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WO2018236166A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

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Publication number
WO2018236166A1
WO2018236166A1 PCT/KR2018/007040 KR2018007040W WO2018236166A1 WO 2018236166 A1 WO2018236166 A1 WO 2018236166A1 KR 2018007040 W KR2018007040 W KR 2018007040W WO 2018236166 A1 WO2018236166 A1 WO 2018236166A1
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WIPO (PCT)
Prior art keywords
lithium
negative electrode
group
current collector
metal
Prior art date
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Ceased
Application number
PCT/KR2018/007040
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English (en)
Korean (ko)
Inventor
박은경
장민철
손병국
최정훈
강동현
정보라
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LG Chem Ltd
Original Assignee
LG Chem Ltd
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Publication date
Priority claimed from KR1020180070931A external-priority patent/KR102115602B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201880020721.5A priority Critical patent/CN110495021B/zh
Priority to JP2019530009A priority patent/JP7037016B2/ja
Priority to EP18819672.9A priority patent/EP3540825B1/fr
Priority to US16/467,186 priority patent/US11063290B2/en
Publication of WO2018236166A1 publication Critical patent/WO2018236166A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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 metal particles.
  • 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.
  • the present invention provides a lithium secondary battery including a positive electrode, a negative electrode, and a separator interposed therebetween and an electrolyte, wherein the negative electrode is formed with metal particles on the negative electrode current collector, Thereby forming a lithium metal on the negative electrode current collector in the negative electrode.
  • the lithium metal formed on the anode current collector is formed through a single 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.
  • FIGS. 7 to 10 are frontal scanning electron microscopic images of the lithium metal layer prepared in Example 1, Example 2, Example 3 and Comparative Example 1.
  • 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 positive electrode 10 including a positive electrode collector 11 and a positive electrode mixture 12; A cathode 20 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 generally formed on the negative electrode current collector 21, but in the present invention, only the negative electrode current collector 21 having the metal particles 27 on the surface thereof is used, Lithium ions released from the positive electrode mixture 13 by charging form a lithium metal layer (not shown) as a negative electrode mixture on the negative electrode collector 21, so that a negative electrode collector / Thereby constituting a typical 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 metal particles 27 made of a metal or a quasi-metal capable of forming an alloy with lithium, the lithium metal layer 23 can be easily formed, and a denser thin film structure can be formed.
  • 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.
  • the anode current collector 21 constituting the cathode has a thickness of 3 to 500 ⁇ , and metal particles 27 are formed on the surface thereof.
  • Li nucleation over potential may occur depending on the material of the anode current collector when the lithium metal layer is formed through charging with the cathode free electrode, and the initial coulon efficiency may be reduced due to such resistance.
  • the metal particles 27 are formed, Li nucleation over potential may be almost zero when Li ions are precipitated as Li by charge transfer depending on the material of the metal particles 27.
  • the metal particles 27 may be a metal or a metal capable of being alloyed with lithium and may be selected from the group consisting of aluminum, gold, bismuth, germanium, magnesium, manganese, molybdenum, sodium, nickel, osmium, phosphorus, lead, palladium, platinum, plutonium, At least one member selected from the group consisting of rhodium, ruthenium, sulfur, antimony, selenium, silicon, tin, strontium, tantalum, tellurium, titanium, uranium, vanadium, tungsten, zinc and zirconium, I use gold.
  • the metal particles 27 may be contained in an amount of 0.1 to 40% by weight relative to the current collector, and preferably in an amount of 1 to 20% by weight.
  • the content of the metal particles (27) is less than 0.1 wt%, the particles are not uniformly formed and the plating efficiency of the Li metal is inferior. If it exceeds 40 wt%, the weight of the current collector becomes large, It can be formed as a layer rather than as a particle.
  • the formation of the metal particles 27 is not particularly limited in the present invention, and a known method can be used.
  • a dry method such as chemical vapor deposition (CVD), sputtering, e-beam evaporation, atomic layer deposition (ALD), or vacuum evaporation may be performed.
  • the precursor containing the metal of the metal particles 27 may be formed through a heat treatment after coating.
  • the precursor may be a known precursor such as chloride or nitride.
  • dewetting is caused by a change in the surface energy of the material and a coagulation phenomenon that is inherent in the material, thereby changing the coating layer into a nano dot shape.
  • the heat treatment is performed at a temperature of about 250 DEG C for 10 minutes, the catalytic material coating layer changes into a metal particle form.
  • These metal particles 27 serve as a seed for growing lithium ions into the lithium metal layer 23 from the lithium ions transferred from the positive electrode.
  • the formed lithium metal layer 23 has a uniform and dense microstructure on the cathode current collector 21.
  • the metal particles 27 exist in the form of an island, not a continuous layer of the coating layer, on the anode current collector 21 in order to serve as a seed. At this time, the metal particles 27 are formed on the anode current collector 21 with a gap of 1 nm or more and less than 10 ⁇ ⁇ , preferably, a gap of 1 nm or more and less than 2 ⁇ ⁇ .
  • 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 implementation of the lithium secondary battery having the negative electrode free structure including the negative electrode collector 21 in which the metal particles 27 are formed can be realized by various methods. In the present invention, however, by controlling the composition used for the positive electrode material mixture 13 do.
  • 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 absorbing and desorbing lithium ions,
  • a lithium transition metal oxide is typically used as a lithium transition metal compound contained in a cathode active material capable of realizing a battery having excellent 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 enhancing 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 electrode active material exhibits stable characteristics while maintaining a low resistance characteristic even in an environment in which lithium ions are continuously inserted and desorbed.
  • the thickness of the coating layer is 1 to 100 nm. When the thickness of the coating film is in the above range, the ion conductive property of the cathode active material is excellent.
  • the average particle diameter of the cathode active material is 1 to 30 ⁇ ⁇ , and in one embodiment, 8 to 12 ⁇ ⁇ .
  • 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 not more than 100 mu m, and 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 collector 51 , And grows from the metal particles (57).
