WO2023126674A1 - 二次電池の充電方法 - Google Patents

二次電池の充電方法 Download PDF

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Publication number
WO2023126674A1
WO2023126674A1 PCT/IB2022/000724 IB2022000724W WO2023126674A1 WO 2023126674 A1 WO2023126674 A1 WO 2023126674A1 IB 2022000724 W IB2022000724 W IB 2022000724W WO 2023126674 A1 WO2023126674 A1 WO 2023126674A1
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Prior art keywords
charging
secondary battery
negative electrode
current density
solid electrolyte
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PCT/IB2022/000724
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English (en)
French (fr)
Japanese (ja)
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WO2023126674A8 (ja
Inventor
将太郎 土井
義隆 小野
裕行 田中
建三 押原
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Renault SAS
Nissan Motor Co Ltd
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Renault SAS
Nissan Motor Co Ltd
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Priority to EP22915266.5A priority Critical patent/EP4459738A4/en
Priority to CN202280084109.0A priority patent/CN118435424A/zh
Priority to JP2023570473A priority patent/JP7663135B2/ja
Priority to US18/724,119 priority patent/US20250070285A1/en
Publication of WO2023126674A1 publication Critical patent/WO2023126674A1/ja
Publication of WO2023126674A8 publication Critical patent/WO2023126674A8/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • 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
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • 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
    • H01M4/13—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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/448—End of discharge regulating measures
    • 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 invention relates to a method of charging a secondary battery.
  • Rechargeable batteries for motor drives are required to have extremely high output characteristics and high energy compared to consumer lithium secondary batteries used in mobile phones and laptop computers. Therefore, lithium secondary batteries, which have the highest theoretical energy among all practical batteries, have attracted attention and are being rapidly developed.
  • lithium secondary batteries which are currently in widespread use, use a combustible organic electrolyte as the electrolyte.
  • a liquid-type lithium secondary battery requires stricter safety measures against liquid leakage, short circuit, overcharge, etc. than other batteries.
  • a solid electrolyte is a material composed mainly of an ionic conductor capable of conducting ions in a solid. Therefore, in the all-solid lithium secondary battery, in principle, various problems due to the combustible organic electrolytic solution do not occur unlike conventional liquid-type lithium secondary batteries. In general, the use of a high-potential, large-capacity positive electrode material and a large-capacity negative electrode material can significantly improve the output density and energy density of the battery.
  • a promising candidate is an all-solid lithium secondary battery that uses a sulfide-based material as a positive electrode active material and metallic lithium or a lithium-containing alloy as a negative electrode active material.
  • the negative electrode potential decreases as the charging progresses.
  • metallic lithium precipitates on the negative electrode and dendrite (dendritic) crystals precipitate (this phenomenon is also referred to as metallic lithium electrodeposition).
  • the electrodeposition of metallic lithium occurs, there is a problem that the deposited dendrite penetrates the solid electrolyte layer and causes an internal short circuit of the battery.
  • Japanese Unexamined Patent Application Publication No. 2020-009724 discloses a method of charging a secondary battery that utilizes a deposition-dissolution reaction of metallic lithium as a negative electrode reaction for the purpose of both suppressing short-circuiting of the battery and shortening the charging time.
  • the charging method includes a first charging step of charging the secondary battery with a first current density I1, and after the first charging step, charging the secondary battery with a second current density I2 higher than the first current density I1.
  • X/Y is 0.5. It is characterized in that the secondary battery is charged at the first current density I1 until it reaches 5 or more.
  • an object of the present invention is to provide means for further suppressing short circuits in secondary batteries.
  • the inventors have conducted extensive studies to solve the above problems. As a result, in the charging process corresponding to the "first charging process" described in JP-A-2020-009724, at least one pause and/or discharge is performed, and the (State of Charge) reaches 4.5%. The inventors have found that the above problem can be solved by charging so as not to exceed the SOC, and have completed the present invention.
  • the uncharged state is defined as SOC 0%
  • the state where the current value is 20% or less of the constant current value after charging at a constant current and charging at a constant voltage after reaching 4.2 V is defined as SOC 100%. bottom.
  • One embodiment of the present invention is a secondary battery having a positive electrode current collector, a positive electrode active material layer, a solid electrolyte layer, and a negative electrode current collector in this order, and utilizing a deposition-dissolution reaction of metallic lithium as a reaction of the negative electrode.
  • the charging method has a multi-step charging process including at least a first charging process and a second charging process.
  • metallic lithium is deposited on the solid electrolyte layer side surface of the negative electrode current collector to form a negative electrode active material layer. and forms a deposited Li layer composed of the lithium metal.
