WO2023031638A1 - 電気デバイス用正極材料ならびにこれを用いた電気デバイス用正極および電気デバイス - Google Patents

電気デバイス用正極材料ならびにこれを用いた電気デバイス用正極および電気デバイス Download PDF

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WO2023031638A1
WO2023031638A1 PCT/IB2021/000602 IB2021000602W WO2023031638A1 WO 2023031638 A1 WO2023031638 A1 WO 2023031638A1 IB 2021000602 W IB2021000602 W IB 2021000602W WO 2023031638 A1 WO2023031638 A1 WO 2023031638A1
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positive electrode
conductor
active material
electrode active
solid electrolyte
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PCT/IB2021/000602
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English (en)
French (fr)
Japanese (ja)
Inventor
淳史 伊藤
美咲 藤本
航 荻原
一生 大谷
珍光 李
正樹 小野
正浩 諸岡
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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 PCT/IB2021/000602 priority Critical patent/WO2023031638A1/ja
Priority to US18/688,573 priority patent/US20250125337A1/en
Priority to EP21955282.5A priority patent/EP4398336A4/en
Priority to JP2023544786A priority patent/JP7756168B2/ja
Priority to CN202180101952.0A priority patent/CN117941093A/zh
Publication of WO2023031638A1 publication Critical patent/WO2023031638A1/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
    • 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
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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 positive electrode material for electrical devices, a positive electrode for electrical devices using the same, and an electrical device.
  • 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 the conventional liquid-type lithium secondary battery.
  • 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.
  • elemental sulfur (S 8 ) has an extremely large theoretical capacity of about 1670 mAh/g, and has the advantage of being low cost and abundant as a resource.
  • Japanese Patent Application Laid-Open No. 2014-17241 discloses that conductive carbon having a predetermined specific surface area is immersed in a sulfur solution.
  • a method for producing thin film sulfur-coated conductive carbon includes isolation from solution. According to the literature, the obtained thin film sulfur-coated conductive carbon easily diffuses electrons and lithium ions inside the sulfur, so by using this as a positive electrode mixture, an all-solid with excellent discharge capacity and rate characteristics It is said that it can provide a type lithium sulfur battery.
  • an object of the present invention is to provide a means for improving cycle durability in an electrical device using a positive electrode active material containing sulfur.
  • the present inventors have diligently studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by covering the surface of the composite material particles in which the positive electrode active material containing sulfur is filled in the pores of the porous conductor with an electron conductor. was completed.
  • One form of the present invention is for an electric device, which has composite material particles containing a positive electrode active material containing sulfur in the pores of a porous conductor, and an electronic conductor covering the surface of the composite material particles. It is a positive electrode material.
  • FIG. 1 is a perspective view showing the appearance of a flat laminated all-solid lithium secondary battery that is an embodiment of the present invention.
  • 2 is a cross-sectional view taken along line 2--2 shown in FIG. 1.
  • FIG. 3 is a cross-sectional schematic diagram of a positive electrode material in the prior art.
  • FIG. 4 is a cross-sectional schematic diagram of a positive electrode material according to one embodiment of the present invention.
  • One form of the present invention is for an electric device, which has composite material particles containing a positive electrode active material containing sulfur in the pores of a porous conductor, and an electronic conductor covering the surface of the composite material particles. It is a positive electrode material. According to the positive electrode material for an electrical device according to the present embodiment, cycle durability can be improved in an electrical device using a sulfur-containing positive electrode active material.
  • the present invention will be described by taking as an example a stacked type (internal parallel connection type) all-solid lithium secondary battery, which is one form of an electric device.
  • the solid electrolyte that constitutes the all-solid-state lithium secondary battery is a material mainly composed of an ion conductor capable of conducting ions in a solid state. Therefore, the all-solid-state lithium secondary battery has the advantage that, unlike conventional liquid-type lithium secondary batteries, various problems due to the combustible organic electrolyte do not occur in principle.
  • the use of high-potential, high-capacity positive electrode materials and high-capacity negative electrode materials also has the advantage that the output density and energy density of the battery can be greatly improved.
  • FIG. 1 is a perspective view showing the appearance of a flat laminated all-solid lithium secondary battery that is an embodiment of the present invention.
  • 2 is a cross-sectional view taken along line 2--2 shown in FIG. 1.
  • FIG. 1 By using a laminate type, the battery can be made compact and have a high capacity.
  • laminated battery hereinafter also simply referred to as "laminated battery"
  • FIGS. 1 and 2 will be described in detail as an example.
