WO2022092273A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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Publication number
WO2022092273A1
WO2022092273A1 PCT/JP2021/040054 JP2021040054W WO2022092273A1 WO 2022092273 A1 WO2022092273 A1 WO 2022092273A1 JP 2021040054 W JP2021040054 W JP 2021040054W WO 2022092273 A1 WO2022092273 A1 WO 2022092273A1
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negative electrode
containing material
efa
secondary battery
aqueous electrolyte
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English (en)
French (fr)
Japanese (ja)
Inventor
佑治 五島
雄太 黒田
史治 新名
達郎 佐々
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2022559265A priority Critical patent/JP7734326B2/ja
Priority to CN202180072096.0A priority patent/CN116349024A/zh
Priority to EP21886390.0A priority patent/EP4239709A4/en
Priority to US18/032,431 priority patent/US20230290939A1/en
Publication of WO2022092273A1 publication Critical patent/WO2022092273A1/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
    • H01M4/38—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
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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 disclosure relates to a non-aqueous electrolyte secondary battery.
  • Si-containing materials are attracting attention as materials that give high capacity.
  • the Si-containing material is a material capable of electrochemically occluding and releasing lithium ions, and can be charged and discharged with a much larger capacity than a graphite material.
  • Patent Document 1 includes a negative electrode containing a Si-containing material and a non-aqueous electrolyte solution containing lithium hexafluoride phosphate and having an acid content of 50 ppm or more and 200 ppm or less, in terms of the discharge termination voltage of the battery.
  • a non-aqueous electrolyte secondary battery in which the potential of the negative electrode is 0.6 V or more and 1.5 V or less with respect to the Li electrode.
  • the Si-containing material can increase the capacity of the non-aqueous electrolyte secondary battery, but has a problem of deterioration of charge / discharge cycle characteristics.
  • deterioration of the charge / discharge cycle characteristics of the non-aqueous electrolyte secondary battery using the Si-containing material can be suppressed, but further improvement is desired.
  • an object of the present disclosure is to suppress deterioration of charge / discharge cycle characteristics in a non-aqueous electrolyte secondary battery having a negative electrode active material containing a Si-containing material.
  • the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, the negative electrode has a negative electrode active material containing a Si-containing material, and the Si-containing material has a silicate phase and a silicate phase.
  • a first Si-containing material having silicon particles dispersed in the silicate phase and a second Si-containing material having a carbon phase and silicon particles dispersed in the carbon phase are included, and the positive electrode is initially charged and discharged.
  • the difference (Efc-Efa) between the efficiency (Efc) and the initial charge / discharge efficiency (Efa) of the negative electrode is 1% ⁇ Efc-Efa ⁇ 8%.
  • deterioration of charge / discharge cycle characteristics can be suppressed.
  • the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, the negative electrode has a negative electrode active material containing a Si-containing material, and the Si-containing material has a silicate phase and a silicate phase.
  • a first Si-containing material having silicon particles dispersed in the silicate phase and a second Si-containing material having a carbon phase and silicon particles dispersed in the carbon phase are included, and the positive electrode is initially charged and discharged.
  • the difference (Efc-Efa) between the efficiency (Efc) and the initial charge / discharge efficiency (Efa) of the negative electrode is 1% ⁇ Efc-Efa ⁇ 8%.
  • Efc-Efa satisfies the range of 1% ⁇ Efc-Efa ⁇ 8%, and has a silicate phase in the negative electrode and a first Si-containing material having silicon particles dispersed in the silicate phase, and a carbon phase and the inside of the carbon phase.
  • the second Si-containing material is selectively used for discharge in a region where the potential rise at the end of discharge of the negative electrode is large. Since the use of the first Si-containing material, which is easily deteriorated, is restricted, it is considered that the progress of deterioration of the first Si-containing material is suppressed and the deterioration of the charge / discharge cycle characteristics is suppressed.
  • the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode are when a unipolar cell using a positive electrode or a negative electrode as the working electrode and metallic lithium as the counter electrode is charged and discharged under predetermined conditions. It means the ratio of the initial discharge capacity to the initial charge capacity of.
  • the method for producing the unipolar cell and the charging / discharging conditions are described in the column of Examples.
  • non-aqueous electrolyte secondary battery of the present disclosure is not limited to the embodiment described below. Further, the drawings referred to in the description of the embodiment are schematically described.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 shown in FIG. 1 has a wound electrode body 14 in which a positive electrode 11 and a negative electrode 12 are wound via a separator 13, a non-aqueous electrolyte, and an upper and lower electrode body 14, respectively.
