WO2021069951A1 - Matériau actif d'électrode positive de batterie secondaire au lithium-ion - Google Patents

Matériau actif d'électrode positive de batterie secondaire au lithium-ion Download PDF

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WO2021069951A1
WO2021069951A1 PCT/IB2019/001263 IB2019001263W WO2021069951A1 WO 2021069951 A1 WO2021069951 A1 WO 2021069951A1 IB 2019001263 W IB2019001263 W IB 2019001263W WO 2021069951 A1 WO2021069951 A1 WO 2021069951A1
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active material
positive electrode
electrode active
negative electrode
secondary battery
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PCT/IB2019/001263
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English (en)
Japanese (ja)
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小野正樹
光山知宏
諸岡正浩
金澤昭彦
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日産自動車株式会社
ルノー エス． ア． エス．
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Priority to PCT/IB2019/001263 priority Critical patent/WO2021069951A1/fr
Priority to JP2021550712A priority patent/JP7248136B2/ja
Publication of WO2021069951A1 publication Critical patent/WO2021069951A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/58—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
    • 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 active material for a lithium ion secondary battery.
  • the secondary battery for driving the motor is required to have extremely high output characteristics and high energy as compared with the consumer lithium ion secondary battery used for mobile phones, notebook computers, and the like. Therefore, the lithium-ion secondary battery, which has the highest theoretical energy among all realistic batteries, is attracting attention and is currently being rapidly developed.
  • the lithium ion secondary battery currently widely used uses a flammable organic electrolyte as an electrolyte.
  • a flammable organic electrolyte as an electrolyte.
  • safety measures against liquid leakage, short circuit, overcharge, etc. are required more strictly than other batteries.
  • the solid electrolyte is a material composed mainly of an ionic conductor capable of conducting ions in a solid. Therefore, in the all-solid-state lithium ion secondary battery, various problems caused by the flammable organic electrolytic solution do not occur in principle unlike the conventional liquid-based lithium ion secondary battery. Further, in general, when a high potential / large capacity positive electrode material and a large capacity negative electrode material are used, the output density and energy density of the battery can be significantly improved.
  • An all-solid-state lithium-ion secondary battery using elemental sulfur (S) or a sulfide-based material as the positive electrode active material is a promising candidate.
  • Japanese Patent Application Laid-Open No. 2002-154815 describes a lithium ion secondary battery using polycarbon sulfide as a positive electrode active material.
  • Japanese Patent Application Laid-Open No. 2002-154815 describes polycarbon sulfide showing a predetermined Raman spectrum in response to the problem that the charge / discharge cycle life of a battery is shortened when the sulfur content of polycarbon sulfide is increased in order to increase the capacity. We are proposing to use it.
  • an object of the present invention is to provide a means capable of achieving a high output lithium ion secondary battery having a high capacity, high charge / discharge cycle durability, and excellent rate characteristics.
  • the present invention contains at least carbon and sulfur, in the Raman spectrum, the height of the peaks present in 980 ⁇ 1000 cm -1 of the main peak existing on the 1430 ⁇ 1450 cm -1 Raman shift relative to height A B It is a positive electrode active material for a lithium ion secondary battery having a ratio B / A of 0.3 or more.
  • One form of the present invention contains at least carbon and sulfur, in the Raman spectrum, the height of the peaks present in 980 ⁇ 1000 cm -1 of the main peak existing on the 1430 ⁇ 1450 cm -1 Raman shift relative to height A It is a positive electrode active material for a lithium ion secondary battery having a ratio B / A of B of 0.3 or more.
  • Organosulfur compounds containing carbon and sulfur as the main constituent elements have a high capacity and are more reversible than elemental sulfur, so they are attracting attention as positive electrode active materials that can achieve high capacity of lithium ion secondary batteries. Has been done.
  • the produced compound may contain a low molecular weight or high molecular weight polysulfide compound.
  • the sulfur content is increased in order to increase the capacity, the proportion of the polysulfide compound increases, but there is a problem that the cycle durability of the battery is lowered due to decomposition of the polysulfide compound during charging and discharging.
  • the life is improved by reducing the proportion of polysulfide bonds.
  • polycarbon sulfide as described in JP-A-2002-154815 is applied to an all-solid-state battery, sufficient rate characteristics cannot be obtained.
  • the present inventors have found that in the Raman spectrum of the cathode active material containing carbon and sulfur, the peak of 980 ⁇ 1000 cm -1 of the main peak existing on the 1430 ⁇ 1450 cm -1 Raman shift relative to height A It was found that the above-mentioned problems can be solved by setting the ratio of the height B of the above to a certain level or more.
  • the positive electrode active material of the present invention is considered to be a polycarbon sulfide having a structure as shown in FIG. 1A, although it is not clear because it is insoluble in a solvent and analysis means are limited.
  • included in the polysulfide carbon C-S bond of the sulfur atom, i.e. the ratio of sulfur atoms bonded to sp 2 carbon is higher than the conventional polysulfide carbon.
  • a C-S bond is relatively small poly hydrogen sulfide, which is a low active sulfur -C-S bond of the sulfur atom (sp 3 sulfur atoms bonded to carbon) High proportion, low proportion of highly active sulfur. As a result, the electrode reaction activity becomes low, and it is considered that it is difficult to obtain sufficient rate characteristics in the all-solid-state battery.
  • FIG. 2 schematically shows the overall structure of a laminated (internal parallel connection type) all-solid-state lithium-ion secondary battery (hereinafter, also simply referred to as “laminated secondary battery”) according to an embodiment of the present invention. It is a cross-sectional view.
