WO2017193778A1 - Électrode au métal lithium et son procédé de préparation, électrode négative secondaire au métal lithium et pile - Google Patents

Électrode au métal lithium et son procédé de préparation, électrode négative secondaire au métal lithium et pile Download PDF

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WO2017193778A1
WO2017193778A1 PCT/CN2017/081106 CN2017081106W WO2017193778A1 WO 2017193778 A1 WO2017193778 A1 WO 2017193778A1 CN 2017081106 W CN2017081106 W CN 2017081106W WO 2017193778 A1 WO2017193778 A1 WO 2017193778A1
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lithium
foam
lithium metal
metal
electrode
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English (en)
Chinese (zh)
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王平华
李慧
夏圣安
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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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
    • H01M4/13—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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy 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 invention relates to the technical field of lithium batteries, in particular to a lithium metal electrode and a preparation method thereof, a lithium metal secondary electrode negative electrode and a battery.
  • a lithium metal secondary battery is a rechargeable lithium battery in which a lithium metal electrode is used as a negative electrode.
  • Lithium metal secondary batteries mainly include lithium metal air batteries and lithium sulfur batteries, depending on the material of the positive electrode.
  • lithium metal Since lithium metal has a very high theoretical specific capacity (3860 mAh/g), a most negative reduction potential (-3.04 V, relative to a hydrogen standard potential), and a very small density (0.59 g/cm 3 ), lithium metal is secondary The energy density of the battery is much greater than other battery systems (for example, the theoretical energy density of a lithium metal air battery can reach 11140 Wh/kg, and the theoretical energy density of a lithium sulfur battery can reach 2680 Wh/kg).
  • the lithium metal electrode currently used for a lithium metal secondary battery mainly uses a sheet metal lithium or a form in which metal lithium particles are coated on a sheet electrode substrate.
  • the inventors have found that at least the following problems exist in the prior art: the existing lithium metal electrode for a lithium metal secondary battery may undergo volume expansion during charge and discharge, affecting the lithium metal secondary battery. Stability and cycle performance; at the same time, during long-term charge and discharge, lithium will deposit on the surface of the negative electrode to form lithium dendrites. When the lithium dendrite grows to penetrate the separator of the lithium metal secondary battery, it will cause a short circuit and cause an explosion. .
  • embodiments of the present invention provide a lithium metal electrode having a small volume change and a small amount of dendrite generation during charge and discharge, a preparation method thereof, a lithium metal secondary electrode negative electrode, and a battery.
  • a lithium metal electrode comprising: a foam electrode substrate having a plurality of cell cavities; and metal lithium particles distributed in at least one cell cavity of the foam electrode substrate; the foam electrode substrate
  • the material is a foam metal material or a carbon foam material.
  • the electrode substrate is a foam electrode substrate having a plurality of pore cavity structures, and the metal lithium particles are distributed in at least one pore cavity of the foam electrode substrate.
  • the pore cavity of the foam electrode substrate can effectively limit the volume expansion of the metal lithium particles during charge and discharge, thereby effectively improving the stability and cycle performance of the lithium metal secondary battery using the lithium metal electrode as a negative electrode.
  • the pore cavity of the foam electrode substrate can effectively increase the surface area of the lithium metal electrode, which not only greatly improves the high current fast charging capability of the lithium metal secondary battery using the lithium metal electrode as the negative electrode, but also effectively reduces lithium.
  • the formation of dendrites avoids battery short-circuit problems caused by lithium dendrites piercing the diaphragm, improving Safety performance of lithium metal secondary batteries.
  • the metal lithium particles may be distributed in more than 20% of the plurality of pore cavities.
  • Metal lithium particles may be distributed in the plurality of pore cavities of 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more.
  • the metal lithium particles are also distributed in regions other than the plurality of cell cavities on the foam electrode substrate due to limitations in the preparation process conditions.
  • the number of the metallic lithium particles distributed in the pore cavity of the foam electrode substrate is greater than the number of the metallic lithium particles distributed in a region other than the plurality of pore cavities; or
  • the density of the metallic lithium particles in the pore cavity of the foam electrode substrate is greater than the density of the metallic lithium particles distributed in a region other than the plurality of pore cavities.
  • the present invention is ensured by controlling the relationship between the number and density of metallic lithium particles distributed in the pore cavity of the foam electrode substrate and the number and density of metallic lithium particles distributed in regions other than the plurality of pore cavities.
  • the performance of the lithium metal electrode provided by the examples.
  • the pore cavity of the foam electrode substrate may have a diameter of from 100 nanometers to 50 micrometers. If the diameter of the pore cavity of the foam electrode substrate is too small, the metallic lithium particles do not easily enter the pore cavity, thereby increasing the difficulty in preparing the lithium metal electrode of the present embodiment. If the diameter of the pore cavity of the foam electrode substrate is too large, the number of pore cavities of the foam electrode substrate may be reduced in the case where the size of the lithium metal electrode is constant, and the volume expansion of the metal lithium particles is not good. Limiting the effect, thereby affecting the performance of the lithium metal electrode.
