WO2021103523A1 - Composition for anode, and protective film, anode, and device comprising same - Google Patents

Composition for anode, and protective film, anode, and device comprising same Download PDF

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Publication number
WO2021103523A1
WO2021103523A1 PCT/CN2020/098881 CN2020098881W WO2021103523A1 WO 2021103523 A1 WO2021103523 A1 WO 2021103523A1 CN 2020098881 W CN2020098881 W CN 2020098881W WO 2021103523 A1 WO2021103523 A1 WO 2021103523A1
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lithium
protective film
anode
lithium metal
present application
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PCT/CN2020/098881
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English (en)
French (fr)
Inventor
Maohua Chen
Daguang Li
Yuansen Xie
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Ningde Amperex Technology Limited
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Priority to JP2021517839A priority Critical patent/JP7177921B2/ja
Priority to EP20894239.1A priority patent/EP3948991A4/en
Publication of WO2021103523A1 publication Critical patent/WO2021103523A1/en

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 application relates to a composition used in the technical field of energy storage technologies, and a protective film comprising the composition. Particularly, the present application relates to a composition for preparing a protective film for a lithium metal anode and a protective film prepared therefrom. Further, the present application also relates to an electrochemical device and an electronic device comprising the lithium metal anode.
  • Lithium-ion batteries have advantages, such as large specific energy, high working voltage, low self-discharge rate, small volume, and light weight, and are widely used in applications of consumer electronics.
  • advantages such as large specific energy, high working voltage, low self-discharge rate, small volume, and light weight, and are widely used in applications of consumer electronics.
  • volume energy density and mass energy density are important parameters for measuring battery performance.
  • Lithium is a metal with the smallest relative atomic mass (6.94) and the lowest standard electrode potential (-3.045 V) among all metal elements, and has a theoretical gram capacity up to 3860 mAh/g. Therefore, using lithium metal as an anode in a battery in combination with certain cathode materials of high energy density can greatly increase the energy density and working voltage of batteries.
  • the lithium metal itself is extremely active, and has a potential of -3.05 V relative to a standard hydrogen electrode.
  • Freshly produced lithium metal has no passivation layer on the surface, and is prone to a series of side reactions with the electrolyte system, for example, reaction with a trace amount of hydrogen fluoride in the electrolyte forming lithium fluoride, or reaction with propylene carbonate, which is a common solvent in the electrolyte, generating C 3 H 6 OCO 2 Li, which causes the lithium metal and electrolyte to be consumed at the same time, and a coulombic efficiency during the cycles much lower than a commercial graphite anode (99%-99.9%) .
  • Silicon film can protect the surface of the lithium metal, and reduce contact between the electrolyte and lithium metal to reduce side reactions; and has high mechanical strength and can inhibit the growth of lithium dendrites.
  • silicon materials chemically react with lithium to form Li x Si.
  • Li x Si has high electronic conductivity, causing electrons to easily pass through the lithium metal and protective film to reach the surface of the protective film and to bind to Li + in the electrolyte. Ultimately, this causes lithium metal deposits to form on the surface of the protective film, leading to a lowered performance of the protective film in reducing side reactions and inhibiting lithium dendrites.
  • the present application provides a composition comprising a silicon material and a lithium ion conductor with low electronic conductivity.
  • the composition can be used to prepare a protective film for an anode.
  • the electronic conductivity of the lithium ion conductor material is less than 1E-5 S/cm.
  • the lithium ion conductor material comprises at least one of LiF, Li 3 PO 4 , Li 3 N, LiPON, Li 2 O, Li 4 SiO 4 , LiAlO 2 , and lithium titanium phosphate (Li x1 Ti y1 (PO 4 ) 3 , wherein 0 ⁇ x1 ⁇ 2 and 0 ⁇ y1 ⁇ 3) , lithium aluminum titanium/germanium phosphate (Li x2 Al y2 (Ti, Ge) z2 (PO 4 ) 3 , wherein 0 ⁇ x2 ⁇ 2, 0 ⁇ y2 ⁇ 1, and 0 ⁇ z2 ⁇ 3) , Li 1+x3+y3 (Al, Ga) x3 (Ti, Ge) 2-x3 Si y3 P 3-y3 O 12 (wherein 0 ⁇ x3 ⁇ 1 and 0 ⁇ y3 ⁇ 1) , lithium lanthanum titanate (Li x4 La y4 TiO 3 , wherein 0 ⁇ x4 ⁇ 2 and 0 ⁇ y4 ⁇ 3) , lithium germanium
  • the silicon material includes silicon, a silicon alloy SiM y , or a combination thereof, wherein y ⁇ 0.05, and M includes at least one of B, Al, P, Fe, Co, Ni, Zn, Ge, Ga, As, Zr, In or Sn.
