WO2020091453A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

Info

Publication number
WO2020091453A1
WO2020091453A1 PCT/KR2019/014582 KR2019014582W WO2020091453A1 WO 2020091453 A1 WO2020091453 A1 WO 2020091453A1 KR 2019014582 W KR2019014582 W KR 2019014582W WO 2020091453 A1 WO2020091453 A1 WO 2020091453A1
Authority
WO
WIPO (PCT)
Prior art keywords
protective layer
lithium
secondary battery
lithium secondary
negative electrode
Prior art date
Application number
PCT/KR2019/014582
Other languages
English (en)
Korean (ko)
Inventor
박은경
장민철
정보라
손병국
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19880365.2A priority Critical patent/EP3761405A4/fr
Priority to US16/982,093 priority patent/US20210104748A1/en
Priority to CN201980018193.4A priority patent/CN111837259B/zh
Priority claimed from KR1020190137138A external-priority patent/KR102328261B1/ko
Publication of WO2020091453A1 publication Critical patent/WO2020091453A1/fr

Links

Images

Classifications

    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M4/64—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 a negative electrode free structure including a negative electrode protective layer.
  • Lithium metal has a low redox potential (-3.045V for a standard hydrogen electrode) and a high weight energy density (3,860mAhg -1 ), and is expected to be a negative electrode material for a high-capacity secondary battery.
  • lithium metal when used as a battery negative electrode, a battery is generally prepared by attaching a lithium foil to a planar current collector.
  • lithium is an alkali metal, it is highly reactive and reacts explosively with water and reacts with oxygen in the atmosphere.
  • 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 as a result of oxidation.
  • the oxide film acts as an insulating film, resulting in lower electrical conductivity, and inhibiting smooth movement of lithium ions, thereby increasing electrical resistance.
  • the present inventors conducted various studies, and as a result of battery assembly, lithium is transported from the positive electrode active material by charging after the battery assembly, so that the lithium metal can be contacted with the atmosphere.
  • a negative electrode free battery structure capable of forming a lithium metal layer on a current collector was designed, and a composition of a positive electrode active material capable of stably forming the lithium metal layer was developed.
  • a lithium secondary battery has been developed in which first to third protective layers are sequentially formed on a negative electrode current collector to prevent deterioration of battery life due to lithium dendrites generated during charging and discharging of a battery.
  • an object of the present invention is to provide a lithium secondary battery with improved performance and lifespan by solving problems caused by reactivity of lithium metal and problems occurring during assembly.
  • the present invention in a lithium secondary battery comprising a positive electrode, a negative electrode and an electrolyte,
  • the negative electrode is a first protective layer formed on the negative electrode current collector
  • a second protective layer formed on the first protective layer and
  • It includes a third protective layer formed on the inside and one surface of the second protective layer,
  • It relates to a lithium secondary battery in which lithium ions are moved from the positive electrode by charging to form lithium metal between the negative electrode current collector in the negative electrode and the first protective layer.
  • the lithium secondary battery according to the present invention is coated in a state of being blocked from the atmosphere through the process of forming a lithium metal layer on the negative electrode current collector, it is possible to suppress the formation of a surface oxide film due to oxygen and moisture in the atmosphere of the lithium metal, As a result, there is an effect that the cycle life characteristics are improved.
  • first to third protective layers may be included on the negative electrode current collector to prevent deterioration of the battery life due to lithium dendrites.
  • FIG. 1 is a schematic view of a lithium secondary battery prepared in the present invention.
  • Li + lithium ions
  • FIG. 3 is a schematic view after the initial charging of the lithium secondary battery prepared in the present invention is completed.
  • Figure 4 is a flow chart showing the change in the negative electrode according to the charge and discharge of the lithium secondary battery prepared in the present invention.
  • the present invention in a lithium secondary battery comprising a positive electrode, a negative electrode and an electrolyte,
  • the negative electrode is a first protective layer formed on the negative electrode current collector
  • a second protective layer formed on the first protective layer and
  • It includes a third protective layer formed on the inside and one surface of the second protective layer,
  • It relates to a lithium secondary battery in which lithium ions are moved from the positive electrode by charging to form lithium metal between the negative electrode current collector in the negative electrode and the first protective layer.
  • FIG. 1 is a cross-sectional view of a lithium secondary battery manufactured according to the present invention, a positive electrode including a positive electrode current collector 11 and a positive electrode mixture 13; A negative electrode comprising a negative electrode current collector 21 and first to third protective layers 22, 23, and 24; And a separation membrane 30 and an electrolyte (not shown) interposed therebetween.
  • the negative electrode of the lithium secondary battery is usually formed with a negative electrode on the negative electrode current collector 21, but in the present invention, only the negative electrode current collector 21 and the first to third protective layers 22, 23, and 24 are used for the negative electrode.
  • lithium ions released from the positive electrode mixture 13 by charging are formed of a lithium metal layer (not shown) as a negative electrode mixture between the negative electrode current collector 21 and the first protective layer 22.
  • a negative electrode having a known negative electrode current collector / cathode mixture is formed to form a conventional lithium secondary battery.
  • the negative electrode-free battery may be a negative electrode-free battery in which a negative electrode is not formed on the negative electrode current collector upon initial assembly, or a negative electrode may be formed on the negative electrode current collector depending on use. It may be a concept including all batteries.
  • the form of lithium metal formed as a negative electrode mixture on the negative electrode current collector is a form in which lithium metal is formed in a layer, and a porous structure in which lithium metal is not formed in a layer (for example, lithium metal It includes all of the structures aggregated in the form of particles).
  • the present invention will be described based on the shape of the lithium metal layer 25 in which the lithium metal is formed as a layer, but it is clear that this description does not exclude a structure in which the lithium metal is not formed as a layer.
  • FIG. 2 is a schematic diagram showing the movement of lithium ions (Li + ) during initial charging of a lithium secondary battery manufactured according to the present invention
  • FIG. 3 is a schematic diagram after completion of initial charging of a lithium secondary battery manufactured according to the present invention.
