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WO2018048166A1 - Électrode comprenant un collecteur de courant d'électrode de structure de réseau tridimensionnel - Google Patents

Électrode comprenant un collecteur de courant d'électrode de structure de réseau tridimensionnel Download PDF

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Publication number
WO2018048166A1
WO2018048166A1 PCT/KR2017/009672 KR2017009672W WO2018048166A1 WO 2018048166 A1 WO2018048166 A1 WO 2018048166A1 KR 2017009672 W KR2017009672 W KR 2017009672W WO 2018048166 A1 WO2018048166 A1 WO 2018048166A1
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WIPO (PCT)
Prior art keywords
electrode
current collector
unit
secondary battery
dimensional network
Prior art date
Application number
PCT/KR2017/009672
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English (en)
Korean (ko)
Inventor
목은경
유민규
엄인성
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170112505A external-priority patent/KR102098154B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780004251.9A priority Critical patent/CN108292736B/zh
Priority to JP2018547249A priority patent/JP6723370B2/ja
Priority to US15/774,192 priority patent/US20180337408A1/en
Priority to EP17849050.4A priority patent/EP3370281B1/fr
Publication of WO2018048166A1 publication Critical patent/WO2018048166A1/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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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 an electrode including a current collector of a three-dimensional network structure.
  • lithium secondary batteries have high energy density and operating potential, have long cycle life, and have low self discharge rate. Is commercially available and widely used.
  • Electrodes are manufactured through a heat treatment process after applying a slurry in which an electrode active material, a binder, and a conductive material are appropriately mixed on a cathode / cathode current collector. That is, the electrode mixture layer including the binder and the conductive material is formed on the positive electrode / cathode current collector.
  • the binder included in the electrode mixture layer is relatively light, so that it is not evenly dispersed in the electrode mixture layer, and the surface is lifted up. This is because the thicker the electrode mixture layer is, the more severe the separation is. Deterioration of cycle characteristics and lifespan of the battery due to separation of the current collector and the active material due to the volume change generated are inevitable.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • unit electrodes having an electrode mixture including an electrode active material are introduced into pores of a unit current collector having a three-dimensional network structure.
  • the present invention was completed.
  • the present invention provides a secondary battery electrode, wherein two or more unit electrodes are stacked in close contact with each other, and adjacent unit electrodes are electrically connected to each other via an electrode mixture. And an electrode mixture containing an electrode active material is introduced into a gap of a unit current collector having a three-dimensional network structure.
  • the electrode may have a structure in which two to ten unit electrodes are stacked.
  • the unit current collector having the three-dimensional network structure may be a conductive metal felt.
  • the average thickness of the unit current collector having the three-dimensional network structure is 30 ⁇ m to 400 ⁇ m.
  • the average diameter of the unit current collector pores having the three-dimensional network structure is 1 ⁇ m to 100 ⁇ m.
  • the unit electrode is a mixture of the unit current collector and the electrode mixture having a three-dimensional network structure.
  • the thickness of the electrode coalescence layer coated on one outer surface of the unit current collector is 10 ⁇ m to 100 ⁇ m.
  • the thickness of the electrode is 50 ⁇ m to 500 ⁇ m.
  • the unit electrodes are joined to each other by a binder in the electrode mixture.
  • a general current collector is additionally interposed between the unit electrodes.
  • the present invention provides a battery cell comprising the secondary battery electrode.
  • the secondary battery electrode includes the steps of: (a) preparing a unit current collector and an electrode slurry of a three-dimensional network structure; (b) coating the electrode slurry on a unit current collector; (c) drying the electrode slurry to form an electrode mixture layer; (d) rolling unit electrodes; And (e) stacking unit electrodes; It may be prepared by a method for manufacturing a secondary battery electrode, characterized in that it comprises a.
  • the secondary battery electrode includes the steps of: (a) preparing a unit current collector and an electrode slurry of a three-dimensional network structure; (b) coating the electrode slurry on a unit current collector; (c) drying the electrode slurry to form an electrode mixture layer; (d) stacking unit electrodes; And (e) rolling the stacked unit electrodes; It may be prepared by a method for manufacturing a secondary battery electrode, characterized in that it comprises a.
