WO2014092473A1 - Électrode pour batterie secondaire, batterie secondaire comprenant celle-ci, et batterie secondaire de type câble - Google Patents

Électrode pour batterie secondaire, batterie secondaire comprenant celle-ci, et batterie secondaire de type câble Download PDF

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WO2014092473A1
WO2014092473A1 PCT/KR2013/011514 KR2013011514W WO2014092473A1 WO 2014092473 A1 WO2014092473 A1 WO 2014092473A1 KR 2013011514 W KR2013011514 W KR 2013011514W WO 2014092473 A1 WO2014092473 A1 WO 2014092473A1
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Prior art keywords
current collector
active material
electrode active
coating layer
electrode
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PCT/KR2013/011514
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English (en)
Korean (ko)
Inventor
권요한
홍장혁
정혜란
김제영
김종훈
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주식회사 엘지화학
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Priority to CN201380006039.8A priority Critical patent/CN104067418B/zh
Priority to JP2014552146A priority patent/JP6316207B2/ja
Priority claimed from KR20130154429A external-priority patent/KR101479460B1/ko
Priority to US14/280,803 priority patent/US9214672B2/en
Publication of WO2014092473A1 publication Critical patent/WO2014092473A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/624—Electric conductive 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • 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 electrode, a secondary battery including the same, and a cable type secondary battery, and more particularly, to prevent detachment of the metal-based electrode active material layer, and to improve the energy density and cycle life characteristics, including the electrode for the secondary battery. It relates to a secondary battery and a cable type secondary battery.
  • a secondary battery is a device that converts external electrical energy into chemical energy and stores it and generates electricity when needed.
  • the term “rechargeable battery” is also used to mean that it can be charged multiple times.
  • Commonly used secondary batteries include lead storage batteries, nickel cadmium batteries (NiCd), nickel hydrogen storage batteries (NiMH), lithium ion batteries (Li-ion), and lithium ion polymer batteries (Li-ion polymer). Secondary batteries offer both economic and environmental advantages over primary batteries that are used once and discarded.
  • Secondary batteries are currently used where low power is used. Examples are devices, handhelds, tools, and uninterruptible power supplies that help start up the car. Recently, the development of wireless communication technology has led to the popularization of portable devices, and there is also a tendency to wirelessize many kinds of conventional devices, and the demand for secondary batteries is exploding. In addition, hybrid vehicles and electric vehicles have been put to practical use in terms of prevention of environmental pollution, and these next-generation vehicles employ technologies that use secondary batteries to reduce value, weight, and extend life.
  • secondary batteries are cylindrical, rectangular or pouch type batteries. This is because the secondary battery is manufactured by mounting an electrode assembly composed of a negative electrode, a positive electrode, and a separator inside a pouch-shaped case of a cylindrical or rectangular metal can or an aluminum laminate sheet, and injecting an electrolyte into the electrode assembly. Therefore, since a certain space for mounting the secondary battery is essentially required, the cylindrical, square or pouch type of the secondary battery has a problem in that it acts as a limitation for the development of various types of portable devices. Accordingly, there is a need for a new type of secondary battery that is easily deformed.
  • a cable type secondary battery which is a battery having a very large ratio of length to cross sectional diameter.
  • desorption of the electrode active material layer may occur due to stress caused by external force or rapid volume expansion of the electrode active material layer during charge and discharge, resulting in a decrease in capacity and deterioration of cycle life characteristics.
  • a polymer binder coating layer may be further formed on the upper surface of the electrode active material layer.
  • the cycle life characteristics of the battery may be improved, but since the polymer binder coating layer has little pores therein, the electrode resistance may increase because it prevents the electrolyte from flowing into the electrode active material layer. have.
  • the reaction potential of the discharge profile is higher than that of the graphite-based electrode active material, when the full cell is manufactured and evaluated for performance, the energy density is low.
  • the problem to be solved by the present invention is to prevent the desorption phenomenon of the metal-based electrode active material layer to ensure excellent battery life characteristics, to improve the energy density, and to smoothly flow the electrolyte into the electrode active material layer of electrode resistance It is possible to prevent an increase and to provide an electrode for a secondary battery having improved electrode flexibility, a secondary battery including the same, and a cable type secondary battery.
  • a current collector In order to solve the above problems, according to an aspect of the present invention, a current collector; An electrode active material layer formed on at least one surface or an entire outer surface of the current collector; A graphite coating layer formed on an upper surface of the electrode active material layer and including graphite, a conductive material, and a first polymer binder; And a porous coating layer formed on an upper surface of the graphite coating layer and including a second polymer binder.
  • the current collector may be a planar current collector, a hollow current collector, a wire current collector, a wound wire current collector, a wound sheet current collector, or a mesh current collector.
  • the weight ratio of the graphite, the conductive material, and the first polymer binder may be 50:10:40 to 90: 1: 9.
  • the pore size formed in the graphite coating layer may be 0.1 ⁇ m to 5 ⁇ m, and the porosity may be 10 to 70%.
  • the conductive material may include any one selected from the group consisting of carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, and graphene, or a mixture of two or more thereof.