  • the secondary battery is charged at a second current density I2 higher than the first current density I1 to increase the thickness of the precipitated Li layer.
  • the first charging step includes performing at least one rest or at least one discharge, and the secondary battery is charged at the first current density I1 so that the SOC does not exceed 4.5%. It is characterized by charging with
  • FIG. 1 is a cross-sectional view schematically showing a flat laminated all-solid lithium secondary battery according to an embodiment of the present invention.
  • One embodiment of the present invention is a secondary battery having a positive electrode current collector, a positive electrode active material layer, a solid electrolyte layer, and a negative electrode current collector in this order, and utilizing a deposition-dissolution reaction of metallic lithium as a reaction of the negative electrode.
  • the charging method has a multi-step charging process including at least a first charging process and a second charging process.
  • metallic lithium is deposited on the solid electrolyte layer side surface of the negative electrode current collector to form a negative electrode active material layer. and forms a deposited Li layer composed of the lithium metal.
  • the secondary battery is charged at a second current density I2 higher than the first current density I1 to increase the thickness of the precipitated Li layer.
  • the first charging step includes performing at least one rest or at least one discharge, and the secondary battery is charged at the first current density I1 so that the SOC does not exceed 4.5%. It is characterized by charging with According to the charging method according to the present embodiment, it is possible to further suppress the short circuit of the secondary battery.
  • FIG. 1 is a cross-sectional view schematically showing a flat laminated all-solid lithium secondary battery according to an embodiment of the present invention.
  • a flat laminated non-bipolar lithium secondary battery hereinafter also simply referred to as a “laminated secondary battery”
  • FIG. 1 when viewed from the electrical connection form (electrode structure) inside the all-solid-state lithium secondary battery according to the present embodiment, non-bipolar (internal parallel connection type) batteries and bipolar (internal series connection type) batteries It can be applied to both.
  • the power generation element 21 has a structure in which a positive electrode, a solid electrolyte layer 17, and a negative electrode are laminated.
  • positive electrode active material layers 13 containing a positive electrode active material here, NMC composite oxide (LiNi 0.8 Mn 0.1 Co 0.1 O 2 )
  • NMC composite oxide LiNi 0.8 Mn 0.1 Co 0.1 O 2
  • the negative electrode has a structure in which negative electrode active material layers 15 containing a negative electrode active material (deposited Li layers made of metallic lithium as a negative electrode active material) are arranged on both sides of a negative electrode current collector 11′′.
  • the positive electrode, the solid electrolyte layer, and the negative electrode are laminated in this order such that one positive electrode active material layer 13 and the adjacent negative electrode active material layer 15 face each other with the solid electrolyte layer 17 interposed therebetween.
  • the adjacent positive electrode, the solid electrolyte layer, and the negative electrode constitute one single cell layer 19. Therefore, in the stacked secondary battery 10a shown in FIG. It can also be said that it has a configuration in which it is connected in parallel to .
  • the positive electrode active material layer 13 is arranged only on one side of each of the outermost positive electrode current collectors located on both outermost layers of the power generating element 21, but the active material layer is provided on both sides.
  • the active material layer is provided on both sides.
  • a current collector having active material layers on both sides may be used as it is as the current collector for the outermost layer, instead of using the current collector exclusively for the outermost layer having the active material layer on only one side.
  • the positive electrode current collector 11′ and the negative electrode current collector 11′′ are attached with a positive electrode current collector (tab) 25 and a negative electrode current collector (tab) 27, which are electrically connected to each electrode (positive electrode and negative electrode), respectively. It has a structure in which it is sandwiched between the ends of the laminate film 29, which is the material, and led out of the laminate film 29.
  • the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are respectively connected to the positive electrode as necessary. It may be attached to the positive electrode current collector 11' and the negative electrode current collector 11'' of each electrode by ultrasonic welding, resistance welding, or the like, via a lead and a negative electrode lead (not shown).
  • the stack secondary battery 10a is applied with a restraining pressure in the stacking direction of the power generation elements 21 by a pressurizing member (not shown). Therefore, the volume of the power generation element 21 is kept constant.
  • the positive electrode current collector is a conductive member that functions as a flow path for electrons that are discharged from the positive electrode toward the external load or flow from the power source toward the positive electrode as the battery reaction (charge/discharge reaction) progresses. .
  • the material that constitutes the positive electrode current collector There are no particular restrictions on the material that constitutes the positive electrode current collector.
  • a constituent material of the positive electrode current collector for example, a metal or a conductive resin may be employed.
  • metals include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or the like may be used.
