WO2019004699A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

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Publication number
WO2019004699A1
WO2019004699A1 PCT/KR2018/007227 KR2018007227W WO2019004699A1 WO 2019004699 A1 WO2019004699 A1 WO 2019004699A1 KR 2018007227 W KR2018007227 W KR 2018007227W WO 2019004699 A1 WO2019004699 A1 WO 2019004699A1
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Prior art keywords
lithium
group
electrolyte
secondary battery
negative electrode
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PCT/KR2018/007227
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English (en)
Korean (ko)
Inventor
박은경
장민철
박창훈
김도연
정보라
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180072890A external-priority patent/KR102093972B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880042247.6A priority Critical patent/CN110785886B/zh
Priority to US16/623,500 priority patent/US11431019B2/en
Priority to EP18823493.4A priority patent/EP3637526B1/fr
Priority to JP2019571353A priority patent/JP7183198B2/ja
Publication of WO2019004699A1 publication Critical patent/WO2019004699A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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 lithium secondary battery having an anode-free structure using a gel polymer electrolyte.
  • the lithium metal has a low redox potential (-3.045 V versus the standard hydrogen electrode) and a large weight energy density (3,860 mAhg -1 ), which is expected as a cathode material for high capacity secondary batteries.
  • lithium metal when used as a battery cathode, a battery is manufactured by attaching a lithium foil on a flat current collector. Lithium reacts explosively with water because it is highly reactive as an alkali metal and reacts with oxygen in the atmosphere It is difficult to manufacture and use in a general environment.
  • lithium metal when exposed to the atmosphere, it has an oxide film such as LiOH, Li 2 O, Li 2 CO 3 or the like as a result of oxidation.
  • the oxide film acts as an insulating film to lower the electrical conductivity and hinder the smooth movement of lithium ions, thereby increasing the electrical resistance.
  • Patent Document 1 Korean Patent Laid-Open Publication No. 10-2016-0052323 " Lithium Electrode and Lithium Battery Including It "
  • the present invention provides a lithium secondary battery comprising a cathode, a cathode and a separator interposed therebetween and an electrolyte, wherein the electrolyte is a gel polymer electrolyte and is moved from the cathode by charging,
  • a lithium secondary battery is provided which forms a lithium metal on a current collector.
  • the lithium metal is formed through one charge at a voltage of 4.5 V to 2.5 V.
  • the negative electrode current collector may further include a protective layer on a side contacting the separator.
  • the lithium secondary battery according to the present invention is coated in a state that it is shielded from the atmosphere through the process of forming the lithium metal layer on the anode current collector, the formation of the surface oxide film due to oxygen and moisture in the atmosphere of lithium metal can be suppressed And as a result, the cycle life characteristics are improved.
  • FIG. 1 is a schematic view of a lithium secondary battery manufactured according to a first embodiment of the present invention.
  • Li + lithium ions
  • FIG. 3 is a schematic diagram of a lithium secondary battery manufactured according to a first embodiment of the present invention after initial charging of the lithium secondary battery has been completed.
  • FIG. 4 is a schematic view of a lithium secondary battery manufactured according to a second embodiment of the present invention.
  • FIG. 5 is a schematic diagram showing the movement of lithium ions (Li + ) during the initial charging of a lithium secondary battery manufactured according to the second embodiment of the present invention.
  • FIG. 6 is a schematic view of a lithium secondary battery manufactured according to a second embodiment of the present invention after initial charging is completed.
  • FIG. 6 is a schematic view of a lithium secondary battery manufactured according to a second embodiment of the present invention after initial charging is completed.
  • FIG. 1 is a cross-sectional view of a lithium secondary battery manufactured according to a first embodiment of the present invention, and includes a cathode including a cathode current collector 11 and a cathode mixture 12; A negative electrode including an anode current collector 21; And a separator 30 and an electrolyte (not shown) interposed therebetween.
  • the negative electrode of the lithium secondary battery is typically formed on the negative electrode collector 21, but in the present invention, the negative electrode collector 21 is used only as an anode-free battery structure,
  • the lithium ion released from the positive electrode mixture 13 forms a lithium metal layer (not shown) as a negative electrode mixture on the negative electrode collector 21, thereby forming a negative electrode having a structure of a known negative electrode collector / negative electrode mixture, Thereby constituting a lithium secondary battery.
  • the negative electrode pre-battery compartment may be a negative electrode-free battery in which no negative electrode is formed on the negative electrode current collector at the time of initial assembly, and a negative electrode may be formed on the negative electrode current collector, It can be a concept that includes all of the cells that are present.
  • the form of the lithium metal formed as the negative electrode mixture on the negative electrode collector may be a form in which the lithium metal is formed as a layer and a structure in which the lithium metal is not formed in the layer A structure in which particles are gathered in the form of particles).
  • FIG. 2 is a schematic diagram showing the movement of lithium ions (Li + ) upon initial charging of a lithium secondary battery manufactured in accordance with the first embodiment of the present invention, and FIG. After the initial charging of the secondary battery is completed.
