WO2023031639A1 - 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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WO2023031639A1
WO2023031639A1 PCT/IB2021/000603 IB2021000603W WO2023031639A1 WO 2023031639 A1 WO2023031639 A1 WO 2023031639A1 IB 2021000603 W IB2021000603 W IB 2021000603W WO 2023031639 A1 WO2023031639 A1 WO 2023031639A1
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Prior art keywords
positive electrode
active material
electrode active
conductor
sulfur
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PCT/IB2021/000603
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English (en)
French (fr)
Japanese (ja)
Inventor
美咲 藤本
淳史 伊藤
正樹 小野
航 荻原
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 US18/688,560 priority Critical patent/US20240356038A1/en
Priority to EP21955283.3A priority patent/EP4398334A4/en
Priority to JP2023544787A priority patent/JPWO2023031639A1/ja
Priority to PCT/IB2021/000603 priority patent/WO2023031639A1/ja
Priority to CN202180101948.4A priority patent/CN117882208A/zh
Publication of WO2023031639A1 publication Critical patent/WO2023031639A1/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
    • H01M4/136—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
    • 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
    • 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
    • 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
    • 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
    • H01M4/62—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
    • 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
    • H01M4/626—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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 present inventors have found that the above problems can be solved by filling the pores of the porous conductor with an electron conductor together with a positive electrode active material containing sulfur, and have completed the present invention.
  • One aspect of the present invention is a positive electrode material for an electrical device, which includes a positive electrode active material containing sulfur and an electronic conductor in the pores of a porous conductor.
  • 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 aspect of the present invention is a positive electrode material for an electrical device, which includes a positive electrode active material containing sulfur and an electronic conductor in the pores of a porous conductor.
  • 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 contains a positive electrode active material containing sulfur and an electronic conductor in the pores of the porous conductor (the positive electrode active material containing sulfur is contained in the pores of the porous conductor , an electronic conductor).
  • 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 (eg, mesoporous carbon) 110 has many pores 110a.
  • a positive electrode active material (for example, sulfur) 120 is filled and arranged inside the pores 110a.
  • 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.
  • a portion of the positive electrode active material 120 pushed out of the pores 110 a is located away from the surface of the porous conductor 110 .
  • the positive electrode active material 120 Since the positive electrode active material 120 has low electron conductivity, a portion of the positive electrode active material 120 distant from the surface of the porous conductor 110 cannot sufficiently transfer electrons (state of (C) in FIG. 3). By repeating charge-discharge cycles in this way, the percentage of the positive electrode active material 120 that does not contribute to the charge-discharge reaction increases, and the cycle durability of the electrical device to which the positive electrode material 100' is applied is reduced.
  • the inside of the pores 110a is filled with an electron conductor 130 (for example, carbon fiber) together with the cathode active material 120. (state of (a) in FIG. 4).
  • the positive electrode active material 120 expands by storing lithium ions.
  • part of the positive electrode active material 120 and part of the electron conductor 130 filled in the pores 110a are both pushed out of the pores 110a (state of (B) in FIG. 4).
  • the positive electrode active material 120 contracts by releasing lithium ions.
  • FIG. 1 in the embodiment shown in FIG.
  • 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, acetylene black, thermal black, carbon black such as lamp black, mesoporous carbon, and coke. , natural graphite, artificial graphite, and the like.
  • activated carbon Ketjenblack (registered trademark) (highly conductive carbon black), (oil) furnace black, channel black, acetylene black, thermal black, carbon black such as lamp black, mesoporous carbon, and coke.
  • activated carbon Ketjenblack (registered trademark) (highly conductive carbon black), (oil) furnace black, channel black, acetylene black, thermal black, carbon black such as lamp black, mesoporous carbon, and coke.
  • 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 electronic conductivity of the porous conductor is preferably 1 ⁇ 10 ⁇ 5 S/m or more, more preferably 1 ⁇ 10 ⁇ 4 S/m or more.
  • the upper limit of the electronic conductivity is not particularly limited, it is usually less than 1 S/m. If the electronic conductivity is within the above range, the utilization efficiency of the positive electrode active material containing sulfur can be sufficiently improved.