  • the molar ratio of the silicon material to the lithium ion conductor material is 1: 5 to 20: 1.
  • the present application also provides a protective film for an anode, which comprises the composition described herein.
  • the anode comprises a lithium metal layer, and the protective film described herein is coated on the lithium metal layer of the anode.
  • the protective film of the present application further comprises Li x Si, wherein 1.5 ⁇ x ⁇ 4.0.
  • Li x Si has a lithium diffusion coefficient of 10 -14 to10 -10 cm 2 /S. In some embodiments, Li x Si has a strength greater than 10 GPa.
  • the protective film according to the present application has a thickness of 0.01 to 5 microns.
  • the present application also provides an anode comprising the composition or the protective film as described herein.
  • the present application provides an electrochemical device comprising the anode as described herein.
  • the present application provides an electronic device comprising the electrochemical device as described herein.
  • Fig. 3 shows an SEM image at the cross section of the protective film according to the present application deposited on lithium metal.
  • the layers in the figure are copper foil 6, lithium foil 7 and protective film 8 according to the present application in order from top to bottom.
  • the terms when being used in combination with a value, may refer to a variation range of less than or equal to ⁇ 10%of the value, for example, less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%.
  • the difference between two numerical values is less than or equal to ⁇ 10%of the average of the values (e.g., less than or equal to ⁇ 5%, less than or equal to ⁇ 4%, less than or equal to ⁇ 3%, less than or equal to ⁇ 2%, less than or equal to ⁇ 1%, less than or equal to ⁇ 0.5%, less than or equal to ⁇ 0.1%, or less than or equal to ⁇ 0.05%) , the two values may be considered "substantially" the same.
  • a list of items connected by the term “one of” or similar terms may mean any of the listed items. For example, if items A and B are listed, then the phrase “one of A and B" means only A or only B. In another example, if items A, B, and C are listed, then the phrase "one of A, B and C" means only A; only B; or only C.
  • the item A may include a single component or multiple components.
  • the item B may include a single component or multiple components.
  • the item C may include a single component or multiple components.
  • a first aspect of the present application relates to a composition comprising a silicon material and a lithium ion conductor material having low electronic conductivity.
  • the electronic conductivity of the lithium ion conductor material is less than about 1E-5 S/cm.
  • the electronic conductivity is less than about 5E-6 S/cm, less than about 1E-6 S/cm, less than about 5E-7 S/cm, less than about 1E-7 S/cm, less than about 5E-8 S/cm, less than about 1E-8 S/cm, less than about 5E-9 S/cm, or less than about 1E-9 S/cm.
  • the electronic conductivity of the lithium ion conductor material needs to be greater than 1E-10 S/cm, for example, greater than about 1E-9 S/cm, greater than about 1E-8 S/cm, greater than about 1E-7 S/cm, greater than about 1E-6 S/cm, greater than about 1E-5 S/cm, greater than about 1E-4 S/cm, or any range therebetween.
  • the lithium ion conductor material comprises at least one of LiF, Li 3 PO 4 , Li 3 N, LiPON, Li 2 O, Li 4 SiO 4 , LiAlO 2 , lithium titanium phosphate (Li x1 Ti y1 (PO 4 ) 3 , wherein 0 ⁇ x1 ⁇ 2 and 0 ⁇ y1 ⁇ 3) , lithium aluminum titanium/germanium phosphate (Li x2 Al y2 (Ti, Ge) z2 (PO 4 ) 3 , wherein 0 ⁇ x2 ⁇ 2, 0 ⁇ y2 ⁇ 1, and 0 ⁇ z2 ⁇ 3) , Li 1+x3+y3 (Al, Ga) x3 (Ti, Ge) 2-x3 Si y3 P 3-y3 O 12 (wherein 0 ⁇ x3 ⁇ 1 and 0 ⁇ y3 ⁇ 1) , lithium lanthanum titanate (Li x4 La y4 TiO 3 , wherein 0 ⁇ x4 ⁇ 2 and 0 ⁇ y4 ⁇
  • the silicon material includes silicon, a silicon alloy SiM y , or a combination thereof, wherein y ⁇ 0.05, and M includes at least one of B, Al, P, Fe, Co, Ni, Zn, Ge, Ga, As, Zr, In or Sn, for example, a combination of In and Sn.