  • lithium ions are removed from the positive electrode mixture 13 in the positive electrode 10, This passes through the separator 30 and moves toward the cathode current collector 21 and forms a cathode 20 by forming a lithium metal layer 23 purely composed of lithium on the cathode current collector 21.
  • the formation of the lithium metal layer 23 through such filling can reduce the thickness of the thin film layer compared to the negative electrode in which the lithium metal layer 23 is sputtered on the conventional anode current collector 21 or the lithium foil and the cathode current collector 21 are joined together. And it is advantageous that the control of the interface characteristics is very easy. In addition, since the bonding strength of the lithium metal layer 23 stacked on the anode current collector 21 is large and stable, there is no problem of being removed from the cathode current collector 21 due to ionization again through discharge.
  • the lithium metal since the lithium metal is not exposed to the atmosphere during the cell assembly process, the problem of problems such as formation of oxide film on the surface due to high reactivity of lithium itself and deterioration of lifetime of the lithium secondary battery due to the high reactivity It can be blocked at its source.
  • a gel polymer electrolyte is used as an electrolyte in the negative electrode pre-battery structure of the present invention.
  • the most widely used ether-based electrolyte has a lithium metal efficiency of 99% or more and the carbonate-based electrolyte has a lithium metal efficiency of 95% or less, the ether-based electrolyte has a low high-voltage stability and can not be used in a high-voltage anode.
  • the reduction stability is low, which causes a continuous reaction with lithium, resulting in a reduction in battery efficiency and lifetime.
  • the crosslinked gel polymer electrolyte of the present invention can inhibit electrolyte decomposition or the like when it is applied to a high voltage anode by a crosslinked structure, and can control the mechanical strength of the electrolyte relative to the electrolyte to provide a lithium dendrite growth, dead Li) can be suppressed and battery life and cell stability can be improved.
  • the gel polymer electrolyte includes a polymer matrix, a lithium salt, and an organic solvent, and includes a crosslinked or non-crosslinked structure, preferably a crosslinked crosslinked gel polymer electrolyte.
  • the polymer matrix includes a functional group selected from the group consisting of a carboxylic group, an acrylate group and a cyano group in the molecular structure, and preferably, the acrylate functional group .
  • the polymer matrix may be one containing at least one polymerizable or crosslinkable functional group in the molecular structure.
  • the monomers having one functional group are not limited to the types, but methyl methacrylate, ethyl methacrylate, buthyl methacrylate, methyl acrylate, Buthyl acrylate, ethylene glycol methyl ether acrylate, ethylene glycol methyl ether methacrylate, acrylonitrile, vinyl acetate ), Carboxyethyl acrylate, methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylate, and the like.
  • icacid, hydroxyethyl methacrylate, hydroxypropyl acrylate, Sites (hydroxypropyl acrylate), vinyl chloride (vinylchloride) and vinyl fluoride (vinyl fluoride) and the like can be used.
  • Examples of the monomer having two or more functional groups include, but are not limited to, trimethylolpropane ethoxylate triacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolpropane trimethacrylate, ethoxylated bisphenol A dimethacrylate, divinyl benzene, and the like can be used.
  • Examples of the monomer having three or more functional groups include trimethylolpropane-ethocylate triacrylate, acrylic acid, trimethylolpropane-ethocylate triacrylate, and the like.
  • lithium salt examples include 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, 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxylate lithium, And the like may be used.
  • the concentration of said dissociable salt relative to the organic solvent may be 0.1 to 5.0 M.
  • the gel polymer electrolyte may have a proper viscosity in the form of a gel, and the dissociable salt may be dissolved in the organic solvent to contribute to effective migration of lithium ions.
  • electrolyte solvent used according to one embodiment of the present invention those commonly used in an electrolyte for a lithium secondary battery may be used without limitation, and for example, ether, ester, amide, linear carbonate, or cyclic carbonate may be used alone Or a mixture of two or more thereof.
  • carbonate compounds which are typically cyclic carbonates, linear carbonates or a mixture thereof can be included.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, A carbonate, a vinylene carbonate, and a halide thereof, or a mixture of two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC) and ethyl propyl carbonate (EPC) , Or a mixture of two or more of them may be used.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • EMC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • EPC ethyl propyl carbonate
  • propylene carbonate and ethylene carbonate which are cyclic carbonates in the carbonate electrolyte solution, are highly viscous organic solvents having a high dielectric constant and can dissociate the lithium salt in the electrolytic solution well.
  • cyclic carbonates such as ethylmethyl carbonate, diethyl carbonate Or a low viscosity, low dielectric constant linear carbonate such as dimethyl carbonate in an appropriate ratio can be used to more advantageously use an electrolytic solution having a high electrical conductivity.
  • esters in the electrolyte solvent examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone And? -Caprolactone, or a mixture of two or more thereof, but the present invention is not limited thereto.
  • crosslinking conventional crosslinking agents or initiators may be used.
  • Non-limiting examples of initiators include benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, t- Organic peroxides such as t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide and hydrogen peroxide, and hydroperoxides such as hydrogen peroxide Azobis (iso-butyronitrile) and AMVN (2,2'-azobis (2-cyanobutane), 2,2'-azobis '-Azobisdimethyl-Valeronitrile), and the like, but the present invention is not limited thereto.