  • the metal lithium particles are prevented from reacting with the external atmosphere
  • the lithium metal electrode further includes: a protective layer coated on the surface of the metallic lithium particles.
  • the material of the protective layer is a lithium ion good conductor material.
  • the material of the protective layer may be selected from the group consisting of Li 2 CO 3 , Li 4 SiO 4 , LiF, Li 3 PO 3 , TiO 2 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , SiO 2 , SnO 2 , SiC. At least one of LiAlO 2 , Al 2 O 3 , NiS, CuS, FeS, MnS, Ag 2 S, and TiS 2 .
  • the metal foam material is selected from at least one of foamed nickel, copper foam, titanium foam, and foamed iron.
  • the carbon foam material is selected from at least one of foamed carbon, foamed carbon nanotubes, and foamed graphene.
  • the graphene used in the foam graphene is at least one selected from the group consisting of graphene oxide, reduced graphene, and element-doped graphene.
  • the graphene oxide may be at least one of a covalent bond functionalized graphene and a non-covalently bonded functional graphene.
  • the element doped in the element doped graphene is at least one selected from the group consisting of nitrogen, sulfur, and phosphorus. It should be noted that the use of the element doped graphene is more advantageous for improving the fast charging capability of the lithium metal secondary battery using the lithium metal electrode provided by the embodiment of the present invention as a negative electrode.
  • a method for preparing a lithium metal electrode comprising:
  • the material of the foam electrode substrate is a foam metal material or a carbon foam material.
  • the electrode substrate is a foam electrode substrate having a plurality of pore cavity structures, and the metal lithium particles are distributed in at least one pore cavity of the foam electrode substrate.
  • the pore cavity of the foam electrode substrate can effectively limit the volume expansion of the metal lithium particles during charge and discharge, and inhibit the growth of lithium dendrites, thereby effectively improving the lithium metal electrode prepared by the preparation method of the embodiment of the present invention as a negative electrode. Lithium metal Secondary battery stability, cycle performance, fast charging capability and safety performance.
  • more than 20% of the plurality of pore cavities may be distributed with metallic lithium particles. It is also possible that 50%, 60%, 70% or more of the plurality of pore cavities are distributed with metallic lithium particles.
  • the metallic lithium particles may be coated by vapor deposition.
  • the metal lithium particles can be uniformly applied to the pore cavity of the foam electrode substrate by vapor deposition.
  • the vapor deposition method may specifically be a vacuum evaporation method; the vacuum evaporation is performed by fixing the foam electrode substrate directly above the metal lithium particle evaporation source, under a pressure of 1 ⁇ 10 ⁇ 2 Pa or less,
  • the metal lithium particle evaporation source is bombarded with an electron beam having a current of 50 to 500 mA and a voltage of 3 to 12 kV, and the bombardment time is 5 to 50 minutes, and the foam electrode substrate and the metal lithium particle evaporation source are The distance is 30 to 150 cm.
  • the distribution of the metallic lithium particles obtained by the above vacuum evaporation conditions is more uniform, which is advantageous for improving the performance of the obtained lithium metal electrode.
  • the metal lithium particles are prevented from reacting with the external atmosphere, and the preparation method further includes: the metal lithium particles The surface is coated with a protective layer; the material of the protective layer is a lithium ion good conductor material.
  • the material of the protective layer is selected from the group consisting of Li 2 CO 3 , Li 4 SiO 4 , LiF, Li 3 PO 3 , TiO 2 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , SiO 2 , SnO 2 , SiC, At least one of LiAlO 2 , Al 2 O 3 , NiS, CuS, FeS, MnS, Ag 2 S, and TiS 2 .
  • the metal foam material is selected from at least one of foamed nickel, copper foam, titanium foam, and foamed iron.
  • the carbon foam material is selected from at least one of foamed carbon, foamed carbon nanotubes, and foamed graphene.
  • the graphene used in the foam graphene is at least one selected from the group consisting of graphene oxide, reduced graphene, and element-doped graphene.
  • the graphene oxide is selected from at least one of a covalently bonded functional graphene and a non-covalently bonded functional graphene.
  • the element doped in the element doped graphene is at least one selected from the group consisting of nitrogen, sulfur, and phosphorus.
  • the protective layer may be coated on the surface of the metallic lithium particles by vapor deposition.
  • the protective layer can be uniformly applied to the surface of the metallic lithium particles by vapor deposition.
  • a lithium metal secondary battery anode comprising: at least one lithium metal electrode according to the first aspect.
  • the pore cavity of the foam electrode substrate can effectively limit the volume expansion of the metal lithium particles during charging and discharging and inhibit the formation of lithium dendrites, thereby, the lithium metal
  • the electrode can effectively improve the stability performance, cycle performance, high current fast charging capability, and safety performance of the lithium metal secondary battery.