  • unit electrodes having a structure in which an electrode mixture is impregnated and coated are laminated on a unit current collector having a three-dimensional network structure, and the unit electrodes are formed through the electrode mixture. It is a connected structure.
  • the structure in which the electrode mixture including the electrode active material is moved into the pores formed in the unit current collector so that the inside of the unit current collector is filled with the electrode mixture can alleviate an increase in the overall electrode thickness.
  • a high capacity battery can be provided.
  • the electrode mixture including the electrode active material is filled in the inside of the current collector, and ultimately, the binder may be uniformly dispersed in the electrode, thereby preventing desorption of the electrode active material, thereby improving the performance of the electrode and extending the life.
  • FIG. 1 is a perspective view schematically showing a unit current collector according to an embodiment of the present invention
  • FIG. 2 is a perspective view schematically showing an electrode in which a unit current collector of FIG. 1 is stacked;
  • FIG. 3 is an enlarged perspective view showing an electrode mixture introduced into the pores of a unit current collector by enlarging a portion of FIG. 2;
  • FIG. 4 is a perspective view schematically showing a state in which an electrode mixture is coated on the unit current collector of FIG. 1;
  • FIG. 6 is a vertical cut plane of an electrode in which the unit current collectors of FIG. 4 are stacked.
  • the present invention is a secondary battery electrode, two or more unit electrodes are stacked in close contact with each other, mutually adjacent unit electrodes are electrically connected via an electrode mixture, each unit electrode is a three-dimensional network structure It is an electrode for secondary batteries characterized by introducing the electrode mixture containing an electrode active material into the space
  • FIG. 1 schematically illustrates a perspective view of a unit current collector according to an embodiment of the present invention
  • FIG. 2 schematically illustrates a perspective view of an electrode in which the unit current collectors of FIG. 1 are stacked.
  • the unit electrode 10 is composed of a unit current collector 11 having a three-dimensional network structure having pores 13, and the pores 13 are formed of the unit current collector. It is composed of open pores penetrating the outer surface and the inside, and the electrode mixture including the electrode active material penetrates between the pores.
  • the electrode for the secondary battery of the present invention since the electrode for the secondary battery of the present invention has a structure in which open pores are formed in the unit current collector itself, when the electrode mixture is coated on the unit current collector, the electrode mixture including the electrode active material flows between the open pores. . Therefore, the electrode mixture including the electrode active material is not only coated on the unit current collector, but also fills pores in the current collector, so that even when the same amount of the electrode mixture is loaded, the electrode mixture is formed on the current collector only.
  • the increase in thickness can be prevented and the increase in internal resistance can be prevented because the distance between the outermost surface of the electrode mixture layer and the surface of the current collector does not increase.
  • the electrode mixture layer containing the electrode active material penetrates into the unit current collector, adhesion between the current collector and the electrode active material is increased, and the electrode mixture containing the electrode active material is filled in the current collector so that the binder is uniformly dispersed in the electrode. Since the electrode active material is prevented from being detached during repeated charging and discharging, the electrode performance is improved and the life is extended, and the impregnation rate of the electrolyte is reduced due to the formation of a thick mixture layer. .
  • the secondary battery electrode according to the present invention has a structure in which the unit electrodes are electrically connected to each other via an electrode mixture with adjacent unit electrodes in a stacked state.
  • the electrode may have a structure in which two to ten unit electrodes are stacked.
  • the electrode may have a structure in which four to ten unit electrodes are stacked.
  • the electrode 100 of the present invention is formed by stacking a plurality of unit electrodes 10, and 2 to 10 unit current collectors having an average thickness (a) of 30 ⁇ m to 400 ⁇ m are formed. The thickness of the entire electrode is laminated to form 50 to 500 ⁇ m.
  • the unit current collector may be formed thicker than the thickness of a general current collector.
  • the average thickness of the unit current collector may be 30 ⁇ m to 400 ⁇ m, preferably 30 ⁇ m to 350 ⁇ m, and more preferably 40 ⁇ m to 300 ⁇ m.