  • the electronic conductivity in this specification is the reciprocal of the electrical resistivity.
  • the electrical resistivity was measured by mixing a sample with 10% by mass of polytetrafluoroethylene (PTFE, Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) and forming a sheet (thickness: 100 ⁇ m). It can be measured by the terminal method.
  • 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 preferably 10 nm or more, and most preferably 10 nm or more.
  • the upper limit is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, particularly preferably 50 nm or less, and most preferably 30 nm or more. 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.
  • the electronic conductor is filled in the pores of the porous conductor together with the positive electrode active material containing sulfur, thereby forming a conductive path on the surface of the positive electrode active material.
  • electrons can be given and received even to the positive electrode active material that has separated from 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, polyacetylene, polyparaphenylene, polyphenylenevinylene, polyacrylonitrile, and polyoxadia.
  • conductive carbon is preferred because it exhibits high electronic conductivity, carbon fiber, graphene, and carbon nanotubes (single-walled carbon nanotube and multi-walled carbon nanotube) are more preferred, and carbon fiber is even more preferred.
  • the electronic conductivity of the electronic conductor is preferably higher than that of the porous conductor.
  • the electron conductivity of the electron conductor is preferably 1 S/m or more, more preferably 1 ⁇ 10 2 S/m or more, and further preferably 1 ⁇ 10 4 S/m or more. More preferably, it is at least ⁇ 10 5 S/m.
  • the upper limit of the electronic conductivity is not particularly limited, it is usually 1 ⁇ 10 7 S/m or less. If the electronic conductivity is within the above range, the utilization efficiency of the positive electrode active material containing sulfur can be further improved.
  • the shape of the electronic conductor is not particularly limited, and a particle, fiber, sheet, or the like can be used as appropriate. Also, the size of the electronic conductor is not particularly limited as long as at least part of the electronic conductor can be filled in the pores of the porous conductor.
  • the amount of the electron conductor is preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass, with respect to 100% by mass of the positive electrode active material containing sulfur. is more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass.
  • the ratio is 0.1% by mass or more, the utilization efficiency of the sulfur-containing positive electrode active material can be further improved.
  • the ratio is 25% by mass or less, the amount of the positive electrode active material does not become too small, so the charge/discharge capacity can be maintained.
  • 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 liquid electrolytes and sulfide solid electrolytes and oxide solid electrolytes exemplified in the column of the negative electrode active material layer can be appropriately employed.
  • 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.
  • the reason why the positive electrode material according to the present embodiment contributes to the excellent cycle durability is that the positive electrode active material containing sulfur and the electron conductor are filled in the pores of the porous conductor. It is presumed that this is due to the well-formed path.
  • the porous conductor, the positive electrode active material containing sulfur, and the electron conductor are subjected to mixing treatment using a mixing means such as a mortar, or milling using a pulverizing means such as a planetary ball mill. Mix thoroughly during processing. The resulting mixture is then heat treated at elevated temperature.
  • the heat treatment melts the sulfur-containing positive electrode active material, and the pores of the porous conductor are filled with the electron conductor together 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 method of performing the above-described heat treatment in a state in which a positive electrode active material containing sulfur and an electron conductor are additionally added to the mixture may be employed. According to such a method, the positive electrode active material, the electron conductor, and the solid electrolyte enter the pores of the porous conductor having pores by heat treatment, forming a large number of three-phase interfaces. A cathode material is obtained.
  • 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 solid electrolyte-impregnated porous conductor can be obtained by heating to a temperature for about 1 to 5 hours. In this composite, 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 and the electron conductor are additionally added to the composite, so that the positive electrode active material is melted and placed inside the pores of the porous conductor.