  • the lithium metal secondary battery negative electrode when the lithium metal secondary battery negative electrode includes a plurality of the lithium metal electrodes, the lithium metal secondary battery negative electrode is used to facilitate the use of the lithium metal secondary battery negative electrode. Also included is a substrate for supporting the lithium metal electrode. A plurality of the lithium metal electrodes may be disposed on the substrate in an array.
  • a lithium metal secondary battery comprising: an outer casing, an electrolyte, a positive electrode, a negative electrode, and a separator, wherein the negative electrode is the lithium metal secondary battery negative electrode according to the third aspect.
  • the metal lithium particles are distributed in the cavity cavity of the foam electrode substrate, and the cavity cavity of the foam electrode substrate can limit the volume expansion of the lithium metal particles and inhibit lithium.
  • the growth of dendrites, therefore, the lithium metal secondary battery using the lithium metal secondary battery negative electrode as a negative electrode has good stability, cycle performance, high current fast charging capability, and safety performance.
  • the lithium metal secondary battery is a lithium metal air battery or a lithium sulfur battery.
  • FIG. 1 is a schematic structural view of a lithium metal electrode provided in Embodiment 1;
  • FIG. 2 is a schematic structural view of another lithium metal electrode provided in Embodiment 1;
  • FIG. 3 is a schematic view showing a cross section of a foam electrode substrate in a lithium metal electrode according to Embodiment 1;
  • Figure 3-1 is a schematic view of a rectangular cross section
  • Figure 3-2 is a schematic view of a square cross section
  • Figure 3-3 is a schematic view of a circular cross section
  • Figure 3-4 is a schematic view of a cross section of a C-shape
  • FIG. 5 is a schematic flow chart of a method for preparing a lithium metal electrode according to Embodiment 2;
  • FIG. 6 is a scanning electron micrograph of a method for preparing a lithium metal electrode according to Embodiment 2;
  • FIG. 7 is a schematic diagram of a method for preparing a foam-reduced graphene in the second embodiment
  • FIG. 8 is a schematic structural view of a lithium metal secondary battery negative electrode provided in Embodiment 3.
  • FIG. 9 is a schematic structural view of another lithium metal secondary battery negative electrode provided in the third embodiment.
  • reference numeral 100 in the drawing denotes a lithium metal electrode
  • 1 denotes a foam electrode substrate
  • 11 denotes a pore cavity
  • 2 denotes metallic lithium particles
  • 300 denotes a lithium metal secondary battery negative electrode
  • 3 denotes a substrate.
  • the present embodiment provides a lithium metal electrode 100 comprising: a foam electrode substrate 1 having a plurality of cell cavities 11, and at least one cell cavity 11 distributed in the foam electrode substrate 1.
  • the material of the foam electrode substrate 1 is a foam metal material or a carbon foam material.
  • the metal foam material and the carbon foam material are three-dimensional materials having a plurality of pore cavity structures.
  • the metal metal particles 2 are distributed in the at least one cell cavity 11 of the foam electrode substrate 1 by using a metal foam material or a carbon foam material as an electrode substrate of the lithium metal electrode, and the cell cavity 11 of the foam electrode substrate 1
  • the volume expansion of the metallic lithium particles 2 during charge and discharge can be effectively limited, thereby effectively improving the stability and cycle performance of the lithium metal secondary battery using the lithium metal electrode 100 as a negative electrode.
  • the cavity cavity 11 of the foam electrode substrate 1 can effectively increase the surface area of the lithium metal electrode 100, which not only greatly improves the high current fast charging capability of the lithium metal secondary battery using the lithium metal electrode as a negative electrode, but also effectively The formation of lithium dendrites is reduced, the short circuit of the battery due to the penetration of the lithium dendrites into the separator is avoided, and the safety performance of the lithium metal secondary battery is improved.
  • the percentage of the channel cavity in which the metal lithium particles are distributed should be controlled.
  • more than 20% of the channel cavity 11 is distributed with metallic lithium particles.
  • 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, More than 70%, more than 75%, more than 80%, more than 85%, more than 90%, more than 95%, and 100% of the pores are distributed with metallic lithium particles.
  • metal lithium particles 2 are all distributed in the cell cavity 11 of the foam electrode substrate 1, as shown in FIG. 2, a plurality of holes on the foam electrode substrate 1 are empty. Metal lithium particles 2 may also be distributed in a region other than the cavity 11, such as the surface of the foam electrode substrate.