  • a foil in which a metal surface is coated with aluminum may be used.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoint of electronic conductivity, battery operating potential, and the like.
  • conductive resin a resin obtained by adding a conductive filler to a non-conductive polymeric material can be used.
  • the current collector may have a single-layer structure made of a single material, or may have a laminated structure in which layers made of these materials are appropriately combined. From the viewpoint of reducing the weight of the current collector, it is preferable to include at least a conductive resin layer made of a resin having conductivity. Moreover, from the viewpoint of blocking movement of lithium ions between the single cell layers, a metal layer may be provided on a part of the current collector.
  • the thickness of the positive electrode current collector is not particularly limited, but an example is 10 to 100 ⁇ m.
  • the positive electrode active material layer contains a positive electrode active material.
  • the type of positive electrode active material is not particularly limited, but layered rock salt type active materials such as LiCoO2 , LiMnO2 , LiNiO2 , LiVO2 , Li(Ni-Mn-Co) O2 , LiMn2O4 , and LiNi0.
  • Spinel -type active materials such as .5Mn1.5O4 , olivine - type active materials such as LiFePO4 and LiMnPO4 , and Si - containing active materials such as Li2FeSiO4 and Li2MnSiO4 .
  • Li 4 Ti 5 O 12 As an oxide active material other than the above, for example, Li 4 Ti 5 O 12 can be mentioned.
  • composite oxides containing lithium and nickel are preferably used, and more preferably Li(Ni-Mn-Co) O2 and those in which a part of these transition metals are replaced with other elements (hereinafter , also simply referred to as “NMC composite oxide”) is used.
  • the NMC composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni and Co are arranged in an orderly manner) atomic layer are alternately stacked via an oxygen atomic layer. It contains one Li atom, and the amount of Li that can be extracted is twice that of the spinel-based lithium manganese oxide, that is, the supply capacity is doubled, and a high capacity can be obtained.
  • NMC composite oxides also include composite oxides in which part of the transition metal element is replaced with another metal element.
  • Other elements in that case include Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, and Cu. , Ag, Zn, etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, Cr, more preferably Ti, Zr, Al, Mg, or Cr from the viewpoint of improving cycle characteristics.
  • a sulfur-based positive electrode active material is used.
  • the sulfur-based positive electrode active material include particles or thin films of organic sulfur compounds or inorganic sulfur compounds, which can release lithium ions during charging and absorb lithium ions during discharging by utilizing the oxidation-reduction reaction of sulfur. Any substance that can Examples of organic sulfur compounds include disulfide compounds, sulfur-modified polyacrylonitrile represented by compounds described in WO 2010/044437, sulfur-modified polyisoprene, rubeanic acid (dithiooxamide), polysulfide carbon, and the like.
  • disulfide compounds sulfur-modified polyacrylonitrile, and rubeanic acid are preferred, and sulfur-modified polyacrylonitrile is particularly preferred.
  • disulfide compound those having a dithiobiurea derivative, a thiourea group, a thioisocyanate group, or a thioamide group are more preferred.
  • sulfur-modified polyacrylonitrile is sulfur-atom-containing modified polyacrylonitrile obtained by mixing sulfur powder and polyacrylonitrile and heating the mixture under an inert gas or under reduced pressure. Its putative structure is described, for example, in Chem. Mater.
  • polyacrylonitrile is ring-closed to form a polycyclic structure, and at least part of S is bonded to C.
  • the compound described in this document has strong peak signals near 1330 cm ⁇ 1 and 1560 cm ⁇ 1 in the Raman spectrum, and further peaks near 307 cm ⁇ 1 , 379 cm ⁇ 1 , 472 cm ⁇ 1 and 929 cm ⁇ 1 . do.
  • inorganic sulfur compounds are preferred because of their excellent stability, and specific examples include sulfur (S), S-carbon composites, TiS2 , TiS3 , TiS4 , NiS, NiS2 , CuS, FeS2 , Li2. S, MoS 2 , MoS 3 and the like.
  • the S-carbon composite includes a sulfur powder and a carbon material, and is in a composite state by subjecting them to heat treatment or mechanical mixing. More specifically, the state in which sulfur is distributed on the surface and in the pores of the carbon material, the state in which sulfur and the carbon material are uniformly dispersed at the nano level and are aggregated into particles, and the state in which fine sulfur It is a state in which the carbon material is distributed on the surface or inside of the powder, or a state in which a plurality of these states are combined.
  • positive electrode active materials may be used together. It goes without saying that positive electrode active materials other than those described above may be used.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited. more preferred.
  • the positive electrode active material layer preferably further contains a solid electrolyte.
