WO2019125064A1 - Électrode négative pour batterie lithium-métal et batterie lithium-métal la comprenant - Google Patents

Électrode négative pour batterie lithium-métal et batterie lithium-métal la comprenant Download PDF

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Publication number
WO2019125064A1
WO2019125064A1 PCT/KR2018/016500 KR2018016500W WO2019125064A1 WO 2019125064 A1 WO2019125064 A1 WO 2019125064A1 KR 2018016500 W KR2018016500 W KR 2018016500W WO 2019125064 A1 WO2019125064 A1 WO 2019125064A1
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Prior art keywords
lithium metal
pore
negative electrode
diameter
pores
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PCT/KR2018/016500
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English (en)
Korean (ko)
Inventor
문재원
유형균
한형석
팽기훈
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180166735A external-priority patent/KR20190076890A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18891822.1A priority Critical patent/EP3598546A4/fr
Priority to US16/500,633 priority patent/US12009522B2/en
Priority to CN201880019235.1A priority patent/CN110462902B/zh
Publication of WO2019125064A1 publication Critical patent/WO2019125064A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/742—Meshes or woven material; Expanded metal perforated material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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 negative electrode for a lithium metal battery and a lithium metal battery including the same.
  • Lithium metal batteries use lithium metal as an anode active material. When metal is discharged, the metal loses electrons and moves to the anode through the electrolyte. When the battery is charged, lithium ions move to the cathode through the electrolyte, Which is an electrochemical reaction. This has the advantage of having a theoretically very high energy capacity as compared with a commercial lithium ion battery using graphite or the like as the negative electrode active material. .
  • the lithium metal battery has not been commercialized because of the difficulty in securing the reversibility of the negative electrode due to the structural limitations of the negative electrode collector proposed so far.
  • the copper foil ( 1 - 1) widely used as an anode current collector in a lithium ion battery is simply transferred to a lithium metal battery, due to a flat structure not including internal pores, It does not provide sufficient space and various directions in which lithium ions are electrodeposited .
  • a porous collector comprising a foam (&) shaped pore.
  • a porous current collector can provide various directions and sufficient space in which the lyrium ion is electrodeposited, so that the pore can be advantageous for initial charging. Nevertheless, owing to the irregular ( 11 (1 0111 )) pore form of the pores, 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the present invention proposes a negative electrode collector capable of suppressing local clogging during repetitive charging and discharging of the battery while providing a variety of directions and sufficient space for allowing lithium ions to enter the lithium ion battery when charging the lithium metal battery , And an optimal cathode and battery design method using the anode current collector.
  • a lyrium metal layer 110 is formed so as to face the first pores of the negative electrode collector
  • a negative electrode for a lithium metal battery is provided.
  • a lithium metal battery which is designed such that the separator faces the second pore (relatively large-diameter pore) of the negative electrode collector using the negative electrode for a lithium metal battery of the embodiment to provide.
  • the negative electrode and the lithium metal battery are designed according to the above embodiments to ensure the reversibility of the lithium metal negative electrode and to improve the lifetime characteristics of the lithium metal battery.
  • FIG. 1 is a cross- 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • FIG. 2 schematically shows a part of a lyrium metal battery to which the anode current collector of the embodiment is applied.
  • Fig. 3 schematically shows a side portion of a negative electrode current collector designed according to one embodiment of the present invention.
  • FIG. 1 schematically shows a side view of a lithium metal cathode designed in an embodiment of the invention.
  • the figure schematically shows a part of a side surface of a lithium metal anode designed in a comparative example of the present invention.
  • FIG. 5 shows the results of sludge discharge performed when the driving of each cell in one embodiment of the present invention and one comparative example is terminated.
  • the term "combination thereof " included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, ≪ / RTI & gt ; and the like . 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • Lithium Metal Battery Cathode In one embodiment of the invention,
  • a lithium metal layer 110 is formed so as to face the first pores of the negative electrode collector
  • a negative electrode for a lithium metal battery is provided.