  • the laminated battery 10a has a rectangular flat shape, and from both sides thereof, a negative electrode collector plate 25 and a positive electrode collector plate 27 for extracting electric power are pulled out.
  • the power generation element 21 is wrapped by the battery exterior material (laminate film 29) of the laminated battery 10a, and the periphery thereof is heat-sealed. It is sealed in the pulled out state.
  • the laminate type battery 10a of the present embodiment has a structure in which a flat and substantially rectangular power generation element 21 in which charge/discharge reactions actually progress is sealed inside a laminate film 29 that is a battery exterior material.
  • the power generation element 21 has a structure in which a positive electrode, a solid electrolyte layer 17, and a negative electrode are laminated.
  • the positive electrode has a structure in which positive electrode active material layers 15 containing a positive electrode active material are arranged on both sides of a positive electrode current collector 11′′.
  • the negative electrode contains a negative electrode active material on both sides of a negative electrode current collector 11′. It has a structure in which the active material layer 13 is arranged, whereby the adjacent positive electrode, solid electrolyte layer and negative electrode form one cell layer 19 .
  • the negative electrode current collector 11′ and the positive electrode current collector 11′′ are attached with a negative electrode current collector plate (tab) 25 and a positive electrode current collector plate (tab) 27, which are electrically connected to the electrodes (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 27 and the negative electrode current collector plate 25 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 current collector has a function of mediating transfer of electrons from the electrode active material layer.
  • Materials constituting the current collector are not particularly limited, and for example, metals and conductive resins can be employed.
  • a current collector is used as a member separate from these electrode active material layers. No need.
  • the negative electrode active material layer 13 contains a negative electrode active material.
  • the types of negative electrode active materials are not particularly limited, but include carbon materials, metal oxides and metal active materials.
  • a silicon-based negative electrode active material or a tin-based negative electrode active material may be used as the negative electrode active material.
  • silicon and tin belong to Group 14 elements and are known to be negative electrode active materials that can greatly improve the capacity of lithium secondary batteries. Since these simple substances can occlude and release a large number of charge carriers (lithium ions, etc.) per unit volume (mass), they become high-capacity negative electrode active materials.
  • a metal containing lithium may be used as the negative electrode active material.
  • a negative electrode active material is not particularly limited as long as it is an active material containing lithium, and examples thereof include metallic lithium and lithium-containing alloys.
  • Lithium-containing alloys include, for example, alloys of Li and at least one of In, Al, Si and Sn.
  • the negative electrode active material preferably contains metallic lithium or a lithium-containing alloy, a silicon-based negative electrode active material, or a tin-based negative electrode active material, and particularly preferably contains metallic lithium or a lithium-containing alloy.
  • the lithium secondary battery as an electrical device deposits metallic lithium as the negative electrode active material on the negative electrode current collector during the charging process, a so-called lithium deposition type. can be of Therefore, in such a form, 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 negative electrode active material layer does not have to exist at the time of complete discharge, depending on the case, a certain amount of the negative electrode active material layer made of metallic lithium may be arranged at the time of complete discharge.
  • the content of the negative electrode active material in the negative electrode active material layer is not particularly limited. more preferred.
  • the negative electrode active material layer preferably further contains a solid electrolyte.
  • a solid electrolyte By including the solid electrolyte in the negative electrode active material layer, the ion conductivity of the negative electrode active material layer can be improved.
  • solid electrolytes include sulfide solid electrolytes and oxide solid electrolytes, and 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 , Li2SP2S 5 - Li2OLiI , Li2S - SiS2 , Li2S -SiS2-LiI, Li2S - SiS2 - LiBr, Li2S - SiS2 -LiCl, Li2S - SiS2 - B2S 3 -LiI, Li2S - SiS2 - P2S5 -LiI , Li2S-B2S3 , Li2SP2S5 - ZmSn ( where m and n are
  • 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 contained in the active material layer is preferably a sulfide solid electrolyte containing the element P, and the sulfide solid electrolyte is a material containing Li 2 SP 2 S 5 as a main component. It is more preferable to have Furthermore, the sulfide solid electrolyte may contain halogens (F, Cl, Br, I).
  • the sulfide solid electrolyte comprises Li6PS5X , where X is Cl, Br or I, preferably Cl .
  • the ionic conductivity (e.g., Li ion conductivity) of the sulfide solid electrolyte at room temperature (25°C) is, for example, preferably 1 x 10-5 S/cm or more, and 1 x 10-4 S/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 examples include compounds having a NASICON structure.