  • a solid electrolyte By including the solid electrolyte in the positive electrode active material layer, the ion conductivity of the positive electrode active material layer can be improved.
  • solid electrolytes include sulfide solid electrolytes and oxide solid electrolytes. From the viewpoint of high ion conductivity, sulfide solid electrolytes are preferred.
  • Examples of sulfide solid electrolytes include LiI - Li2S - SiS2 , LiI - Li2SP2O5 , LiI- Li3PO4 - P2S5 , Li2SP2S5 , LiI - Li3PS4 , LiI -LiBr - Li3PS4 , Li3PS4 , Li2SP2S5 - LiI , Li2SP2S5 - Li2O , Li2SP 2S5 - Li2O -LiI, Li2S - SiS2, Li2S- SiS2 -LiI, Li2S - SiS2 - LiBr , Li2S - SiS2 -LiCl, Li2S - SiS2 -B2S3 - LiI, Li2S - SiS2 - P2S5 - LiI, Li2S-B2S3 , Li2S - P2S5 - LiI, Li2S-B2
  • the sulfide solid electrolyte may have, for example, a Li 3 PS 4 skeleton, a Li 4 P 2 S 7 skeleton, or a Li 4 P 2 S 6 skeleton.
  • sulfide solid electrolytes having a Li3PS4 skeleton include LiI- Li3PS4 , LiI-LiBr- Li3PS4 , and Li3PS4 .
  • sulfide solid electrolytes having a Li4P2S7 skeleton include Li-P-S-based solid electrolytes called LPS (e.g., Li7P3S11 ).
  • the sulfide solid electrolyte for example, LGPS represented by Li(4 - x) Ge (1-x) PxS4 (where x satisfies 0 ⁇ x ⁇ 1) may be used.
  • the sulfide solid electrolyte is preferably a sulfide solid electrolyte containing the element P, and more preferably a material containing Li 2 SP 2 S 5 as a main component.
  • the sulfide solid electrolyte may contain halogens (F, Cl, Br, I).
  • the sulfide solid electrolyte is Li 2 S—P 2 S 5 system
  • the sulfide solid electrolyte may be sulfide glass, crystallized sulfide glass, or a crystalline material obtained by a solid phase method.
  • the sulfide glass can be obtained, for example, by subjecting the raw material composition to mechanical milling (such as a ball mill).
  • Crystallized sulfide glass can be obtained, for example, by heat-treating sulfide glass at a temperature equal to or higher than the crystallization temperature.
  • the ionic conductivity (e.g., Li ion conductivity) of the sulfide solid electrolyte at room temperature (25°C) is, for example, preferably 1 ⁇ 10 -5 S/cm or more, and 1 ⁇ 10 -4 S/cm or more. cm or more is more preferable.
  • the value of the ionic conductivity of the solid electrolyte can be measured by the AC impedance method.
  • oxide solid electrolytes include compounds having a NASICON structure.
  • compounds having a NASICON structure include compounds represented by the general formula Li1 + xAlxGe2 -x ( PO4 ) 3 ( 0 ⁇ x ⁇ 2) (LAGP) and general formula Li1+ xAlxTi2 A compound (LATP) represented by -x ( PO4 ) 3 (0 ⁇ x ⁇ 2) and the like can be mentioned.
  • Other examples of oxide solid electrolytes include LiLaTiO (e.g., Li 0.34 La 0.51 TiO 3 ), LiPON (e.g., Li 2.9 PO 3.3 N 0.46 ), LiLaZrO (e.g., , Li 7 La 3 Zr 2 O 12 ) and the like.
  • the shape of the solid electrolyte examples include particle shapes such as spherical and ellipsoidal shapes, and thin film shapes.
  • the average particle size (D 50 ) is not particularly limited, but is preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the average particle diameter (D 50 ) is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the content of the solid electrolyte in the positive electrode active material layer is, for example, preferably within the range of 1 to 60% by mass, more preferably within the range of 10 to 50% by mass.
  • the positive electrode active material layer may further contain at least one of a conductive aid and a binder in addition to the positive electrode active material and solid electrolyte described above.
  • conductive aids include metals such as aluminum, stainless steel (SUS), silver, gold, copper, and titanium, alloys containing these metals, or metal oxides; carbon fibers (specifically, vapor-grown carbon fibers (VGCF), polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber, activated carbon fiber, etc.), carbon nanotubes (CNT), carbon black (specifically, acetylene black, Ketjenblack (registered trademark) , furnace black, channel black, thermal lamp black, etc.), but are not limited thereto.