  • the laminated secondary battery 10a shown in FIG. 2 has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminated film 29 which is a battery exterior.
  • the power generation element 21 of the laminated secondary battery 10a of the present embodiment includes a positive electrode in which positive electrode active material layers 13 are arranged on both sides of a positive electrode current collector 11', a solid electrolyte layer 17, and a negative electrode. It has a structure in which a negative electrode in which a negative electrode active material layer 15 is arranged is laminated on both sides of a current collector 11 ′′. Specifically, the positive electrode, the solid electrolyte layer, and the negative electrode are laminated in this order so that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto face each other via the solid electrolyte layer 17. ing. As a result, the adjacent positive electrode, solid electrolyte layer, and negative electrode form one cell cell layer 19.
  • the laminated secondary battery 10a shown in FIG. 2 has a configuration in which a plurality of single battery layers 19 are laminated and electrically connected in parallel.
  • the positive electrode current collectors in the outermost layers located in both outermost layers of the power generation element 21 have the positive electrode active material layer 13 arranged on only one side, but active material layers may be provided on both sides. .. That is, instead of using a current collector dedicated to the outermost layer in which the active material layer is provided on only one side, a current collector having active material layers on both sides may be used as it is as the current collector in the outermost layer. Further, by reversing the arrangement of the positive electrode and the negative electrode as in FIG. 2, the negative electrode current collector of the outermost layer is located on both outermost layers of the power generation element 21, and one side of the negative electrode current collector of the outermost layer or Negative electrode active material layers may be arranged on both sides.
  • a positive electrode current collector plate 25 and a negative electrode current collector plate 27 that are conductive to each electrode are attached to the positive electrode current collector 11'and the negative electrode current collector 11', respectively, and the end portion of the laminate film 29 is attached. It has a structure that is led out to the outside of the laminated film 29 so as to be sandwiched between the two.
  • the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are connected to the positive electrode current collector 11'and the negative electrode current collector 11'of each electrode via the positive electrode terminal lead and the negative electrode terminal lead (not shown), respectively, as necessary. It may be attached to'by ultrasonic welding, resistance welding, or the like.
  • all-solid-state battery has been described by taking a laminated type (internal parallel connection type) all-solid-state lithium-ion secondary battery as an example.
  • the type of all-solid-state battery to which the present invention can be applied is not particularly limited, and the positive electrode active material layer electrically bonded to one surface of the current collector and the opposite surface of the current collector are electrically connected. It is also applicable to a bipolar (bipolar) all-solid-state battery including a bipolar electrode having a coupled negative electrode active material layer.
  • FIG. 3 is a sectional view schematically showing a bipolar type (bipolar type) all-solid-state lithium ion secondary battery (hereinafter, also simply referred to as “bipolar type secondary battery”) according to an embodiment of the present invention. ..
  • the bipolar secondary battery 10b shown in FIG. 3 has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminated film 29 which is a battery exterior.
  • a positive electrode active material layer 13 electrically bonded to one surface of the current collector 11 is formed, and the current collector 11 has a positive electrode active material layer 13. It has a plurality of bipolar electrodes 23 having an electrically coupled negative electrode active material layer 15 formed on the opposite surface. Each bipolar electrode 23 is laminated via a solid electrolyte layer 17 to form a power generation element 21.
  • the solid electrolyte layer 17 has a structure in which the solid electrolyte is formed into layers.
  • the bipolar electrodes 23 and the solid electrolyte layer 17 are alternately laminated. That is, the solid electrolyte layer 17 is sandwiched between the positive electrode active material layer 13 of the one bipolar electrode 23 and the negative electrode active material layer 15 of the other bipolar electrode 23 adjacent to the one bipolar electrode 23. Has been done.
  • the adjacent positive electrode active material layer 13, the solid electrolyte layer 17, and the negative electrode active material layer 15 constitute one cell cell layer 19. Therefore, it can be said that the bipolar secondary battery 10b has a configuration in which the cell cell layers 19 are laminated.
  • the positive electrode active material layer 13 is formed on only one side of the outermost layer current collector 11a on the positive electrode side located in the outermost layer of the power generation element 21.
  • the negative electrode active material layer 15 is formed on only one side of the outermost layer current collector 11b on the negative electrode side located in the outermost layer of the power generation element 21.
  • a positive electrode current collector plate (positive electrode tab) 25 is arranged so as to be adjacent to the outermost layer current collector 11a on the positive electrode side, and this is extended to form a battery exterior. It is derived from the laminated film 29.
  • the negative electrode current collector plate (negative electrode tab) 27 is arranged so as to be adjacent to the outermost layer current collector 11b on the negative electrode side, and is similarly extended and led out from the laminated film 29.
  • the number of times the cell cell layer 19 is laminated is adjusted according to the desired voltage. Further, in the bipolar type secondary battery 10b, the number of times the cell cell layer 19 is laminated may be reduced as long as a sufficient output can be secured even if the thickness of the battery is made as thin as possible. Even in the bipolar secondary battery 10b, in order to prevent external impact and environmental deterioration during use, the power generation element 21 is vacuum-sealed in the laminated film 29 which is the battery exterior, and the positive electrode current collector plate 25 and the negative electrode current collector are collected. It is preferable to have a structure in which the electric plate 27 is taken out from the laminated film 29.
  • the current collector has a function of mediating the movement of electrons from one surface in contact with the positive electrode active material layer to the other surface in contact with the negative electrode active material layer.
  • the materials that make up the current collector There are no particular restrictions on the materials that make up the current collector.