  • the gel polymer electrolyte according to the present invention comprises preparing a precursor composition by mixing a crosslinkable monomer, a dissociable salt, and an organic solvent; And crosslinking the three or more crosslinkable monomers by applying heat or ultraviolet rays to the precursor composition.
  • a crosslinked polymer matrix having a net structure is formed Of the gel polymer electrolyte.
  • the anode current collector 21 in which the lithium metal layer 23 can be formed by charging is not particularly limited as long as the anode current collector 21 has electrical conductivity without causing chemical change in the lithium secondary battery.
  • Examples of the surface treatment include surface treatment of surfaces of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel with carbon, nickel, titanium or silver, or aluminum-cadmium alloy.
  • the anode current collector 21 may be formed in various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric having fine irregularities on its surface.
  • the positive electrode active material used in the present invention is not particularly limited as long as the positive electrode active material is a material capable of intercalating and deintercalating lithium ions, And a lithium transition metal oxide as a positive electrode active material capable of realizing a battery having excellent charge and discharge efficiency.
  • lithium transition metal oxide a layered compound such as lithium cobalt oxide (LiCoO 2 ) or lithium nickel oxide (LiNiO 2 ), which contains two or more transition metals and is substituted with, for example, at least one transition metal;
  • LiCoO 2 lithium cobalt oxide
  • LiNiO 2 lithium nickel oxide
  • a lithium nickel oxide, a spinel-based lithium nickel manganese composite oxide, a spinel-based lithium manganese oxide in which a part of Li is substituted with an alkaline earth metal ion, an olivine-based lithium metal phosphate, and the like is not limited to these.
  • the lithium transition metal oxide is used for the positive electrode material mixture 13 together with a binder and a conductive material as a positive electrode active material.
  • the lithium source for forming the lithium metal layer 23 becomes the lithium transition metal oxide. That is, when the lithium ion in the lithium transition metal oxide is charged in a voltage range within a certain range, the lithium ion is desorbed to form the lithium metal layer 23 on the anode current collector 21.
  • the lithium ion in the lithium transition metal oxide is not easily released or the lithium metal layer 23 can not be formed due to the absence of lithium that can be involved in charging and discharging at the operating voltage level, and only the lithium transition metal oxide
  • the irreversible capacity is largely lowered and the capacity and lifetime characteristics of the lithium secondary battery are deteriorated.
  • the initial charge capacity is 200 mAh / g or more
  • a lithium metal compound which is a highly irreversible substance having an initial irreversible capacity of 30% or more.
  • the term 'high irreversible substance' referred to in the present invention may be used in the same manner as 'high capacity irreversible substance' in other terms.
  • irreversible capacity (first cycle charge capacity - first cycle discharge capacity) of the first cycle of charge and discharge may be large.
  • the irreversible capacity of the generally used cathode active material is about 2 to 10% of the initial charging capacity.
  • the lithium metal compound as the highly irreversible material that is, the initial irreversible capacity is 30% or more, preferably 50% Lithium metal compounds may be used together.
  • the lithium metal compound may have an initial charge capacity of 200 mAh / g or more, preferably 230 mAh / g or more. The use of such a lithium metal compound serves as a lithium source capable of forming the lithium metal layer 23 while raising the irreversible capacity of the lithium transition metal oxide as the cathode active material
  • the lithium metal compound represented by the present invention can be represented by the following chemical formulas (1) to (8).
  • a ⁇ 1 and M 1 is at least one element selected from the group consisting of Mn, Fe, Co, Cu, Zn, Mg and Cd)
  • M 2 is P, B, C, Al, Sc, Sr, Ti, V, Zr, Mn, Fe, Co, Cu, Zn, Cr, Mg, Nb, Mo, and Cd.
  • M < 4 > is at least one element selected from the group consisting of Cu and Ni).
  • 0.5, -0.1? H? 0.5 and M 5 is at least one element selected from the group consisting of Mn, Fe, Co, Cu, Zn, Mg and Cd to be)
  • M 6 is at least one element selected from the group consisting of Cr, Al, Ni, Mn, and Co.
  • M 7 is at least one element selected from the group consisting of Cr, Al, Ni, Mn, and Co
  • M 8 represents an alkaline earth metal
  • k / (k + m + n) is from 0.10 to 0.40
  • m / (k + m + n) is 0.20 to 0.50
  • n / (k + m + n) is 0.20 to 0.50.
  • the lithium metal compounds represented by Chemical Formulas 1 to 8 differ in irreversible capacity depending on the structure thereof, and they can be used singly or in combination, and serve to increase the irreversible capacity of the cathode active material.
  • the irreversible capacity of the high irreversible substance represented by the general formulas (1) and (3) varies depending on the kind thereof.
  • the irreversible capacity is as shown in Table 1 below.
  • the lithium metal compound represented by the general formula (2) preferably belongs to the space group Immm.
  • the Ni, M composite oxide forms a planar tetrahedral coordination (Ni, M) O4 and the side (Side formed with OO) and forms a primary chain.