  • the first polymer binder is polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafulopropylene (polyvinylidene fluoride-) co-hexafluoro propylene, polyvinylidene fluoride-co-trichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile ), Polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate acetate), cellulose acetate butyrate, cellulose acetate Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, Any one selected from the group consisting of carboxyl
  • the size of the pores formed in the porous coating layer 0.01 ⁇ m to 10 ⁇ m, porosity may be 5 to 95%.
  • the porous coating layer may further include inorganic particles.
  • the weight ratio of the inorganic particles and the second polymer binder may be 10:90 to 95: 5.
  • the inorganic particles may be inorganic particles having a dielectric constant of 5 or more, inorganic particles having a lithium ion transfer ability, or a mixture thereof.
  • the inorganic particles having a dielectric constant of 5 or more include BaTiO 3 , Pb (Zr x , Ti 1-x ) O 3 (PZT, where 0 ⁇ x ⁇ 1), and Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), (1-x) Pb (Mg 1/3 Nb 2/3 ) O 3 -xPbTiO 3 (PMN-PT, where , 0 ⁇ x ⁇ 1), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , SiC, SiO 2 , It may be any one selected from the group consisting of AlOOH, Al (OH) 3 and TiO 2 or a mixture of two or more thereof.
  • the inorganic particles having the lithium ion transfer ability include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium Aluminum Titanium Phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), (LiAlTiP) x O y series glass (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), lithium germanium thiophosphate (Li x Ge y P z S w , 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ w ⁇ 5), lithium nitride (Li 3 PO 4
  • the average particle diameter of the inorganic particles may be 10 nm to 5 ⁇ m.
  • the second polymer binder may be polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafuluropropylene (polyvinylidene fluoride-) co-hexafluoro propylene, polyvinylidene fluoride-co-trichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile ), Polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate acetate), cellulose acetate butyrate, cellulose acetate Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, Any one selected from the group consisting of carboxyl
  • the secondary battery electrode may be a negative electrode.
  • the electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Ni or Fe metals (Me) ; Alloys composed of the metals (Me); And oxides (MeOx) of the metals (Me); any one of the active material particles selected from the group consisting of, or a mixture of two or more thereof.
  • the negative electrode is a secondary battery electrode of the secondary battery of the present invention Is provided.
  • the lithium ion supply core portion containing an electrolyte;
  • An internal current collector having an open structure formed around an outer surface of the lithium ion supply core part, an internal electrode active material layer formed on an outer surface of the internal current collector, and an outer surface of the internal electrode active material layer, and formed of graphite, a conductive material, and a first polymer
  • An internal electrode having a graphite coating layer including a binder, and a porous coating layer formed on an outer surface of the graphite coating layer and including a second polymer binder;
  • a separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode;
  • an external electrode formed surrounding the outer surface of the separation layer, the external electrode including an external current collector and an external electrode active material layer, the cable type secondary battery having a horizontal cross section and extending in the longitudinal direction.
  • the internal current collector of the open structure may be a wound wire current collector, a wound sheet current collector, or a mesh current collector.
  • the internal electrode is a cathode, and the internal electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Metals such as Ni or Fe (Me); Alloys composed of the metals (Me); And oxides (MeOx) of the metals (Me); any one of the active material particles selected from the group consisting of, or a mixture of two or more thereof.
  • the internal electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Metals such as Ni or Fe (Me); Alloys composed of the metals (Me); And oxides (MeOx) of the metals (Me); any one of the active material particles selected from the group consisting of, or a mixture of two or more thereof.
  • the external electrode may include an external electrode active material layer formed to surround the outer surface of the separation layer and an external current collector formed to surround the outer surface of the external electrode active material layer, or an external house formed to surround the outer surface of the separation layer.
  • External electrode active material layer formed surrounding the outer surface of the whole and the outer current collector, or the outer current collector formed surrounding the outer surface of the separation layer and the outer surface formed to contact the separation layer surrounding the outer surface of the outer current collector
  • An external electrode active material layer provided with an electrode active material layer or surrounding the outer surface of the separation layer and covered with the outer electrode active material layer, and having an outer current collector formed while enclosing the outer surface of the separation layer with a spaced apart state; It may be.
  • the lithium ion supply core portion containing an electrolyte;
  • An inner electrode including an inner current collector having an open structure formed around an outer surface of the lithium ion supply core and an inner electrode active material layer formed on an outer surface of the inner current collector;
  • a separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode;
  • a porous coating layer formed surrounding the outer surface of the separation layer, the graphite-based coating layer including an external current collector, an external electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder.
  • the external electrode is a cathode
  • the external electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Metals such as Ni or Fe (Me); Alloys composed of the metals (Me); And it may include any one active material particles selected from the group consisting of oxides (MeOx) of the metals (Me) or a mixture of two or more thereof.
  • the external electrode may include a porous coating layer including a second polymer binder formed to surround the outer surface of the separation layer, and surround the outer surface of the porous coating layer and include graphite, a conductive material, and a first polymer binder.
  • An external current collector having an associated coating layer, an external electrode active material layer formed surrounding the outer surface of the graphite coating layer, and an external current collector formed surrounding the outer surface of the external electrode active material layer, or an external current collector formed surrounding the outer surface of the separation layer,
  • the outer current collector is formed to surround the outer surface of the outer current
  • a porous coating layer is formed surrounding the outer surface of the associated coating layer and the graphite coating layer, and includes a second polymer binder. It may be to.
