
  • the conductive network layer randomly provides a linear reaction site in the three-dimensional space from the standpoint of lithium ions penetrated therein, so that lithium electrodeposited on the surface of the conductive wires is ordered in any particular direction. It is possible to provide a negative electrode assembly which cannot grow freely, thereby suppressing orderly growth of lithium such as dendritic growth.
  • the negative electrode assembly can be manufactured by only linear contact or point contact using linear binders, there is provided a method of manufacturing a negative electrode assembly that provides excellent mechanical adhesion without increasing the internal resistance of the negative electrode. Can be.
  • the performance of the linear binder can be expressed by pressing and heating without an organic solvent, there is no performance deterioration due to the drying process and impurities due to the organic solvent, environmentally friendly with less environmental load The manufacturing process of a negative electrode assembly can be obtained.
  • FIG. 1A is a perspective view of a negative electrode assembly according to an embodiment of the present invention
  • FIG. 1B is a cross-sectional view taken along line II ′ of FIG. 1A
  • FIG. 1C is a partially enlarged view illustrating conductive wires of the negative electrode assembly.
  • FIG. 2A is a perspective view of a negative electrode assembly according to another embodiment of the present invention
  • FIG. 2B is a cross-sectional view taken along the line II ′ of FIG. 2A.
  • FIG. 3A is a perspective view of a negative electrode assembly according to still another embodiment of the present invention
  • FIG. 3B is a cross-sectional view taken along the line II ′ of FIG. 3A.
  • 4A and 4B are exploded views and cross-sectional views taken along the line II-II 'of the conductive wires inside the conductive network layer for explaining the lithium reduction reaction of the negative electrode assembly according to the embodiment of the present invention. Scanning electron micrograph image of the conductive wires analyzed after the charge is completed after 100 charge and discharge.
  • FIG. 5A is an enlarged view of conductive wires inside a conductive network layer for explaining lithium oxidation reaction of a negative electrode assembly according to an exemplary embodiment of the present invention
  • FIG. 5B is a part of a negative electrode assembly analyzed after discharge is completed after 100 charge / discharge cycles. Scanning electron micrograph image of.
  • FIGS. 6A and 6B are perspective views illustrating cathode assemblies according to still other embodiments of the present invention, respectively.
  • FIG. 7A and 7B are perspective views illustrating negative electrode assemblies according to still other embodiments of the present invention, respectively.
  • FIGS. 8A and 8B are perspective views illustrating a method of manufacturing a negative electrode assembly according to various embodiments of the present disclosure.
  • FIG. 9A is a perspective view illustrating a method of manufacturing a negative electrode assembly according to still another embodiment of the present invention
  • FIG. 9B is a partially enlarged view of the manufactured conductive network layer.
  • FIG. 10 is a view showing a lithium secondary battery having a negative electrode assembly according to an embodiment of the present invention.
  • the metal fibers disclosed herein are formed by maintaining a metal or alloy in a molten state in a vessel, by quenching and solidifying the molten metal in the atmosphere through an injection hole of the vessel using a pressurization device such as a compressed gas or a piston. It can be made or produced by a condensed drawing method, and is an integral metal fiber body that extends continuously with a substantially uniform thickness over a full length range of substantially 1 cm or more.
  • the metal fibers have the heat resistance, plasticity, and electrical conductivity that the metal has, while at the same time having the advantages of fiber-specific weaving and nonwoven processing.
  • the present invention relates to features and advantages of applying such metal fiber advantages to the electrode structure of a cell.
  • the above-described manufacturing process is illustrative only and the present invention is not limited by this manufacturing process.
  • the thickness, uniformity, structure such as nonwoven fabric and aspect ratio of the metal fibers can be controlled.
  • the term 'separation membrane' as used herein includes a separator generally used in a liquid electrolyte battery using a liquid electrolyte having a small affinity with the separator.
  • the "separation membrane” used herein includes an intrinsic solid electrolyte membrane and / or a gel solid electrolyte membrane in which the electrolyte is strongly bound to the separation membrane, and the electrolyte and the separation membrane are recognized as the same. Therefore, the term separation membrane used herein should be interpreted to include all of them, unless it is clearly distinguished from the solid electrolyte membrane and the gel solid electrolyte membrane.
  • FIG. 1A is a perspective view of a negative electrode assembly 100A according to an embodiment of the present invention
  • FIG. 1B is a cross-sectional view taken along line II ′ of FIG. 1A
  • FIG. 1C is conductive wires of the negative electrode assembly 100A.
  • the cathode assembly 100A may include a conductive network layer 10 made of conductive wires 10W.