  • the lithium metal compound of formula (8) has an alkaline earth metal content of 30 to 45 atomic% and a nitrogen content of 30 to 45 atomic%. When the content of the alkaline earth metal and the content of nitrogen are within the above ranges, the thermal characteristics and lithium ion conduction characteristics of the compound of Formula 1 are excellent.
  • M / (k + m + n) is in the range of 0.30 to 0.45, for example, 0.31 to 0.33, n / (k + m + n) is 0.30 to 0.45, for example, 0.31 to 0.33.
  • a is 0.5 to 1
  • b is 1
  • c is 1 according to an embodiment of the present invention.
  • the cathode active material may be a core-shell structure having a surface coated with a compound of any one of Chemical Formulas 1 to 8 above.
  • the electrode active material When a coating film composed of any one of the above chemical formulas (1) to (8) is formed on the surface of the core active material, the electrode active material exhibits stable characteristics while maintaining low resistance characteristics even in an environment where lithium ions are continuously inserted and desorbed.
  • the thickness of the coating layer is 1 to 100 nm.
  • the ion conductive property of the electrode active material is excellent.
  • the mean particle size of the electrode active material is 1 to 30 ⁇ , and in one embodiment, 8 to 12 ⁇ . When the average particle diameter of the positive electrode active material is in the above range, the capacity characteristics of the battery are excellent.
  • the alkaline earth metal-doped core active material may be, for example, LiCoO 2 doped with magnesium.
  • the content of magnesium is 0.01 to 3 parts by weight based on 100 parts by weight of the core active material.
  • the lithium transition metal oxide is used for the positive electrode material mixture 13 together with a binder and a conductive material as a positive electrode active material.
  • the lithium source for forming the lithium metal layer 23 becomes the lithium transition metal oxide. That is, when the lithium ion in the lithium transition metal oxide is charged in a voltage range within a certain range, the lithium ion is desorbed to form the lithium metal layer 23 on the anode current collector 21.
  • the charging range for forming the lithium metal layer 23 is one charging at 0.01 to 0.2C in the voltage range of 4.5V to 2.5V. If the charging is performed below the above range, the formation of the lithium metal layer 23 becomes difficult. On the other hand, if the charging is carried out above the above range, damage of the cell occurs, It does not.
  • the lithium metal layer 23 thus formed forms a uniform continuous or discontinuous layer on the cathode current collector 21.
  • the anode current collector 21 when the anode current collector 21 is in the form of a foil, it may have a continuous thin film form, and when the anode current collector 21 has a three-dimensional porous structure, the lithium metal layer 23 may be discontinuously formed . That is, the discontinuous layer is distributed discontinuously, and a region where the lithium metal layer 23 exists and a region where the lithium metal layer 23 does not exist exist in a specific region, and a region where the lithium metal layer 23 is not present exists in the region where the lithium compound exists And the region in which the lithium metal layer 23 is present is distributed without continuity, by distributing the region where the lithium metal layer 23 is present, such as an island type.
  • the lithium metal layer 23 formed through such charging and discharging has a thickness of at least 50 nm and less than 100 mu m, preferably 1 mu m to 50 mu m, for the function as a cathode. If the thickness is less than the above range, the charge and discharge efficiency of the battery drastically decreases. On the other hand, when the thickness is in the above range, the life characteristics and the like are stable, but the energy density of the battery is lowered.
  • the lithium metal layer 23 proposed in the present invention can be manufactured as a negative electrode-free battery without lithium metal at the time of assembling the battery, so that compared with the lithium secondary battery assembled using the conventional lithium foil, No or little oxide layer is formed on the lithium metal layer 23 due to the reactivity. Thus, degradation of life of the battery due to the oxidation layer can be prevented.
  • the lithium metal layer 23 is moved by the filling of the highly irreversible material, which can form a more stable lithium metal layer 23 as compared with the case where the lithium metal layer 23 is formed on the anode.
  • a lithium metal is attached on the anode, a chemical reaction between the anode and the lithium metal may occur.
  • the positive electrode mixture 13 contains the above-mentioned positive electrode active material and a lithium metal compound.
  • the positive electrode mixture 13 further includes a conductive material, a binder, and other additives commonly used in lithium secondary batteries .
  • the conductive material is used to further improve the conductivity of the electrode active material.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Polyphenylene derivatives and the like can be used.
  • a binder may be further included for bonding the positive electrode active material, the lithium metal compound, and the conductive material to the current collector.
  • the binder may include a thermoplastic resin or a thermosetting resin.
  • a thermoplastic resin for example, there may be mentioned polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride- Hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer Ethylene-chlorotrifluoroethylene cop
  • the filler is optionally used as a component for suppressing the expansion of the electrode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery.
  • an olefin polymer such as polyethylene or polypropylene, or a fibrous material such as glass fiber or carbon fiber is used.
  • the positive electrode mixture (13) of the present invention is formed on the positive electrode collector (11).
  • the positive electrode collector generally has a thickness of 3 ⁇ to 500 ⁇ .
  • the cathode current collector 11 is not particularly limited as long as it has high conductivity without causing chemical change in the lithium secondary battery. Examples of the cathode current collector 11 include stainless steel, aluminum, nickel, titanium, sintered carbon, Surface-treated with carbon, nickel, titanium, silver, or the like may be used.