  • 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 content of the solid electrolyte in the negative 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 negative electrode active material layer may further contain at least one of a conductive aid and a binder in addition to the negative electrode active material and solid electrolyte described above.
  • the thickness of the negative electrode active material layer varies depending on the intended configuration of the lithium secondary battery, it is preferably in the range of 0.1 to 1000 ⁇ m, for example.
  • the solid electrolyte layer is a layer interposed between the positive electrode active material layer and the negative electrode active material layer and essentially containing a solid electrolyte.
  • the specific form of the solid electrolyte contained in the solid electrolyte layer is not particularly limited, and the solid electrolytes exemplified in the column of the negative electrode active material layer and their preferred forms can be similarly employed.
  • the solid electrolyte layer may further contain a binder in addition to the predetermined solid electrolyte described above.
  • the thickness of the solid electrolyte layer varies depending on the structure of the target lithium secondary 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 positive electrode active material layer contains the positive electrode material for electrical devices according to one embodiment of the present invention.
  • the positive electrode material for an electric device is characterized by comprising composite material particles containing a sulfur-containing positive electrode active material in pores of a porous conductor, and an electronic conductor covering the surface of the composite material particles. do.
  • FIG. 3 is a cross-sectional schematic diagram of a positive electrode material 100' in the prior art.
  • FIG. 4 is a cross-sectional schematic diagram of the positive electrode material 100 which concerns on one Embodiment of this invention.
  • a porous conductor for example, porous carbon
  • a positive electrode active material for example, sulfur
  • the positive electrode active material 120 is also arranged on the surface of the porous conductor 110 other than the pores 110a.
  • the inside of the pores 110a is filled with the positive electrode active material 120 (the state of (a) in FIG. 3).
  • the positive electrode active material 120 expands by storing lithium ions.
  • part of the positive electrode active material 120 filled in the inside of the pores 110a is pushed out of the pores 110a (state of (B) in FIG. 3).
  • the positive electrode active material 120 contracts by releasing lithium ions.
  • part of the positive electrode active material 120 pushed out of the pores 110a is separated from the surface of the porous conductor 110, and electrons cannot be transferred (state of (C) in FIG. 3).
  • the surface of the composite material particles in which the positive electrode active material 120 is filled inside the pores 110a is an electron conductor (for example, graphene) (state of (a) in FIG. 4).
  • the positive electrode active material 120 expands by storing lithium ions.
  • a part of the positive electrode active material 120 filled inside the pores 110a is pushed out of the pores 110a (state of (B) in FIG. 4).
  • the positive electrode active material 120 contracts by releasing lithium ions.
  • a porous conductor is made of a conductive material and has pores (voids) inside.
  • a positive electrode active material containing sulfur which will be described later, many contacts are formed between the walls of the pores and the positive electrode active material, and electrons are exchanged through the contacts.
  • the type of the porous conductor is not particularly limited, and carbon materials, metal materials, conductive polymer materials, and the like can be used as appropriate, with carbon materials being preferred.
  • carbon materials include activated carbon, Ketjenblack (registered trademark) (highly conductive carbon black), (oil) furnace black, channel black, thermal black, carbon black such as lamp black, mesoporous carbon, coke, and natural graphite. , carbon particles (carbon support) made of artificial graphite and the like.
  • activated carbon Ketjenblack (registered trademark) (highly conductive carbon black), (oil) furnace black, channel black, thermal black, carbon black such as lamp black, mesoporous carbon, coke, and natural graphite.
  • carbon particles (carbon support) made of artificial graphite and the like.
  • at least one selected from the group consisting of activated carbon, carbon black and mesoporous carbon is preferable, and at least one selected from the group consisting of activated carbon and mesoporous
  • the main component of the carbon material is carbon.
  • “mainly composed of carbon” means containing carbon atoms as the main component, and is a concept that includes both consisting only of carbon atoms and consisting essentially of carbon atoms.
  • the expression “substantially composed of carbon atoms” means that 2 to 3% by mass or less of impurities can be mixed.
  • the BET specific surface area of the porous conductor (preferably carbon material) is preferably 200 m 2 /g or more, more preferably 500 m 2 /g or more, and further preferably 800 m 2 /g or more. It is preferably 1200 m 2 /g or more, particularly preferably 1500 m 2 /g or more, most preferably 1500 m 2 /g or more.