  • 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 so as to contain the metal particles 57 on the negative electrode 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-methyl-2-pyrrolidone, 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 a positive electrode.
  • Au metal particles were formed on the copper collector using an atomic layer deposition method. At this time, the Au metal particles were measured at an average particle diameter of 50 nm, and the element content of the electron scanning microscope (JSM-7610F, JEOL) was observed to be 8 wt% based on the weight of Cu.
  • JSM-7610F, JEOL the electron scanning microscope
  • An electrode assembly was fabricated between the positive electrode prepared in (1) and the negative electrode current collector of (2) through a porous polyethylene separator, and the electrode assembly was placed inside the case. Then, an electrolyte was injected into the lithium battery, .
  • the electrolyte was prepared by dissolving 1 M LiPF 6 and 2 wt% VC (Vinylene Carbonate) in an organic solvent having a volume ratio of 1: 2: 1 of ethylene carbonate (EC): dimethyl carbonate (DEC) Was used.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone, 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 a positive electrode.
  • Ag metal particles were formed on the copper collector using an atomic layer deposition method. At this time, Ag metal particles were measured with an average particle diameter of 50 nm. As a result of the analysis with an electron scanning microscope (JSM-7610F, JEOL), the Ag metal particles were observed at 15 wt% based on Cu weight.
  • An electrode assembly was fabricated between the positive electrode prepared in (1) and the negative electrode current collector of (2) through a porous polyethylene separator, and the electrode assembly was placed inside the case. Then, an electrolyte was injected into the lithium battery, .
  • the electrolyte was prepared by dissolving 1 M LiPF 6 and 2 wt% VC (Vinylene Carbonate) in an organic solvent having a volume ratio of 1: 2: 1 of ethylene carbonate (EC): dimethyl carbonate (DEC) Was used.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone, 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 a positive electrode.
  • Zn metal particles were formed on the copper collector by atomic layer deposition. At this time, the Zn metal particles were measured with an average particle diameter of 50 nm. As a result of an analysis by a scanning electron microscope (JSM-7610F, JEOL), 15% by weight of Cu was observed.
  • An electrode assembly was fabricated between the positive electrode prepared in (1) and the negative electrode current collector of (2) through a porous polyethylene separator, and the electrode assembly was placed inside the case. Then, an electrolyte was injected into the lithium battery, .
  • the electrolyte was prepared by dissolving 1 M LiPF 6 and 2 wt% VC (Vinylene Carbonate) in an organic solvent having a volume ratio of 1: 2: 1 of ethylene carbonate (EC): dimethyl carbonate (DEC) Was used.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone, 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 a positive electrode.
  • Au metal particles were formed on the copper collector using an atomic layer deposition method. At this time, the Au metal particles were measured at an average particle diameter of 50 nm, and the element content of the electron scanning microscope (JSM-7610F, JEOL) was observed to be 8 wt% based on the weight of Cu.
  • JSM-7610F, JEOL the electron scanning microscope
  • EO PEO
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the protective film-forming solution was coated on the copper current collector and dried at 80 ° C. for 6 hours to form a protective film (thickness: 10 ⁇ m) on the copper current collector.
  • An electrode assembly was fabricated between the positive electrode prepared in (1) and the negative electrode current collector of (2) via a separator of porous polyethylene, and the electrode assembly was placed inside the case, .
  • the electrolyte was prepared by dissolving 1 M LiPF 6 and 2 wt% VC (Vinylene Carbonate) in an organic solvent having a volume ratio of 1: 2: 1 of ethylene carbonate (EC): dimethyl carbonate (DEC) Was used.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone, 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 a positive electrode.
  • Au metal particles were formed on the copper collector using an atomic layer deposition method. At this time, the Au metal particles were measured at an average particle diameter of 50 nm, and the element content of the electron scanning microscope (JSM-7610F, JEOL) was observed to be 8 wt% based on the weight of Cu.
  • JSM-7610F, JEOL the electron scanning microscope
  • a LiPON coating layer was formed on the copper current collector by sputtering in a vacuum chamber of N 2 atmosphere using a Li 3 PO 4 target for 25 minutes. 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.
  • An electrode assembly was fabricated between the anode prepared in (1) and the anode current collector 21 in (2) through a porous polyethylene separator. After the electrode assembly was positioned inside the case, Free battery.
  • the electrolyte was prepared by dissolving 1 M LiPF 6 and 2 wt% VC (Vinylene Carbonate) in an organic solvent having a volume ratio of 1: 2: 1 of ethylene carbonate (EC): dimethyl carbonate (DEC) was used.
  • a negative electrode pre-battery having an ordinary positive electrode without the use of L2N was prepared.
  • LCO LiCoO 2
  • Super-P binder (PVdF) was mixed at a weight ratio of 95: 2.5: 2.5 to 30 ml of N-methyl-2-pyrrolidone, 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 a positive electrode.
  • a copper current collector was used for the anode current collector 21.
  • 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. .
  • a separator of porous polyethylene placing the electrode assembly in the case, and injecting electrolyte.
  • VC Vinyl Carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • LiFePO 4 was used as a positive electrode, and lithium secondary carbonate containing fluorine-containing organic compound fluoroethylene carbonate and inorganic salt sodium fluorofluoroborate borate A battery was produced.
  • LiFePO4, acetylene black and PVDF were mixed in a ratio of 90: 5: 5, and a positive electrode slurry was prepared using NMP as a solvent.
  • An anode current collector (rolled copper foil collector) was used.
  • the prepared negative electrode pre-charged battery was charged and discharged under the conditions of charging 0.2C, 4.25V CC / CV (5% current cut at 1C) and discharging 0.5C CC 3V to prepare a lithium secondary battery having a lithium metal layer.
  • FIGS. 7 to 10 are frontal scanning electron microscopic images of the lithium metal layer prepared in Example 1, Example 2, Example 3 and Comparative Example 1.
  • the lithium metal layer of Example 1 has uniform particle shape as compared with lithium of Comparative Example 1 (see FIG. 10), lithium in the resin disappears, and the surface is uniform. 8 and 9 (Examples 2 and 3), it can be seen that the particle size of lithium also becomes thick in the case of Ag under the same conditions. In comparison, in the case of Comparative Example 1 (see Fig. 10), it can be seen that the lithium metal layer can not be uniformly formed without metal particles.
  • the batteries of Examples 1 to 5 and Comparative Examples 1 and 2 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 form a lithium metal layer A lithium secondary battery was fabricated. Next, initial charge-discharge and Coulomb efficiency of the lithium secondary battery were measured, and the results are shown in Table 2 below.