  • the region other than the cell cavity 11 is not capable of restricting the volume expansion of the metallic lithium particles 2, nor inhibiting the formation of lithium dendrites, and therefore, in order to secure the performance of the lithium metal electrode 100 of the present embodiment, on the foam electrode substrate 1
  • metal lithium particles 2 are also distributed in a region other than the plurality of cell cavities 11, optionally, the number of metal lithium particles distributed in the cell cavity 11 of the foam electrode substrate 1 is larger than that distributed in a plurality of cell cavities
  • the number of metallic lithium particles 2 in the region other than 11 or the density of metallic lithium particles distributed in the pore cavity of the foam electrode substrate is larger than the density of metallic lithium particles distributed in regions other than the plurality of pore cavities.
  • the number of metallic lithium particles 2 distributed in the pore cavity 11 of the foam electrode substrate 1 is larger than the number of metallic lithium particles 2 distributed in a region other than the plurality of pore cavities 11, and is distributed in the foam electrode substrate.
  • the density of the metallic lithium particles 2 in the pore cavity 1 is also greater than the density of the metallic lithium particles 2 distributed in the regions other than the plurality of pore cavities 11.
  • the diameter of the cavity 11 of the foam electrode substrate 1 may be 100 nm to 50 ⁇ m, for example, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700. Nano, 800 nm, 900 nm, 1 micron, 5 micron, 10 micron, 15 micron, 20 micron, 25 micron, 30 micron, 35 micron, 40 micron, 45 micron, etc. If the diameter of the cell cavity 11 of the foam electrode substrate 1 is too small, the metal lithium particles 2 do not easily enter the cell cavity 11, thereby increasing the difficulty in preparation of the lithium metal electrode 100 of the present embodiment.
  • the number of the cell cavities 11 of the foam electrode substrate 1 may be reduced in the case where the size of the lithium metal electrode 100 is constant, and the volume expansion of the metal lithium particles 2 cannot be performed. To a very good limiting effect, thus affecting the performance of lithium metal electrodes.
  • the metal lithium particles 2 may be nano metal lithium particles having a diameter of 100 nm or less, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 in diameter.
  • the use of nano metallic lithium particles can increase the capacity, rapid charging performance, and cycle performance in a high temperature environment of a lithium metal secondary battery.
  • the shape of the cross section of the foam electrode substrate 1 is not strictly limited, and any conventional means in the art, such as a rectangle (as shown in FIG. 3-1), a square (such as Figure 3-2 shows a circle, as shown in Figure 3-3, and a C-shape (as shown in Figure 3-4).
  • the metal lithium particles 2 are prevented from reacting with the external atmosphere, and the surface of the metallic lithium particles 2 may be coated with a protective layer ( Not shown in the figure).
  • the material of the protective layer is a good lithium ion conductor material, and the lithium ion good conductor material has a good lithium ion conduction effect, and the metal lithium particle is prevented from reacting with the external atmosphere while ensuring the reactivity of the metal lithium particle, thereby ensuring
  • the lithium metal electrode 100 provided in this embodiment functions as a lithium metal secondary battery of a negative electrode.
  • the material of the protective layer may be Li 2 CO 3 , Li 4 SiO 4 , LiF, Li 3 PO 3 , TiO 2 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , SiO 2 , SnO 2 , SiC, LiAlO 2 . At least one of Al 2 O 3 , NiS, CuS, FeS, MnS, Ag 2 S, and TiS 2 .
  • the material of the foam electrode substrate 1 may be selected from materials that are not intercalated with lithium.
  • the metal foam material may be foamed nickel, copper foam, titanium foam or foamed iron, and a metal foam material may be used alone or in combination with a plurality of foam metal materials.
  • the carbon foam material can be foamed carbon, Foamed carbon nanotubes or foamed graphene can be used alone or in combination with a variety of carbon foam materials.
  • foamed graphene is a three-dimensional material having a skeleton structure and a pore cavity structure formed by stacking graphene sheets. Compared with other metal foam materials and carbon foam materials, foamed graphene has higher strength and superior electrical properties. Therefore, in the present embodiment, the foam electrode substrate is preferably made of foamed graphene.
  • the distribution of metallic lithium particles 2 in the pore cavity 11 of the foamed graphene is shown in Fig. 4, and the metallic lithium particles 2 are uniformly distributed in the pore cavity 11 of the foamed graphene.
  • the graphene used for the foamed graphene may be at least one of graphene oxide, reduced graphene, and element-doped graphene.
  • the graphene oxide may be at least one of a covalent bond functionalized graphene and a non-covalently bonded functional graphene; the element doped with the element doped graphene may be at least one of nitrogen, sulfur, and phosphorus.
  • the element doping changes the molecular structure of the graphene, the lithium metal negative electrode which is doped with elemental doped graphene as the material of the foam electrode substrate 1 has a physical and chemical double lithium storage function, and thus element-doped graphite is used.
  • the olefin is more advantageous for improving the rapid charging ability of the lithium metal secondary battery using the lithium metal electrode provided in the present embodiment as a negative electrode.
  • This embodiment provides a method for preparing a lithium metal electrode.