  • the pore volume of the porous conductor is preferably 1.0 mL/g or more, more preferably 1.3 mL/g or more, and even more preferably 1.5 mL/g or more.
  • the BET specific surface area and pore volume of the porous conductor can be measured by nitrogen adsorption/desorption measurement. This nitrogen adsorption/desorption measurement is performed using BELSORP mini manufactured by Microtrac Bell Co., Ltd. at a temperature of -196°C by a multipoint method. The BET specific surface area is obtained from the adsorption isotherm in the relative pressure range of 0.01 ⁇ P/P 0 ⁇ 0.05. Also, the pore volume is determined from the volume of adsorbed N2 at a relative pressure of 0.96.
  • the pore diameter (average pore diameter) of the porous conductor is not particularly limited, but the lower limit is preferably 0.5 nm or more, more preferably 1 nm or more, further preferably 2 nm or more, further preferably 5 nm. It is particularly preferable that it is above.
  • the upper limit is preferably 500 nm or less, more preferably 100 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less. If the pore diameter is within the above range, electrons can be sufficiently supplied to the active material located away from the pore walls in the sulfur-containing positive electrode active material arranged inside the pores.
  • the pore size of the porous conductor can be calculated by nitrogen adsorption/desorption measurement in the same manner as described above.
  • the average particle size (primary particle size) when the porous conductor is particulate is not particularly limited, but is preferably 2 to 50 ⁇ m, more preferably 2 to 20 ⁇ m. More preferably ⁇ 10 ⁇ m.
  • the "particle diameter” means the maximum distance L among the distances between any two points on the outline of the particle.
  • the value of the "average particle size” is the average value of the particle size ( For example, a value calculated as the average particle diameter of 100 particles) is adopted.
  • the positive electrode material according to this embodiment essentially contains a sulfur-containing positive electrode active material as a positive electrode active material.
  • the type of the positive electrode active material containing sulfur is not particularly limited, but examples thereof include elemental sulfur (S) and lithium sulfide (Li 2 S), as well as particles or thin films of organic sulfur compounds or inorganic sulfur compounds. Any substance can be used as long as it can release lithium ions during charging and absorb lithium ions during discharging by utilizing a reduction reaction.
  • Inorganic sulfur compounds are particularly preferred because of their excellent stability, and specific examples include elemental sulfur (S), TiS 2 , TiS 3 , TiS 4 , NiS, NiS 2 , CuS, FeS 2 , Li 2 S, MoS 2 , MoS 3 , MnS, MnS 2 , CoS, CoS 2 and the like.
  • S, Li 2 S, S-carbon composite, TiS 2 , TiS 3 , TiS 4 , FeS 2 and MoS 2 are preferable, elemental sulfur (S) and lithium sulfide (Li 2 S), TiS 2 and FeS 2 is more preferable, and elemental sulfur (S) and lithium sulfide (Li 2 S) are particularly preferable from the viewpoint of high capacity.
  • the positive electrode material according to this embodiment may further contain a sulfur-free positive electrode active material in addition to the sulfur-containing positive electrode active material.
  • the ratio of the content of the sulfur-containing positive electrode active material to 100% by mass of the total amount of the positive electrode active material is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.
  • the positive electrode material according to this embodiment essentially contains an electron conductor.
  • electrons can be transferred to and from the positive electrode active material that has separated from the surface of the porous conductor due to charging and discharging.
  • the ratio of the positive electrode active material that does not contribute to the charge-discharge reaction can be kept low, so that the electrical device to which the positive electrode material is applied has improved cycle durability.
  • the type of electronic conductor is not particularly limited as long as it has higher electronic conductivity than the positive electrode active material containing sulfur, but is selected from conductive carbon, metal, metal oxide, metal sulfide and conductive polymer. At least one is preferred.
  • conductive carbon include carbon fiber, graphene, carbon nanotubes (single-wall carbon nanotubes and multi-wall carbon nanotubes), carbon nanohorns, carbon nanoballoons, fullerenes, and the like.
  • metals include nickel, titanium, aluminum, copper, platinum, iron, chromium, tin, zinc, indium, antimony, vanadium, and alloys containing at least one of these metals.
  • alloys include stainless steel (SUS), Inconel (registered trademark), Hastelloy (registered trademark), and other Fe--Cr alloys and Ni--Cr alloys.
  • metal oxides include titanium oxide (TiO 2 ) zinc oxide (ZnO), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), indium tin oxide (ITO), vanadium oxide ( V 2 O 5 ), triiron tetroxide (Fe 3 O 4 ), zirconium oxide (ZrO 2 ), tungsten (IV) oxide (WO 2 ), and the like.