  • lithium ions are desorbed from the positive electrode mixture 13 in the positive electrode 10, It passes through the separator 30 and the first to third protective layers 22, 23, and 24 to move toward the negative electrode current collector 21, and on the negative electrode current collector 21, more specifically, the negative electrode current collector 21 ) And the first protective layer 22 to form a lithium metal layer 25 made of purely lithium to form the negative electrode 20.
  • Formation of the lithium metal layer 25 through such charging is compared with a negative electrode that sputters the lithium metal layer 25 on the conventional negative electrode current collector 21, or compares the lithium foil and the negative electrode current collector 21 to a thin film layer. It can be formed, and has the advantage of very easy control of interfacial properties. In addition, since the bonding strength of the lithium metal layer 25 stacked on the negative electrode current collector 21 is large and stable, there is no problem of being removed from the negative electrode current collector 21 due to an ionization state through discharge.
  • the lithium metal is formed in a negative electrode free battery structure and there is no exposure to lithium metal in the air during the battery assembly process, problems such as the formation of an oxide film on the surface due to the high reactivity of the lithium itself and the decrease in the life of the lithium secondary battery accordingly. It can be blocked at the source.
  • the negative electrode current collector 21 constituting the negative electrode is generally made to a thickness of 3 to 50 ⁇ m.
  • the negative electrode current collector 21 in which the lithium metal layer 25 can be formed by charging is not particularly limited as long as it has conductivity without causing a chemical change in the lithium secondary battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, or the like, aluminum-cadmium alloy, or the like may be used.
  • the negative electrode current collector 21 may be used in various forms, such as a film, sheet, foil, net, porous body, foam, non-woven fabric, etc. with fine irregularities formed on the surface.
  • first to third protective layers are sequentially formed on the negative electrode current collector. Specifically, a first protective layer is formed on the negative electrode current collector, a second protective layer is formed on the first protective layer, and a third protective layer is sequentially formed inside and on one surface of the second protective layer.
  • the first protective layer is formed on the negative electrode current collector, prevents a phenomenon that lithium ions are depleted on the surface of the lithium metal after the lithium metal is formed between the negative electrode current collector and the first protective layer by charging, and charges ⁇ It serves to minimize the volume change of lithium metal during discharge, and may be formed of an elastomer having high ion conductivity to perform the role.
  • the first protective layer is PVdF-HFP (poly (vinylidene fluoride-co-hexafluoropropylene)) polymer, polyurethane polymer, polyacrylic polymer, polyethylene polymer, polyether polymer, polysiloxane polymer, polyethylene derivative, polyethylene oxide derivative, Polypropylene oxide derivatives, phosphoric acid ester polymers, poly edgetation lysine (Agitation lysine), polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and ionic dissociating groups. It may, preferably, include PVdF-HFP.
  • the content of HFP in the PVdF-HFP may be 5% by weight or more, and the shore hardness of the polyurethane-based polymer may be 80A or less, and the crosslinking density of the polyacrylic polymer may be 10 -4 mol / g or less. If the shore hardness is too low, the volume of the battery may increase due to too much electrolyte impregnation, and if the crosslinking density is too high, the ionic conductivity may decrease to increase resistance.
  • the ion conductivity of the first protective layer may be 10 -5 to 10 -2 S / cm, preferably 10 -4 to 10 -3 S / cm. If the ion conductivity is less than 10 -5 S / cm, lithium ion may be depleted on the surface of the lithium metal, resulting in deterioration of battery performance. If the ion conductivity exceeds 10 -2 S / cm, the battery Performance is not improved.
  • the thickness of the first protective layer is sufficient if it is applied only enough to have mechanical properties capable of minimizing the change in volume of the lithium metal during charging and discharging. If it is too thick, the thickness of the first protective layer causes an unnecessary increase in the thickness of the electrode.
  • the thickness may be 200 nm to 10 ⁇ m.
  • the second protective layer and the lithium metal are directly connected to each other to make electrical connection therebetween. Accordingly, lithium metal is grown from the second protective layer to the third protective layer and the separator.
  • the first protective layer may further include a lithium salt.
  • the lithium salt is LiNO 3 , LiFSI, LiPF 6 , 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 , LiPF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, and 4-phenyl lithium borate.
  • the second protective layer is formed on the first protective layer, and when lithium dendrite grows and contacts the first protective layer, the lithium dendrite and the second protective layer are electrically connected to each other to form a second protective layer and lithium metal. It prevents electrons from being focused and serves to grow lithium metal in both directions.
  • the second protective layer may be in the form of a three-dimensional structure in which an interior space is formed, and the interior space may be referred to as pores. That is, the second protective layer may be an electrically conductive matrix in which pores are formed.
  • the third protective layer is formed inside the pores and surface of the second protective layer, an electron (e -) of the second protective layer is excellent in electrical conductivity is entirely evenly transmitted to the contained in the second protective layer inside the pores Since the ionic conductivity of the first protective layer is higher than the ionic conductivity of the third protective layer, lithium dendrites are formed only inside the first protective layer by being reduced in the first protective layer rich in lithium ions (Li + ). It serves to prevent the growth of lithium dendrites to the outside of the electrode.
  • the volume ratio of the electrically conductive matrix included in the second protective layer and the ion conductive polymer contained in the third protective layer may be 95: 5 to 50:50, more preferably 80:20 to 60:40. . If the volume ratio of the ion conductive polymer of the third protective layer to the electrically conductive matrix of the second protective layer is less than the above range, the Li ion conductivity of the protective layer is very low, which acts as a large resistance, deteriorating battery performance, and the range. Exceeding the vertical / horizontal electrical conductivity decreases, it is difficult to uniformly transfer electrons to the electrode surface.
  • the sheet resistance of the second protective layer is 5x10 -2 to 1000 ⁇ / sq. It is preferably 10 -2 to 500 ⁇ / sq., More preferably 10 -2 to 300 ⁇ / sq.
  • the sheet resistance exceeds 1000 ⁇ / sq., It may act as a large resistance layer, thereby deteriorating the life characteristics of the battery.