  • a positive electrode material in a preferred form in which the positive electrode active material and the electron conductor are infiltrated and many three-phase interfaces are formed. According to this manufacturing method employing a wet method, a positive electrode material having particularly excellent initial capacity characteristics and charge/discharge rate characteristics can be obtained.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited. It is more preferably in the range of 40 to 80% by mass, particularly preferably in the range of 40 to 75% by mass, most preferably in the range of 40 to 70% by mass. 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 positive electrode material) Activated carbon A (MSC30, manufactured by Kansai Coke and Chemicals Co., Ltd., BET specific surface area exceeding 3000 m 2 /g, average particle size 9 ⁇ m, pore size 2 nm, Electronic conductivity 0.0002 S/m) 9.8 parts by mass, sulfur (manufactured by Aldrich) 48.8 parts by mass, and carbon fiber as an electron conductor (fiber diameter 0.2 ⁇ m, electronic conductivity 100 S/m) After adding 2.4 parts by mass and sufficiently mixing with an agate mortar, the mixed powder was placed in a sealed pressure-resistant autoclave container and heated at 170° C. for 3 hours. Thus, the sulfur was melted and the porous conductor was impregnated with the sulfur in which the electronic conductor was dispersed, thereby obtaining a positive electrode material powder.
  • MSC30 manufactured by Kansai Coke and Chemicals Co., Ltd., BET specific surface area exceeding 3000 m 2 /g,
  • 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 SUS cylindrical convex punch (diameter of 10 mm) was inserted into one side of a Macor cylindrical tube jig (inner diameter: 10 mm, outer diameter: 23 mm, height: 20 mm), and a sulfide solid electrolyte ( 80 mg of Li 6 PS 5 Cl (manufactured by Ampcera) 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 Except that activated carbon B (BET specific surface area exceeding 1000 m 2 /g, average particle diameter 6 ⁇ m, pore diameter 0.8 nm, electronic conductivity 0.0002 S/m) was used as the porous conductor instead of activated carbon A.
  • a test cell was produced by the same method as in Example 1 described above.
  • Example 3 Carbon black (Ketjen Black (registered trademark), manufactured by Lion Corporation, average particle size: 12 ⁇ m, pore size: 2.4 nm, electronic conductivity: 0.01 S/m) was used as the porous conductor instead of activated carbon A.
  • a test cell was produced in the same manner as in Example 1 except for the above.
  • Example 4 Mesoporous carbon A (P(3)010, manufactured by Toyo Tanso Co., Ltd., average particle diameter 5 ⁇ m, pore diameter 10 nm, electronic conductivity 0.125 S / m) was used as the porous conductor instead of activated carbon A.
  • a test cell was produced by the same method as in Example 1 described above.
  • Example 5 Mesoporous carbon B (MJ (4) 150, manufactured by Toyo Tanso Co., Ltd., average particle diameter 8 ⁇ m, pore diameter 150 nm, electronic conductivity 0.07692 S / m) was used as the porous conductor instead of activated carbon A.
  • a test cell was produced by the same method as in Example 1 described above.
  • Example 6 Using the same method as in Example 4 above, except that graphene (thickness of less than 0.01 ⁇ m, electronic conductivity of 7.5 ⁇ 10 5 S/m) was used as the electron conductor instead of carbon fiber. A test cell was produced.
  • Example 7 A test was performed in the same manner as in Example 4 above, except that carbon nanotubes (fiber diameter less than 0.1 ⁇ m, electronic conductivity 5 ⁇ 10 5 S/m) were used as electron conductors instead of carbon fibers. A cell for this purpose was fabricated.
  • Example 8 ZnO (particle size 0.2 ⁇ m, electronic conductivity 0.66667 S/m) was used as the electron conductor instead of carbon fiber, and the amounts of the porous conductor, sulfur, and electron conductor were changed to the porous A test cell was produced in the same manner as in Example 4 described above, except that the conductor was 9.5 parts by mass, the sulfur was 47.6 parts by mass, and the electronic conductor was 4.8 parts by mass.
  • Example 9 A test cell was produced in the same manner as in Example 8 described above, except that SnO 2 (particle size: 0.2 ⁇ m, electronic conductivity: 100 S/m) was used as the electron conductor instead of ZnO.
  • Example 10 A test cell was produced in the same manner as in Example 8 above, except that V 2 O 5 (particle size: 0.2 ⁇ m, electronic conductivity: 1 S/m) was used as the electron conductor instead of ZnO. bottom.
  • Example 11 A test cell was produced in the same manner as in Example 8 described above, except that FeS (particle size: 0.2 ⁇ m, electronic conductivity: 0.2 S/m) was used as the electron conductor instead of ZnO. .