  • Metal sulfides include iron sulfide (FeS), copper (I) sulfide (Cu 2 S), cadmium sulfide (CdS), indium sulfide (III) (In 2 S 3 ), and the like.
  • conductive polymers include carbon polysulfide, polyaniline, polypyrrole, polythiophene (e.g., poly3,4-ethylenedioxythiophene (PDOT)), polyacetylene, polyparaphenylene, polyphenylenevinylene, polyacrylonitrile, and polyoxadia. be done.
  • conductive carbon is preferably at least one selected from the group consisting of conductive carbon and conductive polymer because it exhibits high electronic conductivity, and at least one selected from the group consisting of conductive carbon.
  • conductive carbon is more preferably a seed, more preferably carbon fiber, graphene, carbon nanotube (single-walled carbon nanotube and multi-walled carbon nanotube), and particularly preferably graphene.
  • the shape of the electronic conductor is not particularly limited, and may be particulate, fibrous, sheet-like, or the like as appropriate. From the viewpoint of good coating of the surface of the composite material particles, it is fibrous or sheet-like. is preferred. Also, the size of the electron conductor is not particularly limited, but preferred sizes of the electron conductor are as follows from the viewpoint of good coating of the surfaces of the composite particles.
  • the ratio of the pore diameter of the porous conductor to the average fiber length of the fibrous electron conductor is greater than 0. It is preferably larger than 1, more preferably larger than 0 and 0.1 or less, further preferably larger than 0 and 0.01 or less, and particularly preferably 0.0001 or more and 0.01 or less. or (2) the shape of the electron conductor is a sheet, and the ratio of the pore size of the porous conductor to the average longest diameter in the plane direction of the sheet-like electron conductor is greater than 0 and less than 1. It is preferably greater than 0 and 0.1 or less, more preferably greater than 0 and 0.01 or less, and particularly preferably 0.0001 or more and 0.01 or less.
  • the shape of the electron conductor is fibrous means that the aspect ratio of the electron conductor (long axis length / short axis length) is 5 or more.
  • the average value referred to here is, for example, the average value of 100 electron conductors when the electron conductor is particulate or fibrous.
  • the shape of the electron conductor is sheet-like means that "the ratio of the major axis in the plane direction to the thickness” and “the ratio of the minor axis in the plane direction to the thickness” observed using observation means such as SEM and TEM ratio” is at least 100 or more.
  • the value of the "average fiber length of the fibrous electron conductor” is the average length of the long axis of the fibrous electron conductor observed in several to several tens of visual fields using observation means such as SEM and TEM. A value calculated as a value (for example, the average length of the long axis of 100 fibers) shall be adopted.
  • the value of the "average thickness of the sheet-shaped electronic conductor” is the average longest diameter in the plane direction of the sheet-shaped electronic conductor (for example, , the average value of the average longest diameter in the surface direction of 100 sheets).
  • the mass ratio of the electron conductor to the porous conductor is preferably greater than 0 and less than 1, more preferably 0.01 or more and 0.5 or less, and 0.5. It is more preferably 1 or more and 0.5 or less.
  • the mass ratio is greater than 0, the utilization efficiency of the sulfur-containing positive electrode active material can be further improved.
  • the ratio is less than 1, it is possible to suppress a decrease in charge/discharge capacity.
  • the positive electrode material according to this embodiment preferably further contains an electrolyte in the pores of the porous conductor.
  • electrolyte By containing the electrolyte, charge carriers can smoothly move in and out of the surface of the positive electrode active material containing sulfur, and the output characteristics can be improved.
  • the specific form of the electrolyte is not particularly limited, and solid electrolytes such as the sulfide solid electrolyte and the oxide solid electrolyte exemplified in the column of the liquid electrolyte and the negative electrode active material layer can be appropriately employed. preferable.
  • the electrolyte is a solid electrolyte
  • at least part of the solid electrolyte and at least part of the sulfur-containing positive electrode active material are preferably arranged inside the pores of the porous conductor so as to be in contact with each other.
  • the solid electrolyte contained in the positive electrode material according to the present embodiment is preferably a sulfide solid electrolyte.
  • the sulfide solid electrolyte contains alkali metal atoms.
  • Alkali metal atoms that can be contained in the sulfide solid electrolyte include lithium atoms, sodium atoms, and potassium atoms. Among them, lithium atoms are preferable because of their excellent ion conductivity.