  • the conductive wires 10W of the conductive network layer 10 extend in at least two different directions to contact each other, and have a three-dimensional solid shape with pores 10P formed therein from the surface of the conductive network layer 10. Can be formed.
  • the pore 10P may penetrate the electrolyte as described below, and may provide a movement path of lithium ions due to charging and discharging of the battery.
  • the conductive wires 10W may be metal fibers.
  • the conductive wires 10W may have a conductive surface provided with a metal layer coated on a polymer core wire or carbon fiber. As such, when the conductive wires 10W are formed using a light polymer core wire or carbon fiber, the weight of the conductive wires 10W may be reduced, and thus an energy density of the battery may be expected to increase.
  • the conductive wires 10W are formed between lithium and alloying other than metals, metalloids, nonmetals or combinations thereof that are alloyable and dealloying with lithium as the lithium source. It may be formed of a lithium compound. This will be described later.
  • the conductive wires 10W are the metal fibers which can be easily manufactured and are electrochemically inert at low operating potentials, the metal fibers being any of stainless steel, nickel, titanium and copper or alloys thereof. It may include one or a combination thereof.
  • Other examples of the metal fibers may be noble metals such as gold, platinum, ruthenium and silver or alloys thereof.
  • conductive wires 10W segmented to have a predetermined length. These may have a nonwoven structure within three-dimensional solids, as shown in FIGS. 1A and 1B.
  • the conductive wires 10W can be segmented to have a length of about 2 cm to 8 cm, and because they are formed by bending or tangling and contacting or joining each other, they have pores 10P therein and because of their fibrous properties. It may have flexibility.
  • the conductive wires 10W may have a thickness in the range of 0.1 ⁇ m to 200 ⁇ m.
  • the thickness of the conductive wires 10W is 0.1 ⁇ m or less, it is difficult to manufacture the metallic conductive wires 10W through a process such as drawing or injection, and the conductive wires for forming a conductive network as described below ( 10W) can be difficult to handle for artificial arrangements.
  • the thickness of the conductive wires 10W is 200 ⁇ m or more, the surface area per volume of the conductive wires 10W may be reduced, making it difficult to obtain an improvement in battery performance due to the increase in the surface area, and the energy density may be reduced. have.
  • the conductive wires 10W may have a thickness of 0.1 ⁇ m to 20 ⁇ m, and may have a surface area density to obtain excellent processability and high energy density within this range.
  • the surface area density is defined as the ratio of the surface area / volume per unit length of the conductive wires 10W (eg 4 / diameter if it has a circular cross section), in the thickness range, the surface area density of the conductive wires 10W. May be 2 ⁇ 10 5 (1 / m) to 4 ⁇ 10 7 (1 / m).
  • one surface of the conductive network layer 10 may further be provided with a lead wire 100W for electrical connection between the current collector tab 100T and an internal battery electrode (not shown).
  • the lead wire 100W may be the conductive wires 10W extending outwards or may be directly coupled by soldering to the conductive wires 10W without the current collector tab 100T.
  • negative electrode assembly 100A may include a lithium source for cell reaction.
  • the lithium source may be granulated powder 20P including any one or a combination of lithium and lithium compounds provided in the pores 10P of the conductive network layer 10, as shown in FIG. 1C. have.
  • the lithium source may be pure lithium powder.
  • the lithium compound is, for example, a lithium compound between lithium, which can be alloyed and de-alloyed, and a metal other than the lithium, a metalloid, a nonmetal, or a combination thereof, for example lithium and silicon And compounds of germanium, tin, lead, antimony, bismuth, zinc, aluminum, iron, cadmium and sulfur.
  • the foregoing lithium source materials are exemplary and the present invention is not limited thereto.
  • a known lithium-containing compound used as a conventional anode active material may be used.
  • the lithium source which is provided in powder form, is provided before use of the battery, and may gradually lose some or all of its amount as the battery is charged and discharged.
  • other metal elements constituting the lithium source may serve as the conductive material in the conductive network layer 10.
  • a conductive material may be further added into the pores 10P of the conductive network layer 10 as needed.
  • the conductive material may be, for example, a fine carbon such as carbon black, acetylene black, ketjen black and ultra fine graphite particles, a nano metal particle paste, or a ratio such as an indium tin oxide paste or a carbon nanotube. It may be a nanostructure having a large surface area and low resistance.
  • the conductive wires 100W having a fine size may play the same role as the conductive material, there is an advantage of suppressing an increase in manufacturing cost due to the addition of the conductive material. .
  • the negative electrode assembly may further comprise a suitable binder (also called a binder, not shown).
  • the binder may be, for example, polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyacrylic resin, derivatives thereof, or a combination thereof.
