WO2023243714A1 - 二次電池 - Google Patents

二次電池 Download PDF

Info

Publication number
WO2023243714A1
WO2023243714A1 PCT/JP2023/022418 JP2023022418W WO2023243714A1 WO 2023243714 A1 WO2023243714 A1 WO 2023243714A1 JP 2023022418 W JP2023022418 W JP 2023022418W WO 2023243714 A1 WO2023243714 A1 WO 2023243714A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
group
ocf
active material
secondary battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/022418
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和誠 野本
英晃 西村
史教 水野
健太郎 平賀
貴哉 山田
明平 杉山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Toyota Motor Corp
Original Assignee
Daikin Industries Ltd
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Toyota Motor Corp filed Critical Daikin Industries Ltd
Priority to JP2024528977A priority Critical patent/JP7849477B2/ja
Priority to KR1020247041623A priority patent/KR20250010688A/ko
Priority to CN202380047045.1A priority patent/CN119404340A/zh
Priority to EP23824004.8A priority patent/EP4542686A1/en
Priority to US18/873,956 priority patent/US20260100368A1/en
Publication of WO2023243714A1 publication Critical patent/WO2023243714A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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
    • 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

  • This application discloses a secondary battery.
  • Patent Document 1 discloses that when manufacturing a secondary battery, electrodes and electrolyte layers are pressed at 200 MPa or more and 1000 MPa or less.
  • Patent Document 2 discloses arranging an insulating layer at the peripheral portion of the electrode in order to suppress cracking of the electrolyte layer during high-pressure pressing.
  • Patent Document 3 discloses perfluoropolyether as an additive component of a non-aqueous electrolyte.
  • Patent Document 4 discloses that a perfluoropolyether group-containing compound is present on the surface of the electrode in order to improve the storage stability of the electrode.
  • a secondary battery comprising a first electrode, an electrolyte layer and a second electrode, At least one of the first electrode and the electrolyte layer includes a sulfide solid electrolyte,
  • the first electrode contains a perfluoropolyether represented by the following formula (1), Secondary battery.
  • Rf 1 and Rf 2 are each independently a C1-16 divalent alkylene group which may be substituted with one or more fluorine atoms
  • E 1 and E 2 are each independently a fluorine group, a hydrogen group, a hydroxyl group, an aldehyde group, a carboxylic acid group, a C1-10 alkyl ester group, an amide group which may have one or more substituents
  • R F is a divalent fluoropolyether group.
  • R F is represented by the formula (2): -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (2 )
  • R Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom at each occurrence
  • a, b, c, d, e and f are each independently an integer from 0 to 200
  • the sum of a, b, c, d, e and f is 1 or more
  • the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula, However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.
  • the R F is independently represented by the following formula (2-1), (2-2), (2-3), (2-4) or (2-5) at each occurrence: -(OC 3 F 6 ) d - (OC 2 F 4 ) e - (2-1) [In formula (2-1), d is an integer from 1 to 200, and e is 0 or 1.
  • R 6 is OCF 2 or OC 2 F 4 ;
  • R7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F12 , or two or three groups selected from these groups . It is a combination of two groups, g is an integer from 2 to 100.
  • e is an integer from 1 to 200
  • a, b, c, d and f are each independently an integer of 0 or more and 200 or less
  • the repeating units enclosed in parentheses with a, b, c, d, e, or f can be present in any order in the formula.
  • the R F is represented by the following formula (2-6): -(OCF 2 CF 2 CF 2 ) a -(OCF(CF 3 )CF 2 ) b -(OCF 2 CF(CF 3 )) c -(OCF 2 CF 2 ) d -(OCF(CF 3 )) e - (OCF 2 ) f - (2-6)
  • a, b, c, d, e and f are each independently an integer of 0 to 200, The sum of a, b, c, d, e and f is 1 or more,
  • the repeating units enclosed in parentheses with a, b, c, d, e, or f can be present in any order in the formula.
  • the R F is represented by the following formula (2-7): -(OCF 2 CF 2 ) d -(OCF(CF 3 )) e -(OCF 2 ) f - (2-7)
  • d, e and f are each independently an integer of 0 to 200, The sum of d, e and f is 1 or more, The repeating units suffixed with d, e or f and enclosed in parentheses can be present in any order in the formula.
  • ] is a group represented by, Secondary battery according to aspect 4.