  • the vertical lithium ion conductivity of the second protective layer is 1x10 -6 to 1x10 -3 S / cm at room temperature, preferably 1x10 -5 to 1x10 -3 S / cm, more preferably 1x10 -4 To 1x10 -3 S / cm. If it is less than the above range, the vertical ion conductivity is not good, and thus the battery performance decreases due to a large resistance. If it is above the above range, lithium dendrite grows through the second and third protective layers to cause a problem in battery stability.
  • the electrically conductive matrix may include an electrically conductive material, and may further include a binder.
  • the electrically conductive matrix may include 70 to 90% by weight of the electrically conductive material and 10 to 30% by weight of the binder.
  • the electrically conductive material may be uniformly distributed throughout the electrically conductive matrix so that the protective layer can exhibit uniform electrical conductivity.
  • the form of the electrically conductive material included in the electrically conductive matrix is a form that forms a skeleton forming the electrically conductive matrix, or a form in which a matrix is formed by mixing the electrically conductive material and a binder, or the electrical structure on the skeleton of the matrix It may be in the form of a conductive material coated, in the form of a spun electrically conductive material, or in a mixture of an electrically conductive polymer and an ion conductive polymer.
  • the electrically conductive material may be at least one selected from the group consisting of electrically conductive metals, semiconductors, and electrically conductive polymers.
  • the electrically conductive metal may be at least one selected from the group consisting of gold, silver, aluminum, copper, nickel, zinc, carbon, tin and indium.
  • the semiconductor may be one or more selected from the group consisting of silicon and germanium.
  • the electrically conductive polymer is in the group consisting of PEDOT (poly (3,4-ethylenedioxythiophene)), polyaniline, polypyrrole, polythiophene, polyacetylene, polyphenylene and polyphenylene vinylene It may be one or more selected.
  • the electrically conductive material may be 70 to 90% by volume, preferably 75 to 90% by volume, more preferably 75 to 85% by volume in the electrically conductive matrix. If it is less than the above range, the electrical conductivity of the protective layer may be lowered, and if it is more than the above range, the content of the binder may be relatively lowered and durability of the protective layer may be lowered.
  • the binder includes polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoro propylene, polyvinylidene fluoride-trichloroethylene (polyvinylidene) fluoride-co-trichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, Ethylene vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate (cellulose acetate propionate), cyanoethyl pullulan (cyanoet hylpullulan), cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose, styrene-butadiene rubber (st
  • the binder may be 0 to 40% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight in the electrically conductive matrix. If it is less than the above range, the electrical conductivity of the protective layer may be lowered, and if it is more than the above range, the content of the binder may be relatively lowered and durability of the protective layer may be lowered.
  • the thickness of the second protective layer is sufficient if it is applied only to the extent that it has mechanical properties sufficient to physically suppress the growth of lithium dendrites, and if it is too thick, the thickness of the second protective layer causes an unnecessary increase in the thickness of the electrode.
  • the thickness can be 1 to 10 ⁇ m.
  • the third protective layer is formed on the inside and the surface of the second protective layer, and may serve to physically inhibit the growth of lithium dendrites. Specifically, when the third protective layer is formed inside the second protective layer, it may be formed in the inner pores of the second protective layer.
  • the third protective layer may be formed of a material having excellent strength and low ion conductivity, and the third protective layer may include an ion conductive polymer.
  • the ion conductive polymer is polyvinylidene fluoride, polyethylene oxide, polyethylene glycol, polypropylene glycol, polypropylene oxide, polyethylene succinate, polyethylene adipate, polyethyleneimine, polyepichlorohydrin, poly ⁇ -propiolactone, poly It may be one or more selected from the group consisting of N-propyl aziridine, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate.
  • the second protective layer and the third protective layer may be included in a weight ratio of 3: 7 to 7: 3.
  • the electrically conductive matrix of the second protective layer exceeds the prescribed weight range as described above, the content of the ion conductive polymer of the third protective layer is relatively reduced, so the lithium ion conductivity of the third protective layer is very low. Since there is more lithium growing on the third protective layer, it is difficult to suppress the growth of lithium dendrites.
  • the electrically conductive matrix of the second protective layer is less than a suitable weight outside the prescribed weight range as described above, vertical / horizontal electrical conductivity may be lowered and uniform electron transfer to the electrode surface may be difficult.
  • the ion-conducting polymer may further include a crosslinkable monomer, and the type of the crosslinkable monomer is not particularly limited.
  • the electrolyte solution of the lithium secondary battery of the present invention may include a non-aqueous solvent and a lithium salt.
  • the lithium salt is LiFSI, LiPF 6 , 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 , LiPF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloro borane lithium and 4-phenyl lithium borate.
  • non-aqueous solvent those commonly used in the electrolyte for lithium secondary batteries can be used without limitation, for example, ether, ester, amide, linear carbonate, cyclic carbonate, etc. can be used alone or in combination of two or more. Can be. Among them, a cyclic carbonate, a linear carbonate, or a carbonate compound that is a slurry 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, 2,3-pentylene carbonate, vinylene carbonate, vinyl ethylene carbonate, and any one selected from the group consisting of halides, or a slurry of two or more of them.
  • halides include, but are not limited to, fluoroethylene carbonate (FEC).
  • linear carbonate compound may be any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate or these Among them, two or more kinds of slurries may be used, but are not limited thereto.
  • the carbonate-based organic solvents ethylene carbonate and propylene carbonate, which are cyclic carbonates, are high-viscosity organic solvents and have a high dielectric constant, so that lithium salts in the electrolyte can be better dissociated.
  • an electrolyte having a higher ionic conductivity can be prepared.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or a slurry of two or more of them can be used. However, it is not limited thereto.
  • esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • ⁇ -valerolactone and ⁇ -caprolactone any one or two or more of them may be used, but the present invention is not limited thereto.
  • FIG. 4 is a schematic view showing the principle of preventing the growth of lithium dendrites in the negative electrode where the lithium metal layer 25 is formed through charging the lithium secondary battery.