  • the binder carboxy methyl cellulose (CMC), polybutadiene (polybutadiene), polyisoprene, polybutyl acrylate, polybutyl methacrylate (polybutyl methacrylate) used in the form of a slurry ), Polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene, isobutylene-isoprene rubber, vinylidene fluoride-hexafluoro Propylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrene Butylbutadiene rubber (SBR), butyl acrylate-styrene copolymer, Butyl acrylate-acrylic nitrile copolymer, butyl acrylate-acrylic nitrile-glycidyl me
  • CMC
  • the binder may be another olefin polymer, an acrylic polymer, a diene polymer, a silicon-containing polymer, a vinyl polymer, a fluorine-containing polymer, a thermosetting elastomer, a natural rubber, a latex, a polypeptide, a protein, or a combination thereof.
  • the binder may be a conductive polymer-based material, petroleum pitch, or coal tar.
  • the binder may be a polymer material having an easy binding process and excellent binding force for preparing a linear binder, as described below. This will be described later in more detail with reference to FIGS. 9A and 9B.
  • both of the main surface (10U, 10B) of the electrode assembly (100A) can be made of both the coming and going of the lithium, so that the separation between the separator, and the anode (not shown) facing each other, respectively, Since two anodes can share one cathode assembly, there is an advantage of providing a battery having a high energy density to thickness.
  • a current collector layer (see 100L in FIG. 3A) may be coupled to one of the main surfaces 10U and 10B of the electrode assembly 100A, and the collector may be disposed on the first main surface 10B side. When the entire layer 100T is coupled, the separator and the anode may be sequentially disposed on the second main surface 10U.
  • FIG. 2A is a perspective view of a negative electrode assembly 100B according to another embodiment of the present invention
  • FIG. 2B is a cross-sectional view taken along the line II ′ of FIG. 2A.
  • the negative electrode assembly 100B of FIG. 1A includes a lithium-containing metal foil 20L including any one or a combination of lithium and a lithium compound as a lithium source. 100A).
  • the lithium containing metal foil 20L may be pure lithium foil.
  • the plate-shaped lithium-containing metal foil 20L can not only increase the lithium content, but also can eliminate the space occupied by the lithium powder as compared to the case of applying the powdered lithium source.
  • the porosity of the conductive network layer can be further reduced, thereby increasing the linear density of the conductive wires in the conductive network layer, thereby further increasing the surface area of the battery reaction. Extending the surface area of the cell reaction has the advantage of improving the charge and discharge rate and efficiency of the battery.
  • the lithium alloy is a compound between a metal, a metalloid, a nonmetal, or a combination thereof and lithium, which is capable of alloying and dealloying with lithium as described above, for example, silicon, germanium, tin, Lead, antimony, bismuth, zinc, aluminum, iron, cadmium, sulfur, or any combination thereof, or a compound comprising lithium.
  • these materials are exemplary and the present invention is not limited thereto.
  • a known lithium-containing compound used as a conventional anode active material may be used.
  • the lithium-containing metal foil 20L may be bonded on one main surface of the conductive network layer 10.
  • the lithium-containing metal foil 20L may be formed on an opposite surface of the conductive network layer 10 opposite the anode (not shown), for example, the first main surface of the conductive network layer 10 (see 10B in FIG. 1A). ) May be combined.
  • the lithium-containing metal foil 20L may gradually lose some or all of its amount during the charging and discharging process of the battery.
  • the remaining foil of the lithium foil or the lithium compound may thus function as a current collector.
  • the conductive wires 10W itself can function as a current collector in three-dimensional solid, this current collector function of the foil is not essential.
  • the current collector tab 100T is coupled to the side of the conductive network layer 10, but this is illustrative, and the current collector tab 100T is attached to the lithium-containing metal foil 20L.
  • the lead wire 100W, or only the wire 100W may be combined.
  • another conductive network layer is also bonded to the other main surface of the lithium-containing metal foil 20L to which the conductive network layer 10 is bonded, so that both main surfaces of the negative electrode assembly 100B may be utilized as the negative electrode. have.
  • FIG. 3A is a perspective view of a negative electrode assembly 100C according to another embodiment of the present invention
  • FIG. 3B is a cross-sectional view taken along the line II ′ of FIG. 3A.
  • the electrode assembly 100C may further include a current collector layer 100L together with the conductive network layer 10 and the lithium-containing metal foil 20L. May be coupled to current collector layer 100L.
  • Current collector layer 100T may be a suitable metal layer, such as copper or aluminum.
  • a lithium-containing powder (see 20P in FIG. 1C) may be added instead of the lithium-containing metal foil 20L as the lithium source, and in this case, the current collector layer 100L may be a conductive network layer ( 10) may be coupled directly.