  • the lyrium metal anode of the embodiment has a structure in which the first pores (relatively small-diameter pores) of the negative electrode collector are opposed to the lyrium metal layer 110, and the second pores (pores having a relatively large diameter) are exposed Structure.
  • the second pores (relatively large pores) of the anode current collector are opposed to the separator.
  • the low-pore 12 opposed to the separator is a wide entrance through which lyrium ions (specifically, lithium ions derived from the electrolyte impregnated into the separator membrane) can enter.
  • Lithium ions that enter through such a wide entrance (second pore) are transferred to the lithium metal layer through the phosphorus.
  • various directions in which lithium ions can penetrate into the anode current collector and sufficient space So that the lithium metal battery is repeatedly charged and discharged 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • FIG. 1 is a side view schematically showing the negative electrode current collector.
  • each of the plurality of holes has a first pore formed on one surface of the metal plate, and a second pore is formed on the other surface of the metal plate,
  • the plurality of holes may have a pore structure that is open on both sides of the metal plate, independently of each other.
  • each of the plurality of holes has a relatively small diameter of a first pore formed on one surface of the metal plate, and a diameter of a second pore formed on the other surface of the metal plate is relatively large ,
  • the diameter of the hole may increase in a direction from the first pore to the second pore.
  • the plurality of holes may be formed independently of each other, in a direction from the first pore to the second pore, such that a gradient of the hole increases in diameter.
  • 2 schematically shows a part of a lyrium metal battery to which the anode current collector of the embodiment is applied.
  • lithium metal vapor is deposited on the surface having the relatively small diameter of the first pore
  • the separation membrane can be stacked on the surface where the second pores are located.
  • the anode may be laminated on the other surface of the separator, and the separator may be impregnated with an electrolyte to form a lithium metal battery. 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the lithium ions of the electrolyte move from the separator and pass through the plurality of holes, and can be electrodeposited on the lyrium metal layer.
  • Lithium ions are desorbed from the lithium metal layer and can move to the separation membrane 5 through the plurality of holes.
  • the second pore adjacent to the separation membrane can provide a wide entrance through which the lyrium ion of the electrolyte can easily enter.
  • the hole whose diameter gradually decreases from the second pore to the first pore may be a passage through which lithium ions of the electrolyte move.
  • the plurality of holes may independently have a constant slope in the direction from the second pore to the low pore, and gradually decrease.
  • lithium ions are injected through the wide entrance (second pore)
  • the phrase on the diameter slope of the hole may be in the range of 30 2 to 60 2 , for example, 40 to 50 °. In this range, it is possible to provide various directions in which the lyrium ion can enter and sufficient space, It may be advantageous to suppress the local clogging phenomenon.
  • the plurality of holes may include, independently of each other, 1) a porous structure having openings on both sides of the metal plate, 2) a structure in which the diameter of the pores is reduced from one surface of the metal plate to the other surface It is sufficient to achieve the above advantage.
  • the diameter of the hole has a constant slope and can be increased gradually, or the slope of the diameter of the hole can be within a specific range, and the present invention is not limited by the examples.
  • the plurality of holes are formed such that, independently of each other, the diameter of the first pores (small) 2, for example, 50 to 70.
  • RTI ID 0.0 > 100 / year, < / RTI >
  • each of the plurality of holes may independently have a diameter of the second pore of 7 to 700, for example, 200 to 350 // .
  • the pore diameter of the surface on which the separation membrane is deposited is 7 to 700 / L, for example, 200 to 350 m.
  • the thickness of the substrate on which the plurality of holes are formed may be in a range of 5 to 300, for example, 100 to 150.
  • the plurality of holes may independently include: 1) a structure having a pore structure that is open on both sides of the metal plate, 2) a structure in which the diameter of the pore increases from one surface of the metal plate to the other surface Only , It is sufficient to achieve the above advantage.
  • the fact that the diameter of the first pore, the diameter of the second pore, the thickness of the metal plate, and the degree of change in the hole diameter in the metal plate can each fall within a specific range is merely an example And the present invention is not limited by the examples.
  • the plurality of holes may be independently formed by soft molding, self-assembly of spherical particles, or photo etching. More specifically, an optical angle can be used as in the following embodiments.