  • M includes any of B, Al, P, Fe, Co, Ni, Zn, Ge, Ga, As, Zr, In, or Sn.
  • the molar ratio of the silicon material to the lithium ion conductor material is about 1: 5 to about 20: 1. In some embodiments, the molar ratio of the silicon material to the lithium ion conductor material is about 1: 4, about 1: 3, about 1: 2, about 1: 1, about 1.5: 1, about 2: 1, about 2.5: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1, about 10: 1, about 15: 1, or a range between any two of the above ratios.
  • the second aspect of the present application relates to a protective film for an anode, which comprises the composition described above, and the protective film is coated on the lithium metal layer of the anode.
  • the protective film is coated on the lithium metal layer, that is, between the lithium metal and the electrolyte.
  • the silicon material in the composition can form a lithium-silicon alloy. Therefore, the protective film of the present application also includes Li x Si, wherein 1.5 ⁇ x ⁇ 4.0, for example, x is 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 or any range therebetween.
  • the lithium metal layer involved in the present application may include at least one of lithium metal, a lithium alloy, or a lithium compound.
  • the lithium metal layer may be in the form of a thin film layer or in the form of a powder layer.
  • the lithium metal layer is a thin film layer, lithium metal forms a uniform and dense thin layer on the substrate, for example, a lithium metal layer coated on a copper foil.
  • the lithium metal layer is a powder layer, the lithium metal in the form of a powder is coated on a substrate; and the protective film according to the present application is coated on the surface of the powder particles.
  • the thickness of the protective film according to the present application is about 0.01 to about 5 microns, for example, the thickness is about 0.05, about 0.1, about 0.5, about 1, about 2, about 3, or about 4 microns, or any range therebetween.
  • the molar ratio of the lithium element to the silicon element in the lithium metal layer and the protective film is greater than about 10: 1, for example, greater than about 15: 1, greater than about 20: 1, greater than about 25: 1, or greater than about 30: 1.
  • the protective film provided in the present application can protect the interface of the lithium metal layer, reduce side reactions of the lithium metal layer with the electrolyte, improve coulombic efficiency, inhibit the growth of lithium dendrites, and improve cycle performance.
  • the silicon material in the protective film reacts with lithium to generate Li x Si during the cycle, so that the bonding strength between the protective film and the lithium metal layer is effectively improved, and the protective film is prevented from peeling off during a dramatic volume change.
  • the Li x Si provided in the present application has a high lithium diffusion coefficient (10 -14 to 10 -10 cm 2 /S) and high mechanical strength (>10 GPa) , and can provide a lithium ion transport channel.
  • a material with poor conductivity that is, a lithium ion conductor with low electronic conductivity
  • the protective film can effectively isolate the electrolyte, provide an ion transmission channel, and meanwhile significantly suppress the growth of lithium dendrites.
  • Another aspect of the present application also provides an anode comprising the composition or the protective film as described herein.
  • Another aspect of the present application also provides an electrochemical device comprising the anode as described herein.
  • Another aspect of the present application provides an electronic device comprising the electrochemical device as described herein.
  • the electrochemical device of the present application includes any device in which an electrochemical reaction takes place, and specific examples include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
  • the electrochemical device is a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the electrochemical device is a lithium ion battery.
  • the electrochemical device according to the present application includes a cathode, an anode, and a separator, wherein the cathode comprises a cathode active material, and the anode comprises an anode active material.
  • the cathode includes a current collector and a cathode active material layer provided on the current collector.
  • the specific types of the cathode active material are not particularly limited, and may be selected as desired.
  • the cathode active material comprises a compound that reversibly intercalates and deintercalates lithium ions.
  • the cathode active material comprises a composite oxide that contains lithium and at least one element selected from cobalt, manganese, or nickel.