  • a constituent material of the current collector for example, a metal or a resin having conductivity can be adopted.
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, and the like may be used.
  • the foil may be a metal surface coated with aluminum.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electron conductivity, battery operating potential, adhesion of the negative electrode active material by sputtering to the current collector, and the like.
  • non-conductive polymer material examples include polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), and polyimide.
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PI Polyimide
  • PAI Polyethylene
  • PA Polytetrafluoroethylene
  • SBR Styrene-butadiene rubber
  • PAN Polyacrylonitrile
  • PMA Polymethylacrylate
  • PMMA Polymethylmethacrylate
  • PVC Polyvinyl chloride
  • PVdF polyvinylidene fluoride
  • PS polystyrene
  • Such non-conductive polymer materials can have excellent potential resistance or solvent resistance.
  • a conductive filler may be added to the above-mentioned conductive polymer material or non-conductive polymer material as needed.
  • a conductive filler is inevitably indispensable in order to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it is a conductive substance.
  • materials having excellent conductivity, potential resistance, or lithium ion blocking property include metals and conductive carbon.
  • the metal is not particularly limited, and includes at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, and Sb, or at least one of these metals. It preferably contains an alloy or metal oxide.
  • the conductive carbon is not particularly limited.
  • acetylene black is selected from the group consisting of acetylene black, vulcan (registered trademark), black pearl (registered trademark), carbon nanofiber, Ketjen black (registered trademark), carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene. It contains at least one species.
  • the amount of the conductive filler added is not particularly limited as long as it can impart sufficient conductivity to the current collector, and is generally 5 to 80% by mass with respect to 100% by mass of the total mass of the current collector. Is.
  • the current collector may have a single-layer structure made of a single material, or may have a laminated structure in which layers made of these materials are appropriately combined. From the viewpoint of reducing the weight of the current collector, it is preferable to include a conductive resin layer made of at least a conductive resin. Further, from the viewpoint of blocking the movement of lithium ions between the cell layers, a metal layer may be provided as a part of the current collector.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material includes the predetermined positive electrode active material of the present invention.
  • Positive electrode active material according to the present invention contains at least carbon and sulfur, in the Raman spectrum, the peaks present in 980 ⁇ 1000 cm -1 of the main peak existing on the 1430 ⁇ 1450 cm -1 Raman shift relative to height A It is a positive electrode active material for a lithium ion secondary battery having a height B ratio B / A of 0.3 or more.
  • the positive electrode active material of the present invention preferably contains carbon and sulfur as main constituent elements.
  • the total mass ratio of carbon and sulfur is 90% by mass or more, more preferably 95% by mass or more, still more preferably 96% by mass or more, and even more preferably 97% by mass or more.
  • a high energy density can be obtained.
  • high rate characteristics can be obtained.
  • the positive electrode active material of the present invention preferably has a sulfur mass ratio of 65% by mass or more, preferably 67% by mass or more, and preferably 70% by mass or more. Within the above range, a high energy density can be obtained. In addition, since it is possible to suppress a decrease in the redox activity of sulfur due to the inclusion of elements other than carbon and sulfur, high rate characteristics can be obtained.
  • the composition ratio (atomic ratio) of carbon and sulfur is not particularly limited, but it is preferably 1 ⁇ S / C (atomic ratio) ⁇ 1.5.
  • S / C (atomic ratio) is 1 or more, the capacity per mass of the active material is high, which is preferable.
  • the polysulfide bond (-S-S-S-) is relatively small, so that the rate characteristics and the cycle durability can be improved, which is preferable.
  • the mass ratio of carbon and sulfur in the positive electrode active material can be obtained by the method described in Examples.
  • the atomic ratio of carbon and sulfur can be obtained from the mass ratio.
  • the positive electrode active material of the present invention in the Raman spectrum, the ratio B / A of the height B of the peaks present in 980 ⁇ 1000 cm -1 of the main peak to the height A present 1430 ⁇ 1450 cm -1 Raman shift 0 .3 or more. If the B / A is less than 0.3, the rate characteristics become insufficient. B / A is preferably 0.48 or more, and more preferably 0.61 or more. Within the above range, the effect of the present invention can be further improved.
  • the upper limit of B / A is not particularly limited, but is, for example, 1 or less.
  • the B / A ratio of the positive electrode active material can be obtained by the method described in the examples.
  • the shape of the positive electrode active material is not particularly limited, and examples thereof include a particle shape (spherical shape, a fibrous shape), a thin film shape, and the like.
  • a particle shape sintered shape, a spherical shape, a fibrous shape, a thin film shape, and the like.
  • its average particle size is not particularly limited.
  • the method for preparing the positive electrode active material of the present invention containing carbon and sulfur and having a predetermined Raman spectrum is not particularly limited.
  • a method of synthesizing polycarbon sulfide by electrolytic reduction polymerization of carbon disulfide and heat-treating the synthesized polycarbon sulfide can be mentioned.
  • the electrolytic reduction polymerization of carbon disulfide (CS 2 ) can be carried out, for example, by using a solution obtained by dissolving CS 2 or a supporting electrolyte in a solvent and mixing them. It is considered that when a voltage is applied to the solution using an electrode such as platinum, CS 2 is reduced to generate CS carbene (: CS), which initiates polymerization.
  • CS carbene CS carbene
  • the concentration of CS 2 in the solution is not particularly limited, but it is desirable that the concentration is close to saturation within the range in which CS 2 can be dissolved, depending on the combination of the solvent and supporting electrolyte used.
  • the supporting electrolyte is not particularly limited, but for example, tetrabutylammonium perchlorate or the like can be used.