  • An arranged insulating plates 18 and 19 and a battery case 15 for accommodating the above members are provided.
  • the battery case 15 is composed of a bottomed cylindrical case body 16 and a sealing body 17 that closes an opening of the case body 16.
  • the winding type electrode body 14 instead of the winding type electrode body 14, another form of an electrode body such as a laminated type electrode body in which positive electrodes and negative electrodes are alternately laminated via a separator may be applied.
  • the battery case 15 include a metal outer can such as a cylinder, a square, a coin, and a button, and a pouch outer body formed by laminating a resin sheet and a metal sheet.
  • the case body 16 is, for example, a bottomed cylindrical metal outer can.
  • a gasket 28 is provided between the case body 16 and the sealing body 17 to ensure the airtightness inside the battery.
  • the case body 16 has an overhanging portion 22 that supports the sealing body 17, for example, a part of the side surface portion overhanging inward.
  • the overhanging portion 22 is preferably formed in an annular shape along the circumferential direction of the case body 16, and the sealing body 17 is supported on the upper surface thereof.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are laminated in this order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at the central portion thereof, and an insulating member 25 is interposed between the peripheral portions thereof.
  • the lower valve body 24 When the internal pressure of the non-aqueous electrolyte secondary battery 10 rises due to heat generated by an internal short circuit or the like, for example, the lower valve body 24 is deformed and broken so as to push the upper valve body 26 toward the cap 27, and the lower valve body 24 and the upper valve are broken. The current path between the bodies 26 is cut off. When the internal pressure further rises, the upper valve body 26 breaks and gas is discharged from the opening of the cap 27.
  • the positive electrode lead 20 attached to the positive electrode 11 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 attached to the negative electrode 12 is insulated. It extends to the bottom side of the case body 16 through the outside of the plate 19.
  • the positive electrode lead 20 is connected to the lower surface of the filter 23, which is the bottom plate of the sealing body 17, by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the filter 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the case body 16 by welding or the like, and the case body 16 serves as a negative electrode terminal.
  • the negative electrode 12 has a negative electrode current collector made of, for example, a metal foil, and a negative electrode mixture layer formed on the current collector.
  • a negative electrode current collector for example, a foil of a metal such as copper that is stable in the potential range of the negative electrode, a film in which the metal is arranged on the surface layer, or the like is used.
  • the negative electrode mixture layer contains a negative electrode active material including a Si-containing material.
  • the negative electrode mixture layer preferably contains a binder, a conductive material, or the like.
  • a negative electrode mixture slurry containing a negative electrode active material, a binder, a conductive material, etc. is prepared, and this negative electrode mixture slurry is applied onto a negative electrode current collector and dried to form a negative electrode mixture layer. After that, it can be produced by performing a compression step of compressing the negative electrode mixture layer with a rolling roller or the like.
  • the Si-containing material contained in the negative electrode mixture layer is a first Si-containing material containing silicon particles dispersed in a silicate phase and a silicate phase, and a second Si having a carbon phase and silicon particles dispersed in the carbon phase. Including with contained materials.
  • the suitable first Si-containing material has, for example, substantially uniform fine silicon particles in the amorphous silicate phase from the viewpoint of suppressing deterioration of the charge / discharge cycle characteristics of the battery or increasing the capacity of the battery.
  • Examples thereof include Si-containing materials having a sea-island structure dispersed in a silicon, and represented by the general formula SiO x (0.5 ⁇ x ⁇ 1.6).
  • the content of the silicon particles is preferably 30% by mass or more and 80% by mass or less, preferably 35% by mass or more, based on the total mass of the first Si-containing material, for example, from the viewpoint of increasing the capacity of the battery. , 75% by mass or less, more preferably 55% by mass or more and 70% by mass or less.
  • the average particle size of the silicon particles is generally 500 nm or less, preferably 200 nm or less, and more preferably 50 nm or less before charging / discharging. After charging and discharging, 400 nm or less is preferable, and 50 nm or less is more preferable.
  • the average particle size of the silicon particles is measured by observing the particle cross section of the first Si-containing material using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and specifically, 100 silicon particles. It is calculated as the average value of the longest diameter of.