  • the cathode active material comprises at least one of lithium cobalt oxide (LiCoO 2 ) , a lithium nickel manganese cobalt ternary material, lithium manganese oxide (LiMn 2 O 4 ) , lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ) , and lithium iron phosphate (LiFePO 4 ) .
  • the cathode active material layer can have a coating on its surface or can be mixed with another compound having a coating.
  • the coating may include at least one coating element compound selected from an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • the coating element contained in the coating may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, F or a mixture thereof.
  • the coating can be applied by any method as long as the method does not adversely affect the performance of the cathode active material.
  • the method may include any coating method known to those skilled in the art, such as spraying, dipping, and others.
  • the binder increases the binding of the cathode active material particles to each other and the binding of the cathode active material to the current collector.
  • the binder include, but are not limited to, polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, poly (1, 1-vinylidene fluoride) , polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy resins, Nylon and the like.
  • the cathode active material layer includes a conductive material to impart conductivity to the electrode.
  • the conductive material may include any conductive material as long as it does not cause a chemical change.
  • Non-limiting examples of the conductive material include a carbon-based material (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc. ) , a metal-based material (e.g., a metal powder, a metal fiber, etc., including for example copper, nickel, aluminum, silver, and the like) , a conductive polymer (for example, polyphenylene derivatives) and a mixture thereof.
  • a carbon-based material e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.
  • a metal-based material e.g., a metal powder, a metal fiber, etc., including for example copper, nickel, aluminum, silver, and
  • the current collector used for the cathode of the secondary battery according to the present application may be aluminum (Al) , but is not limited thereto.
  • the electrochemical device of the present application is provided with a separator between the cathode and the anode to prevent a short circuit.
  • the material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and may be any of those disclosed in prior art.
  • the separator includes a polymer or an inorganic substance or the like formed of a material which is stable against the electrolyte according to the present application.
  • the substrate layer is a non-woven fabric, film, or composite film having a porous structure
  • the material of the substrate layer includes at least one of polyethylene, polypropylene, polyethylene terephthalate, and polyimide.
  • a porous polypropylene film, a porous polyethylene film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, and a porous polypropylene-polyethylene-polypropylene composite film may be used.
  • At least one surface of the substrate layer is provided with a surface treatment layer, which may be a polymer layer or an inorganic layer, or a layer formed with a mixture of a polymer and an inorganic material.
  • a surface treatment layer which may be a polymer layer or an inorganic layer, or a layer formed with a mixture of a polymer and an inorganic material.
  • the inorganic layer comprises inorganic particles and a binder.
  • the inorganic particles include one of alumina, silica, magnesia, titania, hafnium dioxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate, or a combination of more than one thereof.
  • the binder includes one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, a polyamide, polyacrylonitrile, a polyacrylic ester, polyacrylic acid, a polyacrylic salt, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, or polyhexafluoropropylene, or a combination of more than one thereof.
  • the polymer layer contains a polymer, and the material of the polymer includes at least one of a polyamide, polyacrylonitrile, a polyacrylic ester, polyacrylic acid, a polyacrylic salt, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene) .
  • the present application also provides an electronic device comprising the electrochemical according to the present application.
  • the electrochemical device according to the present application is suitable for use in electronic devices in various fields.
  • the use of the electrochemical device of the present application is not particularly limited and can be used for any purpose known in the art.
  • the electrochemical device according to the present application is applicable to, without limitation, notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, head-mounted stereo headphones, video recorders, LCD TVs, portable cleaners, portable CD players, minidisc players, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power sources, motors, vehicles, motorcycles, scooters, bicycles, lighting apparatus, toys, game consoles, clocks, electric tools, flash lights, cameras, large batteries for household use, and lithium ion capacitors.
  • Examples 1-11 exemplify technical solutions wherein the lithium metal layer is a thin film layer.
  • the deposition material was deposited on the side of the lithium metal layer of a lithium-coated copper foil by magnetron sputtering.
  • the molar ratio of each component in the material and the thickness of the protective film obtained by the deposition are listed in Table 1 below.
  • Examples 12 and 13 exemplify technical solutions wherein the lithium metal layer is a powder layer.