  • the solid electrolyte contained in the solid electrolyte layer contains alkali metal atoms (e.g., lithium atoms, sodium atoms or potassium atoms; preferably lithium atoms), phosphorus atoms and/or boron atoms. It is.
  • the sulfide solid electrolyte comprises Li6PS5X , where X is Cl, Br or I, preferably Cl . Since these solid electrolytes have high ionic conductivity, they can particularly effectively contribute to the improvement of output characteristics.
  • composite material particles are produced by the following method. First, a porous conductor and a sulfur-containing positive electrode active material are sufficiently mixed by mixing using a mixing means such as a mortar or by milling using a pulverizing means such as a planetary ball mill. The resulting mixture is then heat treated at elevated temperature.
  • a mixing means such as a mortar or by milling using a pulverizing means such as a planetary ball mill. The resulting mixture is then heat treated at elevated temperature.
  • the heat treatment melts the sulfur-containing positive electrode active material, filling the pores of the porous conductor with the positive electrode active material.
  • the heat treatment temperature is not particularly limited, but is preferably 170° C. or higher, more preferably 175° C. or higher, still more preferably 180° C. or higher, and particularly preferably 185° C. or higher.
  • the upper limit of the heat treatment temperature is also not particularly limited, but is, for example, 250° C. or less, preferably 200° C. or less.
  • the heat treatment time is not particularly limited, but may be about 1 to 5 hours.
  • the manufacturing method includes mixing or milling a mixture of the porous conductor and the solid electrolyte.
  • a solid electrolyte e.g., a sulfide solid electrolyte
  • the above-described heat treatment is performed in a state in which a positive electrode active material containing sulfur is additionally added to the mixture.
  • the positive electrode active material and the solid electrolyte penetrate into the pores of the porous conductor having pores by heat treatment, and a preferable positive electrode material is obtained in which a large number of three-phase interfaces are formed. be done.
  • a solution in which a solid electrolyte is dissolved in an appropriate solvent capable of dissolving the solid electrolyte is first prepared, and the porous conductor is impregnated therein.
  • a porous conductor impregnated with a solid electrolyte can be obtained by heating to a temperature for about 1 to 5 hours.
  • the solid electrolyte usually penetrates and adheres to the inside of the pores of the porous conductor.
  • the above-described heat treatment is performed in a state in which the positive electrode active material containing sulfur is additionally added to the composite, thereby melting the positive electrode active material and filling the pores of the porous conductor with the positive electrode active material.
  • Preferred morphologies of composite particles can be obtained that are infiltrated and that form a large number of three-phase interfaces. According to this manufacturing method employing a wet method, composite particles having particularly excellent initial capacity characteristics and charge/discharge rate characteristics can be obtained.
  • the surfaces of the composite particles obtained by the above manufacturing method are coated with an electronic conductor.
  • the coating method is not particularly limited, it is preferable to employ a mechanofusion method using a ball mill or the like. By such a dry coating, the electronic conductor is physically adsorbed on the surface of the composite material particles, thereby forming a coating of the electronic conductor on the surface of the composite material particles.
  • the coating may be formed by coating the surfaces of the composite particles with an electronic conductor plus a binder.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited. more preferred. Note that this content value is calculated based on the mass of only the positive electrode active material, excluding the porous conductor and the solid electrolyte.
  • the positive electrode active material layer may further contain a conductive aid (a material that does not hold the positive electrode active material or solid electrolyte inside pores) and/or a binder.
  • the positive electrode active material layer preferably further contains a solid electrolyte in addition to the positive electrode material described above.
  • the thickness of the positive electrode active material layer varies depending on the intended configuration of the lithium secondary battery, it is preferably in the range of 0.1 to 1000 ⁇ m, for example.
  • the material constituting the current collectors (25, 27) is not particularly limited, and known highly conductive materials conventionally used as current collectors for secondary batteries can be used. Metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable as the constituent material of the current collector plate. From the viewpoint of light weight, corrosion resistance and high conductivity, aluminum and copper are more preferred, and aluminum is particularly preferred. The same material or different materials may be used for the positive electrode collector plate 27 and the negative electrode collector plate 25 .
  • the current collector and the current collector plate may be electrically connected via a positive lead or a negative lead.
  • Materials used in known 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 as shown in FIGS. 1 and 2, a bag-like case using a laminate film 29 containing aluminum that can cover the power generation element is used.