  • the silicate phase of the first Si-containing material preferably contains at least one of an alkali metal element and an alkaline earth metal element, for example, in terms of improving lithium ion conductivity, and in particular, a lithium element. It is preferable to include. Further, the silicate phase of the first Si-containing material preferably contains a lithium silicate represented by the general formula Li 2z SiO (2 + z) (0 ⁇ z ⁇ 2).
  • the suitable second Si-containing material does not contain crystalline carbon in the carbon phase of the second Si-containing material from the viewpoint of suppressing deterioration of the charge / discharge cycle characteristics of the battery or increasing the capacity of the battery.
  • the content of the silicon particles in the second Si-containing material may be 30% by mass or more and 80% by mass or less with respect to the total mass of the second Si-containing material, for example, in order to increase the capacity of the battery. It is preferably 35% by mass or more and 75% by mass or less, and more preferably 55% by mass or more and 70% by mass or less.
  • the average particle size of the silicon particles is generally 500 nm or less, preferably 200 nm or less, and more preferably 100 nm or less before charging / discharging. After charging and discharging, 400 nm or less is preferable, and 100 nm or less is more preferable.
  • a conductive layer made of a highly conductive material may be formed on the particle surface of the first Si-containing material or the second Si-containing material.
  • An example of a suitable conductive layer is a carbon film made of a carbon material.
  • the carbon film is composed of, for example, carbon black, acetylene black, ketjen black, graphite, and a mixture of two or more thereof.
  • Examples of the method of carbon-coating the particle surface of the Si-containing material include a CVD method using acetylene, methane, etc., a method of mixing coal pitch, petroleum pitch, phenol resin, etc. with particles of the Si-containing material and performing heat treatment. can.
  • a carbon film may be formed by fixing carbon powder such as carbon black to the particle surface using a binder.
  • the mass ratio of the second Si-containing material to the first Si-containing material is 0.2 or more, for example, in terms of suppressing deterioration of charge / discharge cycle characteristics. It is preferably 20 or less, and more preferably 2 or more and 10 or less.
  • the total content of the Si-containing material is, for example, 5% by mass or more, 20% by mass, based on the total mass of the negative electrode active material, in terms of suppressing deterioration of charge / discharge cycle characteristics and increasing the capacity of the battery. It is preferably 1% by mass or less, and more preferably 10% by mass or more and 15% by mass or less.
  • the negative electrode active material may contain, for example, a known material capable of occluding and releasing lithium ions.
  • a carbon material is preferable, and graphite particles are particularly preferable, in terms of suppressing deterioration of charge / discharge cycle characteristics.
  • the graphite particles are not particularly limited to natural graphite, artificial graphite and the like.
  • the surface spacing (d 002 ) of the (002) plane of the graphite particles by the X-ray wide-angle diffraction method is, for example, preferably 0.3354 nm or more, more preferably 0.3357 nm or more, and 0.340 nm.
  • the crystallite size (Lc (002)) determined by the X-ray diffraction method of the graphite particles is, for example, preferably 5 nm or more, more preferably 10 nm or more, and more preferably 300 nm or less. It is preferably 200 nm or less, and more preferably 200 nm or less.
  • the content of graphite particles shall be 80% by mass or more and 90% by mass or less with respect to the total mass of the negative electrode active material, for example, in terms of increasing the capacity of the secondary battery and improving the charge / discharge cycle characteristics. Is preferable.
  • binder examples include fluororesin, PAN, polyimide resin, acrylic resin, polyolefin resin, styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) or a salt thereof, polyacrylic acid (PAA) or Examples thereof include the salt (PAA-Na, PAA-K, etc., or a partially neutralized salt), polyvinyl alcohol (PVA), and the like. These may be used alone or in combination of two or more.
  • Examples of the conductive material include carbon-based particles such as carbon black (CB), acetylene black (AB), ketjen black, carbon nanotubes (CNT), and graphite. These may be used alone or in combination of two or more.
  • CB carbon black
  • AB acetylene black
  • CNT carbon nanotubes
  • graphite graphite
  • the positive electrode 11 is composed of a positive electrode current collector such as a metal foil and a positive electrode mixture layer formed on the positive electrode current collector.
  • a positive electrode current collector a foil of a metal such as aluminum that is stable in the potential range of the positive electrode, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the positive electrode mixture layer contains, for example, a positive electrode active material, a binder, a conductive material, and the like.