  • the separation layer may be an electrolyte layer or a separator.
  • the electrolyte layer a gel polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN or PVAC; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); It may be to include an electrolyte selected from.
  • the electrolyte layer may further include a lithium salt.
  • the lithium salt LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, may be one or two or more selected from lithium chloroborane, lithium lower aliphatic carbonate and lithium tetraphenyl borate.
  • the separator may include a porous polymer substrate made of a polyolefin-based polymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-methacrylate copolymer;
  • a porous polymer substrate made of a polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfite and polyethylene naphthalene;
  • a porous polymer substrate formed of a mixture of inorganic particles and a binder polymer made of a polyolefin-based polymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-methacrylate
  • two or more lithium ion supply core portion containing an electrolyte
  • An inner current collector having an open structure formed around an outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed on an outer surface of the inner current collector, and an outer surface of the inner electrode active material layer;
  • a separation layer surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes;
  • an external electrode formed surrounding the outer surface of the separation layer, the external electrode including an external current collector and an external electrode active material layer, the cable type secondary battery having a horizontal cross section and extending in the longitudinal direction.
  • two or more lithium ion supply core portion containing an electrolyte
  • An inner current collector having an open structure formed around an outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed on an outer surface of the inner current collector, and an outer surface of the inner electrode active material layer
  • a graphite-based coating layer comprising a polymer binder, a porous coating layer formed on the outer surface of the graphite-based coating layer, and a separation layer for preventing a short circuit of the electrode formed surrounding the outer surface of the porous coating layer
  • Two or more internal electrodes disposed in parallel to each other; And an outer electrode formed to surround the outer surfaces of the inner electrodes and having an outer current collector and an outer electrode active material layer, the cable type secondary battery having a horizontal cross section and extending in the length direction.
  • two or more lithium ion supply core portion containing an electrolyte;
  • Two or more internal electrodes disposed in parallel with each other including an inner current collector having an open structure formed around an outer surface of each lithium ion supply core and an inner electrode active material layer formed surrounding the outer surface of the inner current collector;
  • a separation layer surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes;
  • a porous coating layer formed surrounding the outer surface of the separation layer, the graphite-based coating layer including an external current collector, an external electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder.
  • a cable type secondary battery having a horizontal cross section including an external electrode and extending in a length direction.
  • two or more lithium ion supply core portion containing an electrolyte;
  • An inner current collector having an open structure formed surrounding the outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed surrounding the outer surface of the inner current collector, and a short circuit of the electrode formed surrounding the outer surface of the inner electrode active material layer
  • Two or more internal electrodes disposed in parallel with each other having a separation layer for preventing;
  • a porous coating layer formed to surround the outer surfaces of the inner electrodes, the graphite-based coating layer including an outer current collector, an outer electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder.
  • a cable-type secondary battery having a horizontal cross-section including an external electrode extending in the longitudinal direction.
  • the capacity of the battery is reduced by suppressing the detachment phenomenon of the electrode active material layer, which may occur due to the stress caused by external force or the sudden volume expansion of the electrode active material layer during charging and discharging.
  • the conductivity of the electrode, and the introduction of a graphite-based coating layer exhibiting excellent battery performance can improve the initial efficiency and cycle life characteristics of the battery.
  • the performance of the battery can be improved by smoothly flowing the electrolyte into the electrode active material layer to prevent the increase of the resistance of the electrode, and by the external force such as bending and twisting, to the graphite coating layer formed on the upper surface of the electrode active material layer. Cracking or falling off can be suppressed, thereby further improving the flexibility of the electrode.
  • FIG. 1 is a view showing a perspective view of an electrode for a cable-type secondary battery including a wire-type current collector according to an embodiment of the present invention.
  • FIG. 2 is a view showing a perspective view of an electrode for a cable type secondary battery including a hollow current collector according to an embodiment of the present invention.
  • FIG 3 is a perspective view of a cable type secondary battery including one internal electrode according to an embodiment of the present invention.
  • FIG. 4 is a view showing a perspective view of a cable-type secondary battery including one internal electrode according to another embodiment of the present invention.
  • FIG. 5 is a cross-sectional view of a cable type secondary battery including two or more internal electrodes according to an embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of a cable type secondary battery including two or more internal electrodes according to another embodiment of the present invention.
  • FIG. 7 is a SEM photograph showing a wire-type electrode having a graphite coating layer prepared according to an embodiment of the present invention.
  • Figure 8 is a SEM photograph showing a wire-type electrode formed with a porous coating layer prepared according to an embodiment of the present invention.
  • FIG. 9 is a graph showing normalized charging and discharging profiles for discharge capacities according to one embodiment and a comparative example of the present invention.
  • FIG. 10 is a graph showing the charge and discharge cycle life characteristics of the battery according to an embodiment and a comparative example of the present invention.
  • the current collector An electrode active material layer formed on at least one surface or an entire outer surface of the current collector; A graphite coating layer formed on an upper surface of the electrode active material layer and including graphite, a conductive material, and a first polymer binder; And a porous coating layer formed on an upper surface of the graphite coating layer and including a second polymer binder.
  • the current collector may be a planar current collector, a hollow current collector, a wire current collector, a wound wire current collector, a wound sheet current collector, or a mesh current collector, but is not limited thereto. According to the shape of the secondary battery, various kinds of current collectors are possible.