  • the cathode current collector 11 may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric having fine irregularities formed on its surface so as to increase the adhesive force with the cathode active material.
  • the method of applying the positive electrode mixture 13 on the current collector may be a method of uniformly dispersing the electrode mixture slurry on the current collector using a doctor blade or the like, a method of die casting, a comma coating method, a screen printing method, and the like.
  • the electrode mixture slurry may be formed on a separate substrate and then bonded to the current collector by a pressing or lamination method, but the present invention is not limited thereto.
  • a protective film 55 may be additionally formed on a surface of the negative electrode in contact with the separator 60. 4, the lithium metal layer 23 passes through the protective film 55 and lithium ions transferred from the positive electrode mixture 43 are discharged onto the negative electrode current collector 51. As a result, .
  • the protective film 55 may be any material capable of smoothly transferring lithium ions, and may be a material used for a lithium ion conductive polymer and / or an inorganic solid electrolyte.
  • the protective film 55 may further include a lithium salt have.
  • the lithium ion conductive polymer there may be mentioned, for example, polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride- (PVDF-HFP), LiPON, Li 3 N, LixLa 1 -x TiO 3 (0 ⁇ x ⁇ 1) and Li 2 S-GeS-Ga 2 S 3 ,
  • PEO polyethylene oxide
  • PAN polyacrylonitrile
  • PMMA polymethylmethacrylate
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-
  • LiPON Li 3 N
  • LixLa 1 -x TiO 3 (0 ⁇ x ⁇ 1
  • Li 2 S-GeS-Ga 2 S 3 Li 2 S-GeS-Ga 2 S 3
  • the present invention is not limited thereto, and any polymer having lithium ion conductivity may be used without limitation
  • the formation of the protective film 55 using the lithium ion conductive polymer is performed by preparing a coating solution in which the lithium ion conductive polymer is dissolved or swollen in a solvent, and then coating the coating solution on the negative electrode current collector 51.
  • the method of application may be selected from known methods in consideration of the characteristics of the material and the like or may be carried out by a new appropriate method.
  • the polymer protective layer composition is dispersed on a current collector and uniformly dispersed using a doctor blade or the like.
  • a method of performing the distribution and dispersion processes in a single process may be used.
  • various coating methods such as dip coating, gravure coating, slit die coating, spin coating, comma coating, bar coating, reverse roll coating reverse roll coating, screen coating, cap coating and the like.
  • the anode current collector 51 is the same as that described above.
  • the drying process may be performed on the protective film 55 formed on the anode current collector 51.
  • the drying process may be a heat treatment at a temperature of 80 to 120 ° C, depending on the type of the solvent used in the lithium ion conductive polymer Or by hot air drying or the like.
  • the solvent to be used is preferably similar to the lithium ion conductive polymer in terms of solubility index, and has a low boiling point. This is because the mixing can be made uniform and then the solvent can be easily removed.
  • a solvent such as N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) acetone, tetrahydrofuran, methylene chloride, chloroform, dimethylformamide, N-methyl-2-pyrrolidone (NMP) Cyclohexane, water or a mixture thereof can be used as a solvent.
  • the lithium ion conductive polymer may further include a material used for this purpose in order to further increase the lithium ion conductivity.
  • the inorganic solid electrolyte is a ceramic-based material, a crystalline or amorphous and crystalline materials can be used, Thio-LISICON (Li 3. 25 Ge 0 .25 P 0. 75 S 4), Li 2 S-SiS 2, LiI- Li 2 S-SiS 2 , LiI-Li 2 SP 2 S 5 , LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 2 SP 2 S 5 , Li 3 PS 4 , Li 7 P 3 S 11 , Li 2 OB 2 O 3 , Li 2 OB 2 O 3 -P 2 O 5 , Li 2 OV 2 O 5 -SiO 2 , Li 2 OB 2 O 3 , Li 3 PO 4 , Li 2 O -Li 2 WO 4 -B 2 O 3 , LiPON, LiBON, Li 2 O-SiO 2, LiI, Li 3 N, Li 5 La 3 Ta 2 O12, Li 7 La 3 Zr 2 O 12,
  • the inorganic solid electrolyte may be mixed with known materials such as a binder and applied in a thick film form through slurry coating. Further, if necessary, the thin film type can be applied through a deposition process such as sputtering.
  • the slurry coating method used may be appropriately selected based on the coating method, the drying method and the content of the solvent mentioned above for the lithium ion conductive polymer.
  • the protective film 55 comprising the above-described lithium ion conductive polymer and / or inorganic solid electrolyte facilitates the formation of the lithium metal layer 23 by increasing the lithium ion transfer rate and at the same time, the lithium metal layer 23 / The effect of suppressing or preventing the generation of lithium dendrite generated when the whole 51 is used as a cathode can be secured at the same time.
  • the thickness of the protective film 55 is required to be limited.
  • the thickness of the protective film 55 may preferably be 10 nm to 50 ⁇ . If the thickness of the protective film 55 is less than the above range, the side reaction and the exothermic reaction between lithium and the electrolyte, which are increased under the conditions of overcharging or high-temperature storage, can not be effectively suppressed and safety can not be improved.