  • Example 12 By the same method as in Example 8 described above, except that carbon polysulfide (particle size: 0.2 ⁇ m, electronic conductivity: 1.5 ⁇ 10 ⁇ 6 S/m) was used as the electron conductor instead of ZnO. , to prepare a test cell.
  • Example 13 Example as described above, except that the amounts of porous conductor, sulfur, and electronic conductor were 9.5 parts by weight of porous conductor, 47.6 parts by weight of sulfur, and 4.8 parts by weight of electronic conductor. A test cell was produced in the same manner as in 4.
  • Example 14 Example as described above, except that the amounts of porous conductor, sulfur, and electronic conductor were 9.1 parts by weight of porous conductor, 45.5 parts by weight of sulfur, and 9.1 parts by weight of electronic conductor. A test cell was produced in the same manner as in 4.
  • Example 15 Example as described above, except that the amounts of porous conductor, sulfur, and electronic conductor were 8.7 parts by weight porous conductor, 43.5 parts by weight sulfur, and 13.0 parts by weight electronic conductor. A test cell was produced in the same manner as in 4.
  • Example 16 A test cell was produced in the same manner as in Example 4 described above, except that (preparation of positive electrode material) was performed by the following method.
  • 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.
  • Example 17 Example above except that the amounts of porous conductor, sulfur, and electronic conductor were 10.0 parts by weight porous conductor, 49.8 parts by weight sulfur, and 0.5 parts by weight electronic conductor. A test cell was produced in the same manner as in 4.
  • Example 1 The above-described example except that carbon fiber was not used as an electron conductor, and that the amounts of the porous conductor (activated carbon A) and sulfur were 10 parts by mass of the porous conductor and 50 parts by mass of sulfur. A test cell was prepared in the same manner as in Example 1.
  • a test cell was placed in a constant temperature bath, and after the cell temperature became constant, constant current discharge was performed to a cell voltage of 0.5 V at a current density of 0.2 mA/cm 2 . This was followed by 2.5 V constant current constant voltage charging at the same current density with a cutoff current of 0.01 mA/cm 2 . Regarding this charge/discharge cycle, the capacity retention rate was obtained from the ratio of the 100th discharge capacity to the 2nd discharge capacity. The results are shown in Table 1 below.
  • conductive carbon As an electronic conductor, a higher capacity retention rate can be obtained. This is probably because conductive carbon has higher electronic conductivity than other materials.
  • a higher capacity retention rate can be obtained. It is believed that this is because sulfur and the electron conductor can easily enter the pores, and a larger amount of sulfur and the electron conductor can be arranged in the pores.
  • 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 dispersed in sulfur increases the amount of sulfur that can contribute to the charge/discharge reaction. When the amount of the electron conductor is in the range of 5 to 30% by mass, there is no significant difference in the effect of improving the capacity retention rate. It is considered that this is because when the amount of the electron conductor exceeds a certain amount, the presence of the electron conductor saturates the effect of improving the utilization efficiency of sulfur.
  • the amount of the electron conductor is preferably 10% by mass or less, more preferably 5% by mass or less, from the balance between cycle durability and charge/discharge capacity.
  • 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 Laminated film, 100, 100' Positive electrode material, 110 Porous conductor (mesoporous carbon), 110a Pores, 120 Positive electrode active material (sulfur), 130 Electronic conductor (carbon fiber).