  • the E 1 -Rf 1 and the E 2 -Rf 2 are each independently a group selected from the group consisting of -CF 3 , -CF 2 CF 3 , and -CF 2 CF 2 CF 3 , The secondary battery according to any one of aspects 1 to 6.
  • the first electrode has a first active material layer, The first active material layer contains the perfluoropolyether at 1% by volume or more and 25% by volume or less, The secondary battery according to any one of aspects 1 to 7.
  • the first electrode is a positive electrode, The secondary battery according to any one of aspects 1 to 8.
  • the first electrode includes the sulfide solid electrolyte and the perfluoropolyether; The secondary battery according to any one of aspects 1 to 9.
  • the secondary battery of the present disclosure tends to have low resistance.
  • a secondary battery 100 includes a first electrode 10, an electrolyte layer 20, and a second electrode 30.
  • at least one of the first electrode 10 and the electrolyte layer 20 includes a sulfide solid electrolyte.
  • the first electrode 10 includes perfluoropolyether represented by the following formula (1).
  • the sulfide solid electrolyte that can be included in electrodes and electrolyte layers has high chemical reactivity, and therefore may react with other materials to cause alteration and deterioration. In this case, the ionic conductivity of the electrodes and electrolyte layer tends to decrease.
  • the predetermined PFPE contained in the first electrode 10 is capable of imparting lubricity to various battery materials and has low reactivity with the sulfide solid electrolyte. That is, when the first electrode 10 contains a predetermined amount of PFPE, even when the first electrode 10 is pressed at low pressure, the density of the material in the first electrode 10 can be increased due to the lubricating effect of PFPE. That is, the filling rate of the material in the first electrode 10 becomes high, and the resistance of the first electrode 10 is easily reduced.
  • the perfluoropolyether is represented by the following formula (1).
  • Rf 1 and Rf 2 are each independently a C1-16 divalent alkylene group which may be substituted with one or more fluorine atoms.
  • R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
  • a, b, c, d, e and f may each independently be an integer of 0 to 100.
  • repeating units may be linear or branched.
  • -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF (CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF (CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF (CF 3 )CF 2 )-, and , -(OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) -.
  • -(OC 5 F 10 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) It may be any one of CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, and -(OCF 2 CF 2 CF 2 CF(CF 3 ))-.
  • -(OC 4 F 8 )- is -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )- , -(OCF 2 CF 2 CF(CF 3 ))-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF( It may be any of CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )-, and -(OCF 2 CF(C 2 F 5 ))-.
  • -(OC 3 F 6 )- (that is, in the above formula (2), when R Fa is a fluorine atom), -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 ) -, and -(OCF 2 CF (CF 3 )) -.
  • -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-.
  • R F may be a group represented by any of the following formulas (2-1) to (2-5), each occurrence independently.
  • R 6 is OCF 2 or OC 2 F 4
  • R7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F12 , or two or three groups selected from these groups . It is a combination of two groups, g is an integer from 2 to 100. ];
  • f is an integer from 1 to 200
  • a, b, c, d and e are each independently an integer of 0 to 200
  • the repeating units enclosed in parentheses with a, b, c, d, e, or f can be present in any order in the formula.
  • d is an integer preferably from 5 to 200, more preferably from 10 to 100, even more preferably from 15 to 50, for example from 25 to 35.
  • the above formula (2-1) is preferably a group represented by -(OCF 2 CF 2 CF 2 ) d - or -(OCF(CF 3 )CF 2 ) d -, and more preferably, It is a group represented by -(OCF 2 CF 2 CF 2 ) d -.
  • e is 0. In another embodiment, e is 1.
  • e and f are each independently an integer preferably from 5 to 200, more preferably from 10 to 200. Further, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the above formula (2-2) preferably represents -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 CF 2 CF 2 ) 2 ) It is a group represented by f -.