  • the composition of the protective film 55 In the case of the ion conductive polymer, a long time is required for the composition of the protective film 55 to be impregnated or swelled by the electrolytic solution, and the movement of the lithium ion is lowered, thereby deteriorating the overall battery performance.
  • the rechargeable lithium battery of the second embodiment has the same structure as that of the first embodiment except for the protective film 55.
  • the lithium secondary battery includes a cathode 40, a cathode 50, separators 30 and 60 interposed therebetween, and an electrolyte (not shown)
  • the separation membranes 30 and 60 may be omitted.
  • the separators 30 and 60 may be made of a porous substrate.
  • the porous substrate may be any porous substrate commonly used in an electrochemical device.
  • a polyolefin porous film or a nonwoven fabric may be used , And is not particularly limited thereto.
  • the separation membranes 30 and 60 according to the present invention are not particularly limited in their materials and physically separate the positive and negative electrodes and have an electrolyte and an ion permeability and are usually made of a lithium secondary battery as separators 30 and 60
  • Any material may be used without particular limitation, but it is preferably a porous, nonconductive or insulating material, particularly a material having a low resistance against ion movement of the electrolytic solution and an excellent ability to impregnate the electrolytic solution.
  • a polyolefin-based porous membrane or nonwoven fabric may be used, but it is not particularly limited thereto.
  • polyolefin-based porous film examples include polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, and polypentene, such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene and ultra-high molecular weight polyethylene, One can say.
  • polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, and polypentene, such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene and ultra-high molecular weight polyethylene, One can say.
  • the nonwoven fabric may contain, in addition to the polyolefin-based nonwoven fabric, a polyphenylene oxide, a polyimide, a polyamide, a polycarbonate, a polyethyleneterephthalate, a polyethylene naphthalate, Polybutyleneterephthalate, polyphenylenesulfide, polyacetal, polyethersulfone, polyetheretherketone, polyester, and the like may be used alone or in combination of two or more.
  • the nonwoven fabric may be a spunbond or a meltblown fiber composed of long fibers.
  • the nonwoven fabric may be a porous web.
  • the thickness of the separation membrane (30, 60) is not particularly limited, but is preferably in the range of 1 to 100 mu m, more preferably in the range of 5 to 50 mu m. If the thickness of the separation membranes 30 and 60 is less than 1 ⁇ , the mechanical properties can not be maintained. If the separation membranes 30 and 60 are more than 100 ⁇ , the separation membranes 30 and 60 serve as a resistance layer, thereby deteriorating the performance of the battery.
  • the pore size and porosity of the separation membrane (30, 60) are not particularly limited, but the pore size is preferably 0.1 to 50 ⁇ m and the porosity is preferably 10 to 95%. If the pore size of the separator 30 or 60 is less than 0.1 ⁇ m or the porosity is less than 10%, the separator 30 or 60 acts as a resistive layer. If the pore size exceeds 50 ⁇ m or the porosity is 95% The mechanical properties can not be maintained.
  • the electrolyte of the lithium secondary battery is a lithium salt-containing electrolyte, which is a non-aqueous electrolyte consisting of a non-aqueous organic solvent electrolyte and a lithium salt, and may include, but is not limited to, an organic solid electrolyte or an inorganic solid electrolyte.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butyrolactone, -Dimethoxyethane, 1,2-diethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, 4-methyl-
  • the organic solvent may be selected from the group consisting of diethyl ether, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivative, Dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl propionate, ethyl propionat
  • the electrolyte salt contained in the non-aqueous electrolyte is a lithium salt.
  • the lithium salt can be used without limitation as those conventionally used in an electrolyte for a lithium secondary battery.
  • the lithium salt anion F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 - , (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, ( CF 3 SO 2) 3 C - from the group consisting of -, CF 3
  • organic solvent included in the non-aqueous electrolyte examples include those commonly used in electrolytes for lithium secondary batteries, such as ether, ester, amide, linear carbonate, cyclic carbonate, etc., Can be used. Among them, a carbonate compound which is typically a cyclic carbonate, a linear carbonate, or a mixture thereof may be included.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, Propylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halides thereof, or a mixture of two or more thereof.
  • halides include, but are not limited to, fluoroethylene carbonate (FEC) and the like.
  • linear carbonate compound examples include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate And mixtures of two or more of them may be used as typical examples, but the present invention is not limited thereto.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates in the carbonate-based organic solvent, are high-viscosity organic solvents having a high dielectric constant and can dissociate the lithium salt in the electrolyte more easily.
  • cyclic carbonates can be used as dimethyl carbonate and diethyl carbonate When a low viscosity, low dielectric constant linear carbonate is mixed in an appropriate ratio, an electrolyte having a higher electric conductivity can be produced.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether or a mixture of two or more thereof may be used , But is not limited thereto.
  • ester in the organic solvent examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone, or a mixture of two or more thereof, but the present invention is not limited thereto.
  • the injection of the nonaqueous electrolyte solution can be performed at an appropriate stage of the manufacturing process of the electrochemical device according to the manufacturing process and required properties of the final product. That is, it can be applied before assembling the electrochemical device or in the final stage of assembling the electrochemical device.