  • 4A and 4B are exploded views and cross-sectional views taken along the line II-II 'of the conductive wires inside the conductive network layer for explaining the lithium reduction reaction of the negative electrode assembly according to the embodiment of the present invention. Scanning electron micrograph image of the conductive wires analyzed after the charge is completed after 100 charge and discharge.
  • Conductive wires 10W of the negative electrode assembly provide a reaction site for the reduction reaction of lithium.
  • lithium ions moving from the positive electrode to the negative electrode assembly through the electrolyte may be transferred from the surface of the conductive network layer 10 to the interior through the pores 10P of the conductive network layer 10.
  • Lithium ions delivered to the interior of the conductive network layer 10 are in close proximity to the conductive wires that provide a linear reaction site disposed three-dimensionally within the conductive network layer, and on any surface of the conductive wire selected therefrom. It will be electrodeposited as shown in 4a and 4b. From among the conductive wires adjacent to the lithium ions, it is arbitrary and spatially non-directional in which conductive wires lithium ions are electrodeposited. Therefore, lithium electrodeposited on the surface of the conductive wires does not grow in any particular direction in the inner space of the conductive network layer, whereby dendritic growth of lithium in the conductive network can be suppressed.
  • a conductive network layer having a nonwoven structure is fabricated using a fiber process such as entanglement, and the current collector tab is subjected to a conventional soldering process.
  • a conventional soldering process was bonded to the conductive network layer.
  • Pure lithium powder was used as a lithium source, the lithium powder was filled in the conductive network layer, and an electrolyte layer and an anode were sequentially stacked on the conductive network layer to form a cell, and the electrical characteristics thereof were evaluated.
  • 4C is a photographic image obtained by cutting and then finally charging the cell after 100 times of charging and discharging of the cell.
  • lithium was evenly deposited on the surfaces of the stainless wires to form the lithium film layer CL in FIG. 4B.
  • the fiber diameter was thickened to about 12 to 14 ⁇ m, and the lithium film layer CL has a thickness of about 2 ⁇ m to 3 ⁇ m.
  • the volume of the lithium coating layer formed during charging may be larger than the volume of the conductive wire therein.
  • an active material that reversibly reacts with lithium according to the alloying and dealloing mechanism or the intercalation and deintercalation mechanism is bulkier than lithium. Accordingly, the volume occupied by the active material in the electrode is generally larger than the occupied volume of lithium participating in the battery reaction.
  • the volume of conductive wires occupying in the negative electrode assembly may be smaller than that of lithium participating in the reaction, so that when using conventional active materials based on the same lithium volume, There is an advantage that can reduce the size of the negative electrode assembly.
  • Electrodeposition to the conductive wire has a thermodynamically more stable energy state compared to lithiation reactions such as intercalation or alloying that occur in negative active materials such as lithium compounds during charging.
  • the reaction predominantly occurs on the conductive wires. 4C supports this fact, in the case where a lithium containing alloy is used as the lithium source, the reduction reaction of lithium occurs selectively or dominantly on the conductive wire, and the lithium containing alloy powder may gradually disappear.
  • the Example mentioned above is a case where lithium powder is used as a lithium source, it is the same also when the lithium containing foil or the lithium compound containing conductive wire is used as a lithium source.
  • the lithium containing foil or the lithium compound containing conductive wire is used as a lithium source.
  • lithium provided to the outside by de-alloing during discharge may be reduced by lithium by conductive wire when charging, and the reduction of lithium is conductive
  • the mobility of lithium is not caused by charging of the battery, i.e., by the lithium insertion and lithium alloying reaction involving lithium diffusion in the layered structure, in the conductive network layer.
  • the charging speed can be increased and the charging efficiency can be improved.
  • dendritic growth due to reduction of lithium does not appear in the conductive network layer.
  • the conductive wires arranged three-dimensionally in the conductive network layer randomly provide linear reaction sites in the three-dimensional space from the standpoint of lithium ions penetrating into the conductive network layer.
  • Lithium electrodeposited on the surface of the field cannot grow in any particular direction in the inner space of the conductive network layer.
  • orderly growth of lithium such as dendritic growth in the conductive network layer can be suppressed.
  • the growth of the lithium resin body may be terminated when the lithium resin body grows and reaches another conductive wire adjacent to the conductive wire with the lithium resin body attached thereto.
  • the dendritic growth of lithium may not be sustained outside the conductive network layer, for example, beyond the separator.
  • 5A is an enlarged view of conductive wires inside a conductive network layer for explaining a lithium oxidation reaction of a negative electrode assembly according to an embodiment of the present invention
  • 5B is a scan of conductive wires analyzed after discharge is completed after 100 charge / discharge cycles. An electron micrograph image.