  • the concentration of the supporting electrolyte in the solution is not particularly limited, but is preferably 0.05 to 0.5 M, and more preferably 0.1 to 0.3 M. Within the above range, the polymerization reaction can proceed favorably.
  • acetonitrile for example, acetonitrile, N, N-dimethylformamide, hexamethylphosphoric acid triamide, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, acetone, dimethyl sulfoxide, propylene carbonate and the like can be used.
  • the applied voltage is not particularly limited, but is preferably 3 to 6 V, and more preferably 4 to 5 V.
  • the voltage is 3 V or higher, the polymerization can proceed favorably.
  • the voltage is 6 V or less, the electrolytic efficiency is unlikely to decrease due to gas generation, so that the polymerization can proceed favorably.
  • the reaction time of electrolytic reduction polymerization is not particularly limited and can be adjusted as appropriate.
  • the synthesized polycarbon sulfide is preferably heat-treated. This makes it possible to remove low molecular weight components and increase the proportion of active sulfur.
  • the heat treatment is preferably carried out under reduced pressure or under an inert gas atmosphere.
  • the dew point is preferably ⁇ 30 ° C. or lower, and more preferably the dew point is ⁇ 40 ° C. or lower.
  • the heat treatment temperature is preferably 80 to 250 ° C, still more preferably 80 to 200 ° C, and even more preferably 130 to 200 ° C. If the temperature is 80 ° C. or higher, the structure is likely to change to an electrochemically active sulfur-rich structure, which is preferable. Further, when the temperature is 250 ° C. or lower, thermal decomposition of polycarbon sulfide is unlikely to occur, which is preferable.
  • the heat treatment time is preferably 0.5 to 12 hours, more preferably 2 to 8 hours, and even more preferably 4 to 8 hours. If it is 0.5 hours or more, the effect of heat treatment (structural change and dehydration) can be sufficiently obtained. If it is 12 hours or less, the effect according to the heat treatment time can be obtained, which is preferable.
  • the positive electrode active material layer contains carbon and sulfur, and may contain a positive electrode active material (other positive electrode active material) other than the positive electrode active material of the present invention having a predetermined Raman spectrum.
  • positive electrode active material for example, elemental sulfur (S), lithium sulfide (Li 2 S), particles or a thin film of the organic sulfur compounds other than polysulfide carbon or inorganic sulfur compound and the like, redox sulfur A substance capable of releasing lithium ions during charging and occluding lithium ions during discharging can be used by utilizing the reaction.
  • elemental sulfur S
  • lithium sulfide Li 2 S
  • redox sulfur A substance capable of releasing lithium ions during charging and occluding lithium ions during discharging can be used by utilizing the reaction.
  • a positive electrode active material containing no sulfur may be contained.
  • the sulfur-free positive electrode active material include layered rock salt type active materials such as LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , and Li (Ni-Mn-Co) O 2 , LiMn 2 O 4 , LiNi 0.
  • spinel-type active materials such as 5 Mn 1.5 O 4
  • olivine-type active materials such as LiFePO 4 and LiMnPO 4
  • Si-containing active materials such as Li 2 FeSiO 4 and Li 2 MnSiO 4.
  • the oxide active material other than the above include Li 4 Ti 5 O 12 .
  • the content of the positive electrode active material of the present invention with respect to the total amount of the positive electrode active material is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. It is more preferably 95% by mass or more, and particularly preferably 100% by mass.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but is preferably in the range of 40 to 99% by mass, preferably in the range of 50 to 90% by mass, for example. More preferred.
  • the positive electrode active material layer preferably further contains a solid electrolyte. Since the positive electrode active material layer contains a solid electrolyte, the ionic conductivity of the positive electrode active material layer can be improved. Examples of the solid electrolyte include sulfide solid electrolytes and oxide solid electrolytes, and sulfide solid electrolytes are preferable.
  • Examples of the sulfide solid electrolyte include LiI-Li 2 S-SiS 2 , LiI-Li 2 S-P 2 O 5 , LiI-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5 , LiI-Li 3 PS 4 , LiI-LiBr-Li 3 PS 4, Li 3 PS 4 , Li 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -Li I, Li 2 S-P 2 S 5- Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 , Li 2 S-SiS 2- LiI, Li 2 S-SiS 2- LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2- B 2 S 3- LiI, Li 2 S-SiS 2- P 2 S 5- LiI, Li 2 SB 2 S 3 , Li 2 SP 2 S 5- Z m S n (where m and
  • 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. ..
  • Examples of the sulfide solid electrolyte having a Li 3 PS 4 skeleton include LiI-Li 3 PS 4 , LiI-LiBr-Li 3 PS 4, and Li 3 PS 4 .
  • examples of the sulfide solid electrolyte having a Li 4 P 2 S 7 skeleton include a Li-PS-based solid electrolyte called LPS (for example, Li 7 P 3 S 11 ).
  • the sulfide solid electrolyte for example, LGPS represented by Li (4-x) Ge (1-x) P x S 4 (x satisfies 0 ⁇ x ⁇ 1) may be used.
  • the sulfide solid electrolyte is preferably a sulfide solid electrolyte containing a P element, and the sulfide solid electrolyte is more preferably a material containing Li 2 SP 2 S 5 as a main component.
  • the sulfide solid electrolyte may contain halogens (F, Cl, Br, I).
  • the sulfide solid electrolyte may be sulfide glass, crystallized sulfide glass, or a crystalline material obtained by the solid phase method.
  • the sulfide glass can be obtained, for example, by performing mechanical milling (ball mill or the like) on the raw material composition.