  • the plurality of holes may be formed in a metal plate using a soft mold of a cone, a cone, or a polyhedron.
  • the soft mold may be an elastomer, for example, polydimethylsiloxane (PDMS) ≪ / RTI > Specifically, in order to realize the shape of a soft mold, etching can be performed on a metal or non-metal substrate using photolithography, and the desired shape can be transferred to the elastomer.
  • the substrate may be a Si wafer and is not limited to the material because photolithography is applicable to all applicable substrates.
  • soft mold There are three ways to use soft mold. There is a method of applying conductivity to the soft mold itself and utilizing it as a stamper for patterning, and a method of using only the metal layer to be used. Specifically, as a method of imparting conductivity, it is possible to utilize a method of plating the entire surface of a soft mold by using an electroless plating method, sputtering a metal on a soft mold, and then forming a pore by removing a tip portion. When the metal part having pores is removed, a desired metal plate can be obtained. When this is used, the diameter of the hole, the diameter of the first pore, and / or the diameter of the second pore may be formed in each of the ranges described above.
  • spherical particles having a Gaussian distribution according to the diameter of the particles can be used to obtain a soft mold-like shape.
  • the size of the spherical particles may be in the range of 1 to 30 / ffli, and the pores may be self-assembled by liquid phase precipitation, It can be implemented as a mechanism.
  • the spherical particles are dropped on the substrate completely immersed in the liquid, they are accumulated according to the particle size due to gravity, and a cone shape, a cone shape, or a polygonal shape similar to the soft mold is distributed on the surface.
  • the diameter of the hole, the diameter of the first pore, and / or the diameter of the second pore may be formed in each range. .
  • the light to be irradiated may be ultraviolet (UV), and may have a wavelength band of 10 nt to 500 nm in general. More specifically, the central wavelength can be located at 300 nm to 500 nm.
  • UV ultraviolet
  • a photoresist and a photomask are positioned so that light can be formed on a metal plate so that a desired hole is formed, a part of the metal except the photoresist and the photomask is etched.
  • the size of the photoresist and the photomask may be sequentially adjusted to form the plurality of holes having a gradient. In this case, the diameter of the hole, the diameter of the first pore, and / or the diameter of the second pore may be formed in the aforementioned ranges.
  • the plurality of holes may each have a truncated cone, a truncated cone, or a polygonal prism shape by independently controlling the formation method and conditions thereof.
  • each of the plurality of holes may be formed into a truncated cone shape.
  • a narrower upper surface may form the first pore
  • a second pore may be formed, and the slope thereof may coincide with the diameter slope of the hole.
  • the shapes listed above are merely examples, and the present invention is not limited thereto. Porosity
  • the metal plate may include copper ( 1); Or copper may be made of a number of days (0, 1) and the alloy (1 0 ⁇ of other metals.
  • the metal plate is made of a without causing chemical changes in the battery copper (0 1) or a copper alloy ((3 ⁇ 4- during 10 material having a high conductivity, it is not particularly limited.
  • the metal plate may be a film, a sheet, a foil, or the like having a thickness of 3 to 500, e.g., 100 to 150, and the plurality of holes may be formed on the metal plate.
  • the metal tube may be formed with fine irregularities on its surface to increase the adhesion of the lyrium metal layer and / or the separator.
  • the rutum metal layer can be deposited in a battery.
  • the lithium metal layer can be deposited on the negative electrode collector by replacing the negative electrode of a conventional battery with the negative electrode collector of the embodiment described above and repeating charging and discharging. Lyrium metal battery
  • a negative electrode including a negative electrode including the negative electrode collector according to one embodiment of the present invention and a lyrium metal layer facing the first pore of the negative electrode collector, An electrolyte impregnated in the separator, and a cathode opposite to the other surface of the separator. 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the lithium metal layer is deposited on the surface of the negative electrode collector of the above embodiment where the first pores having a relatively small diameter are located and the separator is stacked on the surface where the second pores having a relatively large diameter are located.
