WO2023243716A1 - 二次電池及びその製造方法 - Google Patents

二次電池及びその製造方法 Download PDF

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Publication number
WO2023243716A1
WO2023243716A1 PCT/JP2023/022423 JP2023022423W WO2023243716A1 WO 2023243716 A1 WO2023243716 A1 WO 2023243716A1 JP 2023022423 W JP2023022423 W JP 2023022423W WO 2023243716 A1 WO2023243716 A1 WO 2023243716A1
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group
active material
formula
ocf
electrode
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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
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Daikin Industries Ltd
Toyota Motor Corp
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Daikin Industries Ltd
Toyota Motor Corp
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Priority to CN202380046945.4A priority Critical patent/CN119318036A/zh
Priority to US18/874,426 priority patent/US20250372651A1/en
Priority to KR1020247041625A priority patent/KR20250010689A/ko
Priority to JP2024528978A priority patent/JP7849478B2/ja
Publication of WO2023243716A1 publication Critical patent/WO2023243716A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
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    • 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
    • H01M2004/027—Negative 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
    • H01M2300/0065—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 and a method for manufacturing the same.
  • Patent Document 1 discloses the use of predetermined porous silicon particles as a negative electrode active material in order to suppress an increase in confining pressure of a battery during charging.
  • Patent Document 2 discloses silicon clathrate particles having voids as an active material whose volume changes little due to charging and discharging.
  • 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 includes an active material having voids and 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.
  • 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.
  • ] is a group represented by, A secondary battery according to aspect 3.
  • 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 negative electrode, the active material having the voids includes Si or a Si alloy; The secondary battery according to any one of aspects 1 to 8.
  • the first electrode includes the sulfide solid electrolyte, the active material having the voids, and the perfluoropolyether.
  • the secondary battery according to any one of aspects 1 to 9.
  • a method for manufacturing a secondary battery comprising: forming a first electrode composite material to obtain a first electrode; forming an electrolyte mixture to obtain an electrolyte layer, and forming a second electrode composite material to obtain a second electrode; including; At least one of the first electrode composite material and the electrolyte composite material includes a sulfide solid electrolyte,
  • the first electrode composite material includes an active material having voids and a perfluoropolyether represented by the following formula (1), When molding the first electrode composite material, a pressure of more than 0 kN/cm and not more than 15 kN/cm is applied to the first electrode composite material.
  • 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.
  • 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 an active material having voids and a perfluoropolyether represented by the following formula (1).
  • the first electrode 10 may be a negative electrode or a positive electrode.
  • the second electrode 30 is a positive electrode.
  • the first electrode 10 may have various configurations as long as it contains an active material having voids and a predetermined perfluoropolyether and can function appropriately as a negative electrode or a positive electrode of a secondary battery.
  • Active material with voids During charging and discharging of a secondary battery, the volume of the active material changes as carrier ions are inserted into or released from the active material. Excessive expansion of the active material during charging or discharging may adversely affect the cycle characteristics of the battery. In order to alleviate the expansion of the active material, it is considered effective to form voids in the active material. That is, in an active material having voids, expansion during charging or discharging is absorbed by the voids, and volume change tends to be small.
  • the active material may be porous so that it has voids, or it may be hollow so that it has voids.
  • the voids in the active material may exist only inside the active material, or may reach the surface from the inside of the active material, or may exist only inside the active material and those that extend from the inside to the surface. There may be a mixture of those that reach.
  • the active material may have voids in the primary particles themselves (for example, have voids inside the primary particles), or may be agglomerated in a state where a plurality of primary particles have aggregated to become secondary particles.
  • the primary particles may have voids between them. Note that the void has a size that can absorb the volume expansion of the active material.
  • the void may or may not be filled with perfluoropolyether, which will be described later.
  • the voids do not have to be minute voids such as those used for carrier ion intercalation. Whether or not the active material has voids can be determined, for example, by observing a cross section of the active material using a scanning electron microscope (SEM) or the like.
  • the porosity of the active material is not particularly limited.
  • the porosity of the active material may be 1% or more, 2% or more, 3% or more, or 4% or more, and may be 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less. It's okay.