  • an electrode active material layer may be formed on at least one surface of an upper surface or a lower surface of the current collector.
  • the inside of the current collector may be formed.
  • the electrode active material layer may be formed on at least one of a surface existing in the surface and an external surface, and in the case of a wire-type current collector, the electrode active material layer may be formed on the entire surface of the current collector.
  • an electrode active material layer may be formed on at least one of a surface existing inside and a surface existing outside of the current collector. It may be formed surrounding.
  • FIG. 1 is a view showing a perspective view of an electrode for a cable type secondary battery including a wire-type current collector according to an embodiment of the present invention
  • Figure 2 includes a hollow current collector, according to an embodiment of the present invention It is a figure which shows the perspective view of the cable type secondary battery electrode.
  • an electrode 10 for a cable type secondary battery includes a wire type current collector 11; An electrode active material layer 12 formed surrounding the entire surface of the wire-shaped current collector 11; A graphite coating layer 13 formed surrounding the upper surface of the electrode active material layer 12 and including graphite, a conductive material, and a first polymer binder; And a porous coating layer 14 formed surrounding the upper surface of the graphite coating layer 13 and including a second polymer binder, and extending in the longitudinal direction.
  • the cable type secondary battery electrode 10 may include one or more wires wound in a coil shape or the like, or one or more wire composites in which two or more wires are twisted in a spiral shape are wound in a coil shape or the like to form an inside of the cable type secondary battery. Can be used as an electrode.
  • the cable-type secondary battery electrode 20 according to the present invention, the hollow current collector 21; An electrode active material layer 22 formed on a surface existing outside the hollow current collector 21; A graphite coating layer 23 formed surrounding the upper surface of the electrode active material layer 22 and including graphite, a conductive material, and a first polymer binder; And a porous coating layer 24 formed surrounding the upper surface of the graphite coating layer 23 and including a second polymer binder, and extending in the longitudinal direction.
  • the cable type secondary battery electrode 20 may be used as an external electrode of the cable type secondary battery.
  • the electrode active material layer formed on the current collector may have a detachment phenomenon of the electrode active material layer due to sudden volume expansion during charge and discharge or stress caused by external force due to deformation of the shape, or from the current collector. You can go off completely. As a result, the electrical conductivity at the electrode is poor, the capacity is not realized, the initial efficiency is low. In addition, the cycle life characteristics of the battery become very poor.
  • the metal-based negative electrode active material layer formed by a method such as electroplating or anodizing since the polymer binder and the conductive material do not exist, the detachment phenomenon may be more serious.
  • the reaction potential of the discharge profile is higher than that of the graphite electrode active material, when the full cell is manufactured, the energy density is lower than that of the graphite electrode active material.
  • a graphite coating layer made of graphite, a conductive material and a first polymer binder is formed on the outer surface of the electrode active material layer, and the porous surface made of the second polymer binder is formed on the outer surface of the graphite coating layer.
  • the graphite coating layer may serve as a buffer region that can alleviate the separation of the electrode active material layer, includes a conductive material having excellent conductivity, and the graphite coating layer itself has excellent battery characteristics. As a result, the detachment phenomenon of the electrode active material layer can be prevented and contributed to the improvement of initial efficiency and cycle life characteristics.
  • the weight ratio of the graphite, the conductive material and the first polymer binder may be 50:10:40 to 90: 1: 9.
  • pores may be formed in the graphite coating layer to enable the inflow of the electrolyte, and such pores should be smaller than the size of the particles constituting the electrode active material layer in order to suppress the detachment of the electrode active material layer, and the electrolyte may be the electrode. It is preferable that the solvation radius of the lithium ions of the electrolyte be greater than the solvating radius of the electrolyte solution to facilitate the inflow to the inlet. In order to satisfy these conditions, the pore size formed in the graphite coating layer may be 0.1 ⁇ m to 5 ⁇ m. And in order to achieve the above effect, the porosity of the graphite coating layer may be 10 to 70%.
  • the conductive material is not particularly limited as long as it is an electronic conductive material that does not cause chemical change in the secondary battery.
  • carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotubes, graphene and the like can be used, it is possible to use metal powder, conductive metal oxide, organic conductive material and the like.
  • Products currently available as conductive materials include acetylene black series (Chevron Chemical Company or Gulf Oil Company), EC series (Armak Company), Vulcan ( Vulcan), XC-72 (manufactured by Cabot Company), and Super P (manufactured by MMM).
  • the first polymer binder may include polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), and polyvinylidene fluoride-hexafuluropropylene (polyvinylidene fluoride).
  • PVDF polyvinylidene fluoride
  • HFP hexafluoro propylene
  • PVF polyvinylidene fluoride-hexafuluropropylene
  • the porous coating layer it is possible to form a porous pore structure through phase separation or phase inversion in the manufacturing process.
  • the pores formed in the porous coating layer should be smaller than the size of the particles constituting the electrode active material layer to suppress the detachment of the electrode active material layer, the electrolyte is larger than the solvation radius of lithium ions of the electrolyte in order to facilitate the inflow to the electrode It is preferable.
  • the size of the pores formed in the porous coating layer may be 0.01 ⁇ m to 10 ⁇ m.
  • the porosity of the porous coating layer may be 5 to 95%.
  • the porous coating layer may further include inorganic particles.