  • the average thickness of the unit current collector is thinner than 30 ⁇ m, the strength of the current collector is significantly lowered. If the average thickness of the unit current collector is larger than 400 ⁇ m, the electrode mixture layer is difficult to penetrate into the current collector, which is not preferable. .
  • the unit current collector is preferably made of a material having high electrical conductivity.
  • the unit current collector may be made of a conductive metal felt having a three-dimensional network structure. Since the electrode of the present invention uses a conductive metal felt as a current collector, the flexibility of the metal felt itself also makes it suitable for use in a flexible battery.
  • the material having high electrical conductivity is not particularly limited as long as it does not have a chemical effect by reacting with the electrode mixture, and for example, aluminum (Al), magnesium (Mg), iron (Fe), nickel (Ni), and chromium. (Cr), copper (Cu), stainless steel (Stainless Steel) or one or more selected from the group consisting of alloys thereof, and may vary in detail depending on the potential of the electrode and the composition of the electrode mixture.
  • the aspect ratio of the metal fibers constituting the conductive metal felt may be in the range of 10 to 1,000, more preferably 10 to 500, most preferably 30 to 150.
  • the pores 13 formed in the unit current collector 11 may be formed in various sizes, and may be 1 ⁇ m to 100 ⁇ m, more preferably in consideration of particle diameters of the electrode active material, the conductive agent, and the binder included in the electrode mixture.
  • the average diameter of the pores may be formed in the range of 10 ⁇ m to 90 ⁇ m, most preferably 20 ⁇ m to 80 ⁇ m.
  • the average diameter of the open pores is smaller than 1 ⁇ m, since the electrode mixture having a larger particle size is less likely to move inside the pores, the particle size range of the applicable electrode active material may be limited. It is not preferable because there is a problem that the strength of the current collector is weakened.
  • the open pores may have a structure in which an electrode mixture including an electrode active material is introduced, and the electrode mixture may be rolled after coating the electrode slurry on the unit current collector to induce introduction of the electrode mixture into the pores. Process may be included.
  • the viscosity of the electrode mixture falls within a predetermined range.
  • the viscosity of the electrode mixture may be selected in consideration of the size and coating method of the open pores formed in the current collector in the range of 2,000 cP or more to 12,000 cP or less.
  • an electrode mixture having a high viscosity may be used.
  • a low viscosity electrode mixture is used. It is preferable.
  • the extra electrode mixture not introduced into the open pores formed in the current collector may form a coating layer in a state that is applied to one side or both sides of the unit current collector.
  • FIG. 4 schematically illustrates a perspective view of a unit electrode coated with an electrode mixture on the unit current collector of FIG. 1, and FIG. 5 schematically illustrates a vertical cut plane along the line AA ′ of FIG. 4.
  • the unit current collector 201 is coated with the electrode mixture 202, and the viscosity of the electrode mixture may be selected within the range of viscosity 2,000 cP to 12,000 cP according to the coating method.
  • the electrode mixture 202 is introduced into at least some of the pores 203.
  • the coating amount of the electrode mixture is larger than the amount that can be introduced into the open pores formed in the current collector, the extra electrode mixture not introduced into the pores will form the electrode mixture layer 204 on the outer surface of the current collector. .
  • the thickness d of the electrode mixture layer may be uniformly formed.
  • the thickness of the electrode coalescence layer coated on one outer surface of the unit current collector may be 10 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 80 ⁇ m.
  • the bonding force between adjacent unit electrodes may be weak, and when the thickness of the electrode mixture layer is thicker than 100 ⁇ m, the electrolyte impregnation rate may be low. The problem of inferior mobility of lithium transfer may occur, which is not preferable.
  • a plurality of unit electrodes formed by coating an electrode mixture on an electrode current collector having open pores formed thereon are laminated to form one electrode, and the thickness of the electrode is coated on the outer surface of the current collector to the thickness of the electrode current collector.
  • the thickness of the electrode may be freely set to have a desired capacity in consideration of the thickness of the electrode mixture layer, and the thickness of the electrode may be 50 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 500 ⁇ m, and most Preferably from 200 ⁇ m to 450 ⁇ m.