  • the porosity of the active material can be determined, for example, as follows. First, a cross section of the first electrode 10 containing an active material is formed by ion milling. Then, the cross section is observed with a SEM to obtain a photograph of the particles. From the obtained photograph, the active material part and the void part in the active material are clearly distinguished using image analysis software, and the result is binarized.
  • the area of the active material part and the void part is determined, and the porosity (%) is calculated from the following formula.
  • the specific conditions for calculating the porosity may be, for example, the conditions specifically described in Patent Document 2 (Japanese Unexamined Patent Publication No. 2020-087886).
  • Porosity (%) 100 x (void area) / ((active material area) + (void area))
  • the active material having voids may be a negative electrode active material or a positive electrode active material.
  • the active material having voids is a negative electrode active material
  • the effects of the technology of the present disclosure are obtained. It is likely to become even higher.
  • Si-based active materials containing Si or Si alloys tend to expand in volume during charging, the presence of voids in the active materials can alleviate the expansion in volume.
  • Specific examples of Si-based active materials containing Si or Si alloys include those having a clathrate structure. Whether or not the Si-based active material has a clathrate structure can be easily determined from Raman spectra, XRD, and the like.
  • the ratio I 325 /I 205 of the maximum peak intensity I 325 at 325 ⁇ 10 cm ⁇ 1 measured by Raman spectroscopy to the maximum peak intensity I 205 at 205 ⁇ 10 cm ⁇ 1 is in the range of 1.03 or more and 1.21.
  • the Si-based active material has a clathrate structure
  • the first electrode 10 may be a positive electrode
  • the active material having voids may be a positive electrode active material such as a sulfur-based active material (such as elemental sulfur or Li 2 S).
  • a positive electrode active material tends to expand in volume during discharge, the volume expansion can be alleviated by the active material having voids.
  • the active material may have an oxide film or the like formed thereon, and may contain impurities such as carbon.
  • the active material having voids may be in the form of particles, for example.
  • the size of the active material having voids is not particularly limited.
  • the average particle diameter of the active material having voids may be, for example, 1 nm or more, 5 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 300 nm or more, or 500 nm or more, and also 50 ⁇ m or less, 30 ⁇ m or less, 10 ⁇ m or less. Or it may be 5 ⁇ m or less.
  • the average particle diameter of the active material is the particle diameter (median diameter) at an integrated value of 50% in a volume-based particle size distribution determined by a laser diffraction/scattering method.
  • PFPE Perfluoropolyether
  • the first electrode 10 contains a predetermined perfluoropolyether (PFPE), even if a low-pressure press is employed during the manufacture of the secondary battery, PFPE
  • PFPE perfluoropolyether
  • PFPE is thought to have a high affinity for the surfaces of various battery materials because it has ether bonds. It is believed that it can suitably exist in the voids between the solid electrolyte materials. As a result, the lubricating effect of the first electrode 10 is further enhanced, and even when the first electrode 10 is pressed at low pressure, it becomes easier to increase the density of the material in the first electrode 10, and the resistance of the first electrode 10 is further reduced. It becomes easier.
  • 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
  • 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.
  • Rf 1 and Rf 2 are each independently a C1-16 divalent alkylene group which may be substituted with one or more fluorine atoms.
  • the "C1-16 divalent alkylene group" in the C1-16 divalent alkylene group optionally substituted with one or more fluorine atoms may be a straight chain or , may be branched, preferably a straight or branched C1-6 alkylalkylene group, particularly a C1-3 alkylene group, more preferably a straight-chain C1-6 alkylene group , especially a C1-3 alkylene group.
  • the "C1-16 divalent alkylene" in the C1-16 divalent alkylene group optionally substituted with one or more fluorine atoms is a straight chain, It may be a branched chain, and is preferably a straight or branched C1-6 fluoroalkylene group, particularly a C1-3 fluoroalkylene group, specifically -CF 2 CH 2 -, and It may be -CF 2 CF 2 CH 2 -, and more preferably a linear C1-6 perfluoroalkylene group, especially a C1-3 perfluoroalkylene group, specifically -CF 2 - , -CF 2 CF 2 -, and -CF 2 CF 2 CF 2 -.