  • the preparation method includes the following steps:
  • step 201 a foam electrode substrate having a plurality of cell cavities is prepared.
  • Step 202 coating metal lithium particles in at least one of the cavity cavities of the foam electrode substrate; wherein the material of the foam electrode substrate is a foam metal material or a carbon foam material.
  • the electrode substrate is a foam electrode substrate having a plurality of pore cavity structures, and the metal lithium particles are distributed in at least one pore cavity of the foam electrode substrate.
  • the pore cavity of the foam electrode substrate can effectively limit the volume expansion of the metal lithium particles during charge and discharge, thereby effectively improving the stability of the lithium metal secondary battery using the lithium metal electrode prepared by the preparation method of the present embodiment as a negative electrode. Cycle performance.
  • the pore cavity of the foam electrode substrate can effectively increase the surface area of the lithium metal electrode, which not only greatly improves the high current fast charging capability of the lithium metal secondary battery using the lithium metal electrode as the negative electrode, but also effectively reduces lithium.
  • the formation of dendrites avoids the short circuit of the battery caused by the lithium dendrite piercing the separator, and improves the safety performance of the lithium metal secondary battery.
  • the coating conditions should be controlled to control the percentage of the pore cavity in which the metal lithium particles are distributed to a certain value, for example, more than 20% of the pore cavity 11 can be made.
  • metallic lithium particles distributed therein, or 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, and 75%.
  • 80% or more, 85% or more, 90% or more, 95% or more, and 100% of the pores are distributed with metal lithium particles.
  • metallic lithium particles may be applied to regions other than the plurality of cell cavities on the foam electrode substrate.
  • the region other than the pore cavity cannot restrict the volume expansion of the metallic lithium particles and the formation of lithium dendrites cannot be suppressed, in order to ensure the performance of the lithium metal electrode prepared in the present embodiment, the coating of the metallic lithium particles is completed. Thereafter, the metallic lithium particles in all or part of the region other than the plurality of pore cavities coated on the foam electrode substrate can be removed, so that the amount of metallic lithium particles coated in the pore cavity of the foam electrode substrate is larger than that of the coating.
  • the number of metallic lithium particles in a region other than the plurality of pore cavities, or the density of metallic lithium particles coated in the pore cavity of the foam electrode substrate is greater than that coated in a region other than the plurality of pore cavities Density of metallic lithium particles, or coating
  • the amount and density of metallic lithium particles overlying the pore cavity of the foam electrode substrate are greater than the metallic lithium particles coated in regions other than the plurality of pore cavities.
  • the metal lithium particles in the regions other than the plurality of cell cavities coated on the foam electrode substrate can be removed by a gas purge.
  • the coating method of the metal lithium particles is not particularly limited in this embodiment, and a method of coating metal lithium particles commonly used in the art may be, for example, a vapor deposition method.
  • the vapor deposition method may specifically be a physical vapor deposition method, and more specifically, may be a vacuum evaporation method.
  • the specific conditions of the vacuum evaporation are not particularly limited in the embodiment, and the conventional technical means in the field may be used.
  • the thickness of the metallic lithium particle coating can be controlled by controlling the time of vacuum evaporation.
  • an optional condition for coating the lithium metal particles by vacuum evaporation is: fixing the foam electrode substrate directly above the evaporation source of the metal lithium particles, below 1 ⁇ 10 ⁇ 2 Pa Under pressure, the metal lithium particle evaporation source is bombarded with an electron beam with a current of 50-500 mA and a voltage of 3-12 kV. The bombardment time is 5 to 50 minutes, and the distance between the foam electrode substrate and the metal lithium particle evaporation source is 30. ⁇ 150 cm.
  • Another optional condition for coating lithium metal particles by vacuum evaporation is that the metal lithium particles are placed in a crucible of a vacuum evaporation apparatus as an evaporation source, and the foam electrode substrate is horizontally fixed directly above the evaporation source and evaporated. Source 80 cm position. Then, vacuum treatment is performed. When the pressure drops to 1 ⁇ 10 ⁇ 3 Pa, the pressure is stabilized and the electron beam bombards the evaporation source lithium metal particles to start evaporation, wherein the electron beam voltage is 7.5 kV and the current is 70. mA, the evaporation time is 20 minutes. After the vapor deposition is completed, it is naturally cooled in a vacuum state, and the furnace is vented to complete the coating of the metallic lithium particles.
  • the distribution of the metallic lithium particles obtained by the above vacuum evaporation conditions is more uniform, which is advantageous for improving the performance of the obtained lithium metal electrode.
  • the preparation method provided in this embodiment may further include: step 203,
  • the surface of the metallic lithium particles is coated with a protective layer, wherein the material of the protective layer is a lithium ion good conductor material.
  • the lithium ion good conductor material has a good lithium ion conduction effect, and ensures the reactivity of the metal lithium particles while avoiding the contact of the metallic lithium particles with the external atmosphere, thereby ensuring the lithium metal electrode prepared by the preparation method provided by the embodiment.