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PCT/IB2021/000603 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 WO2023031639A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025196468A1 (ja) * 2024-03-21 2025-09-25 日産自動車株式会社 リチウム二次電池用正極およびこれを用いたリチウム二次電池

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230395788A1 (en) * 2020-10-26 2023-12-07 Nissan Motor Co., Ltd. Positive Electrode Material for Electric Device, Positive Electrode for Electric Device and Electric Device Using Positive Electrode Material for Electric Device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014017241A (ja) 2012-06-13 2014-01-30 Nagase Chemtex Corp 薄膜硫黄被覆導電性カーボンの製造方法、薄膜硫黄被覆導電性カーボン、正極合材及び全固体型リチウム硫黄電池
KR20150143224A (ko) * 2014-06-13 2015-12-23 주식회사 엘지화학 리튬-황 전지용 양극 활물질, 이의 제조방법 및 이를 포함한 리튬-황 전지
JP2016009682A (ja) * 2014-06-24 2016-01-18 現代自動車株式会社Ｈｙｕｎｄａｉｍｏｔｏｒ Ｃｏｍｐａｎｙ リチウム硫黄電池用陽極
JP2019510337A (ja) * 2016-01-20 2019-04-11 コーネル ユニバーシティ マルチドメイン硫黄電極及びその製造方法
JP2020161288A (ja) * 2019-03-26 2020-10-01 東京電力ホールディングス株式会社 硫黄正極合材およびその製造方法、硫黄正極、リチウム硫黄固体電池
JP2021027032A (ja) * 2019-08-06 2021-02-22 高麗大学校産学協力団Ｋｏｒｅａ Ｕｎｉｖｅｒｓｉｔｙ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｂｕｓｉｎｅｓｓ Ｆｏｕｎｄａｔｉｏｎ 正極活物質製造方法及び正極活物質
JP2021517108A (ja) * 2018-08-08 2021-07-15 エルジー・ケム・リミテッド 硫黄−炭素複合体、この製造方法、これを含む正極及びリチウム二次電池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6314382B2 (ja) * 2013-07-25 2018-04-25 株式会社村田製作所 リチウム−硫黄二次電池用の電極材料及びリチウム−硫黄二次電池並びにリチウム−硫黄二次電池用の電極材料の製造方法
CN105810915B (zh) * 2016-05-16 2018-05-25 北京化工大学 一种石墨烯包覆嵌硫有序介孔碳球复合材料的制备及作为锂硫电池正极材料的应用
KR102244916B1 (ko) * 2018-04-30 2021-04-27 주식회사 엘지화학 리튬-황 전지용 양극 활물질 및 그 제조방법
KR102543246B1 (ko) * 2018-07-03 2023-06-14 주식회사 엘지에너지솔루션 황-탄소 복합체, 이를 포함하는 리튬-황 전지용 양극 및 리튬-황 전지
JP7383254B2 (ja) * 2019-02-25 2023-11-20 日産自動車株式会社 硫黄活物質含有電極組成物、並びにこれを用いた電極および電池
JP2021136126A (ja) * 2020-02-26 2021-09-13 学校法人 関西大学 複合材料、リチウム硫黄電池用の正極、リチウム硫黄電池、及び複合材料の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014017241A (ja) 2012-06-13 2014-01-30 Nagase Chemtex Corp 薄膜硫黄被覆導電性カーボンの製造方法、薄膜硫黄被覆導電性カーボン、正極合材及び全固体型リチウム硫黄電池
KR20150143224A (ko) * 2014-06-13 2015-12-23 주식회사 엘지화학 리튬-황 전지용 양극 활물질, 이의 제조방법 및 이를 포함한 리튬-황 전지
JP2016009682A (ja) * 2014-06-24 2016-01-18 現代自動車株式会社Ｈｙｕｎｄａｉｍｏｔｏｒ Ｃｏｍｐａｎｙ リチウム硫黄電池用陽極
JP2019510337A (ja) * 2016-01-20 2019-04-11 コーネル ユニバーシティ マルチドメイン硫黄電極及びその製造方法
JP2021517108A (ja) * 2018-08-08 2021-07-15 エルジー・ケム・リミテッド 硫黄−炭素複合体、この製造方法、これを含む正極及びリチウム二次電池
JP2020161288A (ja) * 2019-03-26 2020-10-01 東京電力ホールディングス株式会社 硫黄正極合材およびその製造方法、硫黄正極、リチウム硫黄固体電池
JP2021027032A (ja) * 2019-08-06 2021-02-22 高麗大学校産学協力団Ｋｏｒｅａ Ｕｎｉｖｅｒｓｉｔｙ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｂｕｓｉｎｅｓｓ Ｆｏｕｎｄａｔｉｏｎ 正極活物質製造方法及び正極活物質

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4398334A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025196468A1 (ja) * 2024-03-21 2025-09-25 日産自動車株式会社 リチウム二次電池用正極およびこれを用いたリチウム二次電池

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