  • E 1 and E 2 each independently have a fluorine group, a hydrogen group, a hydroxyl group, an aldehyde group, a carboxylic acid group, a C1-10 alkyl ester group, or one or more substituents.
  • This is a monovalent group selected from the group consisting of an amide group which may have one or more substituents, and an amino group which may have one or more substituents.
  • E 1 and E 2 are each independently preferably a fluorine group.
  • E 1 -Rf 1 and 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 It may be.
  • each occurrence of R F is independently a divalent fluoropolyether group.
  • R F preferably represents 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.
  • 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.
  • the sum of a, b, 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 sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
  • 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).
  • the ratio of e 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.
  • e/f ratio a ratio of e to f
  • the e/f ratio 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.
  • 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.
  • It may be a group represented by
  • 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 content of PFPE in the first electrode 10 is not particularly limited, and can be appropriately selected depending on the desired performance.
  • the first electrode 10 has the first active material layer 11 described below, even higher effects are likely to be obtained when the first active material layer 11 contains the above-mentioned PFPE at 1 volume % or more and 25 volume % or less. .
  • the first active material layer 11 contains the above-mentioned PFPE, for example, 1% by volume or more, 3% by volume or more, 5% by volume or more, 7% by volume or more, 8% by volume or more, 9% by volume or more, 10% by volume or more, 11 volume% or more, 12 volume% or more, and 25 volume% or less, 24 volume% or less, 22 volume% or less, 20 volume% or less, 18 volume% or less, 16 volume% or less, 14 volume% or less, or 12 volume% May contain the following:
  • the volume fraction of PFPE in the first active material layer 11 is measured as follows. That is, the volume of the first active material layer 11 is measured in advance using an optical microscope or SEM.
  • the content volume of PFPE is determined by washing the first active material layer 11 with a solvent (one that can dissolve PFPE but not dissolving other electrode materials), collecting the filtrate in which PFPE is dissolved by suction filtration, etc., and using the collected solvent. It may be identified by GC-MS analysis, or if the solvent has a boiling point significantly different from that of PFPE, it may be extracted by distillation and the volume of PFPE may be directly measured. Thereby, the volume ratio of PFPE to the volume of the first active material layer 11 measured in advance is calculated.
  • 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-described active material having voids and a predetermined 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 positive 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 positive electrode active material described below.
  • negative electrode active materials include Si-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.
  • the negative electrode active material is a Si-based active material containing Si or a Si alloy, even higher effects by the technique of the present disclosure are likely to be obtained.
  • 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, for example.
  • the negative electrode active material may have voids, for example, it may be porous or hollow.
  • the positive electrode active material described below includes an active material with voids
  • the negative electrode active material may have voids, may not have voids, or may have voids or have voids. It may also be a combination with one that does not have one.
  • 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.
  • a solid electrolyte electrolyte solution
  • electrolyte solution electrolyte solution
  • even higher effects are likely to be obtained when the negative electrode active material layer contains at least a solid electrolyte as an electrolyte, especially when the negative electrode active material layer does not contain any liquid other than the above-mentioned PFPE.
  • the first electrode 10 includes a sulfide solid electrolyte, an active material having the above-mentioned voids, and the above-mentioned PFPE (for example, the first active material layer 11 includes the sulfide solid electrolyte and the above-mentioned voids), and the above-mentioned PFPE), even higher effects are likely to be obtained.
  • the solid electrolyte one known as a solid electrolyte for secondary batteries may be used.
  • the solid electrolyte may be an inorganic solid electrolyte or an organic polymer electrolyte.
  • inorganic solid electrolytes have excellent ionic conductivity and heat resistance.
  • oxide solid electrolytes such as lithium lanthanum zirconate, LiPON, Li 1+X Al X Ge 2-X (PO 4 ) 3 , Li-SiO glass, and Li-Al-S-O glass.
  • 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.
  • a lithium salt is dissolved at a predetermined concentration in a carbonate-based solvent can be used.
  • carbonate-based solvents include fluoroethylene carbonate (FEC), ethylene carbonate (EC), and dimethyl carbonate (DMC).
  • the lithium salt include LiPF 6 and the like.
  • Examples of the conductive additive that can be included in the negative 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 negative electrode current collector or a positive electrode current collector.