  • the lithium film layer CL electrodeposited on the conductive network layer during charging of the battery may be ionized during discharge of the battery and detached from the surface of the conductive wires.
  • the lithium film layer CL may be detached to expose the surfaces of the conductive wires 10W again.
  • the lithium film layer CL may disappear and the surfaces of the stainless wires of the conductive network layer may be exposed.
  • the electrolyte may be evenly impregnated into the conductive network layer by the pores of the conductive network layer, whereby lithium electrodeposited on the conductive wires is uniformly oxidized over the entire volume of the conductive network layer. It can be seen that the excessive consumption of lithium ions does not appear. As such, upon completion of the oxidation process of lithium, the thickness of the conductive wires is reduced.
  • the standard electrode potential (0.0 V) of lithium metal can be used as electromotive force without the problem of internal short circuit of the battery due to dendritic growth of lithium, the capacity of the battery Close to the capacity, it is possible to maximize the energy density.
  • irreversibility of the negative electrode, such as excessive consumption of lithium does not appear upon reduction of lithium, it may also contribute to improving the capacity of the battery by increasing the reversible capacity of the positive electrode.
  • the movement of lithium ions because the pores in the conductive network layer provides a passage for lithium ions
  • the mobility of lithium ions can be significantly improved as compared with the conventional negative electrode assembly. Accordingly, according to the embodiment of the present invention, the efficiency of charging and discharging the secondary battery can be improved.
  • the conductive network layer may undergo a volume change of the conductive wires as lithium is electrodeposited and detached on the conductive wires as the battery is charged and discharged.
  • the volume change of the entire conductive network layer can be mitigated by the pores in the conductive network layer.
  • the mechanical stability of the battery package can be secured.
  • FIGS. 6A and 6B are perspective views illustrating cathode assemblies 100D and 100E, respectively, in accordance with yet other embodiments of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.
  • the conductive network layer 10 of the negative electrode assembly 100D may include a conductive network layer 10 having a pore 10P therein and forming a three-dimensional shape.
  • the conductive network layer 10 may have a lattice structure formed by conductive wires 10W_1 and 10W_2 that extend in parallel and cross each other.
  • the lattice structure is provided by stacking two or more, for example, first and second sub network layers 10_1 and 10_2 made of conductive wires 10w to form a three-dimensional solid, and such a sub network layer 10_1.
  • the pores 10P may be provided therein by lamination of 10_2.
  • the negative electrode assembly 100D may further include a lithium source.
  • the lithium source may be a lithium-containing metal foil 20L.
  • the conductive network layer 10 may extend from the contact surface of the lithium containing metal foil 20L to the backside to surround the lithium containing metal foil 20l.
  • the conductive wires 10W_1 and 10W_2 may surround the lithium-containing metal foil 20L as one fiber body at least partially extending integrally.
  • only a portion of the conductive network layer 10 only the first sub network layer 10_1, surrounds the lithium containing metal foil 20l, and the second sub network layer 10_2 is It may be stacked on the first sub network layer 10_1.
  • the lithium source comprises a compound of lithium including metals, metalloids, and nonmetallic elements capable of dealloying lithium, together with or in place of the lithium-containing metal foil 20L. It may be provided in the form of powder or as pure lithium powder in the pores of the conductive network layer 10 or by forming the conductive wires 10 with these lithium compounds.
  • the lithium source provided as described above may be partially or totally dissipated according to the use of the battery, while the oxidation and reduction reaction of lithium according to the charging and discharging of the battery occurs predominantly by electrodeposition and detachment of the conductive wires.
  • other metal elements of the lithium compound constituting the lithium source may serve as the conductive material in the conductive network layer 10.
  • the cathode assembly 100E may include a conductive network layer 10 that forms a three-dimensional conformation of another structure.
  • the conductive network layer 10 may have a lattice structure formed by woven conductive wires 10W_1 and 10W_2.
  • the woven structure is provided by stacking two or more, for example, first and second sub-network layers 10_1 and 10_2 made of conductive wires 10W to form a three-dimensional solid, or one continuous conductive network. It may be provided by winding up layers so as to have pores therein.
  • the negative electrode assembly 100E may further include a lithium source, and the lithium source shown in FIG. 6B is a lithium containing metal foil 20l.
  • the lithium source may be provided in the pores of the conductive network layer 10 in powder form, together with or in place of the lithium containing metal foil 20l, the source in powder form It may be a pure lithium powder or a lithium compound powder including a lithium compound including lithium and other metals, metalloids, and nonmetallic elements other than lithium and lithium capable of de-alloying lithium.