  • lithium dendrites grow in the lithium metal layer 25 as charging and discharging of the lithium secondary battery progress, and accordingly, the lithium metal layer 25 and the second protective layer 23 are electrically Contact. Thereafter, electrons of the second protective layer 23 having excellent electrical conductivity are uniformly transmitted to the entire surface, and ions of the first protective layer 22 are more than the ionic conductivity of the third protective layer 24 included in the second protective layer. Since the conductivity is high, lithium dendrites are reduced only in the first protective layer 22 rich in lithium ions, and are formed only inside the first protective layer 22, thereby preventing the growth of lithium dendrites outside the lithium electrode. Can be.
  • the first to third protective layers are included on the negative electrode current collector, and as the protective layers perform respective roles, a lithium secondary battery having excellent life characteristics can be provided.
  • the positive electrode mixture 13 may use various positive electrode active materials depending on the type of battery, and the positive electrode active material used in the present invention is not particularly limited as long as it is a material capable of absorbing and releasing lithium ions. Lithium transition metal oxide is typically used as a positive electrode 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 ) and lithium nickel oxide (LiNiO 2 ) containing two or more transition metals and substituted with one or more transition metals; Lithium manganese oxide substituted with one or more transition metals, lithium nickel-based oxide, spinel-based lithium nickel-manganese composite oxide, spinel-based lithium manganese oxide in which a part of Li is substituted with alkaline earth metal ions, olivine-based lithium metal phosphate, and the like.
  • LiCoO 2 lithium cobalt oxide
  • LiNiO 2 lithium nickel oxide
  • Lithium manganese oxide substituted with one or more transition metals lithium nickel-based oxide, spinel-based lithium nickel-manganese composite oxide, spinel-based lithium manganese oxide in which a part of Li is substituted with alkaline earth metal ions, olivine-based lithium metal phosphate, and the like.
  • the above-described lithium transition metal oxide is used as a positive electrode active material 13 together with a binder and a conductive material as a positive electrode active material.
  • the lithium source for forming the lithium metal layer 25 in the negative electrode free battery structure of the present invention becomes the lithium transition metal oxide. That is, when the lithium ions in the lithium transition metal oxide are charged in a specific range of voltage, lithium ions are desorbed to form the lithium metal layer 25 on the negative electrode current collector 21.
  • lithium ions in the lithium transition metal oxide do not easily generate desorption on their own, or there is no lithium that can be related to charge and discharge at the operating voltage level, so it is very difficult to form the lithium metal layer 25, and only the lithium transition metal oxide is used.
  • the irreversible capacity is greatly reduced, causing a problem that the capacity and life characteristics of the lithium secondary battery are lowered.
  • the initial charge capacity is 200 mAh / g or more when one charge is performed at 0.01 to 0.2C in a voltage range of 4.5V to 2.5V
  • a lithium metal compound which is a high irreversible material having an initial irreversible of 30% or more is used together.
  • the term 'high irreversible material' referred to in the present invention may be used in the same way as 'large capacity irreversible material' in other terms, which is the irreversible capacity ratio of the first cycle of charge / discharge, that is, "(first cycle charge capacity-first cycle discharge capacity).
  • / First cycle charge capacity "means a large material. That is, the highly irreversible material may irreversibly provide excessive lithium ions during the first cycle of charging and discharging.
  • the irreversible capacity of the first cycle of charge / discharge (first cycle charge capacity-first cycle discharge capacity) may be a positive electrode material.
  • the irreversible capacity of the positive electrode active material used is about 2 to 10% of the initial charge capacity, but in the present invention, the lithium metal compound which is a high irreversible material, that is, the initial irreversible capacity is 30% or more of the initial charge capacity, preferably 50% or more.
  • Lithium metal compounds can be used together.
  • an initial charge capacity of 200 mAh / g or more, preferably 230 mAh / g or more, may be used. Due to the use of such a lithium metal compound, it acts as a lithium source capable of forming the lithium metal layer 25 while increasing the irreversible capacity of the lithium transition metal oxide, which is a positive electrode active material.
  • the lithium metal compound presented in the present invention may be a compound represented by the following Chemical Formulas 1 to 8.
  • a is 0 ⁇ a ⁇ 1
  • M 1 is one or more elements 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, It is one or more elements selected from the group consisting of Cu, Zn, Cr, Mg, Nb, Mo and Cd.
  • M 3 is one or more elements selected from the group consisting of Cr, Al, Ni, Mn, and Co.
  • M 4 is one or more elements selected from the group consisting of Cu and Ni.
  • M 5 is one or more elements selected from the group consisting of Mn, Fe, Co, Cu, Zn, Mg and Cd to be)
  • i 0.05 ⁇ i ⁇ 0.5
  • M 6 is one or more elements selected from the group consisting of Cr, Al, Ni, Mn, and Co.
  • j is 0.05 ⁇ j ⁇ 0.5
  • M 7 is one or more elements selected from the group consisting of Cr, Al, Ni, Mn, and Co.
  • M 8 represents an alkaline earth metal, k / (k + m + n) is 0.10 to 0.40, m / (k + m + n) is 0.20 to 0.50, and n / (k + m + n) is 0.20 to 0.50.
  • the lithium metal compounds of Chemical Formulas 1 to 8 differ in irreversible capacity depending on their structure, and they can be used alone or in combination, and serve to increase the irreversible capacity of the positive electrode active material.
  • the highly irreversible materials represented by Chemical Formulas 1 and 3 have different irreversible capacities according to their types, and have numerical values as shown in Table 1 below as an example.
  • the lithium metal compound of Formula 2 belongs to the space group Immm, of which Ni, M composite oxide forms a planar coordination (Ni, M) O 4 , and the planar coordination structure faces each other. It is more preferable to share the opposite side (a side formed of OO) and form a primary chain.
  • the lithium metal compound of the formula (8) has an alkaline earth metal content of 30 to 45 atomic%, and a nitrogen content of 30 to 45 atomic%. At this time, when the content of the alkaline earth metal and the content of nitrogen are within the above range, the thermal properties and lithium ion conduction properties of the compound of Formula 8 are excellent.
  • k / (k + m + n) is 0.15 to 0.35, for example 0.2 to 0.33
  • m / (k + m + n) is 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.
  • the positive electrode active material may have a core-shell structure having a surface coated with a compound of any one of Formulas 1 to 8.
  • the electrode active material When a coating film 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 in which lithium ions are continuously inserted and desorpted.
  • the thickness of the coating film is 1 to 100 nm.
  • the ion-conducting properties of the electrode active material are excellent.