  • the thickness of the electrode is smaller than 50 ⁇ m, it is difficult to achieve the purpose of providing a high capacity battery, and when the electrode is larger than 500 ⁇ m, when the number of stacked unit electrodes increases, when rolling after lamination or secondary battery It is not preferable because the phenomenon that the electrode is inclined or pushed to one side may occur at the time of use.
  • the electrode 300 is formed by stacking five unit electrodes 310, 320, 330, 340, and 350 in close contact with each other. It is electrically connected via.
  • the unit electrodes may have a structure in which the unit electrodes are bonded to each other by a binder in the electrode mixture, and due to the presence of the binder, the electrode mixture and the unit The bonding force between the collectors can also be increased.
  • a general current collector having no porous structure may be interposed in various shapes between the unit electrodes to be stacked. At least one current collector may be interposed in one electrode.
  • an anode may be an aluminum current collector
  • a cathode may be a copper foil current collector.
  • the electrode 300 can roll the unit electrode in order to reduce the thickness of the unit electrode by introducing the electrode mixture into the pores inside the current collector, the method of stacking the individual unit electrodes after rolling May be used, and the unit electrodes may be rolled in a state of stacking the unit electrodes without individually rolling the unit electrodes.
  • the present invention provides a battery cell having a structure in which at least one of the positive electrode or the negative electrode including the secondary battery electrode and the electrolyte is formed in the cell case, and the electrolyte flows into the open pores of the unit current collector from the secondary battery electrode. Since the electrode mixture introduced into the open pores of the unit current collector may be impregnated in the electrolyte, the capacity may be prevented from being reduced.
  • the present invention also provides a method for manufacturing the above secondary battery electrode
  • It provides a method of manufacturing a secondary battery electrode comprising a.
  • the electrode for secondary batteries coats the electrode slurry on the unit current collector having a porous structure
  • the electrode slurry may move to pores inside the unit current collector to fill the electrode slurry inside the unit current collector.
  • the electrode slurry since the electrode slurry is dried and the unit electrodes are rolled in the state in which the electrode slurry is filled in the current collector, the thickness of the unit electrodes may be uniformly formed.
  • the present invention is a manufacturing method of the electrode for secondary batteries
  • It provides a method of manufacturing a secondary battery electrode comprising a.
  • the electrode for secondary batteries coats the electrode slurry on the unit current collector having a porous structure
  • the electrode slurry may move to the pores of the unit current collector to fill the electrode slurry inside the unit current collector.
  • the electrode slurry is dried while the electrode slurry is filled in the unit current collector, the unit electrodes on which the electrode mixture layer is formed are stacked, and the stacked unit electrodes are rolled.
  • the present invention also provides a lithium secondary battery comprising the electrode.
  • the lithium secondary battery may be composed of the positive electrode, the negative electrode, the separator and the lithium salt-containing non-aqueous electrolyte, and is prepared by putting the electrolyte into a porous separator between the positive electrode and the negative electrode in a conventional manner known in the art. Can be.
  • the electrode according to the present invention may be one or more selected from the positive electrode or the negative electrode. That is, both the positive electrode and / or the negative electrode may have an electrode structure according to the present invention, and only one electrode of the positive electrode and the negative electrode may have the electrode structure according to the present invention and is not particularly limited and may be appropriately selected as necessary. Can be.
  • the positive electrode may be prepared by, for example, applying a slurry of a mixture of a positive electrode active material, a conductive material, and a binder onto a unit current collector having a three-dimensional network structure according to the present invention, followed by drying. More may be added.
  • the conductive material is typically added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
  • the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • the negative electrode may be prepared by, for example, applying a slurry of a mixture of a negative electrode active material, a conductive material, and a binder onto a unit current collector having a three-dimensional network structure according to the present invention, followed by drying. More may be added.
  • the negative electrode active material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2
  • the positive electrode according to the present invention is a positive electrode, and contains a lithium transition metal oxide generally used as a positive electrode active material
  • the positive electrode has a loading amount of 700 mg / 25 cm 2
  • the electrode is a negative electrode and includes a carbon material generally used as a negative electrode active material
  • the loading amount of the negative electrode may be up to 300 mg / 25 cm 2 or more.