  • the crystallized sulfide glass can be obtained, for example, by heat-treating the sulfide glass at a temperature equal to or higher than the crystallization temperature.
  • the ionic conductivity (for example, Li ion conductivity) of the sulfide solid electrolyte at room temperature (25 ° C.) is preferably 1 ⁇ 10 -5 S / cm or more , for example, 1 ⁇ 10 -4 S / cm. It is more preferably cm or more.
  • the value of the ionic conductivity of the solid electrolyte can be measured by the AC impedance method.
  • Examples of the oxide solid electrolyte include compounds having a NASICON type structure and the like.
  • a compound having a NASICON type structure a compound (LAGP) represented by the general formula Li 1 + x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2), a general formula Li 1 + x Al x Ti 2
  • LAGP a compound represented by the general formula Li 1 + x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2)
  • a general formula Li 1 + x Al x Ti 2 examples thereof include a compound (LATP) represented by ⁇ x (PO 4 ) 3 (0 ⁇ x ⁇ 2).
  • LiLaTIO for example, Li 0.34 La 0.51 TiO 3
  • LiPON for example, Li 2.9 PO 3.3 N 0.46
  • LiLaZrO for example, Li LaZrO
  • the shape of the solid electrolyte examples include a particle shape such as a true spherical shape and an elliptical spherical shape, and a thin film shape.
  • its average particle size (D 50 ) is not particularly limited, but is preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the average particle size (D 50 ) is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the content of the solid electrolyte in the positive electrode active material layer is, for example, preferably in the range of 1 to 60% by mass, and more preferably in the range of 10 to 50% by mass.
  • the positive electrode active material layer may further contain at least one of a conductive auxiliary agent and a binder in addition to the positive electrode active material and the solid electrolyte described above.
  • the conductive auxiliary agent examples include metals such as aluminum, stainless steel (SUS), silver, gold, copper, and titanium, alloys or metal oxides containing these metals; carbon fibers (specifically, vapor-grown carbon fibers). (VGCF), polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber, activated carbon fiber, etc.), carbon nanotube (CNT), carbon black (specifically, acetylene black, Ketjen black (registered trademark)) , Furness black, channel black, thermal lamp black, etc.), but is not limited to these. Further, a particulate ceramic material or a resin material coated with the above metal material by plating or the like can also be used as a conductive auxiliary agent.
  • metals such as aluminum, stainless steel (SUS), silver, gold, copper, and titanium, alloys or metal oxides containing these metals
  • carbon fibers specifically, vapor-grown carbon fibers). (VGCF), polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, rayon
  • these conductive auxiliaries from the viewpoint of electrical stability, it is preferable to contain at least one selected from the group consisting of aluminum, stainless steel, silver, gold, copper, titanium, and carbon, and aluminum, stainless steel. It is more preferable to contain at least one selected from the group consisting of silver, gold, and carbon, and it is further preferable to contain at least one carbon. Only one kind of these conductive auxiliaries may be used alone, or two or more kinds thereof may be used in combination.
  • the shape of the conductive auxiliary agent is preferably particulate or fibrous.
  • the shape of the particles is not particularly limited, and may be any shape such as powder, sphere, rod, needle, plate, columnar, indefinite, flint, and spindle. It doesn't matter.
  • the average particle size (primary particle size) when the conductive auxiliary agent is in the form of particles is not particularly limited, but is preferably 0.01 to 10 ⁇ m from the viewpoint of the electrical characteristics of the battery.
  • the “particle size of the conductive auxiliary agent” means the maximum distance L among the distances between any two points on the contour line of the conductive auxiliary agent.
  • the particle size of the particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The value calculated as the average value of is adopted.
  • the content of the conductive auxiliary agent in the positive electrode active material layer is not particularly limited, but is preferably 0 to 10% by mass with respect to the total mass of the positive electrode active material layer. , More preferably 2 to 8% by mass, and even more preferably 4 to 7% by mass. Within such a range, a stronger electron conduction path can be formed in the positive electrode active material layer, which can effectively contribute to the improvement of battery characteristics.
  • the binder is not particularly limited, and is, for example, polybutylene terephthalate, polyethylene terephthalate, polyvinylidene fluoride (PVDF) (including a compound in which a hydrogen atom is replaced with another halogen element), polyethylene, polypropylene, polymethyl.
  • PVDF polyvinylidene fluoride
  • the thickness of the positive electrode active material layer varies depending on the configuration of the target all-solid-state battery, but is preferably in the range of 0.1 to 1000 ⁇ m, for example.
  • the method for producing the positive electrode active material layer is not particularly limited. Conventionally known methods can be referred to as appropriate.
  • the negative electrode active material layer contains a negative electrode active material.
  • the type of the negative electrode active material is not particularly limited, and examples thereof include a carbon material, a metal oxide, and a metal active material.
  • the carbon material include natural graphite, artificial graphite, mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, soft carbon and the like.
  • the metal oxide include Nb 2 O 5 and Li 4 Ti 5 O 12 .
  • a silicon-based negative electrode active material or a tin-based negative electrode active material may be used.
  • silicon and tin belong to Group 14 elements and are known to be negative electrode active materials that can greatly improve the capacity of a non-aqueous electrolyte secondary battery. Since these simple substances can occlude and release a large number of charge carriers (lithium ions, etc.) per unit volume (mass), they are high-capacity negative electrode active materials.
  • Si alone as the silicon-based negative electrode active material.
  • a silicon oxide such as SiO x (0.3 ⁇ x ⁇ 1.6) disproportionated into two phases, a Si phase and a silicon oxide phase.