  • the electrode active material has an average particle diameter of 1 to 30 ⁇ m, and according to one embodiment, 8 to 12 ⁇ m. When the average particle diameter of the positive electrode active material is within the above range, the capacity characteristics of the battery are excellent.
  • the core active material doped with the alkaline earth metal may be, for example, LiCoO 2 doped with magnesium.
  • the magnesium content is 0.01 to 3 parts by weight based on 100 parts by weight of the core active material.
  • the above-described lithium transition metal oxide is used as a positive electrode active material 13 together with a binder and a conductive material as a positive electrode active material.
  • the lithium source for forming the lithium metal layer 25 in the negative electrode free battery structure of the present invention becomes the lithium transition metal oxide. That is, when the lithium ions in the lithium transition metal oxide are charged in a specific range of voltage, lithium ions are desorbed to form the lithium metal layer 25 on the negative electrode current collector 21.
  • the charging range for forming the lithium metal layer 25 is performed once at a voltage range of 4.5V to 2.5V at 0.01 to 0.2C. If the charging is performed below the above range, it is difficult to form the lithium metal layer 25. On the contrary, when the above-mentioned range is exceeded, damage and damage of the cell occurs and overcharge occurs, so that charging and discharging are properly performed. It does not proceed.
  • the formed lithium metal layer 25 forms a uniform continuous or discontinuous layer on the negative electrode current collector 21.
  • the negative electrode current collector 21 when the negative electrode current collector 21 is in the form of a foil, it may have a continuous thin film form, and when the negative electrode current collector 21 has a three-dimensional porous structure, the lithium metal layer 25 may be discontinuously formed. . That is, the discontinuous layer has a shape in which the lithium metal layer 25 is present and a non-existent region exists in a specific region, but a lithium compound is present in the region where the lithium metal layer 25 does not exist. By distributing the region to be isolated, disconnected or separated like an island type, it means that the region where the lithium metal layer 25 is present is distributed without continuity.
  • the lithium metal layer 25 formed through such charging and discharging has a thickness of at least 50 nm, 100 ⁇ m or less, and preferably 1 ⁇ m to 50 ⁇ m for functioning as a negative electrode. If the thickness is less than the above range, the battery charging and discharging efficiency decreases rapidly. On the contrary, if the thickness exceeds the above range, the life characteristics and the like are stable, but there is a problem that the energy density of the battery is lowered.
  • the lithium metal layer 25 proposed in the present invention is manufactured by using a negative electrode-free battery without lithium metal when assembling the battery, so that the lithium generated in the assembly process is high compared to a lithium secondary battery assembled using a conventional lithium foil. Due to the reactivity, no or little oxide layer is formed on the lithium metal layer 25. Due to this, it is possible to prevent the degradation of the life of the battery due to the oxide layer.
  • the lithium metal layer 25 is moved by charging of a high irreversible material, which can form a more stable lithium metal layer 25 compared to forming the lithium metal layer 25 on the positive electrode.
  • a chemical reaction between the positive electrode and lithium metal may occur.
  • the positive electrode mixture 13 comprises the positive electrode active material and the lithium metal compound, wherein the positive electrode mixture 13 may further include a conductive material, a binder, and other additives commonly used in lithium secondary batteries. have.
  • the conductive material is used to further improve the conductivity of the electrode active material.
  • the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • 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 fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder, 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 to bond 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, polyethylene, polypropylene, polytetrafluoro ethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoro alkylvinyl ether copolymer, vinylidene fluoride- Hexa fluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoro Roethylene copolymer, ethylene-chlorotrifluoroethylene copoly
  • the filler is selectively used as a component that suppresses 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.
  • olefinic polymers such as polyethylene and polypropylene, or fibrous materials such as glass fibers and carbon fibers are used.
  • the positive electrode mixture 13 of the present invention is formed on the positive electrode current collector 11.
  • the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • the positive electrode current collector 11 is not particularly limited as long as it has high conductivity without causing a chemical change in the lithium secondary battery, and examples thereof include stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. Surfaces treated with carbon, nickel, titanium, silver, or the like may be used.
  • the positive electrode current collector 11 may be used in various forms such as a film, sheet, foil, net, porous body, foam, non-woven fabric, etc. with fine irregularities formed on the surface to increase the adhesion with the positive electrode active material.
  • the method of applying the positive electrode mixture 13 on the current collector is a method in which the electrode mixture slurry is distributed over the current collector and then uniformly dispersed using a doctor blade, etc., die casting, comma coating and methods such as (comma coating) and screen printing.
  • the electrode mixture slurry may be bonded to the current collector by pressing or lamination, but is not limited thereto.
  • the lithium secondary battery includes a positive electrode 10, a negative electrode 20, and a separator 30 interposed therebetween, and the separator 30 may be excluded depending on the type of battery. have.
  • the separation membrane 30 may be made of a porous substrate, and the porous substrate may be any porous substrate that is commonly used in electrochemical devices.
  • the porous substrate may be any porous substrate that is commonly used in electrochemical devices.
  • a polyolefin-based porous membrane or non-woven fabric may be used. It is not particularly limited.
  • the separator 30 according to the present invention is not particularly limited in its material, and physically separates the positive electrode and the negative electrode, and has an electrolyte and ion permeability, and is typically used as a separator 30 in a lithium secondary battery.
  • it can be used without limitation, it is a porous, non-conductive or insulating material, and it is particularly preferable to have low resistance to ion migration of the electrolyte and excellent electrolyte-moisturizing ability.
  • a polyolefin-based porous membrane (membrane) or a non-woven fabric may be used, but is not particularly limited thereto.
  • polyolefin-based porous membrane 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, respectively, or formed of polymers thereof.
  • 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, respectively, or formed of polymers thereof.