  • formula (2-2) may be a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
  • R 6 is preferably OC 2 F 4 .
  • R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or independently selected from these groups. It is a combination of two or three groups, more preferably a group selected from OC 3 F 6 and OC 4 F 8 .
  • the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, but includes, for example, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -, -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -
  • g is preferably an integer of 3 or more, more preferably 5 or more.
  • the above g is preferably an integer of 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either straight chain or branched chain. , preferably linear.
  • the above formula (2-3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
  • e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • the above R F is a group represented by the above formula (2-1).
  • the above R F is a group represented by the above formula (2-2).
  • the above R F is a group represented by the above formula (2-3).
  • the above R F is a group represented by the above formula (2-4).
  • the above R F is a group represented by the above formula (2-5).
  • R F is represented by the following formula (2-7): -(OCF 2 CF 2 ) d -(OCF(CF 3 )) e -(OCF 2 ) f - (2-7)
  • d, e and f are each independently an integer of 0 to 200, The sum of d, e and f is 1 or more, The repeating units suffixed with d, e or f and enclosed in parentheses can be present in any order in the formula.
  • the ratio of d to f may be 0.5 to 4, preferably 0.6 to 3, and more preferably 0.7 to 4. 2, and even more preferably 0.8 to 1.4.
  • d/f ratio 0.5 to 4 or less, lubricity and chemical stability are further improved.
  • the smaller the d/f ratio the better the lubricity.
  • the stability of the compound can be further improved.
  • the larger the d/f ratio the more stable the fluoropolyether structure is. In this case, the value of f is preferably 0.8 or more.
  • the number average molecular weight of the R F moiety is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000. ⁇ 10,000.
  • the number average molecular weight of R F is a value measured by 19 F-NMR.
  • the first electrode 10 may include a first active material layer 11 and a first current collector 12.
  • the first active material layer 11 may include the above-mentioned PFPE.
  • the first active material layer 11 may be a positive electrode active material layer or a negative electrode active material layer.
  • the second active material layer 31 is a negative electrode active material layer.
  • the total content of PFPE, the positive electrode active material, and optionally an electrolyte, a conductive aid, and a binder is 85% by volume or more, 90% by volume or more, or 95% by volume or more, assuming that the entire positive electrode active material layer is 100% by volume.
  • the remainder may be voids or other components.
  • the shape of the positive electrode active material layer is not particularly limited, and may be, for example, a sheet-like positive electrode active material layer having a substantially flat surface.
  • the thickness of the positive electrode active material layer is not particularly limited, and may be, for example, 0.1 ⁇ m or more, 1 ⁇ m or more, or 10 ⁇ m or more, or 2 mm or less, 1 mm or less, or 500 ⁇ m or less.
  • Lithium-containing compounds as positive electrode active materials include lithium cobalt oxide, lithium nickel oxide, Li 1 ⁇ Ni 1/3 Co 1/3 Mn 1/3 O 2 ⁇ , lithium manganate, and spinel-based lithium compounds (Li 1+x Mn 2-x-y M y O 4 (M is one or more selected from Al, Mg, Co, Fe, Ni and Zn), lithium titanate, phosphorous
  • Various lithium-containing oxides such as acid metal lithium (such as LiMPO 4 , where M is one or more selected from Fe, Mn, Co, and Ni) may be used.
  • the positive electrode active material contains a lithium-containing oxide containing at least Li, at least one of Ni, Co, and Mn, and O as constituent elements.
  • One type of positive electrode active material may be used alone, or two or more types may be used in combination.
  • a protective layer containing an ion-conductive oxide may be formed on the surface of the positive electrode active material. This makes it easier to suppress reactions between the positive electrode active material and sulfide (for example, sulfide solid electrolyte described below).
  • ion conductive oxides include Li 3 BO 3 , LiBO 2 , Li 2 CO 3 , LiAlO 2 , Li 4 SiO 4 , Li 2 SiO 3 , Li 3 PO 4 , Li 2 SO 4 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 , Li 2 ZrO 3 , LiNbO 3 , Li 2 MoO 4 , Li 2 WO 4 and the like.