  • the inorganic particles of the porous coating layer are filled with each other by the second polymer binder in a state of being in contact with each other, thereby forming an interstitial volume between the inorganic particles, the inorganic particles
  • the interstitial volume between them may be empty to form pores.
  • the weight ratio of the inorganic particles and the polymer binder may be 10:90 to 95: 5 in order to secure appropriate porosity.
  • the inorganic particles that can be used in the present invention are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles that can be used in the present invention are not particularly limited as long as the oxidation and / or reduction reactions do not occur in the operating voltage range (for example, 0 to 5 V on the basis of Li / Li + ) of the applied electrochemical device.
  • the ionic conductivity of the electrolyte may be improved by contributing to an increase in the dissociation degree of the electrolyte salt, such as lithium salt, in the liquid electrolyte.
  • the inorganic particles may include high dielectric constant inorganic particles having a dielectric constant of 5 or more, or 10 or more.
  • inorganic particles having a dielectric constant of 5 or more include BaTiO 3 , Pb (Zr x , Ti 1-x ) O 3 (PZT, where 0 ⁇ x ⁇ 1), Pb 1-x La x Zr 1- y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), (1-x) Pb (Mg 1/3 Nb 2/3 ) O 3 -xPbTiO 3 (PMN-PT, Where 0 ⁇ x ⁇ 1), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , SiC, SiO 2 , AlOOH,
  • the inorganic particles may be used as inorganic particles having a lithium ion transfer ability, that is, inorganic particles containing a lithium element, but having a function of moving lithium ions without storing lithium.
  • inorganic particles having a lithium ion transfer capacity include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2 -39P 2 (LiAlTiP) x O y series glasses such as O 5 (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3 ,
  • the size of the inorganic particles is not limited, but for proper porosity of the porous coating layer, the average particle diameter may be 10 nm to 5 ⁇ m.
  • the second polymer binder may be polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafulopropylene (polyvinylidene fluoride-) co-hexafluoro propylene), polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone ), Polyvinylacetate, ethylene vinyl co-vinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butylate acetate butyrate), cellulose acetate propionate, Cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose , Styrene-butadiene rubber, acrylonit
  • the current collector stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Or it is preferably made of a conductive polymer, the outer current collector of the open structure, stainless steel, aluminum, nickel, titanium, calcined carbon, copper; Stainless steel surface-treated with carbon, nickel, titanium, or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Conductive polymers; A metal paste comprising a metal powder of Ni, Al, Au, Ag, Al, Pd / Ag, Cr, Ta, Cu, Ba, or ITO; Or a carbon paste containing carbon powder which is graphite, carbon black or carbon nanotubes.
  • the current collector collects electrons generated by the electrochemical reaction of the electrode active material or serves to supply electrons required for the electrochemical reaction.
  • a metal such as copper or aluminum is used.
  • it is relatively more flexible than using a metal such as copper or aluminum.
  • it is possible to achieve the light weight of the battery by using a polymer current collector in place of the metal current collector.
  • Such conductive materials may be polyacetylene, polyaniline, polypyrrole, polythiophene, polysulfuride, ITO (Indum Thin Oxide), silver, palladium and nickel, and the conductive polymer may be polyacetylene, polyaniline, polypyrrole, polythiol Offen, polysulfuritride and the like can be used.
  • the non-conductive polymer used for the current collector is not particularly limited in kind.
  • the secondary battery electrode may be a negative electrode, wherein the electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Metals (Me) which are Cu, Co, Ni or Fe; Alloys composed of the metals (Me); And an oxide (MeOx) of the metals (Me); any one active material particles selected from the group consisting of or a mixture of two or more thereof.
  • the electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Metals (Me) which are Cu, Co, Ni or Fe; Alloys composed of the metals (Me); And an oxide (MeOx) of the metals (Me); any one active material particles selected from the group consisting of or a mixture of two or more thereof.
  • the electrode active material layer of the present invention functions to move ions through a current collector, and the movement of these ions is caused by interaction through occlusion of ions from the electrolyte layer and release of ions into the electrolyte layer.
  • the secondary battery of the present invention includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte, the negative electrode is the secondary battery electrode of the present invention.
  • the secondary battery of the present invention may be a secondary battery of a special type such as a cable type secondary battery as well as a secondary battery of a general type of a stack type, a winding type, a stack / folding type.
  • the cable-type secondary battery having a horizontal cross section according to an aspect of the present invention extending in the longitudinal direction, the lithium ion supply core portion containing an electrolyte;
  • An internal current collector having an open structure formed around an outer surface of the lithium ion supply core part, an internal electrode active material layer formed on an outer surface of the internal current collector, and an outer surface of the internal electrode active material layer, and formed of graphite, a conductive material, and a first polymer
  • An internal electrode having a graphite coating layer including a binder, and a porous coating layer formed on an outer surface of the graphite coating layer and including a second polymer binder;
  • a separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode;
  • an external electrode formed surrounding the outer surface of the separation layer and having an external current collector and an external electrode active material layer.
  • the open structure refers to a structure in which the open structure is a boundary surface, and a structure in which material moves from inside to outside through this boundary surface is free, and the outer current collector of the open structure is a wound wire-type house. It may be a whole, a wound sheet current collector or a mesh current collector, but is not limited thereto.