  • 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, respectively, or formed of polymers thereof.
  • the nonwoven fabric is, for example, polyphenylene oxide, polyimide, polyamide, polycarbonate, polyethylene terephthalate, polyethylenenaphthalate, etc. , Polybutylene terephthalate, polyphenylenesulfide, polyacetal, polyethersulfone, polyetheretherketone, polyester, etc. Or it is possible to form a non-woven fabric made of a polymer mixed with them, and such a non-woven fabric is a fiber form forming a porous web, and includes a spunbond or meltblown form composed of long fibers.
  • the thickness of the separator 30 is not particularly limited, but is preferably in the range of 1 to 50 ⁇ m, and more preferably in the range of 5 to 30 ⁇ m.
  • the thickness of the separator 30 is less than 1 ⁇ m, the probability of a short circuit during charging and discharging of the battery is high, and when it exceeds 50 ⁇ m, the electrolyte filling the pores of the separator should be injected in excess and the energy density of the battery There is a problem that is degraded.
  • the pore size and porosity of the separator 30 are not particularly limited, but the pore size is 0.1 to 50 ⁇ m, and the porosity is preferably 10 to 95%. When the pore size of the separator 30 is less than 0.1 ⁇ m or the porosity is less than 10%, the separator 30 acts as a resistance layer, and when the pore size exceeds 50 ⁇ m or the porosity exceeds 95% Mechanical properties cannot be maintained.
  • the shape of the lithium secondary battery as described above 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 type, preferably It may be a stack-folding type.
  • the electrode assembly After preparing the electrode assembly in which the positive electrode, the separator, and the negative electrode are sequentially stacked, they are placed in a battery case, and then an electrolyte is injected into the upper portion of the case, sealed with a cap plate and a gasket, and assembled to produce a lithium secondary battery. .
  • the lithium secondary battery can be classified into various batteries, such as lithium-sulfur batteries, lithium-air batteries, lithium-oxide batteries, and lithium solid-state batteries, depending on the type of anode material and separator used. It can be classified into coin type, pouch type, etc. and can be divided into bulk type and thin film type according to size. The structure and manufacturing method of these batteries are well known in the art, so detailed descriptions thereof are omitted.
  • the lithium secondary battery according to the present invention can be used as a power source for devices requiring high capacity and high rate characteristics.
  • a power tool moving by being powered by an omni-directional motor is provided; Electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); An electric two-wheeled vehicle including an electric bicycle (E-bike) and an electric scooter (Escooter); Electric golf carts; A power storage system, and the like, but is not limited thereto.
  • a mixture of LCO (LiCoO 2 ) and L 2 N (Li 2 NiO 2 ) in a weight ratio of 9: 1 to N-methylpyrrolidone (N-Methyl-2-pyrrolidone) was used as a positive electrode active material, and the positive electrode active material :
  • a conductive material (super-P): binder (PVdF) was mixed in a weight ratio of 95: 2.5: 2.5 and then mixed with a paste face mixer for 30 minutes to prepare a slurry composition.
  • the slurry composition prepared above was coated on a current collector (Al Foil, 20 ⁇ m thick) and dried at 130 ° C. for 12 hours to prepare a positive electrode having a loading of 3 mAh / cm 2 .
  • LiNO 3 was added to prepare a first protective layer, which was used as the surface of a copper current collector (cathode current collector).
  • the first protective layer was formed on the copper current collector by transfer.
  • PVDF polyvinylidene fluoride
  • SBC Hass release film
  • a PVDF-filled layer is formed in the interior space of the three-dimensional structure formed by Cu, and the copper is used as the second protective layer and the PVDF is called a third protective layer.
  • the weight ratio of Cu and PVDF in the second protective layer and the third protective layer was 50:50.
  • the second and third protective layers formed on the release film were transferred to one surface of the first protective layer to form first to third protective layers on the copper current collector.
  • a negative electrode-free lithium secondary battery of Example 1 was prepared including the negative electrode current collector, first to third protective layers, electrolyte solution, separator and positive electrode.
  • the porosity of the separator was 48.8%.
  • a negative electrode-free lithium secondary battery of Example 2 was manufactured in the same manner as in Example 1, except that germanium (Ge) was used as the second protective layer.
  • a cathode-free lithium secondary battery of Example 2 was manufactured in the same manner as in Example 1, except that L 2 N (Li 2 NiO 2 ) was not used as the positive electrode active material.
  • the negative electrode-free lithium secondary battery of Comparative Example 1 was manufactured in the same manner as in Example 1, except that the second and third protective layers were not included. That is, the negative electrode-free lithium secondary battery of Comparative Example 1 includes only the first protective layer.
  • a negative electrode-free lithium secondary battery of Comparative Example 2 was manufactured in the same manner as in Example 1, except that the first and second protective layers were not included. That is, the negative electrode-free lithium secondary battery of Comparative Example 2 includes only the third protective layer.
  • a negative electrode-free lithium secondary battery of Comparative Example 3 was manufactured in the same manner as in Example 1, except that the second protective layer was not included. That is, the negative electrode-free lithium secondary battery of Comparative Example 3 includes only the first and third protective layers.
  • the negative electrode of Comparative Example 4 was carried out in the same manner as in Example 1, except that the first to third protective layers were not included, and L 2 N (Li 2 NiO 2 ) was not used as the positive electrode active material. A free lithium secondary battery was prepared. That is, the negative electrode-free lithium secondary battery of Comparative Example 4 does not include all of the first to third protective layers.
  • the capacity of the lithium secondary battery is 50% compared to the initial discharge capacity of the lithium secondary battery in which the lithium metal layer 23 is formed by performing charging and discharging at a temperature of 60 ° C under the condition of 0.2C / 0.5C based on discharge 3mAh / cm 2
  • the number of cycles above was measured, and the results are shown in Table 2 below.
  • Examples 1 and 2 including all of the first to third protective layers and using the high-reversible material L 2 N do not short, and the capacity retention ratio compared to the initial discharge capacity is 50% or more.
  • the number of cycles was measured as high as 27 and 22 cycles.
  • Example 3 the high irreversible material, L 2 N, was not used, and no short occurred, but the number of cycles having a capacity retention ratio of 50% or more compared to the initial discharge capacity was measured as low as 9 cycles.
  • Comparative Examples 1 to 4 which did not contain one or more of the first to third protective layers, or did not include all of them, shorts occurred and showed very unstable charging and discharging characteristics.