  • the anode may be laminated on the other surface of the separator, and the separator may be impregnated with an electrolyte to form a rutum metal battery. Its structure is the same as described in detail in connection with Figs. 1 and 2 above.
  • a porous current collector including a copper foil (0 1 - >) or a foam (3 ⁇ 4)) type of pores having no flat pores is used as a negative electrode current collector, The capacity decrease is severe.
  • the lithium metal battery of the embodiment includes the above-described negative electrode current collector, the storage and desorption of lyrium can be stably performed in the negative electrode including the above-described negative electrode current collector during repeated charging and discharging of the battery. And life characteristics can be improved.
  • battery components other than the cathode will be described in detail.
  • an electrolytic solution containing a non-aqueous organic solvent and a lithium salt may be used.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvent may be used.
  • the carbonate-based solvent include dimethyl carbonate (DMC), diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl ethyl carbonate (ethylene carbonate, propylene carbonate 1), butylene carbonate and the like can be used.
  • ester solvent methyl acetate, ethyl acetate, 11 propyl acetate, 1,1-dimethyl ethyl acetate, methyl propionate, ethyl propionate, Lactone, Decanolide, valerolactone, mevalonolactone, caprolactone, and the like may be used.
  • ether solvent dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like can be used.
  • ketone solvent cyclohexanone and the like can be used.
  • alcoholic solvent ethyl alcohol, isopropyl alcohol and the like can be used.
  • aprotic solvent R-CN (R is a linear, branched or cyclic hydrocarbon group of C2 to C20, An amide such as nitrile, dimethylformamide, etc., which may contain a bonding aromatic ring or an ether bond, dioxolane such as 1,3-dioxolane, sulfolane, and the like.
  • the non-aqueous organic solvent may be used alone or in admixture of one or more. If the non-aqueous organic solvent is used in combination, the mixing ratio may be appropriately adjusted according to the desired cell performance. .
  • the carbonate-based solvent it is preferable to use a mixture of a cyclic carbonate and a chain carbonate.
  • mixing the cyclic carbonate and the chain carbonate in a volume ratio of about 1: 1 to about 1: 9 may provide excellent performance of the electrolytic solution.
  • the non-aqueous organic solvent may further include the aromatic hydrocarbon-based organic solvent in the carbonate-based solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based solvent may be mixed in a volume ratio of about 1: 1 to about 30: 1.
  • the aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by the following formula (1).
  • each of 3 ⁇ 4 to 11 6 independently represents hydrogen, halogen, 01 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the aromatic hydrocarbon-based organic solvent is selected from the group consisting of benzene, fluorobenzene,
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound represented by the following formula (2) to improve battery life.
  • ⁇ and 3 ⁇ 4 are each independently hydrogen, halogen, cyano (0), a nitro group 02) or ⁇ a fluoroalkyl group of 1 to 05, wherein at least one of the and 3 ⁇ 4 is a halogen group, A cyano group (0 ratio, nitrogage 0 2 ), or a fluoroalkyl group of 01 to 05.
  • ethylene carbonate-based compound examples include difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene Carbonates, cyanoethylene carbonate, fluoroethylene carbonate, and the like.
  • the amount of the vinylene carbonate or the ethylene carbonate-based compound can be appropriately adjusted to improve the service life.
  • the lithium salt is dissolved in the non-aqueous organic solvent to act as a source of lithium ions in the battery to enable operation of a basic lithium secondary battery, and a material capable of promoting the movement of lithium ions between the positive electrode and the negative electrode to be.
  • the lithium salt Representative examples are LiPF 6, LiBF 4, LiSbF 6 , LiAsF 6, LiC 4 F 9 S0 3, L1CIO 4, LiA10 2, LiAlCU, LiN (C x F 2x + 1 S0 2) (C y F 2y + 1 SiO 2 ) (where x and y are natural numbers), LiCl, Lil, LiB (C 2 C> 4 ) 2 (lithium bis (oxalato) borate LiBOB)
  • the concentration of the lithium salt is preferably within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is within the above range, the electrolyte has appropriate conductivity and viscosity It can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the separator separates the negative electrode and the positive electrode and provides a passage for lithium ion.