  • the laminated film may be, for example, a laminated 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 laminated 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 battery according to this embodiment is suitably used as a power source for driving EVs and HEVs.
  • the all-solid-state lithium secondary battery which is an embodiment of an electric device, has been described. It can be changed as appropriate.
  • bipolar batteries that include a bipolar electrode having a negative electrode active material layer with a
  • the electric device does not have to be an all-solid lithium secondary battery. That is, the solid electrolyte layer may further contain a conventionally known liquid electrolyte (electrolytic solution).
  • the amount of the liquid electrolyte (electrolyte solution) that can be contained in the solid electrolyte layer is not particularly limited, but the amount is such that the shape of the solid electrolyte layer formed by the solid electrolyte is maintained and the liquid electrolyte (electrolyte solution) does not leak. is preferably the amount of
  • a lithium secondary battery to which the positive electrode material according to the present embodiment is applied is not limited to a laminated flat shape.
  • the wound type lithium secondary battery may have a cylindrical shape, or may have a rectangular flat shape obtained by deforming such a cylindrical shape. , is not particularly limited.
  • An assembled battery is an object configured by connecting a plurality of batteries. Specifically, at least two or more are used, and serialization or parallelization or both of them are used. By connecting in series and in parallel, it is possible to freely adjust the capacity and voltage.
  • a plurality of batteries can be connected in series or in parallel to form a small detachable assembled battery.
  • a plurality of these detachable small battery packs are further connected in series or in parallel to form a large-capacity, large-capacity battery suitable for vehicle drive power sources and auxiliary power sources that require high volumetric energy density and high volumetric output density.
  • a battery or an assembled battery formed by combining a plurality of these batteries can be mounted on the vehicle.
  • a plug-in hybrid electric vehicle with a long EV driving range and an electric vehicle with a long driving range per charge can be configured by mounting such a battery.
  • Batteries or assembled batteries made by combining a plurality of these, for example, in the case of automobiles, hybrid vehicles, fuel cell vehicles, electric vehicles (all four-wheeled vehicles (commercial vehicles such as passenger cars, trucks, buses, light vehicles, etc.) , two-wheeled vehicles (motorcycles) and three-wheeled vehicles) will provide a long-lasting and highly reliable automobile.
  • the application is not limited to automobiles, for example, it can be applied to various power sources for other vehicles, such as moving bodies such as trains, and power sources for installation such as uninterruptible power supplies. It can also be used as
  • Example 1 (Preparation of Solid Electrolyte Impregnated Porous Conductor)
  • a solid electrolyte Li 6 PS 5 Cl, manufactured by Ampcera
  • 100 mL of super-dehydrated ethanol manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
  • the solid electrolyte was dissolved in ethanol by stirring.
  • a porous conductor porous carbon, average particle size: 5 ⁇ m, pore size: 30 nm
  • the container containing the dispersion was connected to a vacuum device, and the inside of the container was evacuated to 1 Pa or less by an oil rotary pump while stirring the dispersion in the container with a magnetic stirrer. Since the solvent ethanol volatilized under reduced pressure, the ethanol was removed over time, leaving the porous conductor impregnated with the solid electrolyte in the container. After the ethanol was removed under reduced pressure in this way, the material was heated to 180° C. under reduced pressure and subjected to heat treatment for 3 hours to prepare a solid electrolyte-impregnated porous conductor.
  • test cell all-solid lithium secondary battery
  • the battery was fabricated in a glove box in an argon atmosphere with a dew point of ⁇ 68° C. or less.
  • a cylindrical convex punch (10 mm diameter) made of SUS was inserted into one side of a cylindrical tube jig made by Macor (inner diameter 10 mm, outer diameter 23 mm, height 20 mm), and a solid electrolyte (Ampcera Co.) 80 mg of Li 6 PS 5 Cl) was added.
  • a positive electrode active material layer with a diameter of 10 mm and a thickness of about 0.06 mm was formed on one side of the solid electrolyte layer by inserting a material that also serves as an electric body and pressing for 3 minutes at a pressure of 300 MPa.
  • the lower cylindrical convex punch (which also serves as the negative electrode current collector) is extracted, and as the negative electrode, a lithium foil (manufactured by Nilaco Corporation, thickness 0.20 mm) punched to a diameter of 8 mm and an indium foil (thickness 0.20 mm manufactured by Nilaco) punched to a diameter of 9 mm ( Nilaco Co., Ltd., thickness 0.30 mm), put it from the bottom of the cylindrical tube jig so that the indium foil is located on the side of the solid electrolyte layer, insert the cylindrical convex punch again, and apply a pressure of 75 MPa.