  • VGCF vapor-grown carbon fibers
  • CNT carbon nanotubes
  • carbon black specifically, acetylene black, Ketjenblack (registered trademark) , furnace black, channel black, thermal lamp black, etc.
  • a particulate ceramic material or resin material coated with the above metal material by plating or the like can also be used as a conductive aid.
  • conductive aids from the viewpoint of electrical stability, it is preferable to include at least one selected from the group consisting of aluminum, stainless steel, silver, gold, copper, titanium, and carbon. , silver, gold, and carbon, and more preferably at least one carbon. These conductive aids may be used alone or in combination of two or more.
  • the shape of the conductive aid is preferably particulate or fibrous.
  • the shape of the particles is not particularly limited, and may be powdery, spherical, rod-like, needle-like, plate-like, columnar, amorphous, scaly, spindle-like, or the like. I don't mind.
  • the average particle size (primary particle size) when the conductive aid is particulate is not particularly limited, but is preferably 0.01 to 10 ⁇ m from the viewpoint of the electrical characteristics of the battery.
  • the "particle diameter of the conductive aid” means the maximum distance L among the distances between any two points on the outline of the conductive aid.
  • the value of the "average particle size of the conductive aid” is the particle size of particles observed in several to several tens of fields of view using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). shall be calculated as the average value of
  • the content of the conductive aid in the positive electrode active material layer is not particularly limited, but is preferably 0 to 10% by mass with respect to the total mass of the positive electrode active material layer. , more preferably 2 to 8% by mass, and still more preferably 4 to 7% by mass. Within such a range, it is possible to form a stronger electron conduction path in the positive electrode active material layer, which can effectively contribute to the improvement of battery characteristics.
  • the binder is not particularly limited, but includes, for example, the following materials.
  • PVDF polyvinylidene fluoride
  • polyethylene polypropylene, polymethylpentene, polybutene, polyethernitrile, polytetrafluoroethylene
  • Polyacrylonitrile polyimide, polyamide, ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR), ethylene-propylene-diene copolymer, styrene-butadiene-styrene block copolymer and hydrogenated products thereof
  • thermoplastic polymers such as styrene/isoprene/styrene block copolymers and their hydrogenated products, tetrafluoroethylene/hexafluoropropylene copolymers (FEP), tetrafluoroethylene/perfluoroalkyl vinyl
  • the thickness of the positive electrode active material layer varies depending on the configuration of the intended all-solid-state battery, but for example, it is preferably in the range of 0.1 to 1000 ⁇ m, more preferably 40 to 100 ⁇ m.
  • the solid electrolyte layer is a layer containing a solid electrolyte as a main component and interposed between the negative electrode active material layer and the positive electrode active material layer. Since the specific form of the solid electrolyte contained in the solid electrolyte layer is the same as described above, detailed description is omitted here.
  • the content of the solid electrolyte in the solid electrolyte layer is, for example, preferably in the range of 10 to 100% by mass, more preferably in the range of 50 to 100% by mass, and in the range of 90 to 100% by mass. is more preferable.
  • the solid electrolyte layer may further contain a binder in addition to the solid electrolyte described above. Since the specific form of the binder that can be contained in the solid electrolyte layer is the same as described above, detailed description is omitted here.
  • the thickness of the solid electrolyte layer varies depending on the configuration of the target all-solid-state battery, but from the viewpoint of improving the volume energy density of the battery, it is preferably 600 ⁇ m or less, more preferably 500 ⁇ m or less, More preferably, it is 400 ⁇ m or less.
  • the lower limit of the thickness of the solid electrolyte layer is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and still more preferably 10 ⁇ m or more.
  • the negative electrode current collector is a conductive member that functions as a flow path for electrons that are emitted from the negative electrode toward the power source or flow from an external load toward the negative electrode as the battery reaction (charge/discharge reaction) progresses. .
  • the material that constitutes the negative electrode current collector There are no particular restrictions on the material that constitutes the negative electrode current collector.
  • a metal or a conductive resin can be employed as in the case of the positive electrode current collector.
  • the thickness of the negative electrode current collector is not particularly limited, but an example is 10 to 100 ⁇ m.
  • the all-solid-state battery according to this embodiment is a so-called lithium deposition type battery in which lithium metal is deposited on the negative electrode current collector during the charging process.
  • a layer of lithium metal (deposited Li layer) deposited on the negative electrode current collector in the charging process is the negative electrode active material layer of the lithium secondary battery according to the present embodiment. Therefore, the thickness of the negative electrode active material layer increases as the charging process progresses, and the thickness of the negative electrode active material layer decreases as the discharging process progresses.