  • organic solid electrolyte examples include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, Polymers containing ionic dissociation groups, and the like can be used.
  • a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, Polymers containing ionic dissociation 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 and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
  • non-aqueous electrolytes may be used in the form of, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride and the like are added It is possible.
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further added to impart nonflammability, or a carbon dioxide gas may be further added to improve high-temperature storage characteristics.
  • the shape of the above-described lithium secondary battery is not particularly limited and may be, for example, a jelly-roll type, a stack type, a stack-folding type (including a stack-Z-folding type), or a lamination- Stack-folding type.
  • An electrode assembly in which the positive electrode, the separator, and the negative electrode are sequentially stacked is prepared, and then inserted into a battery case. Then, an electrolyte is injected into the upper part of the case and sealed with a cap plate and a gasket to assemble a lithium secondary battery .
  • the lithium secondary battery can be classified into various types of batteries such as a lithium-sulfur battery, a lithium-air battery, a lithium-oxide battery, and a lithium total solid battery depending on the type of the anode material and the separator used.
  • Coin type, pouch type, etc. and can be divided into a bulk type and a thin film type depending on the size.
  • the structure and the manufacturing method of these cells are well known in the art, and detailed description thereof will be omitted.
  • the lithium secondary battery according to the present invention can be used as a power source for a device requiring a high capacity and a high rate characteristic.
  • the device include a power tool which is powered by an electric motor and moves; An electric vehicle including an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like; An electric motorcycle including an electric bike (E-bike) and an electric scooter (Escooter); An electric golf cart; And a power storage system, but the present invention is not limited thereto.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone and then LMO (LiMnO 2 ) was added so as to have a weight ratio of 30% to LCO. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the LCO added at this time was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • Dimethoxyethane LiFSI was dissolved in 100 ml of a non-aqueous electrolyte solvent so as to have a concentration of 4 M to prepare an electrolytic solution.
  • the weight ratio of PVDF to ETPTA polymer to electrolyte weight ratio was 3: 2
  • the ratio of PVDF polymer to ETPTA polymer was 2: 8
  • the ratio of benzoyl peroxide was added in an amount of 0.7 wt%.
  • a composition for a gel polymer electrolyte was prepared.
  • a lithium secondary battery was manufactured by preparing an electrode assembly between the positive electrode and the negative electrode collector prepared in the above (1) through a separator and a gel polymer electrolyte of (2), and positioning the electrode assembly inside the case.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone and then LMO (LiMnO 2 ) was added so as to have a weight ratio of 30% to LCO. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the LCO added at this time was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • a non-aqueous electrolyte solution of DMC was dissolved in 100 ml of LiFSI to a concentration of 3 M to prepare an electrolytic solution.
  • the weight ratio of PVDF to ETPTA polymer to electrolyte weight ratio was 3: 2
  • the ratio of PVDF polymer to ETPTA polymer was 2: 8
  • the ratio of benzoyl peroxide was added in an amount of 0.7 wt%.
  • a lithium secondary battery was manufactured by preparing an electrode assembly between the positive electrode and the negative electrode collector prepared in the above (1) through a separator and a gel polymer electrolyte of (2), and positioning the electrode assembly inside the case.
  • LFP LiFePO 4
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone, and then LMO (LiMnO 2 ) was added so that the weight ratio of LFP was 30%. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the added LFP was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • Dimethoxyethane LiFSI was dissolved in 100 ml of a non-aqueous electrolyte solvent so as to have a concentration of 4 M to prepare an electrolytic solution.
  • the weight ratio of PVDF to ETPTA polymer to electrolyte weight ratio was 3: 2
  • the ratio of PVDF polymer to ETPTA polymer was 2: 8
  • the ratio of benzoyl peroxide was added in an amount of 0.7 wt%.
  • a composition for a gel polymer electrolyte was prepared.
  • a lithium secondary battery was manufactured by preparing an electrode assembly between the positive electrode and the negative electrode collector prepared in the above (1) through a separator and a gel polymer electrolyte of (2), and positioning the electrode assembly inside the case.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone and then LMO (LiMnO 2 ) was added so as to have a weight ratio of 30% to LCO. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the LCO added at this time was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, ((CF 3 SO 2 ) 2 NLi) was mixed with 8 g of polyethylene oxide (MV: 4,000,000) in 50 ml of acetonitrile solvent, PEO repeating unit) to prepare a solution for forming a protective film.
  • the solution for forming a protective film was coated on a copper current collector and dried at 80 DEG C for 6 hours to form a protective film (thickness: 10 mu m) on the copper current collector.
  • Dimethoxyethane LiFSI was dissolved in 100 ml of a non-aqueous electrolyte solvent so as to have a concentration of 4 M to prepare an electrolytic solution.
  • the weight ratio of PVDF to ETPTA polymer to electrolyte weight ratio was 3: 2
  • the ratio of PVDF polymer to ETPTA polymer was 2: 8
  • the ratio of benzoyl peroxide was added in an amount of 0.7 wt%.
  • a composition for a gel polymer electrolyte was prepared.