  • Any separator may be used as long as it is commonly used in a lithium battery. That is, a material having a low resistance against the ion movement of the electrolyte and an excellent ability to impregnate the electrolyte can be used.
  • a material having a low resistance against the ion movement of the electrolyte and an excellent ability to impregnate the electrolyte can be used.
  • selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof and may be nonwoven fabric or woven fabric.
  • a polyolefin-based polymer separator such as polyethylene, polypropylene and the like is mainly used for a lithium ion battery, and a coated separator containing a ceramic component or a polymer substance may be used for heat resistance or mechanical strength, It can be used as a structure.
  • the positive electrode may include a positive electrode collector and a positive electrode mixture layer positioned on the positive electrode collector. 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the anode is prepared by mixing an active material and a binder, and optionally a conductive material, a filler, etc., in a solvent to prepare a slurry-like electrode mixture, and applying the electrode mixture to each electrode current collector.
  • the method of manufacturing the electrode is well known in the art, and therefore, a detailed description thereof will be omitted herein.
  • the positive electrode active material is lithium cobalt oxide (0> 02), Lyrium nickel oxide (Nishi 02) layered compounds or one or more transition compounds substituted with a metal such as; My + ⁇ formula - ⁇ wherein, X is 0 to 0.33), - 110 3,
  • the cathode current collector generally has a thickness of 3-500.
  • a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • Examples of the positive electrode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum or stainless steel A surface treated with carbon, nickel, titanium, silver or the like may be used.
  • the current collector may have fine irregularities on its surface to increase the adhesive force of the cathode active material, and various forms such as a film, a sheet, a foil, a net, a porous substrate, a foam, and a nonwoven fabric are possible.
  • the conductive material is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite, carbon black, acetylene black, ketjen black, Carbon black such as black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride, aluminum and nickel powder, Conductive whiskey such as potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the lithium metal battery of the embodiment can be used not only in a battery cell used as a power source of a small device but also as a unit battery in a middle or large battery module including a plurality of battery cells. Production Example 1
  • a first pore having a relatively small diameter is formed on one surface 120a of the metal plate, and a second pore having a relatively larger diameter than the first pore is formed on the other surface 120b of the metal plate. And a plurality of holes passing through the inside of the metal plate and connecting the first pores and the second pores were manufactured.
  • an electrolytic copper foil having a thickness of 16 _ was used as a metal plate serving as a base material of the anode current collector 120.
  • a first photo-resist layer was uniformly deposited on one side of the electrolytic copper foil.
  • a first photomask (not shown) including a circular opening having a diameter of 81 a photo-mask was attached, followed by irradiation with ultraviolet light (UV) at a dose of 90 to 110 mJ / cm 2 to form a pattern by the first photomask
  • the first photomask is removed, and immersion is performed in a developer composed of NaOH and water (H 2 O) to remove the first photoresist layer having the pattern formed by the first photomask, Thereby removing the photoresist layer present in the portion to be etched.
  • Etching was carried out using Etching solution composed of HNO 3 (3 ⁇ 40) to form pores in the metal by proceeding wet etching.
  • a positive / negative photolithography process can be used to etch and pattern the metal.
  • each of the photomasks includes a circular opening formed at equal intervals on the basis of each pore center point.
  • each of the holes penetrates the inside of the metal plate from the diameter of the first pore, and the diameter gradually increases (the thickness of the electrolytic copper foil / the diameter of the hole per chip is increased by 0.84375) , will have a gradient of the form up to the diameter of the second pores, the porosity is 20 to 30 ⁇ 1%.
  • a lithium metal anode was fabricated using the anode current collector 120 of Production Example 1, except that the first pores (relatively small-diameter pores) of the anode current collector and the lithium metal grease face each other.
  • Example 2 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • a lithium metal battery was fabricated with a structure that faces the second pores (relatively large-diameter pores) and the separator.