  • the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • a solid electrolyte such as a polymer
  • the solid electrolyte may also serve as a separator.
  • the lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium.
  • a nonaqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte and the like are used as the nonaqueous electrolyte, but are not limited thereto.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, 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 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
  • lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2, and the like, may be prepared by cyclic carbonate of EC or PC, which is a highly dielectric solvent, and DEC, DMC, or EMC, which are low viscosity solvents.
  • Lithium salt-containing non-aqueous electrolytes can be prepared by adding them to a mixed solvent of linear carbonates.
  • the present invention also provides a secondary battery in which an electrode assembly composed of the electrode for secondary batteries is sealed inside the battery case together with an electrolyte, and the secondary battery may be used in a battery cell used as a power source for a small device.
  • a battery pack including a plurality of battery cells used as a power source for medium and large devices requiring high temperature stability, long cycle characteristics, high rate characteristics, and the like may be preferably used as a unit battery in a device including the battery pack as a power source. Can be.
  • the device specifically includes a power tool that is powered by a mobile electronic device, a battery-based motor; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf carts; It may be any one selected from the system for power storage, but is not limited thereto.
  • Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
  • Electric motorcycles including electric bicycles (E-bikes) and electric scooters (E-scooters)
  • Electric golf carts It may be any one selected from the system for power storage, but is not limited thereto.
  • Cathode active material LiNi 0 . 55 Mn 0 . 30 Co 0 . 15 O 2 , Denka black as a conductive material , and polyvinylidene fluoride (polyvinylidene fluoride) as a binder were mixed in a weight ratio of 96: 2: 2, and NMP (N-methyl pyrrolidone) was added to prepare a slurry.
  • the slurry was coated on aluminum felt having an average diameter of pores of 20 ⁇ m, an aspect ratio of 100, and a thickness of 40 ⁇ m to obtain a unit anode. After drying the unit positive electrode in a vacuum oven at 120 °C, laminated two dried unit positive electrode and rolled to prepare a positive electrode. At this time, the thickness of the electrode including the current collector was 75 ⁇ m.
  • Lithium metal 40 ⁇ m was attached to copper (Cu) foil as a counter electrode, and a polyolefin separator was interposed between the positive electrode and the counter electrode, followed by ethylene carbonate (EC) and ethyl methyl carbonate (DEC).
  • EC ethylene carbonate
  • DEC ethyl methyl carbonate
  • P-type half cell was prepared by injecting an electrolyte solution in which 1 M lithium hexafluorophosphate (LiPF 6 ) was dissolved in a solvent mixed at a volume ratio of 50:50.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the average diameter of the current collector pores was changed as shown in Table 1.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the thickness of the aluminum felt was changed to 55 ⁇ m and the thickness of the electrode including the current collector was adjusted to 102 ⁇ m.
  • a lithium secondary battery was manufactured in the same manner as in Example 5, except that the average diameter of the current collector pores was changed as shown in Table 1.
  • Cathode active material LiNi 0 . 55 Mn 0 . 30 Co 0 . 15 O 2 , Denka black as a conductive material , and polyvinylidene fluoride (polyvinylidene fluoride) as a binder were mixed in a weight ratio of 96: 2: 2, and NMP (N-methyl pyrrolidone) was added to prepare a slurry.
  • the positive electrode slurry was applied in three layers between the two aluminum and the outer surface, and dried in a vacuum oven at 120 ° C. to prepare a positive electrode. At this time, the thickness of the electrode was 75 ⁇ m including the thickness of the current collector, the thickness of the current collector is 12 micrometers.
  • Lithium metal 40 ⁇ m was attached to copper (Cu) foil as a counter electrode, and a polyolefin separator was interposed between the positive electrode and the counter electrode, followed by ethylene carbonate (EC) and ethyl methyl carbonate (DEC).
  • EC ethylene carbonate
  • DEC ethyl methyl carbonate
  • P-type half cell was prepared by injecting an electrolyte solution in which 1 M lithium hexafluorophosphate (LiPF 6 ) was dissolved in a solvent mixed at a volume ratio of 50:50.
  • a lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that the thickness of the electrode including the current collector was changed as in Table 1.