  • the electrolyte that may be included in the positive electrode active material layer may be a solid electrolyte, a liquid electrolyte (electrolyte solution), or a combination thereof.
  • a solid electrolyte as an electrolyte
  • the positive electrode active material layer does not contain any liquid other than the above-mentioned PFPE.
  • even higher effects are likely to be obtained when the positive electrode includes a sulfide solid electrolyte and the above-mentioned PFPE (for example, when the positive electrode active material layer includes the sulfide solid electrolyte and the above-mentioned PFPE).
  • Li 2 S-P 2 S 5 Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Si 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -LiI-LiBr, Sulfide solids such as LiI-Li 2 S-P 2 S 5 , LiI-Li 2 SP 2 O 5 , LiI-Li 3 PO 4 -P 2 S 5 , Li 2 S-P 2 S 5 -GeS 2
  • An example is an electrolyte.
  • sulfide solid electrolytes especially sulfide solid electrolytes containing at least Li, S, and P as constituent elements, have high performance.
  • the solid electrolyte may be amorphous or crystalline.
  • the solid electrolyte may be in the form of particles, for example.
  • One type of solid electrolyte may be used alone, or two or more types may be used in combination.
  • the electrolyte may contain predetermined carrier ions (for example, lithium ions).
  • the electrolyte may be, for example, a non-aqueous electrolyte.
  • the composition of the electrolytic solution may be the same as that known as the composition of electrolytic solutions for secondary batteries.
  • an electrolyte in which a lithium salt is dissolved in a carbonate solvent at a predetermined concentration can be used.
  • carbonate solvents include fluoroethylene carbonate (FEC), ethylene carbonate (EC), and dimethyl carbonate (DMC).
  • Examples of the lithium salt include LiPF 6 and the like.
  • Examples of conductive additives that can be included in the positive electrode active material layer include vapor grown carbon fiber (VGCF), acetylene black (AB), Ketjen black (KB), carbon nanotube (CNT), and carbon nanofiber (CNF).
  • Examples include carbon materials such as; metal materials such as nickel, aluminum, and stainless steel.
  • the conductive aid may be, for example, in the form of particles or fibers, and its size is not particularly limited. One type of conductive aid may be used alone, or two or more types may be used in combination.
  • binders examples include butadiene rubber (BR) binders, butylene rubber (IIR) binders, acrylate butadiene rubber (ABR) binders, styrene butadiene rubber (SBR) binders, and polyvinylidene fluoride.
  • PVdF polyvinylidene fluoride-based binders, polytetrafluoroethylene (PTFE)-based binders, polyimide (PI)-based binders, and the like.
  • One binder may be used alone, or two or more binders may be used in combination.
  • the first electrode 10 may include a first current collector 12 in contact with the first active material layer 11 described above.
  • the first current collector 12 may be a positive electrode current collector or a negative electrode current collector.
  • the second current collector 32 is a negative electrode current collector.
  • the positive electrode current collector any common positive electrode current collector for batteries can be employed. Further, the positive electrode current collector may be in the form of a foil, a plate, a mesh, a punched metal, a foam, or the like.
  • the positive electrode current collector may be made of metal foil or metal mesh. In particular, metal foil has excellent handling properties.
  • the positive electrode current collector may be made of a plurality of foils. Examples of metals constituting the positive electrode current collector include Cu, Ni, Cr, Au, Pt, Ag, Al, Fe, Ti, Zn, Co, and stainless steel. In particular, from the viewpoint of ensuring oxidation resistance, the positive electrode current collector may contain Al.
  • the positive electrode current collector may have some kind of coating layer on its surface for the purpose of adjusting resistance or the like.
  • the positive electrode current collector may be a metal foil or a base material on which the above-mentioned metal is plated or vapor-deposited. Further, when the positive electrode current collector is made of a plurality of metal foils, there may be some kind of layer between the plurality of metal foils.
  • the thickness of the positive electrode current collector is not particularly limited. For example, it may be 0.1 ⁇ m or more or 1 ⁇ m or more, or 1 mm or less or 100 ⁇ m or less.