  • LiNio .8 Mno Coo .1 .1 O 2 using a conductive material as carbon black, and a binder polyvinylidene fluoride denpul ( ⁇ ), respectively, and the positive electrode active material in the positive electrode active material: conductive material: binder weight ratio of In a mixed solvent of 96: 2: 2 was added to the solvent, to prepare a cathode active material slurry.
  • Width 34 TM, height 51 TM, thickness of 12 TM 3.15 per side of the aluminum housing The anode active material slurry was applied to the anode active material slurry in a loading (1.03 1 ) column, dried and rolled, and then pulverized in a circular shape (diameter: 1.40)
  • electrolytic solution examples include a solvent mixed with ethylene carbonate (3 ⁇ 4), diethyl carbonate (), and dimethyl carbonate (1: 2: 1 by volume) The total amount of 1, 6 and 10% of fluoroethylene
  • a polyethylene separator (thickness: 20 11111 ) was interposed between the lyrium metal anode of Example 1 and the anode of Example 1, and the electrolytic solution was injected thereinto. Then, 12032 coin cells 1) was prepared and obtained as the lyrium metal cell of Example 2.
  • a lithium metal anode was fabricated using the anode current collector 120 of Production Example 1 and having a structure in which the second pores (relatively large-diameter pores) of the anode current collector and the lithium metal foil 110 were opposed to each other.
  • FIG. 5A shows the charge capacity per cycle of the electrons
  • FIG. 5B shows the discharge capacity per cycle of the battery
  • FIG. 5C shows the charge / discharge efficiency of each battery in each cycle.
  • the lower 12 pores (relatively large-diameter pores) of the negative electrode collector (Production Example 1) were opposed to the lithium metal layer and the first pores of the negative electrode collector These small pores are designed to face the membrane.
  • the first pores opposed to the separation membrane can be clogged because lithium ions can not smoothly flow in and out of the lithium metal battery during repeated charging and discharging processes.
  • the second pores (pores having a relatively large diameter) of the negative electrode collector of Preparation Example 1 were opposed to the separator, 2019/125064 1 »(: 1 ⁇ 1 ⁇ 2018/016500
  • the pores are designed to face the lyrium metal layer.
  • the second pore opposed to the separation membrane provides a wide entrance through which lithium ions (specifically, lithium ions derived from electrolyte impregnated in the separation membrane) can easily enter.
  • Lithium ions that enter through such a wide entrance (second pore) are transferred to the lithium metal layer through the phosphorus.
  • holes (1 101 Li provides various directions in which lithium ions can enter and sufficient space to suppress local clogging in repeated charge and discharge processes of lithium metal batteries,
  • FIG. 3 to 5 Refer to, although common to the entire manufacturing example 1 to the negative electrode current collector,
  • the lyrium metal battery (Comparative Example 2) designed such that the first pores (relatively small-diameter pores) of the negative electrode collector face the separation membrane is driven only in the 85th cycle only;
  • FIG. 6A shows the charge capacity per cycle of the battery
  • FIG. 6B shows the discharge capacity per cycle of the battery. 6A and 6B, even if the negative electrode collector of Production Example 1 is commonly used,

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

Abstract

La présente invention concerne une électrode négative pour une batterie lithium-métal et une batterie lithium-métal. Plus particulièrement, un mode de réalisation de la présente invention concerne une électrode négative pour une batterie lithium-métal, qui 1) utilise un collecteur de courant d'électrode négative (120) qui présente des premiers pores dans une surface (120a) d'une plaque métallique, ainsi que des seconds pores, ayant un diamètre plus grand que les premiers pores, dans l'autre surface (120b) de la plaque métallique, et comprend une pluralité de trous traversant l'intérieur de la plaque métallique et reliant les premiers et second pores; et 2) possède une couche lithium-métal (110) formée de manière à faire face aux premiers pores du collecteur de courant d'électrode négative. Un autre mode de réalisation de la présente invention encore concerne une batterie lithium-métal qui utilise l'électrode négative pour une batterie lithium-métal de l'un des modes de réalisation et est conçu pour qu'un séparateur se trouve face aux seconds pores (ayant un diamètre plus grand) du collecteur de courant d'électrode négative.