  • the lithium source may be provided by forming the conductive wires 10 with the above-described lithium compound.
  • the conductive wires 10W of the cathode assemblies 100D, 100E can be manufactured to have the lattice configuration shown in FIGS. 6A and 6B due to the fibrous properties.
  • This configuration has a relatively regular arrangement as compared to the conductive wires 10W having the nonwoven structure of FIGS. 1A to 5B, but the three-dimensional three-dimensional structure is made through the pores of the conductive network layer 10 during charging of the battery. From the standpoint of lithium ions moving inside, the three-dimensional linear reduction sites can be random, so that dendritic growth of lithium can be suppressed.
  • the conductive network it may have a knitted structure, a multilayer fabric structure that can be obtained through a general fiber process.
  • FIG. 7A and 7B are perspective views illustrating cathode assemblies 100F and 100G, respectively, according to still other embodiments of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.
  • the conductive network layers 10 of the cathode assemblies 100F and 100G form a three-dimensional solid state in which the porosity is increased in the anode direction.
  • subconductive network layers having different porosities may be stacked to provide varying porosities. For example, as illustrated in FIG. 7A, a nonwoven fabric having a second porosity greater than the first porosity in the anode direction is formed on the first sub conductive network layer 10_1 of the nonwoven fabric having the first porosity. It may be provided by stacking two sub conductive network layers 10_2. Similarly, as shown in FIG.
  • the lattice structure having the second porosity greater than the first porosity in the anode direction on the first sub-conductive network layer 10_1 having the first porosity is formed. It may be provided by stacking two sub conductive network layers 10_2.
  • the porosity of the sub conductive network layers 10_2 can be controlled by adjusting the density of the conductive wires. For example, when the first sub conductive network layer 10_1 and the second sub conductive network layer 10_2 have the same volume, the density of the conductive wires of the second sub conductive network layer 10_2 is equal to the first sub conductive network layer 10_1. It may be less than the density of the conductive wires of the conductive network layer 10_1. Accordingly, the size of the pores 10P_1 and 10P_2 increases in the conductive network layer 10 toward the anode direction.
  • the nonwoven structure and the lattice structure are disclosed respectively, but this is exemplary, and the inside of the conductive network layer is a subconductive network layer of a nonwoven structure having a small porosity and the surface of the lattice subconductive network having a large porosity. It may be a layer.
  • the embodiment of the present invention is not limited to stacking sub conductive network layers having different porosities so as to form a conductive network layer in which the porosity is thus changed.
  • the conductive wire layers are randomly deployed at high density, the conductive wires are randomly deployed at low density thereon, and then an integrated conductive network layer having porosity is changed through a process such as entanglement.
  • the conductive network layer may be formed through another spinning fiber process.
  • the porosity increases from the inside of the conductive network layer to the surface of the anode direction, the portion of the conductive network layer 10 bonded to the lithium-containing metal foil 20l and the surface of the anode direction.
  • the part has a relatively large porosity, the middle part has a small porosity, and toward the anode side, the structure which has a big porosity, a small porosity, and a big porosity is also possible.
  • Electrodeposition and desorption of lithium ions can occur more dominantly in interiors with smaller porosity than on three-dimensional surfaces. Accordingly, uniformity of electrodeposition and desorption of lithium ions over the entire volume of the conductive network layer 10 may be improved, or electrodeposition and desorption of lithium ions may be induced locally only in the conductive network layer 10.
  • FIGS. 8A and 8B are perspective views illustrating a method of manufacturing the negative electrode assemblies 100H and 100I according to various embodiments of the present disclosure. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.
  • the negative electrode assemblies 100H and 100I may include linear binders 30W.
  • the linear binders 30W may be polymer fibers fibrillated from a suitable polymer material by a fiberization process such as melt spinning and / or thermal stretching process.
  • the polymer fibers may be long filaments, short filaments, staples, multifilaments, monofilaments or composites thereof, but the present invention is not limited thereto.
  • the polymer material may be, for example, polypropylene terephthalate (PPT), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), or polyacrylic resin.
  • the polymer material is carboxy methyl cellulose (CMC), polybutadiene, polyisoprene, polybutyl acrylate, polybutyl acrylate, polybutyl methacrylate, which are applied in the form of a conventional slurry.