  • the electrolyte layer 20 is disposed between the first electrode 10 and the second electrode 30 and can function as a separator.
  • the electrolyte layer 20 contains at least an electrolyte, and may optionally further contain a binder or the like.
  • the electrolyte layer 20 may further contain other components such as a dispersant and the above-mentioned PFPE.
  • the content of each component in the electrolyte layer 20 is not particularly limited, and may be determined as appropriate depending on the desired battery performance.
  • the shape of the electrolyte layer 20 is not particularly limited, and may be in the form of a substantially flat sheet, for example.
  • the thickness of the electrolyte layer 20 is not particularly limited, and may be, for example, 0.1 ⁇ m or more or 1 ⁇ m or more, or 2 mm or less or 1 mm or less.
  • the electrolyte included in the electrolyte layer 20 may be appropriately selected from those exemplified as electrolytes that can be included in the above-mentioned positive electrode active material layer.
  • the performance of the electrolyte layer 20 containing a solid electrolyte, especially a sulfide solid electrolyte, and more particularly, a sulfide solid electrolyte containing at least Li, S, and P as constituent elements is high.
  • the electrolyte is a solid electrolyte
  • the solid electrolyte may be amorphous or crystalline.
  • the electrolyte is a solid electrolyte
  • the solid electrolyte may be in the form of particles, for example.
  • One type of electrolyte may be used alone, or two or more types may be used in combination.
  • the above-described sulfide solid electrolyte is contained in at least one of the first electrode 10 and the electrolyte layer 20. That is, the PFPE included in the first electrode 10 can contact at least one of the sulfide solid electrolyte included in the first electrode 10 and the sulfide solid electrolyte included in the electrolyte layer 20.
  • the sulfide solid electrolyte is unlikely to change or deteriorate, and the high ionic conductivity of the sulfide solid electrolyte is maintained. easy to be
  • the binder that can be included in the electrolyte layer 20 may be appropriately selected, for example, from among the binders that can be included in the above-mentioned positive electrode active material layer.
  • the second electrode 30 may be a positive electrode or a negative electrode.
  • the second electrode 30 is a negative electrode.
  • the second electrode 30 is not particularly limited in its configuration as long as it can function appropriately as a positive electrode or a negative electrode of a secondary battery.
  • the second electrode 30 may include a second active material layer 31 and a second current collector 32.
  • the second active material layer 31 may or may not contain the above-mentioned predetermined PFPE.
  • the second active material layer 31 contains a predetermined PFPE, its specific configuration may be similar to the configuration of the first active material layer 11.
  • the second active material layer 31 may be a positive electrode active material layer or a negative electrode active material layer.
  • the first active material layer 11 is a positive electrode active material layer
  • the second active material layer 31 is a negative electrode active material layer.
  • the negative electrode active material layer contains at least a negative electrode active material, and may optionally further contain an electrolyte, a conductive aid, a binder, and the like.
  • the negative electrode active material layer may also contain various other additives. For example, it may contain the above-mentioned PFPE.
  • the content of each component in the negative electrode active material layer may be determined as appropriate depending on the desired battery performance. For example, when the entire solid content of the negative electrode active material layer is 100% by mass, the content of the negative electrode active material may be 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and 100% by mass. % or less, 95% by mass or less, or 90% by mass or less.
  • the total of the negative electrode active material and optionally an electrolyte, a conductive aid, a binder, and PFPE is 85 volume% or more, 90 volume% or more, or 95 volume% or more, with the entire negative electrode active material layer being 100 volume%. The remainder may be voids or other components.