  • the thickness of the negative electrode active material layer (lithium metal layer) at the time of full charge is not particularly limited, it is usually 0.1 to 1000 ⁇ m.
  • the current collector and the current collector plate may be electrically connected via a positive lead or a negative lead.
  • Materials used in known lithium secondary batteries can also be employed as the constituent materials of the positive and negative electrode leads.
  • the parts taken out from the exterior should be heat-shrunk with heat-resistant insulation so that they do not come into contact with peripheral equipment or wiring and cause electric leakage and affect the product (for example, automobile parts, especially electronic equipment, etc.). Covering with a tube or the like is preferred.
  • the battery exterior material As the battery exterior material, a known metal can case can be used, and a bag-like case using a laminate film 29 containing aluminum that can cover the power generating element can also be used.
  • the laminate film may be, for example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order, but is not limited thereto.
  • a laminate film is desirable from the viewpoint that it is excellent in high power output and cooling performance and can be suitably used for batteries for large equipment for EV and HEV.
  • the outer package is more preferably a laminate film containing aluminum.
  • the stacked secondary battery according to this embodiment has a structure in which a plurality of single cell layers are connected in parallel, so that it has a high capacity and excellent cycle durability. Therefore, the stacked secondary battery according to this embodiment is suitably used as a power source for driving EVs and HEVs.
  • the secondary battery is charged at a first current density I1 to deposit metallic lithium on the solid electrolyte layer side surface of the negative electrode current collector to activate the negative electrode.
  • the solid electrolyte layer and the negative electrode current collector of the all-solid-state lithium secondary battery according to the present embodiment are both solid and have some unevenness on the surface.
  • the initial charge is started, lithium is deposited in the space between the solid electrolyte layer and the negative electrode active material layer starting from the contact point where the solid electrolyte layer and the negative electrode current collector are in contact.
  • the charging method according to the present embodiment in the first charging step, charging is performed at a relatively low current density I1 until the SOC does not exceed 4.5%, so that dendrites grow rapidly starting from the contact point. can be prevented.
  • concentration of electric charges can be alleviated by resting.
  • an electrical discharge can be applied instead of or in addition to resting to dissolve the grown dendrites and cut the dendrite path.
  • the number of fine dendrites on the solid electrolyte layer side surface of the deposited Li layer formed in the first charging step can be reduced (deposited Li layer can form a smoother surface on the side of the solid electrolyte layer). Therefore, it becomes possible to suppress a short circuit more significantly than the conventional technique described in Japanese Patent Application Laid-Open No. 2020-009724.
  • First charging step In the first charging step, by charging the secondary battery at a first current density I1, metallic lithium is deposited on the surface of the negative electrode current collector on the side of the solid electrolyte layer to form a part of the negative electrode active material layer. and forms a deposited Li layer made of the metallic lithium. Then, the first charging step includes at least one rest or at least one discharge, and charges the secondary battery at a first current density I1 such that the SOC does not exceed 4.5%. It is characterized by
  • the first current density I1 is not particularly limited as long as it is smaller than the second current density I2 in the second charging step described later, but is preferably less than 0.22 (mA/cm 2 ), more preferably 0. 0.01 (mA/cm 2 ) or more and 0.21 (mA/cm 2 ) or less, more preferably 0.02 (mA/cm 2 ) or more and 0.10 (mA/cm 2 ) or less.
  • the first current density I1 is less than 0.22 (mA/cm 2 )
  • the deposition and growth of dendrites are less likely to occur, and the effect of suppressing the short circuit of the secondary battery is enhanced.
  • the first current density I1 is 0.01 (mA/cm 2 ) or more, the charging time can be shortened.
  • the charging rate (C) in the first charging step is preferably less than 0.05 (C), more preferably It is 0.0023 (C) or more and 0.048 (C) or less, more preferably 0.0045 (C) or more and 0.023 (C) or less.
  • the charge rate (C) is less than 0.05 (C)
  • the deposition and growth of dendrites are less likely to occur, and the short-circuit suppressing effect of the secondary battery is enhanced.
  • the charging rate (C) is 0.0023 (C) or higher, the charging time can be shortened.
  • 1C is a current value at which the battery is fully charged (100% charged) when charged for one hour at that current value.
  • the first charging step includes at least one pause or at least one discharge.
  • rest refers to a state in which charging and discharging are not performed.
  • the rest time per time is not particularly limited, but is preferably 0.005 hours (18 seconds) or more, more preferably 0.01 hours (36 seconds) or more, and further It is preferably 0.02 hours (72 seconds) or more.
  • the rest time is 0.01 hour (36 seconds) or longer, the concentration of electric charges is further alleviated, and the short-circuit suppressing effect of the secondary battery is further enhanced.