  • a lithium-indium negative electrode was formed by pressing for 3 minutes at .
  • test cell all solid lithium secondary in which the negative electrode current collector (punch), the lithium-indium negative electrode, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector (punch) are laminated in this order battery) was produced.
  • Example 2 By the same method as in Example 1 above, except that the composite particles and the electronic conductor were blended so that the mass ratio of the electronic conductor to the porous conductor in the composite particles was 0.05. , to prepare a test cell.
  • Example 3 By the same method as in Example 1 above, except that the composite particles and the electronic conductor were blended so that the mass ratio of the electronic conductor to the porous conductor in the composite particles was 0.1. , to prepare a test cell.
  • Example 4 By the same method as in Example 1 above, except that the composite particles and the electronic conductor were blended so that the mass ratio of the electronic conductor to the porous conductor in the composite particles was 0.2. , to prepare a test cell.
  • Example 5 By the same method as in Example 1 above, except that the composite particles and the electronic conductor were blended so that the mass ratio of the electronic conductor to the porous conductor in the composite particles was 0.5. , to prepare a test cell.
  • Example 6 A test cell was produced in the same manner as in Example 3 described above, except that carbon nanotubes (average fiber length: 5 ⁇ m) were used as the electron conductor instead of graphene.
  • Example 7 A test cell was produced in the same manner as in Example 3 described above, except that carbon fiber (average fiber length: 10 ⁇ m) was used as the electron conductor instead of graphene.
  • Example 8 A test cell was produced in the same manner as in Example 1 described above, except that porous carbon (average particle size: 4.8 ⁇ m, pore size: 1 nm) was used as the porous conductor.
  • Example 9 A test cell was produced in the same manner as in Example 1 described above, except that porous carbon (average particle size: 6 ⁇ m, pore size: 5 nm) was used as the porous conductor.
  • Example 10 A test cell was produced in the same manner as in Example 1 described above, except that porous carbon (average particle size: 5 ⁇ m, pore size: 100 nm) was used as the porous conductor.
  • Example 11 A test cell was produced in the same manner as in Example 1 described above, except that porous carbon (average particle size: 5 ⁇ m, pore size: 500 nm) was used as the porous conductor.
  • Example 12 A test cell was produced in the same manner as in Example 3 above, except that PDOT (3,4-ethylenedioxythiophene) (average longest diameter: 5 ⁇ m) was used as the electron conductor instead of graphene. .
  • Example 13 Graphene (average longest diameter 2.5 ⁇ m) is used as an electron conductor, and the composite material particles and the electron conductor are combined so that the mass ratio of the electron conductor to the porous conductor in the composite material particles is 15.
  • a test cell was produced in the same manner as in Example 1 described above, except that the mixture was blended as follows.
  • cycle durability One cycle was a process of full charging with a 0.05C-2.5V constant current and constant voltage charge under the condition of a cutoff current of 0.01C, followed by discharging at a current density of 0.05C with a cutoff voltage of 0.5V. This cycle was repeated 100 times, and the capacity retention rate was obtained from the ratio of the 100th discharge capacity to the initial discharge capacity.
  • graphene As an electronic conductor, a higher capacity retention rate can be obtained. This is believed to be due to the high electronic conductivity of graphene. In addition, it is considered that the graphene is sheet-like, so that the surfaces of the composite particles can be satisfactorily coated.
  • the capacity retention rate can be sufficiently improved. This is probably because even if the amount of the electron conductor is small, the presence of the electron conductor on the surface of the composite particles increases the amount of sulfur that can contribute to the charge-discharge reaction. It should be noted that there is a tendency that as the amount of the electron conductor is increased, the capacity retention rate is improved.
  • 10a layered battery 11′ negative electrode current collector, 11′′ positive electrode current collector, 13 negative electrode active material layer, 15 positive electrode active material layer, 17 solid electrolyte layer, 19 cell layer, 21 power generation element, 25 negative electrode current collector , 27 Positive electrode current collector, 29 Laminate film, 100, 100' Positive electrode material, 110 Porous conductor (porous carbon), 110a Pores, 120 Positive electrode active material (sulfur), 130 Electronic conductor (graphene).

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PCT/IB2021/000602 2021-09-02 2021-09-02 電気デバイス用正極材料ならびにこれを用いた電気デバイス用正極および電気デバイス Ceased WO2023031638A1 (ja)

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