  • the material of the protective layer may be Li 2 CO 3 , Li 4 SiO 4 , LiF, Li 3 PO 3 , TiO 2 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , SiO 2 , SnO 2 , SiC, LiAlO 2 . At least one of Al 2 O 3 , NiS, CuS, FeS, MnS, Ag 2 S, and TiS 2 .
  • the method of applying the protective layer is not particularly limited in this embodiment, and any conventional means in the art, such as a vapor deposition method.
  • the vapor deposition method may specifically be a physical vapor deposition method, and more specifically, may be a vacuum evaporation method.
  • an optional vacuum evaporation coating is used to place the LiF particles in a crucible of a vacuum evaporation apparatus as an evaporation source to level the foam electrode substrate coated with metallic lithium particles. It is fixed directly above the evaporation source and 30 to 150 cm away from the evaporation source; then vacuum treatment is performed, and when the pressure drops below 1 ⁇ 10 -2 Pa, the electron beam bombardment of the evaporation source LiF particles is started, and evaporation is started.
  • the electron beam voltage is 3 to 12 kV
  • the current is 50 to 500 mA
  • the evaporation time is 5 to 50 minutes.
  • LiF particles are placed in a crucible of a vacuum evaporation apparatus as an evaporation source, and a metal electrode coated with a lithium metal particle is used.
  • the horizontal position was fixed directly above the evaporation source and 80 cm away from the evaporation source; then vacuum treatment was performed, and when the pressure was lowered to 1 ⁇ 10 -3 Pa, the electron beam bombardment of the evaporation source LiF particles was started, and evaporation was started.
  • the electron beam voltage was 7.5 kV
  • the current was 70 mA
  • the evaporation time was 5 minutes. After the vapor deposition is completed, it is naturally cooled in a vacuum state, and ventilated to obtain a lithium metal electrode coated with a protective layer.
  • the preparation of the foam electrode substrate having a plurality of cell cavities in step 201 specifically includes preparing a foam electrode substrate, and the requirements of the lithium metal electrode on the lithium metal electrode to the foam electrode substrate The dimensions are tailored and the steps of removing impurities from the foam electrode substrate.
  • the step of preparing the foam electrode substrate can be omitted. Wherein, removing the impurities on the foam electrode substrate can make the metal lithium particles adhere more closely to the foam electrode substrate, and the impurities on the foam electrode substrate can be removed by ion beam bombardment.
  • An optional ion beam bombardment condition is: bombarding the foam electrode substrate with an ion beam having a voltage of 150-300 volts and a current of 0.1-0.5 amps under a vacuum pressure of 0.1 to 10 Pa, and the bombardment time is 1-20. minute.
  • Another optional ion beam bombardment condition is to bombard the foam electrode substrate with an ion beam of 200 volts and a current of 0.2 amps at a vacuum pressure of 5 Pa, with a bombardment time of 5 minutes.
  • the material of the foam electrode substrate may be selected from materials that are not intercalated with lithium.
  • the metal foam material may be foamed nickel, copper foam, titanium foam or foamed iron, and a metal foam material may be used alone or in combination with a plurality of foam metal materials.
  • the carbon foam material may be foamed carbon, foamed carbon nanotubes or foamed graphene, and a carbon foam material may be used alone or in combination with a plurality of carbon foam materials.
  • the graphene used for the foamed graphene may be at least one of graphene oxide, reduced graphene, and element-doped graphene.
  • the graphene oxide may be at least one of a covalently bonded functionalized graphene and a non-covalently bonded functional graphene; the element doped with the elemental doped graphene may be at least one of nitrogen, sulfur, and phosphorus.
  • foamed metal materials such as foamed nickel, copper foam, titanium foam, and foamed iron may be directly purchased or may be prepared by depositing a metal on an organic foam material using an organic foam material such as a polyurethane foam as a template. The organic foam material is then removed by heat decomposition or dissolution of an organic solvent to obtain a foamed metal material.
  • the above foamed carbon can be produced by depositing carbon on an organic foam material such as a polyurethane foam, and then removing the organic foam material by heat decomposition or organic dissolution.
  • Foam graphene can be obtained by freeze-drying graphene, freeze-drying graphene, or depositing graphene on metal foam by using a metal foam material such as foamed nickel as a template, and then removing the metal foam material. The method is obtained.
  • the foam-reduced graphene and the foam-doped graphene can be obtained by reducing or elementally doping the foamed graphene oxide.
  • an optional method for preparing foam-reduced graphene is as foam nickel (a foam having a density of 420-440 g/cm 3 and a thickness of 1.6 mm-2.0 mm can be used).
  • Nickel a foam having a density of 420-440 g/cm 3 and a thickness of 1.6 mm-2.0 mm can be used.