  • the range of x is more preferably 0.5 ⁇ x ⁇ 1.5, and even more preferably 0.7 ⁇ x ⁇ 1.2.
  • a silicon-containing alloy silicon-containing alloy-based negative electrode active material
  • examples of the negative electrode active material containing a tin element include Sn alone, tin alloys (Cu—Sn alloy, Co—Sn alloy), amorphous tin oxide, tin silicon oxide and the like.
  • SnB 0.4 P 0.6 O 3.1 is exemplified as the amorphous tin oxide.
  • SnSiO 3 is exemplified as the tin silicon oxide.
  • 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 a lithium-containing active material, and examples thereof include metallic lithium and lithium-containing alloys.
  • the lithium-containing alloy include alloys of Li and at least one of In, Al, Si and Sn.
  • two or more kinds of negative electrode active materials may be used in combination.
  • a negative electrode active material other than the above may be used.
  • the present invention exerts a particularly excellent effect when the expansion and contraction of the negative electrode active material during charging and discharging is large.
  • the negative electrode active material preferably contains metallic lithium, a silicon-based negative electrode active material, or a tin-based negative electrode active material, and particularly preferably contains metallic lithium. Further, from the viewpoint of obtaining a battery having a high energy density, it is preferable to use an all-solid-state battery having metallic lithium as a negative electrode active material.
  • the shape of the negative electrode active material examples include a particle shape (spherical shape, fibrous shape), a thin film shape, and the like.
  • its average particle size (D 50 ) is preferably in the range of, for example, 1 nm to 100 ⁇ m, more preferably in the range of 10 nm to 50 ⁇ m, and further preferably in the range of 100 nm. It is in the range of ⁇ 20 ⁇ m, and particularly preferably in the range of 1 to 20 ⁇ m.
  • the value of the average particle size (D 50 ) of the active material can be measured by the laser diffraction / scattering method.
  • the content of the negative electrode active material in the negative electrode active material layer is not particularly limited, but is, for example, in the range of 0 to 100% by mass, preferably in the range of 0 to 99% by mass, and is preferably 50. More preferably, it is in the range of ⁇ 90% by mass.
  • the negative electrode active material layer may further contain a solid electrolyte, a conductive auxiliary agent and / or a binder as well as the positive electrode active material layer.
  • Solid electrolyte layer is a layer interposed between the positive electrode active material layer and the negative electrode active material layer, and contains a solid electrolyte (usually as a main component). Since the specific form of the solid electrolyte contained in the solid electrolyte layer is the same as that described above, detailed description thereof will be omitted here.
  • the content of the solid electrolyte in the solid electrolyte layer is preferably in the range of, for example, 10 to 100% by mass, and more preferably in the range of 50 to 100% by mass, based on the total mass of the solid electrolyte layer. It is preferably in the range of 90 to 100% by mass, and more preferably in the range of 90 to 100% by mass.
  • the solid electrolyte layer may further contain a binder in addition to the above-mentioned solid electrolyte. Since the specific form of the binder that can be contained in the solid electrolyte layer is the same as that described above, detailed description thereof will be omitted here.
  • the thickness of the solid electrolyte layer varies depending on the configuration of the target all-solid-state battery, but is preferably in the range of 0.1 to 1000 ⁇ m, and more preferably in the range of 0.1 to 300 ⁇ m. preferable.
  • the material constituting the current collector plates (25, 27) is not particularly limited, and a known highly conductive material conventionally used as a current collector plate for a secondary battery can be used.
  • a known highly conductive material conventionally used as a current collector plate for a secondary battery can be used.
  • the constituent material of the current collector plate for example, metal materials such as aluminum, carbon-coated aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable.
  • the same material may be used or different materials may be used for the positive electrode current collector plate 25 and the negative electrode current collector plate 27.
  • the current collector 11 and the current collector plates (25, 27) may be electrically connected via a positive electrode lead or a negative electrode lead.
  • materials used in known lithium ion secondary batteries can be similarly adopted.
  • the part taken out from the exterior is heat-shrinkable with heat-resistant insulation so that it does not come into contact with peripheral devices or wiring and leak electricity, affecting the product (for example, automobile parts, especially electronic devices). It is preferable to cover with a tube or the like.
  • the battery exterior As the battery exterior, a known metal can case can be used, or a bag-shaped case using a laminated film 29 containing aluminum, which can cover the power generation element as shown in FIG. 2, can be used.
  • the laminate film for example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used, but the laminate film is not limited thereto.
  • a laminated film is desirable from the viewpoint of high output and excellent cooling performance, and can be suitably used for batteries for large devices for EVs and HEVs. Further, since the group pressure applied to the power generation element from the outside can be easily adjusted, a laminated film containing aluminum is more preferable for the exterior body.
  • the all-solid-state lithium-ion secondary battery of this embodiment has an excellent output characteristic at a high rate because it has a configuration in which a plurality of single battery layers are connected in series. Therefore, the all-solid-state lithium-ion secondary battery of this embodiment is suitably used as a power source for driving EVs and HEVs.
  • FIG. 4 is a perspective view showing the appearance of a laminated all-solid-state lithium ion secondary battery according to an embodiment of the present invention.
  • the flat laminated secondary battery 50 has a rectangular flat shape, and positive electrode tabs 58 and negative electrode tabs 59 for extracting electric power are pulled out from both side portions thereof.
  • the power generation element 57 is wrapped by the battery exterior (laminate film 52) of the laminated secondary battery 50, and the periphery thereof is heat-sealed.