Landscapes

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

Abstract

La présente invention concerne une batterie secondaire au lithium comprenant une électrode positive, une électrode négative, et un électrolyte, l'électrode négative comprenant une première couche protectrice formée sur un collecteur de courant d'électrode négative, une deuxième couche protectrice formée sur la première couche protectrice, et des troisièmes couches protectrices formées à l'intérieur de la deuxième couche protectrice et sur une surface de celle-ci ; et des ions lithium sont déplacés à partir de l'électrode positive au moyen d'une charge pour former un métal lithium entre un collecteur de courant d'électrode négative et la première couche protectrice à l'intérieur de l'électrode négative.
PCT/KR2019/014582 2018-10-31 2019-10-31 Batterie secondaire au lithium WO2020091453A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19880365.2A EP3761405A4 (fr) 2018-10-31 2019-10-31 Batterie secondaire au lithium
US16/982,093 US20210104748A1 (en) 2018-10-31 2019-10-31 Lithium secondary battery
CN201980018193.4A CN111837259B (zh) 2018-10-31 2019-10-31 锂二次电池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0131662 2018-10-31
KR20180131662 2018-10-31
KR1020190137138A KR102328261B1 (ko) 2018-10-31 2019-10-31 리튬 이차전지
KR10-2019-0137138 2019-10-31

Publications (1)

Publication Number Publication Date
WO2020091453A1 true WO2020091453A1 (fr) 2020-05-07

Family

ID=70464265

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/014582 WO2020091453A1 (fr) 2018-10-31 2019-10-31 Batterie secondaire au lithium

Country Status (1)

Country Link
WO (1) WO2020091453A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111933951A (zh) * 2020-08-25 2020-11-13 中南大学 一种锂金属活性前驱材料及其制备和应用
CN113258127A (zh) * 2021-05-31 2021-08-13 浙江大学 一种集流体-负极一体化的双极型锂二次电池及其方法
WO2022027550A1 (fr) * 2020-08-07 2022-02-10 宁德时代新能源科技股份有限公司 Collecteur de courant polymère, son procédé de préparation, et batterie secondaire, module de batterie, bloc-batterie et appareil s'y rapportant
US20230135791A1 (en) * 2020-05-08 2023-05-04 Lg Energy Solution, Ltd. Negative electrode current collector for lithium free battery, electrode assembly including the same, lithium free battery
EP4044294A4 (fr) * 2020-05-08 2024-01-03 Lg Energy Solution, Ltd. Collecteur de courant d'électrode négative pour batterie sans lithium, ensemble électrode comprenant celui-ci et batterie sans lithium

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050041661A (ko) * 2003-10-31 2005-05-04 삼성에스디아이 주식회사 리튬 금속 전지용 음극 및 이를 포함하는 리튬 금속 전지
KR20140082074A (ko) * 2012-12-21 2014-07-02 삼성전자주식회사 보호 음극, 이를 포함하는 리튬 공기 전지, 및 리튬 이온 전도성 보호막의 제조방법
KR20160052323A (ko) 2014-10-29 2016-05-12 주식회사 엘지화학 리튬 전극 및 이를 포함하는 리튬 전지
KR20180007798A (ko) * 2016-07-14 2018-01-24 주식회사 엘지화학 리튬 금속이 양극에 형성된 리튬 이차전지와 이의 제조방법
KR20180010423A (ko) * 2016-07-21 2018-01-31 주식회사 엘지화학 리튬 코발트 산화물을 합성하기 위한 양극 활물질을 포함하는 리튬 이차전지, 이의 제조방법
WO2018191025A1 (fr) * 2017-04-10 2018-10-18 Nanotek Instruments, Inc. Batterie secondaire au métal lithium contenant une couche de polymère de protection d'anode et procédé de fabrication
KR20180131662A (ko) 2017-05-30 2018-12-11 대주전자재료 주식회사 신규한 피리디닐 트리아졸로피리딘 유도체 및 이의 용도
KR20190137138A (ko) 2017-04-07 2019-12-10 로베르트 보쉬 게엠베하 요 레이트 센서 및 요 레이트 센서를 작동시키기 위한 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050041661A (ko) * 2003-10-31 2005-05-04 삼성에스디아이 주식회사 리튬 금속 전지용 음극 및 이를 포함하는 리튬 금속 전지
KR20140082074A (ko) * 2012-12-21 2014-07-02 삼성전자주식회사 보호 음극, 이를 포함하는 리튬 공기 전지, 및 리튬 이온 전도성 보호막의 제조방법
KR20160052323A (ko) 2014-10-29 2016-05-12 주식회사 엘지화학 리튬 전극 및 이를 포함하는 리튬 전지
KR20180007798A (ko) * 2016-07-14 2018-01-24 주식회사 엘지화학 리튬 금속이 양극에 형성된 리튬 이차전지와 이의 제조방법
KR20180010423A (ko) * 2016-07-21 2018-01-31 주식회사 엘지화학 리튬 코발트 산화물을 합성하기 위한 양극 활물질을 포함하는 리튬 이차전지, 이의 제조방법
KR20190137138A (ko) 2017-04-07 2019-12-10 로베르트 보쉬 게엠베하 요 레이트 센서 및 요 레이트 센서를 작동시키기 위한 방법
WO2018191025A1 (fr) * 2017-04-10 2018-10-18 Nanotek Instruments, Inc. Batterie secondaire au métal lithium contenant une couche de polymère de protection d'anode et procédé de fabrication
KR20180131662A (ko) 2017-05-30 2018-12-11 대주전자재료 주식회사 신규한 피리디닐 트리아졸로피리딘 유도체 및 이의 용도