  • Nickel As a template, the nickel foam is placed in a quartz vacuum high-temperature tube sintering furnace, heated to 800-1200 ° C under a protective gas atmosphere and held for 30-60 min, and then methane gas, methane gas is continuously introduced into the sintering furnace.
  • the introduction time was 8 to 12 minutes, and the above sintering furnace was rapidly cooled to room temperature at a rate of 80 to 100 ° C / min to obtain foamed nickel coated with graphene oxide.
  • the obtained nickel oxide coated with graphene oxide is immersed in a mixed solution of polymethyl methacrylate (PMMA) and ethyl lactate having a mass fraction of 3% to 5% for 5 to 10 minutes to reduce the graphene oxide, and then It is naturally dried at room temperature, and then incubated at a temperature of 150 to 200 ° C for 0.5 to 1 h to obtain a reduced graphene-coated foamed nickel coated with PMMA.
  • PMMA polymethyl methacrylate
  • ethyl lactate having a mass fraction of 3% to 5% for 5 to 10 minutes to reduce the graphene oxide
  • the reduced graphene-encapsulated foamed nickel coated with PMMA is placed in a dilute hydrochloric acid solution having a concentration of 3 to 4 mol/L, and magnetically stirred for 4 to 8 hours to completely etch nickel foam by hydrochloric acid to obtain a nickel-removed nickel.
  • Template of PMMA coated foam to reduce graphene is immersed in an acetone solution at 55-65 ° C for 1 to 2 hours to remove PMMA, and the foam-reduced graphene from which PMMA is removed is obtained, washed in deionized water, freeze-dried, The heat treatment gives a pure foam-reduced graphene.
  • foam-reduced graphene as an example, referring to FIG. 7, another optional method for preparing foam-reduced graphene is: using foamed nickel as a template, and placing the nickel foam in a quartz vacuum high-temperature tube sintering furnace in a protective gas The temperature was raised to 1000 ° C in the atmosphere and kept for 60 min, then methane gas was continuously introduced into the above sintering furnace, the methane gas was introduced for 10 min, and the sintering furnace was rapidly cooled to room temperature at a rate of 80 ° C / min to obtain oxidized.
  • Graphene coated foamed nickel is: using foamed nickel as a template, and placing the nickel foam in a quartz vacuum high-temperature tube sintering furnace in a protective gas The temperature was raised to 1000 ° C in the atmosphere and kept for 60 min, then methane gas was continuously introduced into the above sintering furnace, the methane gas was introduced for 10 min, and the sintering furnace was rapidly cooled to room
  • the obtained nickel oxide coated with graphene oxide is immersed in a mixed solution of polymethyl methacrylate (PMMA) and ethyl lactate having a mass fraction of 3% to 5% for 10 minutes to reduce graphene oxide and then at room temperature. It is naturally dried and then kept at a temperature of 200 ° C for 1 h to obtain a reduced graphene-encapsulated foamed nickel coated with PMMA.
  • PMMA polymethyl methacrylate
  • ethyl lactate having a mass fraction of 3% to 5% for 10 minutes to reduce graphene oxide and then at room temperature. It is naturally dried and then kept at a temperature of 200 ° C for 1 h to obtain a reduced graphene-encapsulated foamed nickel coated with PMMA.
  • the obtained surface-coated PMMA-reduced graphene-encapsulated foamed nickel was placed in a dilute hydrochloric acid solution having a concentration of 4 mol/L, and magnetically stirred for 8 hours to completely etch the nickel foam
  • the coated foam reduces graphene.
  • the obtained PMMA-coated foam-reduced graphene is immersed in an acetone solution at 60 ° C for 2 hours to remove PMMA, thereby obtaining PMMA-removed foam-reduced graphene, which is purified by deionized water washing, freeze-drying, and heat treatment.
  • the foam reduces graphene.
  • the foamed reduced graphene prepared by the above method has a uniform cavity distribution and a moderate cavity diameter, which is favorable for improving the performance of the finally obtained lithium metal electrode.
  • the present embodiment provides a lithium metal secondary battery negative electrode 300, which includes at least one lithium metal electrode 100 provided by any of the above embodiments. .
  • the cell cavity 11 of the foam electrode substrate 1 can effectively limit the volume expansion of the lithium metal particles 2 during charge and discharge and increase the surface area of the lithium metal electrode, reducing the lithium dendrites.
  • the battery is short-circuited due to the lithium dendrite piercing the separator. Therefore, the lithium metal electrode 100 can be used as the negative electrode of the lithium metal secondary battery, thereby effectively improving the stability, cycle performance, and largeness of the lithium metal secondary battery. Fast current charging capability and safety performance.
  • the number of the lithium metal electrodes 100 should be based on the size of the lithium metal electrode 100, the capacity of the lithium metal electrode 100, the size of the lithium metal secondary battery negative electrode 300, and lithium.
  • the capacity requirement of the metal secondary battery 300 is determined.