  • the power generation element 57 pulls out the positive electrode tab 58 and the negative electrode tab 59 to the outside. It is sealed in a closed state.
  • the power generation element 57 corresponds to the power generation element 21 of the laminated secondary battery 10a shown in FIG. 2 described above.
  • the power generation element 57 is formed by stacking a plurality of single battery layers (single cells) 19 composed of a positive electrode (positive electrode active material layer) 13, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 15.
  • the all-solid-state battery of this embodiment is not limited to a flat shape.
  • the wound all-solid-state battery may have a cylindrical shape, or may be deformed into a rectangular flat shape.
  • the cylindrical shape is not particularly limited, for example, a laminated film may be used for the exterior body, or a conventional cylindrical can (metal can) may be used.
  • the power generation element is exteriorized with an aluminum laminate film. By this form, weight reduction can be achieved.
  • the extraction of tabs 58 and 59 shown in FIG. 4 is not particularly limited.
  • the positive electrode tab 58 and the negative electrode tab 59 may be pulled out from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of each and taken out from each side. It is not limited to.
  • the terminal in the winding type all-solid-state battery, the terminal may be formed by using, for example, a cylindrical can (metal can) instead of the tab.
  • the positive electrode active material of the present invention can be applied to a lithium ion secondary battery other than the all-solid-state battery without limitation.
  • An assembled battery is formed by connecting a plurality of batteries. More specifically, it is composed of serialization, parallelization, or both by using at least two or more. By connecting in series or in parallel, the capacitance and voltage can be adjusted freely.
  • a small assembled battery that can be attached and detached by connecting multiple batteries in series or in parallel. Then, by connecting a plurality of small detachable batteries in series or in parallel, a large capacity and a large capacity suitable for a vehicle driving power source or an auxiliary power source that require a high volume energy density and a high volume output density. It is also possible to form an assembled battery having an output. How many batteries are connected to make an assembled battery, and how many stages of small assembled batteries are stacked to make a large-capacity assembled battery depends on the battery capacity of the vehicle (electric vehicle) to be installed. It may be decided according to the output.
  • the all-solid-state battery according to this embodiment has a high energy density per volume.
  • Vehicle applications such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles are required to have higher capacity and larger size than those used for electric and portable electronic devices. Therefore, the all-solid-state battery according to the present embodiment can be suitably used as a power source for a vehicle, for example, a vehicle drive power source or an auxiliary power source.
  • 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 having a long EV mileage and an electric vehicle having a long one-charge mileage can be configured by mounting such a battery.
  • fuel cell vehicles, electric vehicles (all four-wheeled vehicles (passenger cars, trucks, commercial vehicles such as buses, light vehicles, etc.)) Including two-wheeled vehicles (motorcycles) and three-wheeled vehicles), it is possible to make an automobile with a long mileage.
  • the application is not limited to automobiles, and can be applied to various power sources of other vehicles, for example, moving objects such as trains, and power supplies for mounting such as uninterruptible power supplies. It is also possible to use it as.
  • Example 1 ⁇ Raw materials and reagents used> In the following examples and comparative examples, the following materials were used.
  • a Raman spectrophotometer (Laser Raman spectrophotometer NRS-5600 manufactured by Nippon Spectroscopy Co., Ltd.) was used for the Raman spectrum of polycarbon sulfide.
  • the excitation wavelength was 532 nm, and data in the range of Raman shift 2000 to 200 cm -1 was acquired.
  • a SUS cylindrical convex punch (10 mm diameter) is inserted into one side of a McCall cylindrical tube jig (tube inner diameter 10 mm, outer diameter 23 mm, height 20 mm), and the solid prepared above from the upper side of the cylindrical tube jig. 80 mg of electrolyte was added. After that, another SUS cylindrical convex punch is inserted to sandwich the solid electrolyte, and the solid electrolyte layer having a diameter of 10 mm and a thickness of about 0.6 mm is formed into a cylinder by pressing with a hydraulic press at a pressure of 75 MPa for 3 minutes. Formed in a tube jig.
  • the cylindrical convex punch inserted from the upper side is once pulled out, 7.5 mg of the positive electrode mixture is put on one side of the solid electrolyte layer in the cylindrical tube, and the cylindrical convex punch (also serves as the positive electrode current collector) is again inserted from the upper side. ) was inserted and pressed at a pressure of 300 MPa for 3 minutes to form a positive electrode active material layer (positive electrode mixture layer) having a diameter of 10 mm and a thickness of about 0.06 mm on one side surface of the solid electrolyte layer.
  • the lower cylindrical convex punch (which also serves as the negative electrode current collector) is extracted, and the lithium foil punched to a diameter of 8 mm and the indium foil punched to a diameter of 9 mm are used as the negative electrode so that the lithium foil is on the negative electrode current collector side.
  • a cylindrical convex punch was inserted again from the lower side of the cylindrical tube jig, and pressed at a pressure of 75 MPa for 3 minutes to form a lithium-indium negative electrode.
  • an all-solid-state lithium-ion battery in which a negative electrode current collector, a lithium-indium negative electrode, a solid electrolyte layer, a polycarbon sulfide positive electrode active material layer, and a positive electrode current collector are laminated was produced.
  • Example 2 The synthesized polycarbon sulfide was heat-treated at 130 ° C. for 4 hours under a reduced pressure of 5 Pa or less in an argon atmosphere having a dew point of ⁇ 76 ° C. or lower.