  • the second current collector 32 is a positive 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 negative electrode current collector may contain at least one metal selected from Cu, Ni, and stainless steel.
  • the negative electrode current collector may have some kind of coating layer on its surface for the purpose of adjusting resistance or the like.
  • the negative electrode current collector may be a metal foil or a base material on which the above-mentioned metal is plated or vapor-deposited.
  • the negative 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 negative 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 negative 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-mentioned 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.
  • PFPE has low reactivity with the sulfide solid electrolyte, even if PFPE and the sulfide solid electrolyte come into contact, the sulfide solid electrolyte is unlikely to change or deteriorate, and the sulfide solid electrolyte has a high ion content. Conductivity is easily maintained.
  • 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 negative electrode active material layer.
  • the second electrode 30 may be a positive electrode or a negative electrode.
  • the second electrode 30 is a positive 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 negative electrode active material layer
  • the second active material layer 31 is a positive electrode active material layer.
  • the positive electrode active material layer contains at least a positive electrode active material. Further, the positive electrode active material layer may optionally contain an electrolyte, a conductive aid, a binder, and the like. Furthermore, the positive electrode active material layer may also contain various additives such as the above-mentioned PFPE.
  • the content of each component in the positive electrode active material layer may be determined as appropriate depending on the desired battery performance. For example, when the entire solid content of the positive electrode active material layer is 100% by mass, the content of the positive 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 positive 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, assuming that the entire positive electrode active material layer is 100 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.
  • positive electrode active material those known as positive electrode active materials for secondary batteries may be used.
  • a material with a relatively noble potential (charge/discharge potential) for intercalating and releasing a predetermined carrier ion (for example, lithium ion) is used as the positive electrode active material, and a material that is relatively base is used as the positive electrode active material. It can be used as the above-mentioned negative electrode active material.
  • the positive electrode active material may be, for example, at least one selected from various lithium-containing compounds, elemental sulfur, sulfur compounds, and the like.
  • 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.
  • the shape of the positive electrode active material may be any shape commonly used as a positive electrode active material of batteries.
  • the positive electrode active material may be, for example, particulate.
  • the positive electrode active material may have voids, for example, it may be porous or hollow.
  • the positive electrode active material may have voids, may not have voids, or may have voids or have voids. It may also be a combination with one that does not have one.
  • 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, the above-mentioned sulfide solid electrolyte).
  • 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 ion conductive oxide may have some elements replaced with a doping element such as P or B.
  • the coverage (area ratio) of the protective layer on the surface of the positive electrode active material may be, for example, 70% or more, 80% or more, or 90% or more.
  • the thickness of the protective layer may be, for example, 0.1 nm or more or 1 nm or more, or 100 nm or less or 20 nm or less.
  • 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. In particular, even higher effects are likely to be obtained when the positive electrode active material layer contains at least a solid electrolyte as an electrolyte.
  • the positive 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 positive electrode active material layer include the above-mentioned carbon materials and the above-mentioned metal materials.
  • the binder that can be included in the positive electrode active material layer may be appropriately selected, for example, from among the binders that can be included in the above-mentioned negative 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 negative electrode current collector
  • the second current collector 32 is a positive 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 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.
  • a positive electrode slurry is obtained by dispersing the positive electrode active material and the like constituting the positive 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 electrolyte layer may be obtained by, for example, molding an electrolyte mixture containing an electrolyte and a binder, or may be obtained by press molding.
  • the laminate may be further press-molded.
  • Other members such as terminals are attached to the laminate as necessary.
  • a secondary battery is obtained by housing the laminate in a battery case and sealing it.
  • the steps (1) and (2) above by including the above-mentioned PFPE in the active material layer, even when the active material layer is press-molded at low pressure, the filling of the active material layer can be improved. As a result, a secondary battery with low resistance can be easily obtained. Furthermore, by press-molding the active material layer at low pressure, collapse of the active material having voids can be easily suppressed, and as a result, a secondary battery with excellent cycle characteristics can be easily obtained. Furthermore, in the steps related to (1) to (3) above, the sulfide solid electrolyte is included in at least one of the active material layer and the electrolyte layer, so that PFPE and the sulfide solid electrolyte come into contact with each other. Also, reaction between PFPE and the sulfide solid electrolyte is difficult to occur, and high ionic conductivity as a sulfide solid electrolyte is easily maintained.