  • the batteries prepared in Examples and Comparative Examples were carried out under conditions of 1 / 3C to 1 / 3C (one time charge and discharge) between 4.2V and 2.5V.
  • the lifetime characteristics were evaluated from the discharge capacity retention rate, and the discharge capacity retention rate was expressed as a percentage of the initial capacity after the charge and discharge was repeated 200 times. The results are shown in Table 1.
  • Example 1 20 75 3.431 3.163 92.2 Example 2 30 75 3.864 3.578 92.6 Example 3 50 75 3.715 3.444 92.7 Example 4 80 75 3.449 3.197 92.7 Example 5 20 102 3.313 2.932 88.5 Example 6 30 102 3.753 3.318 88.4 Example 7 50 102 3.623 3.224 89.0 Example 8 80 102 3.330 2.957 88.8 Comparative Example 1 - 75 3.643 3.356 92.1 Comparative Example 2 - 102 3.446 2.939 85.3
  • Examples 1 to 4 and Comparative Example 1 even though the thickness of the electrode is the same as the electrode of the battery of Examples 1 to 4 compared to the battery of Comparative Example 1 or even better, it can be seen that better. .
  • Examples 5 to 8 and Comparative Example 2 is a high-loading electrode having the same electrode thickness, Comparative Example 2 has a much lower life characteristics, while Examples 5 to 8 is confirmed to maintain excellent life characteristics compared to Comparative Example 2 do.
  • the electrode of the present invention shortens the reaction distance due to the decrease in the physical distance between the electrode current collector and the active material compared to the electrode of the comparative example, thereby reducing the resistance in the electrode, and the role of the support that the three-dimensional network structure supports the active material layer. It is believed that this is because the possibility of detachment of the active material layer and the current collector in the electrode is reduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention porte sur une électrode pour un accumulateur, dans laquelle deux électrodes unitaires ou plus sont empilées dans un état de contact étroit entre elles, les électrodes unitaires adjacentes entre elles étant connectées électriquement par un mélange d'électrodes, dans lequel chaque électrode unitaire est conçue de telle sorte que le mélange d'électrodes contenant un matériau actif d'électrode est introduit dans un pore d'un collecteur de courant unitaire ayant une structure de réseau tridimensionnel.
PCT/KR2017/009672 2016-09-09 2017-09-05 Électrode comprenant un collecteur de courant d'électrode de structure de réseau tridimensionnel WO2018048166A1 (fr)

Priority Applications (4)

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CN201780004251.9A CN108292736B (zh) 2016-09-09 2017-09-05 包含具有三维网络结构的电极集电器的电极
JP2018547249A JP6723370B2 (ja) 2016-09-09 2017-09-05 ３次元網状構造の電極集電体を含む電極
US15/774,192 US20180337408A1 (en) 2016-09-09 2017-09-05 Electrode including electrode current collector with three-dimensional network structure
EP17849050.4A EP3370281B1 (fr) 2016-09-09 2017-09-05 Électrode comprenant un collecteur de courant d'électrode de structure de réseau tridimensionnel

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KR20160116187 2016-09-09
KR10-2016-0116187 2016-09-09
KR1020170112505A KR102098154B1 (ko) 2016-09-09 2017-09-04 3차원 망상 구조의 전극 집전체를 포함하는 전극
KR10-2017-0112505 2017-09-04

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EP3598526A1 (fr) 2018-07-17 2020-01-22 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Réseau de fibres métalliques, procédé de production d'un réseau de fibres métalliques électrode et batterie

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Publication number Priority date Publication date Assignee Title
EP3598526A1 (fr) 2018-07-17 2020-01-22 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Réseau de fibres métalliques, procédé de production d'un réseau de fibres métalliques électrode et batterie
WO2020016240A1 (fr) 2018-07-17 2020-01-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Réseau de fibres métalliques, procédé de fabrication d'un réseau de fibres métalliques, électrode et batterie
EP4224545A2 (fr) 2018-07-17 2023-08-09 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Réseau de fibres métalliques, procédé de fabrication d'un réseau de fibres métalliques, électrode et batterie

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