  • the shape of the negative electrode active material layer is not particularly limited, and may be, for example, a sheet-like negative electrode active material layer having a substantially flat surface.
  • the thickness of the negative electrode active material layer is not particularly limited, and may be, for example, 0.1 ⁇ m or more, 1 ⁇ m or more, or 10 ⁇ m or more, or 2 mm or less, 1 mm or less, or 500 ⁇ m or less.
  • negative electrode active material various materials may be employed whose potential (charging and discharging potential) for intercalating and releasing predetermined carrier ions (for example, lithium ions) is lower than that of the above-mentioned positive electrode active material.
  • negative electrode active materials include silicon-based active materials such as Si, Si alloys, and silicon oxide; carbon-based active materials such as graphite and hard carbon; various oxide-based active materials such as lithium titanate; metallic lithium, lithium alloys, etc. It may be at least one selected from the following.
  • One type of negative electrode active material may be used alone, or two or more types may be used in combination.
  • the shape of the negative electrode active material may be any shape commonly used as negative electrode active materials of batteries.
  • the negative electrode active material may be in the form of particles.
  • the negative electrode active material may be hollow, have voids, or be porous.
  • the negative electrode active material may be a primary particle or a secondary particle formed by agglomerating a plurality of primary particles.
  • the average particle diameter D50 of the negative electrode active material may be, for example, 1 nm or more, 5 nm or more, or 10 nm or more, or may be 500 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less.
  • the negative electrode active material may be in the form of a sheet (foil, film) such as lithium foil. That is, the negative electrode active material layer may be made of a sheet of negative electrode active material.
  • the electrolyte that may be included in the negative electrode active material layer may be a solid electrolyte, a liquid electrolyte (electrolyte solution), or a combination thereof. In particular, even higher effects are likely to be obtained when the negative electrode active material layer contains at least a solid electrolyte as an electrolyte.
  • the negative electrode active material layer may include a solid electrolyte, especially a sulfide solid electrolyte, and further a sulfide solid electrolyte containing Li, S, and P as constituent elements.
  • the conductive aid that can be included in the negative electrode active material layer include the above-mentioned carbon materials and the above-mentioned metal materials.
  • the binder that can be included in the negative electrode active material layer may be appropriately selected, for example, from among the binders that can be included in the above-mentioned positive electrode active material layer.
  • the second electrode 30 may include a second current collector 32 in contact with the second active material layer 31 described above.
  • the second current collector 32 may be a positive electrode current collector or a negative electrode current collector.
  • the first current collector 12 is a positive electrode current collector
  • the second current collector 32 is a negative electrode current collector.
  • the negative electrode current collector any common negative electrode current collector for batteries can be employed.
  • the negative electrode current collector may be in the form of a foil, a plate, a mesh, a punched metal, a foam, or the like.
  • the negative electrode current collector may be a metal foil or a metal mesh, or a carbon sheet. In particular, metal foil has excellent handling properties.
  • the negative electrode current collector may be made of a plurality of foils or sheets. Examples of metals constituting the negative electrode current collector include Cu, Ni, Cr, Au, Pt, Ag, Al, Fe, Ti, Zn, Co, and stainless steel.
  • the secondary battery 100 may have each of the above-mentioned configurations housed inside an exterior body.
  • the exterior body any known exterior body for batteries can be used.
  • a plurality of secondary batteries 100 may be arbitrarily electrically connected and arbitrarily stacked on top of each other to form an assembled battery.
  • the assembled battery may be housed inside a known battery case.