  • the ratio of the height B of the peak at around 980 ⁇ 1000 cm -1 of the main peak in the vicinity of 1430 ⁇ 1450 cm -1 Raman shift relative to the height A from the Raman spectra of polysulfides carbon after heat treatment (B / A) is 0. It was 48.
  • Example 3 The synthesized polycarbon sulfide was heat-treated at 130 ° C. for 4 hours under atmospheric pressure in an argon atmosphere with a dew point of ⁇ 76 ° C. or lower.
  • the ratio of the height B of the peak at around 980 ⁇ 1000 cm -1 to the height A of the main peak around 1430 ⁇ 1450 cm -1 of Raman shift in the Raman spectrum of the polysulfide carbon after heat treatment (B / A) is 0. It was 30.
  • constant current discharge is performed at a current density of 0.1 mA / cm 2 to a cell voltage of 0.6 V, followed by the same current density.
  • the 2.0 V constant current constant voltage charge was set to a cutoff current of 0.01 mA / cm 2.
  • the capacity value (mAh / g) per polycarbon sulfide mass was determined from the charge / discharge capacity value obtained after repeating this conditioning charge / discharge cycle 10 times and the mass value of polycarbon sulfide contained in the positive electrode.
  • the rate characteristics were charged at 25 ° C. with a cutoff current of 0.01C at a constant current of 0.2C-2.0V, and then discharged at a constant current of 0.6V with a cutoff voltage at each predetermined discharge rate. It was evaluated by the discharge capacity value obtained at times.
  • FIG. 5 shows the Raman spectrum of the positive electrode active material prepared in Examples 1, 3 and Comparative Example 1
  • FIG. 6 shows the rate characteristics of the batteries prepared in each Example and Comparative Example.
  • the discharge rate characteristic (%) shows the ratio (%) of the discharge capacities of 0.1C, 0.2C, 0.5C, and 1C to the 0.05C discharge capacity.
  • Table 1 shows the B / A of the Raman spectrum of the positive electrode active material prepared in each Example and Comparative Example, the mass ratio of carbon and sulfur, the total mass ratio of carbon and hydrogen, and the rate characteristics of the battery. ..
  • the discharge rate characteristic (%) shows the value (%) of the 1C discharge capacity with respect to the 0.05C discharge capacity.

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Abstract

La présente invention fournit un moyen permettant d'obtenir une batterie secondaire au lithium-ion à haute capacité et à haut rendement qui présente d'excellentes caractéristiques de vitesse et une durabilité de cycle de charge/décharge élevée. La présente invention concerne un matériau actif d'électrode positive de batterie secondaire au lithium-ion qui contient au moins du carbone et du soufre. Le rapport B/A de la hauteur B d'un pic qui est à un décalage Raman de 980–1000 cm-1 sur un spectre Raman pour le matériau actif d'électrode positive de batterie secondaire au lithium-ion à la hauteur A d'un pic principal qui est à 1430–1450 cm-1est d'au moins 0,3.
PCT/IB2019/001263 2019-10-09 2019-10-09 Matériau actif d'électrode positive de batterie secondaire au lithium-ion WO2021069951A1 (fr)

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Citations (8)

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JP2002154815A (ja) * 2000-02-09 2002-05-28 Hitachi Maxell Ltd ポリ硫化カーボン、その製造方法およびそれを用いた非水電解質電池
JP2003123758A (ja) * 2001-10-16 2003-04-25 Hitachi Maxell Ltd ポリ硫化カーボンおよびそれを用いた非水電解質電池
WO2011129103A1 (fr) * 2010-04-16 2011-10-20 株式会社豊田自動織機 Électrode positive pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion comprenant l'électrode positive
WO2016159212A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau de soufre organique et procédé de production associé
JP2017098124A (ja) * 2015-11-25 2017-06-01 日本化学工業株式会社 正極活物質及びそれを用いた非水電池
JP2017095315A (ja) * 2015-11-25 2017-06-01 日本化学工業株式会社 硫化炭素ポリマーの製造方法
JP2018055998A (ja) * 2016-09-29 2018-04-05 国立研究開発法人産業技術総合研究所 電極スラリー及びそれを用いた電極の製造方法
JP2019091538A (ja) * 2017-11-10 2019-06-13 住友ゴム工業株式会社 リチウムイオン蓄電デバイスの製造方法およびリチウムイオン蓄電デバイス

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002154815A (ja) * 2000-02-09 2002-05-28 Hitachi Maxell Ltd ポリ硫化カーボン、その製造方法およびそれを用いた非水電解質電池
JP2003123758A (ja) * 2001-10-16 2003-04-25 Hitachi Maxell Ltd ポリ硫化カーボンおよびそれを用いた非水電解質電池
WO2011129103A1 (fr) * 2010-04-16 2011-10-20 株式会社豊田自動織機 Électrode positive pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion comprenant l'électrode positive
WO2016159212A1 (fr) * 2015-03-31 2016-10-06 国立研究開発法人産業技術総合研究所 Matériau de soufre organique et procédé de production associé
JP2017098124A (ja) * 2015-11-25 2017-06-01 日本化学工業株式会社 正極活物質及びそれを用いた非水電池
JP2017095315A (ja) * 2015-11-25 2017-06-01 日本化学工業株式会社 硫化炭素ポリマーの製造方法
JP2018055998A (ja) * 2016-09-29 2018-04-05 国立研究開発法人産業技術総合研究所 電極スラリー及びそれを用いた電極の製造方法
JP2019091538A (ja) * 2017-11-10 2019-06-13 住友ゴム工業株式会社 リチウムイオン蓄電デバイスの製造方法およびリチウムイオン蓄電デバイス

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