  • CMC carboxy methyl cellulose
  • polybutadiene polybutadiene
  • polyisoprene polybutyl acrylate
  • polybutyl acrylate polybutyl methacrylate
  • polybutyl methacrylate polyhydroxyethyl methacrylate, polyacrylamide, polyisobutylene, isobutylene-isoprene rubber, vinylidene fluoride- Hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE) ), Styrenebutadiene rubber (SBR), butyl acrylate-styrene copolymer (butyl acrylate-sty butyl copolymer, butyl acrylate-acrylic nitrile copolymer, butyl acrylate-acryllic nitrile-glycidyl methacrylate copolymer, isobutyl acrylate-acrylic nitrile copolymer Homogeneous polymers such as isobutylene-styrene copolymers
  • the linear binders 30 may be used to bond the conductive network layer 10 onto adjacent layers such as lithium-containing metal foils, current collector layers, another conductive network layer, separators or solid electrolyte membranes.
  • 8A and 8B illustrate the lithium containing metal foil 20l and the current collector layer 100L, respectively.
  • the linear binders 30W are a dry material, they are formed in a regular lattice pattern as shown in FIG. 8A or randomly developed as shown in FIG. 8B, on the adjacent base layer, so that the binder layers 30A and 30B are formed. ) Can be formed.
  • the linear binders 30W may be developed in one or several layers. The manner of deployment of such linear binders 30W is exemplary only, and the present invention is not limited thereto.
  • the linear binders 30W may have a woven structure, a coarse nonwoven structure, or other woven structure, such as a line pattern, polygonal pattern, or knit without the intersection of the linear binders.
  • the conductive network layer 10 is provided on the binder layers 30A and 30B made of the linear binders 30W, and the adjacent layer is applied by applying pressure to the adjacent layers 20L and 100L and the conductive network layer 10. And a bond between the conductive network layer 10 can be obtained.
  • heat may be applied to the linear binders 30W to induce melting of the linear binders 30, thereby thermally sealing the linear binders 30W.
  • Heat for melting the linear binders 30W may be applied in a manner such as hot air, joule heating, or halogen lamp irradiation. The heating is carried out at a relatively low temperature, for example at 50 ° C. to 400 ° C., preferably at 150 ° C. to 300 ° C., in which the linear binders 30W can be melted, so that an economical manufacturing process is possible. Do.
  • an insulating coating by the binder material may be formed between the adjacent layer and the conductive network layer.
  • the insulating coating not only increases the internal resistance in the negative electrode assembly, but also can passivate reaction sites of the conductive wires in which oxidation and reduction reactions of lithium occur.
  • the linear binders 30 can achieve the coupling between the adjacent layer and the conductive network layer only by line contact or point contact and not by surface contact, without increasing the internal resistance of the cathode. It can also provide good mechanical adhesion.
  • the linear binders 30W may be fused by pressure and heating without an organic solvent such as carbonates, esters, and lactones
  • the negative electrode structure May be carried out in a dry process. Accordingly, there is no drying process due to the organic solvent and performance deterioration due to impurities, and an environment-friendly manufacturing process with less environmental load can be obtained.
  • FIG. 9A is a perspective view illustrating a method of manufacturing the negative electrode assembly 100J according to another embodiment of the present invention
  • FIG. 9B is a partially enlarged view of the manufactured conductive network layer 10.
  • the negative electrode assembly 100J may include linear binders 30W comprising a fibrous polymeric material, petroleum pitch or coal tar as described above.
  • the negative electrode assembly 100J may be linear.
  • the binders 30W are distinguished from the negative electrode assembly 100J of FIGS. 8A and 8B in that they are provided mixed with the conductive wires 10W in the conductive network layer 10.
  • the linear binders 30W to be mixed may be randomly mixed with the conductive wires 10W and a nonwoven structure may be obtained through a process such as entanglement, or a regular structure such as a woven structure may be obtained through a fiber blending process.
  • Such a manufacturing method is exemplary and the present invention is not limited thereto.
  • the conductive network layer 10 may be adhered to the adjacent layer, for example, the lithium-containing metal foil 20L by the linear binders 30W, for which pressure and / or heat may be applied.
  • the embodiment shown in FIGS. 9A and 9B discloses a cathode assembly 100J with an adjacent layer added, there may be no adjacent layer.
  • the linear binders in the conductive network layer 10 may serve to bind the lithium source and the conductive material inside the conductive network layer.
  • the conductive wires 10W and the linear binder 30W are mixed at a suitable mixing ratio, so that a conductive network layer of nonwoven structure can be produced.
  • the negative electrode assembly 100J may be manufactured by invading the lithium source and / or the conductive material in the form of dried particles in the pores 10P of the conductive network layer, and heating and compressing the same.
  • solvents such as water or organic solvents for slurry production are not used
  • the load on the environment is small and a separate process for removing the solvent after invading the particle composition in the conductive network layer is performed. Since the drying process is not necessary, the process can be simplified, productivity can be improved, and equipment can be simplified.