  • the secondary battery 100 may also include other obvious configurations such as necessary terminals. Examples of the shape of the secondary battery 100 include a coin shape, a laminate shape, a cylindrical shape, and a square shape.
  • the secondary battery 100 can be manufactured by applying a known method. For example, it can be manufactured as follows. However, the method for manufacturing the secondary battery 100 is not limited to the following method, and each layer may be formed by dry molding or the like, for example.
  • a negative electrode slurry is obtained by dispersing the negative electrode active material and the like constituting the negative electrode active material layer in a solvent.
  • the solvent used in this case is not particularly limited, and water and various organic solvents can be used, and N-methylpyrrolidone (NMP) may be used.
  • the positive electrode slurry is applied to the surface of the positive electrode current collector or the electrolyte layer described below using a doctor blade, etc., and then dried to form a positive electrode active material layer on the surface of the positive electrode current collector or electrolyte layer. and use it as the positive electrode.
  • the positive electrode active material layer may be press-molded.
  • the linear pressure is about 75 kN/cm, and when the surface pressure is about 7.5 kN/cm, the linear pressure is about 15 kN. /cm.
  • the positive electrode, negative electrode, and electrolyte layer for pressing were each formed into strips, and the composite surface of the positive electrode for pressing and the composite material surface of the electrolyte layer for pressing were overlapped, and the mixture was heated at 165°C as shown in the table below.
  • a laminate (A) of the Al foil, the positive electrode active material layer, and the electrolyte layer was obtained by roll pressing at the pressure shown in 1 and peeling off the Al foil of the electrolyte layer for pressing.
  • the composite material surface of the negative electrode for pressing and the composite material surface of the electrolyte layer for pressing are overlapped, and then roll-pressed at 25° C.
  • a laminate (B) of Cu foil, a negative electrode active material layer, and an electrolyte layer was obtained.
  • the laminate (A) was punched out to a diameter of 11.28 mm, and the laminate (B) was punched out to a diameter of 13.00 mm.
  • the electrolyte layer is further transferred to the laminate (B) using a uniaxial press, and then the laminate (A) and the laminate (B) are superimposed to form an Al foil/positive electrode active material layer.
  • An electrode body having a structure of /electrolyte layer/negative electrode active material layer/Cu foil was obtained.
  • a battery for evaluation was prepared by attaching current extraction tabs to each of the Al foil and Cu foil of the electrode body, and sealing them in a laminate pack using a vacuum laminate sealer.
  • the resistance of the battery for evaluation produced as described above was measured. Specifically, the resistance value of the real axis intercept on the low frequency side of the circular arc component was read using a Nyquist plot obtained by the AC impedance method, and this was identified as the resistance of the battery.
  • PFPE having a specific chemical structure was illustrated, but the chemical structure of PFPE is not limited to this. Further, in the above embodiment, the case where PFPE is included in the positive electrode side is illustrated, but similar effects can be expected when PFPE is included in the negative electrode side. Furthermore, the composition of the positive electrode, electrolyte layer, and negative electrode is not limited to those described above.
  • a secondary battery having the following configuration tends to have low resistance.
  • It has a first electrode, an electrolyte layer, and a second electrode.
  • At least one of the first electrode and the electrolyte layer includes a sulfide solid electrolyte.
  • the first electrode contains a predetermined perfluoropolyether.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
PCT/JP2023/022418 2022-06-17 2023-06-16 二次電池 Ceased WO2023243714A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2024528977A JP7849477B2 (ja) 2022-06-17 2023-06-16 二次電池
KR1020247041623A KR20250010688A (ko) 2022-06-17 2023-06-16 이차 전지
CN202380047045.1A CN119404340A (zh) 2022-06-17 2023-06-16 二次电池
EP23824004.8A EP4542686A1 (en) 2022-06-17 2023-06-16 Secondary battery
US18/873,956 US20260100368A1 (en) 2022-06-17 2023-06-16 Secondary battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022098309 2022-06-17
JP2022-098309 2022-06-17