  • the horizontal cross section may be circular or polygonal, which is a geometrically perfect symmetrical circular and asymmetrical oval structure.
  • the polygon is not particularly limited as long as it is not a two-dimensional sheet-like structure.
  • Non-limiting examples of the polygonal structure include triangles, squares, pentagons, and hexagons.
  • the porous coating layer may further include inorganic particles as described above.
  • the internal electrode is a cathode
  • the internal electrode active material layer is Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Metals such as Ni or Fe (Me); Alloys composed of the metals (Me); And oxides (MeOx) of the metals (Me); any one of the active material particles selected from the group consisting of, or a mixture of two or more thereof.
  • the external electrode is a positive electrode
  • the external electrode active material layer is a positive electrode active material
  • M1 and M2 are independently from each other Al
  • Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo is any one selected from the group
  • x, y and z are independently of each other
  • An active material particle selected from the group consisting of 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, and x + y + z ⁇ 1 as an atomic fraction of oxide composition elements, or two or more thereof Mixtures may be included.
  • the cable type secondary battery of the present invention has a horizontal cross section, has a linear structure elongated in the longitudinal direction with respect to the horizontal cross section, and has flexibility, and thus deformation is free.
  • FIG 3 is a perspective view of a cable type secondary battery including one internal electrode according to an embodiment of the present invention.
  • the cable type secondary battery 100 may include a lithium ion supply core unit 110 including an electrolyte;
  • An internal current collector 120 having an open structure formed surrounding the outer surface of the lithium ion supply core unit 110, an internal electrode active material layer 130 formed on an outer surface of the internal current collector 120, and the internal electrode active material layer ( It is formed on the outer surface of 130, a graphite coating layer 131 including graphite, a conductive material and a first polymer binder, and a porous coating layer formed on the outer surface of the graphite coating layer 131, and including a second polymer binder
  • an external electrode including an external electrode active material layer 150 formed surrounding the outer surface of the separation layer 140 and an external current collector 160 formed surrounding the outer surface of the external electrode active material layer 150.
  • the external electrode may have various structures according to the positions of the external current collector and the external electrode active material layer, the external current collector formed to surround the outer surface of the separation layer and the external current formed to surround the external surface of the external current collector.
  • a structure including an outer electrode active material layer formed surrounding the outer surface of the separation layer and an outer current collector covered in the outer electrode active material layer and surrounding the outer surface of the separation layer in a spaced state; Etc. are possible.
  • the cable-type secondary battery extending in the longitudinal direction with a horizontal cross-section according to another aspect of the present invention, a lithium ion supply core portion containing an electrolyte;
  • An inner electrode including an inner current collector having an open structure formed around an outer surface of the lithium ion supply core and an inner electrode active material layer formed on an outer surface of the inner current collector;
  • a separation layer which prevents a short circuit of the electrode formed surrounding the outer surface of the inner electrode;
  • a porous coating layer formed surrounding the outer surface of the separation layer, the graphite-based coating layer including an external current collector, an external electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder.
  • porous coating layer may further include inorganic particles as described above.
  • the external electrode is a negative electrode
  • the external electrode active material layer includes a negative electrode active material, as described above.
  • FIG. 4 is a diagram illustrating a perspective view of a cable type secondary battery in which a graphite-based coating layer and a porous coating layer are formed on an external electrode, according to an embodiment of the present invention.
  • the cable type secondary battery 200 may include a lithium ion supply core unit 210 including an electrolyte; An inner electrode including an inner current collector 220 having an open structure formed around the outer surface of the lithium ion supply core unit 210 and an inner electrode active material layer 230 formed on an outer surface of the inner current collector 220; A separation layer 240 surrounding the outer surface of the inner electrode to prevent a short circuit of the electrode; And a porous coating layer 252 formed around the outer surface of the separation layer 240 and surrounding the outer surface of the porous coating layer 252 including a second polymer binder, graphite, a conductive material, and a first polymer.
  • Graphite coating layer 251 including a binder, an external electrode active material layer 250 formed surrounding the outer surface of the graphite coating layer 251 and an external current collector formed surrounding the outer surface of the external electrode active material layer 250 ( It may include an external electrode having a 260.
  • the external electrode may be a variety of structures depending on the position of the conductive material coating layer and the porous coating layer, the outer current collector formed surrounding the outer surface of the separation layer, the outer formed around the outer surface of the outer current collector It is formed surrounding the outer surface of the electrode active material layer, the outer electrode active material layer, the graphite-based coating layer including graphite, a conductive material and the first polymer binder, and formed to surround the outer surface of the graphite-based coating layer, the second polymer binder A structure having a porous coating layer comprising a; An outer current collector formed to surround the outer surface of the separation layer, an outer electrode active material layer formed to contact the separation layer and surrounding the outer surface of the outer current collector, formed to surround the outer surface of the outer electrode active material layer, graphite, conductive A structure comprising a graphite coating layer comprising ash and a first polymer binder, and a porous coating layer formed surrounding the outer surface of the graphite coating layer and including a second polymer binder;
  • a structure comprising a graphite coating layer surrounding and formed surrounding the outer surface of the graphite coating layer, the graphite coating layer including graphite, a conductive material, and a first polymer binder, the porous coating layer including a second polymer binder; Etc. are possible.