  • a lithium secondary battery was manufactured by preparing an electrode assembly between the positive electrode and the negative electrode collector prepared in the above (1) through a separator and a gel polymer electrolyte of (3), and positioning the electrode assembly inside the case.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone and then LMO (LiMnO 2 ) was added so as to have a weight ratio of 30% to LCO. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the LCO added at this time was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • a coating layer was formed by sputtering for 25 minutes using a Li 3 PO 4 target in a vacuum chamber in an N 2 atmosphere. It was confirmed that the thickness of the surface coating layer was controlled according to the deposition time, and a protective film (thickness: 0.2 ⁇ ) was formed on the copper current collector. The thickness of the coating layer formed on the surface of the coating layer was confirmed using a scanning electron microscope (JSM-7610F, JEOL).
  • Dimethoxyethane LiFSI was dissolved in 100 ml of a non-aqueous electrolyte solvent so as to have a concentration of 4 M to prepare an electrolytic solution.
  • the weight ratio of PVDF to ETPTA polymer to electrolyte weight ratio was 3: 2
  • the ratio of PVDF polymer to ETPTA polymer was 2: 8
  • the ratio of benzoyl peroxide was added in an amount of 0.7 wt%.
  • a composition for a gel polymer electrolyte was prepared.
  • a lithium secondary battery was manufactured by preparing an electrode assembly between the positive electrode and the negative electrode collector prepared in the above (1) through a separator and a gel polymer electrolyte of (3), and positioning the electrode assembly inside the case.
  • Comparative Example 1 Lithium secondary battery manufacturing
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methylpyrrolidone and then LMO (LiMnO 2 ) was added so as to have a weight ratio of 30% to LCO. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the LCO added at this time was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • Lithium foil (20 ⁇ thick) was laminated on the copper collector to prepare a negative electrode.
  • a lithium secondary battery was prepared by preparing an electrode assembly between the positive electrode and the negative electrode prepared in the above (1) through a separator of porous polyethylene, placing the electrode assembly in the case, and injecting electrolyte.
  • the electrolyte was prepared by dissolving 1 M of LiPF 6 in an organic solvent having a volume ratio of EC (ethylene carbonate): EMC (ethylmethyl carbonate) of 3: 7.
  • LFP LiFePO 4
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone. Then, each was mixed with a paste face mixer for 30 minutes to prepare a slurry composition. The weight of the added LFP was 15 g.
  • the slurry composition prepared above was coated on a current collector (Al Foil, thickness 20 ⁇ ) and dried at 130 ⁇ for 12 hours to prepare respective positive electrodes.
  • Lithium foil (20 ⁇ thick) was laminated on the copper collector to prepare a negative electrode.
  • a lithium secondary battery was prepared by preparing an electrode assembly between the positive electrode and the negative electrode prepared in the above (1) through a separator of porous polyethylene, placing the electrode assembly in the case, and injecting electrolyte. At this time, the electrolyte was prepared by dissolving 1 M of LiBF 4 in fluoroethylene carbonate (FEC).
  • FEC fluoroethylene carbonate
  • the batteries of Examples and Comparative Examples were charged and discharged under the conditions of 0.2C, 4.25V CC / CV (5% current cut at 1C) and discharge 0.5C CC 3V to prepare a lithium secondary battery having a lithium metal layer.
  • the resistance change rate after the initial lithium formation was measured and is shown in Table 2 below.
  • Resistance increase rate (resistance after one month - initial resistance) / initial resistance * 100

Abstract

La présente invention concerne une batterie secondaire au lithium, dans laquelle un métal lithium est formé sur un collecteur de courant d'électrode négative par charge puisque la batterie secondaire au lithium est fabriquée en tant que batterie sans électrode négative. Dans la batterie secondaire au lithium, la formation du métal lithium est réalisée dans un état qui est bloqué à partir de l'air, de telle sorte qu'un film d'oxyde de surface (couche native), qui a été formé sur une électrode négative classique, n'est pas fondamentalement généré, et ainsi la détérioration de l'efficacité de la batterie et des caractéristiques de durée de vie peut être empêchée.
PCT/KR2018/007227 2017-06-26 2018-06-26 Batterie secondaire au lithium WO2019004699A1 (fr)

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CN201880042247.6A CN110785886B (zh) 2017-06-26 2018-06-26 锂二次电池
US16/623,500 US11431019B2 (en) 2017-06-26 2018-06-26 Lithium secondary battery
EP18823493.4A EP3637526B1 (fr) 2017-06-26 2018-06-26 Batterie secondaire au lithium
JP2019571353A JP7183198B2 (ja) 2017-06-26 2018-06-26 リチウム二次電池

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CN110635107A (zh) * 2019-10-24 2019-12-31 邦泰宏图（深圳）科技有限责任公司 无基材的双极固态锂离子电池及其制作方法
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CN115411360A (zh) * 2021-05-26 2022-11-29 张家港市国泰华荣化工新材料有限公司 一种无负极锂金属电池电解液及无负极锂金属电池
CN115411360B (zh) * 2021-05-26 2024-01-30 张家港市国泰华荣化工新材料有限公司 一种无负极锂金属电池电解液及无负极锂金属电池

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