Publications (1)

Publication Number Publication Date
WO2023243714A1 true WO2023243714A1 (ja) 2023-12-21

Family

ID=89191482

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/022418 Ceased WO2023243714A1 (ja) 2022-06-17 2023-06-16 二次電池

Country Status (7)

Country Link
US (1) US20260100368A1 (https=)
EP (1) EP4542686A1 (https=)
JP (1) JP7849477B2 (https=)
KR (1) KR20250010688A (https=)
CN (1) CN119404340A (https=)
TW (1) TWI871671B (https=)
WO (1) WO2023243714A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018508928A (ja) * 2014-12-19 2018-03-29 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 電極形成組成物
JP2018078102A (ja) * 2016-11-02 2018-05-17 ダイキン工業株式会社 電極および電気化学デバイス
JP2018200866A (ja) 2017-05-19 2018-12-20 パナソニックＩｐマネジメント株式会社 非水電解質およびこれを備える二次電池
JP2019524977A (ja) * 2016-07-29 2019-09-05 ブルー カレント、インコーポレイテッド 柔軟な固体状イオン伝導性複合材料および製造方法
WO2021060541A1 (ja) * 2019-09-27 2021-04-01 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5830600A (en) * 1996-05-24 1998-11-03 Sri International Nonflammable/self-extinguishing electrolytes for batteries
JP5850154B2 (ja) 2012-07-11 2016-02-03 トヨタ自動車株式会社 全固体電池の製造方法
JP6318100B2 (ja) * 2015-01-27 2018-04-25 富士フイルム株式会社 全固体二次電池、これに用いる固体電解質組成物および電池用電極シートならびに電池用電極シートおよび全固体二次電池の製造方法
WO2016187448A1 (en) * 2015-05-21 2016-11-24 The University Of North Carolina At Chapel Hill Hybrid solid single-ion-conducting electrolytes for alkali batteries
CN111373595A (zh) 2017-11-21 2020-07-03 丰田自动车株式会社 全固体电池用电极体及其制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018508928A (ja) * 2014-12-19 2018-03-29 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 電極形成組成物
JP2019524977A (ja) * 2016-07-29 2019-09-05 ブルー カレント、インコーポレイテッド 柔軟な固体状イオン伝導性複合材料および製造方法
JP2018078102A (ja) * 2016-11-02 2018-05-17 ダイキン工業株式会社 電極および電気化学デバイス
JP2018147887A (ja) 2016-11-02 2018-09-20 ダイキン工業株式会社 電極および電気化学デバイス
JP2018200866A (ja) 2017-05-19 2018-12-20 パナソニックＩｐマネジメント株式会社 非水電解質およびこれを備える二次電池
WO2021060541A1 (ja) * 2019-09-27 2021-04-01 富士フイルム株式会社 無機固体電解質含有組成物、全固体二次電池用シート、全固体二次電池用電極シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法

Also Published As

Publication number Publication date
TW202414883A (zh) 2024-04-01
US20260100368A1 (en) 2026-04-09
JP7849477B2 (ja) 2026-04-21
KR20250010688A (ko) 2025-01-21
CN119404340A (zh) 2025-02-07
EP4542686A1 (en) 2025-04-23
TWI871671B (zh) 2025-02-01
JPWO2023243714A1 (https=) 2023-12-21

Similar Documents

Publication Publication Date Title
JP4686974B2 (ja) 非水系電解液二次電池用負極およびそれを用いた非水系電解液二次電池
CN1468455A (zh) 高性能锂或锂离子电池
JP2024017797A (ja) 二次電池用負極、二次電池用負極の製造方法、及び、二次電池
JP2015035315A (ja) 非水系二次電池負極用活物質の製造方法、及びその製造方法にて製造された非水系二次電池用活物質、非水系二次電池用負極並びに、非水系二次電池
JP7804864B2 (ja) 電極および電池
US11152623B2 (en) Binder composition for secondary battery, conductive material paste for secondary battery electrode, slurry composition for secondary battery electrode, method of producing slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery
JP7849477B2 (ja) 二次電池
JP7849478B2 (ja) 二次電池及びその製造方法
JP2015173103A (ja) 非水系二次電池負極用活物質並びにそれを用いた負極及び非水系二次電池
EP4542708A1 (en) Secondary battery
JP7700776B2 (ja) 活物質二次粒子、負極合材、これらの製造方法、及び、二次電池
JP7849479B2 (ja) リチウムイオン伝導材料及び二次電池
JP7708140B2 (ja) 二次電池システム
JP2023138137A (ja) リチウムイオン伝導材料及びリチウムイオン二次電池
WO2024116785A1 (ja) 二次電池用電極活物質、及び二次電池
WO2025047898A1 (ja) 組成物、電気化学デバイス用合剤、電気化学デバイス用合剤シート、電気化学デバイス、及び、電気化学デバイス用合剤シートの製造方法
CN121729746A (zh) 组合物、固体电池用合剂、硫化物固体电解质层、电极层、以及二次电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23824004

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18873956

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2024528977

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202380047045.1

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20247041623

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020247041623

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2023824004

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023824004

Country of ref document: EP

Effective date: 20250117

WWP Wipo information: published in national office

Ref document number: 202380047045.1

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2023824004

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 18873956

Country of ref document: US