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Abstract

La présente invention concerne une batterie secondaire au lithium qui est préparée en tant que batterie sans anode et qui a un métal lithium formé sur un collecteur de courant d'anode au moyen d'une charge. La batterie secondaire au lithium a un métal lithium formé tout en étant isolé de l'atmosphère. Par conséquent, un film d'oxyde de surface (couche native), qui est formé sur une anode existante, n'est pas sensiblement produit et, par conséquent, une dégradation en efficacité de batterie et des caractéristiques de durée de vie dues à ce fait peut être empêchée.
PCT/KR2018/007040 2017-06-21 2018-06-21 Batterie secondaire au lithium Ceased WO2018236166A1 (fr)

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CN201880020721.5A CN110495021B (zh) 2017-06-21 2018-06-21 锂二次电池
JP2019530009A JP7037016B2 (ja) 2017-06-21 2018-06-21 リチウム二次電池
EP18819672.9A EP3540825B1 (fr) 2017-06-21 2018-06-21 Batterie secondaire au lithium
US16/467,186 US11063290B2 (en) 2017-06-21 2018-06-21 Lithium secondary battery

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WO2021039242A1 (fr) * 2019-08-30 2021-03-04 パナソニックＩｐマネジメント株式会社 Batterie secondaire au lithium
US20220069339A1 (en) * 2019-01-31 2022-03-03 Panasonic Intellectual Property Management Co., Ltd. Lithium metal secondary battery
US20220278357A1 (en) * 2018-01-05 2022-09-01 Samsung Electronics Co., Ltd. Anodeless lithium metal battery and method of manufacturing the same
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US20220278357A1 (en) * 2018-01-05 2022-09-01 Samsung Electronics Co., Ltd. Anodeless lithium metal battery and method of manufacturing the same
US20220285720A1 (en) * 2018-01-05 2022-09-08 Samsung Electronics Co., Ltd. Anodeless lithium metal battery and method of manufacturing the same
US12334548B2 (en) * 2018-01-05 2025-06-17 Samsung Electronics Co., Ltd. Anodeless lithium metal battery and method of manufacturing the same
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