  • the technology of the present disclosure also has aspects as a method for manufacturing a secondary battery as described below. That is, in one embodiment, the method for manufacturing the secondary battery 100 includes: forming the first electrode composite material to obtain the first electrode 10; forming the electrolyte mixture to obtain the electrolyte layer 20; and forming the second electrode composite material to obtain the second electrode 30; including; At least one of the first electrode composite material and the electrolyte composite material includes a sulfide solid electrolyte,
  • the first electrode composite material includes an active material having voids and a perfluoropolyether represented by the above formula (1), When the first electrode composite material is molded, a pressure of more than 0 kN/cm and 15 kN/cm or less is applied to the first electrode composite material.
  • the first electrode composite material and the second electrode composite material may include materials constituting the above-mentioned negative electrode active material layer or positive electrode active material layer, and the electrolyte composite material may include materials constituting the above-mentioned electrolyte layer. It may contain materials.
  • the pressure when molding the first electrode composite material is as low as 15 kN/cm or less, so that collapse of the active material having voids contained in the first electrode composite material is suppressed. Ru.
  • the first electrode composite material contains a predetermined amount of PFPE, even when the first electrode composite material is pressed at low pressure, the filling rate of the composite material in the first electrode 10 tends to increase.
  • the lower limit of the pressure during pressing is not particularly limited, and may be more than 0 kN/cm, 1 kN/cm or more, 2 kN/cm or more, 3 kN/cm or more, 4 kN/cm or more, 5 kN/cm or more, 6 kN/cm or more, It may be 7 kN/cm or more, 8 kN/cm or more, 9 kN/cm or more, or 10 kN/cm or more.
  • the means and method for applying pressure to the first electrode composite material are not particularly limited either, and various pressurizing means and methods such as roll press and CIP may be employed.
  • the unit of pressure applied to the first electrode composite material is "kN/cm", but this is just an example. That is, the pressure applied to the first electrode composite material is not limited to linear pressure, but may be surface pressure. Even when the pressure applied to the first electrode mixture is surface pressure, the surface pressure can be converted into linear pressure.
  • the specific conversion method is not particularly limited, and surface pressure may be converted to linear pressure by experimentally and statistically identifying the relationship between surface pressure and linear pressure through various experiments. Alternatively, the surface pressure may be theoretically converted into linear pressure by calculation.
  • 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 technology of the present disclosure can be applied not only to lithium ion secondary batteries but also to secondary batteries other than lithium ion secondary batteries (for example, sodium ion secondary batteries). However, the technology of the present disclosure tends to exhibit even higher effects when applied to a lithium ion secondary battery.
  • PFPE has the following formula (I) (m/n is 1.2, number average molecular weight is 5120, terminal R contains CF 3 and CF 2 CF 3 in an average ratio of 1:0.17) It is a liquid substance with the chemical structure shown below.
  • 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 with 50 kN/ A laminate (A) of the Al foil, the positive electrode active material layer, and the electrolyte layer was obtained by roll pressing at a pressure of 1 cm 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 were overlapped and roll pressed at 25° C. under the pressure shown in Table 1 below.
  • a laminate (B) of Cu foil, negative electrode active material layer, and 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.
  • the active material having voids is a negative electrode active material and PFPE is included in the negative electrode side, but the active material having voids is a positive electrode active material and PFPE is included in the positive electrode side. A similar effect can be expected even when it is included.
  • 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, it is easy to achieve both excellent cycle characteristics and 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 includes an active material having voids and a predetermined perfluoropolyether.

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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
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
US20190341614A1 (en) * 2018-05-02 2019-11-07 Ford Global Technologies, Llc Perfluoropolyether additives for lithium ion battery anodes
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

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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
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JP7087968B2 (ja) 2018-11-30 2022-06-21 トヨタ自動車株式会社 活物質、電池、および活物質の製造方法
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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
US20190341614A1 (en) * 2018-05-02 2019-11-07 Ford Global Technologies, Llc Perfluoropolyether additives for lithium ion battery anodes
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

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