  • the upper limit of the rest time is not particularly limited, it is usually 3 hours or less, preferably 2 hours or less, and more preferably 1.5 hours or less.
  • the number of pauses is also not particularly limited, but it is usually 1 to 10 times, preferably 3 to 5 times. When the number of pauses is 3 to 5, the concentration of electric charges is further alleviated, and the short-circuit suppressing effect of the secondary battery is further enhanced.
  • discharging it is preferable to perform a rest after discharging in addition to a rest during or after charging, or instead of a rest during or after charging. In addition to resting during or after charging, the number of rests after discharging is usually 1 to 20 times, preferably 6 to 10 times.
  • the discharge lower limit voltage (cutoff voltage, discharge final voltage) when discharging is performed is not particularly limited, but is preferably 0 to 2.5 V, more preferably 2.0 to 2.5 V, and still more preferably. is 2.3-2.5V. If the discharge lower limit voltage is 2.5 V or less, the path of the dendrite can be sufficiently cut off, so that the effect of suppressing the short circuit of the secondary battery is enhanced. Even when discharging is performed until the discharge lower limit voltage reaches 0 V, a slight deposited Li layer remains between the solid electrolyte layer and the negative electrode current collector.
  • Japanese Patent Laid-Open No. 2020-009724 Short-circuiting of the secondary battery is less likely to occur as compared with the prior art described in the publication.
  • the current density and discharge rate at the time of discharging are not particularly limited, either, as long as they are approximately the same as the first current density and charge rate in the first charging step. That is, the current density during discharge is preferably less than 0.22 (mA/cm 2 ), more preferably 0.01 (mA/cm 2 ) or more and 0.21 (mA/cm 2 ) or less. It is preferably 0.02 (mA/cm 2 ) or more and 0.10 (mA/cm 2 ) or less. Further, the discharge rate (C) during discharge is preferably less than 0.05 (C), more preferably 0.0023 (C) or more and 0.048 (C) or less, still more preferably 0.0045 (C) or more and 0.023(C) or less.
  • the number of discharges is also not particularly limited, but it is usually 1 to 10 times, preferably 3 to 5 times. When the number of times of discharge is 3 to 5, the concentration of electric charges is further alleviated, and the short-circuit suppressing effect of the secondary battery is further enhanced.
  • the first charging step it is essential to perform at least one rest or at least one discharge. From the viewpoint of more effectively suppressing the formation of fine dendrites, at least one discharge is recommended. is preferred, more preferably at least one rest and at least one discharge. When both resting and discharging are performed, it is preferable to rest between charging and discharging. Moreover, when resting and/or discharging is performed multiple times in the first charging step, for example, a cycle of "charging, then resting and/or discharging" may be repeated. At this time, each charging condition, resting condition and/or discharging condition may be the same or different. are preferably the same.
  • the final operation in the first charging step may be charging, resting, or discharging.
  • This embodiment is also characterized in that in the first charging step, the secondary battery is charged at the first current density I1 so that the SOC does not exceed 4.5%.
  • the first charging process when charging is performed multiple times, charging is performed so that the SOC does not exceed 4.5% in each charging (that is, the SOC exceeds 4.5% in the first charging process). never). This is because, as described above, when charging is performed until the SOC exceeds 4.5% as in the conventional technology described in Japanese Patent Laid-Open No. 2020-009724, fine dendrites are sufficiently formed even when resting and discharging are performed. This is because the short circuit of the secondary battery cannot be sufficiently suppressed in some cases.
  • the SOC at the end of the first charging step must be 4.5% or less, preferably 0.5 to 3.0%, more preferably 1.0 to 2.0%. be.
  • the secondary battery is charged at a second current density I2 higher than the first current density I1 to increase the thickness of the deposited Li layer.
  • the second current density I2 is particularly restricted if it is greater than the first current density I1 (if there are multiple first current densities I1, the largest one among them) in the first charging step described above. However, it is preferably 0.22 (mA/cm 2 ) or more, more preferably 0.22 to 1.00 (mA/cm 2 ). When the second current density I2 is 0.22 (mA/cm 2 ) or more, the charging time can be shortened. When the second current density I2 is 1.00 (mA/cm 2 ) or less, the deposition and growth of dendrites are less likely to occur, and the short circuit suppressing effect of the secondary battery is enhanced.
  • the charging rate (C) in the second charging step is preferably 0.05 (C) or more, more preferably It is 0.05 to 0.23 (C).
  • the charging rate (C) is 0.05 (C) or more, the charging time can be shortened.