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3761405A4

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230135791A1 (en) * 2020-05-08 2023-05-04 Lg Energy Solution, Ltd. Negative electrode current collector for lithium free battery, electrode assembly including the same, lithium free battery
EP4044294A4 (fr) * 2020-05-08 2024-01-03 Lg Energy Solution, Ltd. Collecteur de courant d'électrode négative pour batterie sans lithium, ensemble électrode comprenant celui-ci et batterie sans lithium
EP4027413A4 (fr) * 2020-05-08 2024-03-13 Lg Energy Solution, Ltd. Collecteur de courant d'anode pour batterie sans lithium, ensemble électrode comprenant celui-ci et batterie sans lithium
WO2022027550A1 (fr) * 2020-08-07 2022-02-10 宁德时代新能源科技股份有限公司 Collecteur de courant polymère, son procédé de préparation, et batterie secondaire, module de batterie, bloc-batterie et appareil s'y rapportant
US11831024B2 (en) 2020-08-07 2023-11-28 Contemporary Amperex Technology Co., Limited Polymer current collector, preparation method thereof, and secondary battery, battery module, battery pack, and apparatus associated therewith
CN111933951A (zh) * 2020-08-25 2020-11-13 中南大学 一种锂金属活性前驱材料及其制备和应用
CN113258127A (zh) * 2021-05-31 2021-08-13 浙江大学 一种集流体-负极一体化的双极型锂二次电池及其方法
CN113258127B (zh) * 2021-05-31 2023-09-15 浙江大学 一种集流体-负极一体化的双极型锂二次电池及其方法

Similar Documents

Publication Publication Date Title
WO2018034526A1 (fr) Anode comprenant de multiples couches de protection, et batterie secondaire au lithium la comprenant
WO2020091453A1 (fr) Batterie secondaire au lithium
WO2018135915A1 (fr) Procédé de fabrication d'une batterie secondaire au lithium présentant des caractéristiques améliorées de stockage à haute température
WO2018169247A2 (fr) Anode pour pile rechargeable au lithium, procédé de production associé et pile rechargeable au lithium comprenant ladite anode
WO2018143733A1 (fr) Procédé de fabrication d'une batterie secondaire au lithium présentant des propriétés de stockage à haute température améliorées
WO2019004699A1 (fr) Batterie secondaire au lithium
WO2019045399A2 (fr) Batterie secondaire au lithium
WO2018236168A1 (fr) Batterie secondaire au lithium
WO2019013449A1 (fr) Anode comprenant une couche de protection d'électrode et batterie secondaire au lithium l'utilisant
WO2020111543A1 (fr) Matériau actif à électrode positive à base de lithium-manganèse octaédrique, et électrode positive et batterie secondaire au lithium la comprenant
KR20200049674A (ko) 리튬 이차전지
WO2018056615A1 (fr) Électrode négative comprenant de multiples couches de protection et batterie secondaire au lithium la comprenant
WO2020171367A1 (fr) Matériau actif de cathode, son procédé de fabrication et accumulateur au lithium le contenant
WO2022211589A1 (fr) Matériau actif de cathode composite, cathode et batterie au lithium utilisant celui-ci, et son procédé de préparation
WO2022154309A1 (fr) Procédé pour charger et décharger une batterie secondaire
WO2019221410A1 (fr) Électrode négative comprenant une couche de protection d'électrode et batterie secondaire au lithium l'utilisant
WO2021071125A1 (fr) Batterie secondaire au lithium et procédé de fabrication de batterie secondaire au lithium
WO2021060811A1 (fr) Procédé de fabrication de batterie auxiliaire
WO2021040388A1 (fr) Solution électrolytique non aqueuse et batterie secondaire au lithium la comprenant
WO2018236166A1 (fr) Batterie secondaire au lithium
WO2022255665A1 (fr) Mélange maître comprenant un matériau actif d'électrode positive et un additif irréversible, et bouillie d'électrode positive, pour batterie secondaire au lithium, le contenant
WO2020091428A1 (fr) Accumulateur au lithium
WO2018164402A1 (fr) Ensemble d'électrode et pile au lithium comprenant celui-ci
WO2022211521A1 (fr) Composition de revêtement d'électrode au lithium métallique, procédé de fabrication d'électrode au lithium métallique, électrode au lithium métallique et batterie secondaire au lithium
WO2016052881A1 (fr) Procédé de fabrication de batterie rechargeable au lithium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19880365

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019880365

Country of ref document: EP

Effective date: 20200929

NENP Non-entry into the national phase

Ref country code: DE