  • the lithium metal electrode 100 can be directly used as a lithium metal secondary battery negative electrode.
  • the lithium metal secondary battery negative electrode 300 includes a plurality of lithium metal electrodes 100, for example, two, four, five, six, eight, ten, fifteen, etc., in order to facilitate the lithium metal secondary battery negative electrode 300
  • the lithium metal secondary battery negative electrode may further include: a substrate 3 for supporting a lithium metal electrode.
  • the material of the substrate 3 may be a current collector material commonly used in the art, such as copper foil, nickel foil, or the like.
  • the lithium metal electrode 100 can be made into a preform of a certain size and a certain capacity. In use, a certain amount of the lithium metal electrode 100 is loaded onto the substrate 3 according to the requirements of the negative electrode of the lithium metal secondary battery to obtain a lithium metal twice. Battery negative electrode 300.
  • the arrangement of the plurality of lithium metal electrodes 100 on the substrate is not particularly limited, and may be arranged irregularly or according to a certain degree.
  • a plurality of lithium metal electrodes 100 are disposed on the substrate 3 in an array form, and the fabrication of the lithium metal secondary battery negative electrode 300 is facilitated by an array.
  • FIG. 9 shows a lithium metal secondary battery negative electrode 300 including six lithium metal electrodes 100, which are arranged on the substrate 3 in the form of a 3 ⁇ 2 (length ⁇ width) array.
  • the present embodiment provides a lithium metal secondary battery comprising: a casing, an electrolyte, a positive electrode, a negative electrode, and a separator, wherein the negative electrode is the lithium metal secondary battery negative electrode provided in the third embodiment.
  • the metal lithium particles are distributed in the pore cavity of the foam electrode substrate, and the pore cavity of the foam electrode substrate can limit the volume expansion of the lithium metal particles and inhibit the growth of lithium dendrites. Therefore, the lithium metal secondary battery using the lithium metal secondary battery negative electrode as a negative electrode has good stability, cycle performance, high current fast charging capability, and safety performance.
  • the lithium metal secondary battery provided in this embodiment may be any battery conventionally using metal lithium as a negative electrode, including but not limited to a lithium metal air battery and a lithium sulfur battery.
  • the method for preparing a lithium metal secondary battery by using the lithium metal secondary battery negative electrode provided in the third embodiment mainly includes the negative electrode of the lithium metal secondary battery provided in the third embodiment, the positive electrode of the lithium metal secondary battery, the separator, the electrolyte, the outer casing, and the like.
  • the steps of assembling, sealing, and pre-charging the components are the same as the conventional methods for preparing lithium metal secondary batteries in the art, and are not described herein again.
  • the embodiment of the present invention utilizes the feature that the foam electrode substrate has a cavity cavity, and provides a lithium metal electrode using the foam electrode substrate as an electrode substrate.
  • the pore cavity of the foam electrode substrate can effectively limit the volume expansion of the metal lithium particles distributed therein, and effectively inhibit the growth of lithium dendrites, and therefore, the lithium metal secondary battery using the lithium metal electrode as the negative electrode has good stability performance. , cycle performance, high current fast charging capability and safety performance.
  • the surface of the metal lithium particles in the lithium metal electrode provided by the embodiment of the invention is further coated with a protective layer formed of a good lithium ion conductor material, and the metal lithium particles are prevented from being in contact with the external atmosphere while ensuring the reactivity of the metal lithium particles.
  • the lithium metal electrode provided by the embodiment of the invention is applicable to various lithium metal secondary batteries using a metal lithium as a negative electrode, and the lithium metal electrode provided by the embodiment of the invention has a simple preparation method, low cost and wide application range.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention relève du domaine technique des piles au lithium et concerne une électrode au métal lithium et un procédé de préparation associé, une électrode négative secondaire au métal lithium et une pile. Une électrode au métal lithium (100) comprend : un élément de base d'électrode en mousse (1) ayant une pluralité de cavités de canal (11), et des particules de métal lithium (2) réparties à l'intérieur d'au moins une cavité des cavités de canal (11) de l'élément de base d'électrode en mousse (1). Le matériau de l'élément de base d'électrode en mousse (1) est un matériau en mousse métallique ou un matériau en mousse de carbone. Les cavités de canal (11) de l'élément de base d'électrode en mousse (1) peuvent limiter efficacement l'expansion volumique des particules de métal lithium (2) pendant un processus de charge/décharge et réduire la croissance de dendrites de lithium, améliorant ainsi efficacement les propriétés de stabilité, de cyclicité, de charge rapide et de sécurité d'une pile rechargeable au métal lithium disposant de l'électrode en métal lithium (100) en tant qu'électrode négative.
PCT/CN2017/081106 2016-05-12 2017-04-19 Électrode au métal lithium et son procédé de préparation, électrode négative secondaire au métal lithium et pile Ceased WO2017193778A1 (fr)

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