PCT/KR2018/016500 2017-12-22 2018-12-21 Électrode négative pour batterie lithium-métal et batterie lithium-métal la comprenant WO2019125064A1 (fr)

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EP18891822.1A EP3598546A4 (fr) 2017-12-22 2018-12-21 Électrode négative pour batterie lithium-métal et batterie lithium-métal la comprenant
US16/500,633 US12009522B2 (en) 2017-12-22 2018-12-21 Anode for lithium metal battery and lithium metal battery comprising the same
CN201880019235.1A CN110462902B (zh) 2017-12-22 2018-12-21 用于锂金属电池的阳极和包括该阳极的锂金属电池

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914446A (zh) * 2022-04-26 2022-08-16 中国五洲工程设计集团有限公司 一种复合电极、复合电极的制备方法及电池
CN117276468A (zh) * 2023-11-23 2023-12-22 宁德时代新能源科技股份有限公司 负极极片、电池和用电装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1167217A (ja) * 1997-08-14 1999-03-09 Nippon Foil Mfg Co Ltd 二次電池用孔開き集電体及びその製造方法
JP2013069632A (ja) * 2011-09-26 2013-04-18 Toyota Industries Corp 二次電池又はキャパシタ用の集電体
JP2013182810A (ja) * 2012-03-02 2013-09-12 Tdk Corp 集電体、およびそれを用いたリチウムイオン二次電池
KR20170055993A (ko) * 2014-10-14 2017-05-22 후지필름 가부시키가이샤 알루미늄판 및 알루미늄판의 제조 방법
KR20170101853A (ko) * 2014-07-16 2017-09-06 프로로지움 홀딩 인크. 리튬 금속 전극

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471835B (zh) * 2009-07-07 2014-03-19 东洋铝株式会社 具有贯通孔的铝箔
JP2011216364A (ja) * 2010-03-31 2011-10-27 Toyo Aluminium Kk 負極集電体用金属箔
KR101598650B1 (ko) * 2012-08-23 2016-03-03 주식회사 엘지화학 음극 및 이를 포함하는 고용량 리튬이차전지
CN105018776B (zh) * 2014-04-30 2017-09-29 中国科学院金属研究所 一种多孔铜箔的制备工艺及其应用
JP2016058257A (ja) * 2014-09-10 2016-04-21 三菱マテリアル株式会社 リチウムイオン二次電池用正極及びリチウムイオン二次電池
WO2017094526A1 (fr) * 2015-11-30 2017-06-08 日立マクセル株式会社 Électrode pour éléments électrochimiques, et pile rechargeable lithium-ion
WO2017188021A1 (fr) * 2016-04-26 2017-11-02 日立マクセル株式会社 Électrode d'élément électrochimique et batterie secondaire au lithium-ion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1167217A (ja) * 1997-08-14 1999-03-09 Nippon Foil Mfg Co Ltd 二次電池用孔開き集電体及びその製造方法
JP2013069632A (ja) * 2011-09-26 2013-04-18 Toyota Industries Corp 二次電池又はキャパシタ用の集電体
JP2013182810A (ja) * 2012-03-02 2013-09-12 Tdk Corp 集電体、およびそれを用いたリチウムイオン二次電池
KR20170101853A (ko) * 2014-07-16 2017-09-06 프로로지움 홀딩 인크. 리튬 금속 전극
KR20170055993A (ko) * 2014-10-14 2017-05-22 후지필름 가부시키가이샤 알루미늄판 및 알루미늄판의 제조 방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114914446A (zh) * 2022-04-26 2022-08-16 中国五洲工程设计集团有限公司 一种复合电极、复合电极的制备方法及电池
CN114914446B (zh) * 2022-04-26 2024-06-07 中国五洲工程设计集团有限公司 一种复合电极、复合电极的制备方法及电池
CN117276468A (zh) * 2023-11-23 2023-12-22 宁德时代新能源科技股份有限公司 负极极片、电池和用电装置
CN117276468B (zh) * 2023-11-23 2024-04-12 宁德时代新能源科技股份有限公司 负极极片、电池和用电装置

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