  • the mixing process using the solvent-free dry powder described above may improve the yield.
  • FIG. 10 is a view showing a lithium secondary battery having a negative electrode assembly according to an embodiment of the present invention. Reference may be made to the above-described disclosure as long as there is no contradiction with respect to components shown with the same reference numerals as those of the previous figures.
  • the lithium secondary battery 1000 includes a case 300, a negative electrode assembly 100, a separator 500, and a positive electrode assembly 200.
  • the case 300 accommodates the negative electrode assembly 100, the positive electrode assembly 200, and the separator 500 therein, and the negative electrode assembly 100 and the positive electrode are disposed inside the case 300 with the separator 500 interposed therebetween.
  • Assembly 200 may be wound.
  • an electrolyte may be provided between the negative electrode assembly 100 and the positive electrode assembly 200 inside the case 300 to serve as a medium through which the ions generated by ionization of the active material move. Pores in the conductive network layer 10 of the negative electrode assembly 100 may facilitate the impregnation of the electrolyte.
  • the electrolyte is a suitable aqueous electrolyte solution containing salts such as potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCL), zinc chloride (ZnCl 2 ) and sulfuric acid (H 2 SO 4 ), or LiClO 4 , LiPF 6, or the like. It may be a non-aqueous electrolyte such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate containing a lithium salt of the, and the moisture is absorbed by the electrodes (100, 200) and / or separator 500, the battery 1000 is completed Can be. Although not shown, a suitable battery management system for controlling stability and / or power supply characteristics during use of the battery 1000 may be further coupled to the battery 1000.
  • salts such as potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCL), zinc chloride (ZnCl 2 ) and sulfuric acid (H 2 SO 4 ), or LiClO 4
  • Lithium is uniformly electrodeposited and desorbed so that dendritic growth of lithium can be suppressed.
  • a phenomenon in which the negative electrode assembly 100 and the positive electrode assembly 200 are short-circuited with each other by lithium in the battery is prevented, so that the stability of the lithium secondary battery 1000 may be improved.
  • the illustrated cell form discloses a cylindrical shape, this is exemplary, and because of the excellent processability and flexibility due to the fibrous properties of the negative electrode assembly, in addition to the winding type, it can be modified in three dimensions such as stacking, bending and winding up. It is possible to provide a flexible battery which can be attached to a known structure such as square, coin type and pouch type or directly to surfaces such as garments, bags and flexible displays.
  • the negative electrode assembly according to the embodiment of the present invention can not only obtain an output voltage due to the reduction potential of lithium but also improve the irreversibility of charge and discharge, a battery of high output, high capacity, and high efficiency can be obtained. It can be applied as a power source or medium and large battery for power storage.

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Abstract

La présente invention concerne, dans des modes de réalisation, un ensemble électrode négative pour batterie secondaire au lithium, ainsi qu'un procédé de fabrication associé. Selon un mode de réalisation de la présente invention, l'ensemble électrode négative comprend une couche réseau conductrice incluant des fils conducteurs s'étendant dans au moins deux directions différentes et en contact les uns avec les autres, les fils conducteurs comportant des pores formés vers l'intérieur à partir de leurs surfaces et configurant une forme stéréoscopique tridimensionnelle. Le lithium peut passer à travers les pores afin d'être déposé de manière électrolytique sur les fils conducteurs durant la charge de la batterie, et le lithium déposé de manière électrolytique sur les fils conducteurs est ionisé et dé-intercalé durant la décharge de la batterie. Le dépôt électrolytique et la dé-intercalation du lithium peuvent être répétés en fonction de la charge et de la décharge de la batterie.
PCT/KR2013/002066 2012-03-15 2013-03-14 Ensemble électrode négative pour batterie secondaire au lithium, et procédé de fabrication associé WO2013137665A1 (fr)

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KR102069284B1 (ko) * 2018-04-02 2020-01-22 한국과학기술연구원 이차전지 음극 보호용 중간층, 이의 제조방법 및 이를 포함하는 리튬금속 이차전지
KR20220059278A (ko) * 2020-11-02 2022-05-10 주식회사 엘지에너지솔루션 리튬 금속 전지용 음극, 이의 제조방법 및 이를 포함하는 리튬 금속 전지
WO2022092980A1 (fr) * 2020-11-02 2022-05-05 주식회사 엘지에너지솔루션 Électrode négative pour batterie au lithium-métal, son procédé de fabrication et batterie au lithium-métal la comprenant
KR102575021B1 (ko) * 2021-02-26 2023-09-07 조인셋 주식회사 유연성 및 신축성이 있는 집전체를 갖는 이차전지용 전극, 이를 적용한 이차전지

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