  • silicon and lithium fluoride were simultaneously deposited on a lithium metal containing carbon powder, wherein the molar ratio of silicon to lithium was 2: 1, and the thickness of the protective film deposited in Examples 12 and 13 was 0.1 and 0.01 ⁇ m, respectively.
  • Examples 12 and 13 A powder material containing a composite anode protective layer was mixed with conductive carbon black (Super P) , polystyrene butadiene (SBR) , and polystyrene (PS) at a weight ratio of 80: 10: 5: 5, and p-xylene was added as a solvent, to prepare a slurry with a solid content of 0.2, which was then stirred evenly. The slurry was uniformly coated on a copper foil as an anode current collector, and dried at 70°C to obtain an anode. The anode was then cut to have a diameter of 18mm for use.
  • Super P conductive carbon black
  • SBR polystyrene butadiene
  • PS polystyrene
  • Comparative Example 1 no protective film was used, and the lithium-coated copper foil was directly cut to have a diameter of 18 mm for use.
  • Comparative Example 2 only silicon was deposited on the lithium metal layer side of the lithium-coated copper foil, that is, the protective film contained only silicon without a lithium ion conductor having low electronic conductivity.
  • the deposition thickness was 1 micron. The other steps were the same as in Example 1.
  • Comparative Example 3 only lithium fluoride was deposited on the lithium metal layer side of the lithium-coated copper foil, that is, the protective film contained only lithium fluoride without a silicon material.
  • the deposition thickness was 1 micron. The other steps were the same as in Example 1.
  • the lithium metal layer was in the form of a powder layer, but the powder layer did not have the protective film according to the present application.
  • a lithium metal-containing carbon powder without any surface treatment was mixed with conductive carbon black (Super P) , polystyrene butadiene (SBR) , and polystyrene (PS) at a weight ratio of 80: 10: 5: 5, and p-xylene was added as a solvent, to prepare a slurry with a solid content of 0.2, which was then stirred evenly.
  • the slurry was uniformly coated on a copper foil as an anode current collector, and dried at 70°C to obtain an anode.
  • the anode was then cut to have a diameter of 18mm for use.
  • the other steps were the same as in Example 1.
  • the symmetrical battery was activated by discharging and charging for 15 hrs at a current density of 0.1 mA/cm 2 . Then the battery was cyclically discharged and charged at a current density of 0.6 mA/cm 2 , wherein both the charge and discharge time was set as 3 hrs. When the voltage during the cycle dropped sharply to a value of lower than 40 mV, the corresponding number of cycles was recorded as the cycle numbers of the symmetrical battery.
  • the electronic conductivity of LiF and Li 3 PO 4 is less than 10 -10 S/cm; the electronic conductivity of Li 3 N is less than 10 -12 S/cm; and the electronic conductivity of Li 7 La 3 Zr 2 O 12 and Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 is less than 10 -7 S/cm.
  • the ratios of Si to LiF in Examples 1, 4, and 5 are different, resulting in a change in the cycle numbers of the symmetrical batteries. This is because when the proportion of Si is high (Example 4) , due to the high electronic conductivity of Si itself, lithium tends to deposit on the anode protection layer, and lithium dendrites grow, causing a short circuit. When the proportion of Si is low (Example 5) , the bonding strength between the protective layer and lithium metal is reduced, and the protective effect is also reduced.
  • references to “embodiment” , “part of the embodiments” , “one embodiment” , “another example” , “example” , “specific example” or “part of the examples” mean that at least one embodiment or example of the present application includes specific features, structures, materials or characteristics described in the embodiment or example.
  • references to “embodiment” , “part of the embodiments” , “one embodiment” , “another example” , “example” , “specific example” or “part of the examples” mean that at least one embodiment or example of the present application includes specific features, structures, materials or characteristics described in the embodiment or example.

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PCT/CN2020/098881 2019-11-28 2020-06-29 Composition for anode, and protective film, anode, and device comprising same WO2021103523A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021517839A JP7177921B2 (ja) 2019-11-28 2020-06-29 負極に用いられる組成物、並びにこれを含む保護膜、負極及び装置
EP20894239.1A EP3948991A4 (en) 2019-11-28 2020-06-29 COMPOSITION FOR ANODE AND PROTECTIVE FILM, ANODE AND DEVICE WITH THEM

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