  • an electrolyte layer or a separator can be used for the separation layer of this invention.
  • Examples of the electrolyte layer serving as an ion passage include a gel polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAC; Or a solid electrolyte using PEO, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES) or polyvinyl acetate (PVAc); Etc.
  • the matrix of the solid electrolyte is preferably made of polymer or ceramic glass as a basic skeleton.
  • ions may move very slowly in terms of reaction rate, and therefore, it is preferable to use an electrolyte of a gel polymer having easier movement of ions than a solid.
  • the gel polymer electrolyte is not excellent in mechanical properties, it may include a pore structure support or a crosslinked polymer to compensate for this. Since the electrolyte layer of the present invention can function as a separator, a separate separator may not be used.
  • the electrolyte layer of the present invention may further include a lithium salt.
  • Lithium salts can improve ionic conductivity and reaction rate, non-limiting examples of which are LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloro available borane lithium, lower aliphatic carboxylic acid lithium, and tetraphenyl lithium borate, etc. have.
  • the separator is not limited to a kind thereof, but a porous material made of a polyolefin-based polymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer and ethylene-methacrylate copolymer.
  • the present invention includes a protective coating, which is formed on the outer surface of the external electrode to protect the electrode against moisture and external shock in the air as an insulator.
  • a conventional polymer resin can be used.
  • PVC, HDPE or epoxy resin can be used.
  • the cable type secondary battery according to another embodiment of the present invention includes two or more internal electrodes.
  • the internal electrode is a cathode, at least two lithium ion supply core portion containing an electrolyte;
  • An inner current collector having an open structure formed around an outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed on an outer surface of the inner current collector, and an outer surface of the inner electrode active material layer;
  • a separation layer surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes;
  • an external electrode formed surrounding the outer surface of the separation layer, the external electrode including an external current collector and an external electrode active material layer, or two or more lithium ion supply core parts including an electrolyte;
  • An inner current collector having an open structure formed around an outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed on an outer
  • the porous coating layer may further include inorganic particles as described above.
  • a cable type secondary battery 300 including a plurality of internal electrodes of the present invention includes two or more lithium ion supply core portions 310 including an electrolyte;
  • An inner current collector 320 having an open structure formed around an outer surface of each of the lithium ion supply cores 310, an inner electrode active material layer 330 formed on an outer surface of the inner current collector 320, and the inner electrode active material It is formed on the outer surface of the layer 330, the graphite-based coating layer 331 including graphite, a conductive material and the first polymer binder, and formed on the outer surface of the graphite-based coating layer 331, and comprises a second polymer binder Two or more internal electrodes disposed in parallel with each other having the porous coating layer 332; A separation layer 340 surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes; And an external electrode including an external electrode active material layer 350 formed to surround the outer surface of the separation layer 340, and an external current collector 360 formed to surround the outer surface
  • the external electrode is a negative electrode, two or more lithium ion supply core portion containing an electrolyte; Two or more internal electrodes disposed in parallel with each other including an inner current collector having an open structure formed around an outer surface of each lithium ion supply core and an inner electrode active material layer formed surrounding the outer surface of the inner current collector; A separation layer surrounding the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes; And a porous coating layer formed surrounding the outer surface of the separation layer, the graphite-based coating layer including an external current collector, an external electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder.
  • An inner current collector having an open structure formed surrounding the outer surface of each of the lithium ion supply cores, an inner electrode active material layer formed surrounding the outer surface of the inner current collector, and a short circuit of the electrode formed surrounding the outer surface of the inner electrode active material layer
  • Two or more internal electrodes disposed in parallel with each other having a separation layer for preventing;
  • a porous coating layer formed to surround the outer surfaces of the inner electrodes, the graphite-based coating layer including an outer current collector, an outer electrode active material layer, graphite, a conductive material, and a first polymer binder, and a second polymer binder. It includes; an external electrode.
  • the porous coating layer may further include inorganic particles as described above.
  • At least two lithium ion supply core portions 410 including an electrolyte At least two lithium ion supply core portions 410 including an electrolyte;
  • An inner current collector 420 having an open structure formed surrounding the outer surface of each lithium ion supply core unit 410 and an inner electrode active material layer 430 formed surrounding the outer surface of the inner current collector 420.
  • Two or more internal electrodes disposed in parallel to each other;
  • a separation layer 440 which surrounds the outer surfaces of the inner electrodes together to prevent a short circuit of the formed electrodes;
  • a porous coating layer 452 formed surrounding the outer surface of the separation layer 440 and surrounding the outer surface of the porous coating layer 452 including a second polymer binder, graphite, a conductive material, and a first polymer.
  • Graphite coating layer 451 including a binder, an external electrode active material layer 450 formed surrounding the outer surface of the graphite coating layer 451 and an external current collector formed surrounding the outer surface of the external electrode active material layer 450 ( It includes; an external electrode having a 460.
  • the cable type secondary batteries 300 and 400 have internal electrodes formed of a plurality of electrodes, the balance between the negative electrode and the positive electrode can be easily adjusted, and the plurality of electrodes can be prevented, thereby preventing the possibility of disconnection.
  • an electrode active material containing nickel and tin having a thickness of 2.5 ⁇ m was coated on a wire-type copper current collector having a diameter of 125 ⁇ m to form an electrode active material layer.