  • the charge rate (C) is 0.23 (C) or less, the deposition and growth of dendrites are less likely to occur, and the short-circuit suppressing effect of the secondary battery is enhanced.
  • the secondary battery charging method according to the present embodiment is preferably performed during the initial charging, and may be performed during the second and subsequent charging as necessary.
  • the charging method of claim 1 having the features of claim 2; the method of claim 1 or 2 having features of claim 3; A method for charging a secondary battery; a method for charging a secondary battery according to any one of claims 1 to 3, characterized by claim 4.
  • NMC composite oxide LiNi 0.8 Mn 0.1 Co 0.1 O 2
  • aldirodite which is a lithium ion conductive halogen-containing sulfide solid electrolyte
  • a type solid electrolyte Li 6 PS 5 Cl, average particle size (D50) 0.8 ⁇ m
  • acetylene black as a conductive aid
  • SBR styrene-butadiene rubber
  • NMC composite oxide, solid electrolyte, and acetylene black were weighed so as to have a mass ratio of 83.8: 10.8: 5.4, and placed in an agate mortar. After mixing with , further mixing and stirring was performed with a planetary ball mill. 2.7 parts by mass of styrene-butadiene rubber (SBR) was added to 100 parts by mass of the obtained mixed powder, and xylene was added as a solvent to prepare a cathode active material slurry.
  • SBR styrene-butadiene rubber
  • the positive electrode active material slurry prepared above was applied to one surface of an aluminum foil (thickness: 20 ⁇ m) as a positive electrode current collector, and dried to form a positive electrode active material layer (basis weight: 25.0 mg/cm 2 ). formed to produce a positive electrode.
  • the solid electrolyte slurry prepared above was applied to one surface of a stainless steel (SUS430LX) foil (thickness 10 ⁇ m) as a negative electrode current collector, and dried to form a solid electrolyte layer (basis weight: 3.7 mg/cm 2 ) . , a thickness of 20 ⁇ m after pressing).
  • test cell The solid electrolyte layer prepared above was transferred to the exposed surface of the positive electrode prepared above by cold isostatic pressing (CIP).
  • An aluminum positive electrode tab and a nickel negative electrode tab are respectively joined to an aluminum foil as a positive electrode current collector and a stainless steel foil as a negative electrode current collector by an ultrasonic welding machine, and the resulting laminate is an aluminum laminate film.
  • a test cell was produced by putting it inside and vacuum-sealing it.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • cell charging is started at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), and charging is stopped when the SOC reaches 4.5%. and rested for 0.02 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 2 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 3.0%. and rested for 0.02 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 3 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 4 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • This cycle was repeated for 5 cycles.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 5 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • the cell was discharged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 0 V, and rested for 0.5 hours. This cycle was repeated for 5 cycles.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 6 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 1.5 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • This cycle was repeated for 5 cycles.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 7 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • the cell was started to discharge at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), stopped when the voltage reached 2.5 V, and rested for 0.5 h. .
  • This cycle was repeated for 10 cycles.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 8 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 9 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) was performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the first current density I1 the cell is charged at a constant current density of 0.04 mA/cm 2 (equivalent to 0.01 C), and a predetermined time (0.296 h) elapses (SOC is 0.3 % increase), charging was stopped and rested for 0.02 h.
  • This charging and resting operation was repeated five times (the SOC reached 1.5% by the fifth charging, and then resting for 0.02 h).
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • Example 10 A charge/discharge test was performed in the same manner as in Example 1, except that the above (first charging step) and (second charging step) were performed by the following method.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.21 mA/cm 2 (equivalent to 0.048 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • cell charging is started at a constant current density of 0.87 mA/cm 2 (equivalent to 0.20 C), and charging is stopped when the SOC reaches 1.5%. bottom.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.43 mA/cm 2 (equivalent to 0.10 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.22 mA/cm 2 (equivalent to 0.05 C) as the first current density I1, and charging is stopped when the SOC reaches 1.5%. and rested for 0.02 h.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.
  • the test cell was placed in a constant temperature bath at 60°C for 5 hours to raise the temperature of the cell to 60°C.
  • the cell is charged at a constant current density of 0.87 mA/cm 2 (equivalent to 0.20 C) as the first current density I1, and the charging is stopped when the SOC reaches 30%, A rest of 0.02 h was performed.
  • a precipitated Li layer made of metallic lithium was formed on the surface of the negative electrode current collector on the side of the solid electrolyte layer.

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PCT/IB2022/000724 2021-12-27 2022-12-16 二次電池の充電方法 Ceased WO2023126674A1 (ja)

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See also references of EP4459738A4

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