  • a slurry was prepared by mixing a mixture of natural graphite, a conductive material, and polyvinylidene fluoride as a first polymer binder in a weight ratio of 70: 5: 25 in a solvent of N-methyl pyrrolidone.
  • the slurry was coated on the entire outer surface of the electrode active material layer to form a graphite coating layer.
  • FIG. 7 is a SEM photograph showing the shape of the wire type electrode on which the graphite coating layer is formed.
  • Figure 8 is a SEM photograph showing the shape of the porous coating layer formed by this process.
  • the wire-shaped electrode prepared in Example (1) was manufactured to be in the shape of a plate by winding on a horizontal plane, and used as a cathode, and a metal lithium foil was used as a cathode, between the anode and the cathode.
  • An electrode assembly was produced via a polyethylene separator.
  • an electrode active material containing nickel and tin having a thickness of 2.5 ⁇ m was coated on a wire-type copper current collector having a diameter of 125 ⁇ m to form an electrode active material layer.
  • a coin-type half cell was manufactured in the same manner as in Example (2) except that the wire-shaped electrode prepared in Comparative Example (1) was manufactured to be in a plate shape by winding on a horizontal plane, and then used as a negative electrode. Prepared.
  • Charge-discharge characteristics were evaluated using the coin-type half cells prepared in the examples and comparative examples.
  • the charge was kept constant at 5 mV at a constant voltage, and the charge was terminated when the current density became 0.005 C.
  • the discharge was completed in the constant current mode up to 1.5 V at a current density of 0.5 C. Charge and discharge were repeated 30 times under the same conditions.
  • the cathode discharge profile has a lower discharge reaction potential by the graphite coating layer, thereby increasing the discharge potential of the full cell to improve the energy density of the battery. have.
  • the Example is 85.8% and the comparative example showed 78.7%, and it can be seen that the Example was improved by the graphite coating layer.
  • the capacity was reduced to about 40%, while in the example, the capacity was maintained at 98% or more, which shows that the cycle life characteristics were significantly better than in the comparative example.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une électrode pour une batterie secondaire, une batterie secondaire comprenant celle-ci, et une batterie secondaire de type câble, l'électrode comprenant : un collecteur de courant ; une couche de matériau actif d'électrode formée sur au moins une surface de la totalité de la surface externe du collecteur de courant ; une couche de revêtement à base de graphite qui est formée sur la surface supérieure de la couche de matériau actif d'électrode et comprend du graphite, un matériau conducteur, et un premier liant polymère ; et une couche de revêtement poreux qui est formée sur la surface supérieure de la couche de revêtement à base de graphite et comprend un second liant polymère.
PCT/KR2013/011514 2012-12-12 2013-12-12 Électrode pour batterie secondaire, batterie secondaire comprenant celle-ci, et batterie secondaire de type câble WO2014092473A1 (fr)

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CN201380006039.8A CN104067418B (zh) 2012-12-12 2013-12-12 二次电池用电极、包含其的二次电池和线缆型二次电池
JP2014552146A JP6316207B2 (ja) 2012-12-12 2013-12-12 二次電池用電極、それを含む二次電池及びケーブル型二次電池
US14/280,803 US9214672B2 (en) 2012-12-12 2014-05-19 Electrode for secondary battery, secondary battery and cable-type secondary battery comprising the same

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KR10-2012-0144396 2012-12-12
KR20120144396 2012-12-12
KR10-2013-0154429 2013-12-12
KR20130154429A KR101479460B1 (ko) 2012-12-12 2013-12-12 이차전지용 전극, 그를 포함하는 이차전지 및 케이블형 이차전지

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Citations (5)

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KR20000045100A (ko) * 1998-12-30 2000-07-15 고장면 고분자 전해질을 이용한 리튬이온 이차전지의제조방법
US6488721B1 (en) * 2000-06-09 2002-12-03 Moltech Corporation Methods of preparing electrochemical cells
KR20090051546A (ko) * 2007-11-19 2009-05-22 주식회사 엘지화학 다공성 코팅층이 형성된 세퍼레이터 및 이를 구비한전기화학소자
KR20120000744A (ko) * 2010-06-28 2012-01-04 주식회사 엘지화학 케이블형 이차전지용 음극 및 이를 구비하는 케이블형 이차전지
US8119273B1 (en) * 2004-01-07 2012-02-21 The United States Of America As Represented By The Department Of Energy Unique battery with an active membrane separator having uniform physico-chemically functionalized ion channels and a method making the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000045100A (ko) * 1998-12-30 2000-07-15 고장면 고분자 전해질을 이용한 리튬이온 이차전지의제조방법
US6488721B1 (en) * 2000-06-09 2002-12-03 Moltech Corporation Methods of preparing electrochemical cells
US8119273B1 (en) * 2004-01-07 2012-02-21 The United States Of America As Represented By The Department Of Energy Unique battery with an active membrane separator having uniform physico-chemically functionalized ion channels and a method making the same
KR20090051546A (ko) * 2007-11-19 2009-05-22 주식회사 엘지화학 다공성 코팅층이 형성된 세퍼레이터 및 이를 구비한전기화학소자
KR20120000744A (ko) * 2010-06-28 2012-01-04 주식회사 엘지화학 케이블형 이차전지용 음극 및 이를 구비하는 케이블형 이차전지

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