  • a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive material, etc. is applied onto a positive electrode current collector and dried to form a positive electrode mixture layer, and then the positive electrode 11 is formed by a rolling roller or the like. It can be produced by performing a compression step of compressing the positive electrode mixture layer.
  • a lithium transition metal composite oxide or the like is used as the positive electrode active material.
  • the metal element contained in the lithium transition metal composite oxide include Ni, Co, Mn, Al, B, Mg, Ti, V, Cr, Fe, Cu, Zn, Ga, Sr, Zr, Nb, In and Sn. , Ta, W and the like. Above all, it is preferable to contain at least one of Ni, Co and Mn.
  • the general formula LiMO 2 M is Ni and X, X is a metal element other than Ni, and the ratio of Ni is the total number of moles of the metal element excluding Li. 50 mol% or more and 95 mol% or less).
  • X in the above formula include Co, Mn, Al, B, Mg, Ti, V, Cr, Fe, Cu, Zn, Ga, Sr, Zr, Nb, In, Sn, Ta, W and the like. ..
  • Examples of the conductive material include carbon-based particles such as carbon black (CB), acetylene black (AB), ketjen black, carbon nanotubes (CNT), and graphite. These may be used alone or in combination of two or more.
  • CB carbon black
  • AB acetylene black
  • CNT carbon nanotubes
  • graphite graphite
  • binder examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • the difference (Efc-Efa) between the initial charge / discharge efficiency (Efc) of the positive electrode 11 and the initial charge / discharge efficiency (Efa) of the negative electrode 12 is 1% ⁇ Efc-Efa ⁇ 8%, preferably. 2% ⁇ Efc-Efa ⁇ 6%.
  • Efc-Efa satisfies the range of 1% ⁇ Efc-Efa ⁇ 8%, and the negative electrode 12 contains the first Si-containing material and the second Si-containing material.
  • the initial charge / discharge efficiency of the negative electrode 12 is adjusted. Should be adjusted.
  • the initial charge / discharge efficiency of the negative electrode 12 is adjusted, for example, by adjusting the content ratio, composition, etc. of the first Si-containing material and the second Si-containing material.
  • the initial charge / discharge efficiency of the positive electrode 11 and the initial charge / discharge efficiency of the negative electrode 12 are preferably 85% or more, respectively, in terms of suppressing deterioration of charge / discharge cycle characteristics.
  • a porous sheet having ion permeability and insulating property is used.
  • the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
  • an olefin resin such as polyethylene and polypropylene, cellulose and the like are suitable.
  • the separator 13 may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin.
  • a multilayer separator including a polyethylene layer and a polypropylene layer may be used, or a separator having a surface coated with a material such as an aramid resin or ceramic may be used.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte is not limited to the liquid electrolyte (electrolyte solution), and may be a solid electrolyte using a gel-like polymer or the like.
  • the non-aqueous solvent for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be used.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • esters examples include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and methylpropyl carbonate.
  • ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahexyl, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4.
  • -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxy Chain ethers such as ethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl
  • a fluorinated cyclic carbonate ester such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate ester, a fluorinated chain carboxylic acid ester such as methyl fluoropropionate (FMP), or the like. ..
  • the electrolyte salt is preferably a lithium salt.
  • lithium salts include LiBF 4 , LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (P (C 2 O 4 ) F 4 ), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2 ), LiB 10 Cl 10 , LiCl, LiBr, LiI, chloroborane lithium, lower aliphatic carboxylate lithium, Li 2B 4 O 7 , borates such as Li (B (C 2 O 4 ) F 2 ), LiN (SO 2 CF 3 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2 ) ⁇ l , M is an integer of 1 or more ⁇ and other imide salts.
  • lithium salt these may be used alone or in combination of two or more.
  • LiPF 6 is preferably used from the viewpoint of ionic conductivity, electrochemical stability, and the like.
  • concentration of the lithium salt is preferably 0.8 to 1.8 mol per 1 L of the solvent.
  • a lithium transition metal composite oxide having a composition of LiNi 0.88 Co 0.09 Al 0.03 O 2 is used as a positive electrode active material, acetylene black is used as a conductive material, and polyvinylidene fluoride is used as a binder, and the mass ratio is 100.
  • NMP N-methyl-2-pyrrolidone
  • LiPF 6 LiPF 6 at a concentration of 1.4 mol / L in a non-aqueous solvent in which ethylene carbonate (EC), methylethylene carbonate (MEC), and dimethyl carbonate (DMC) were mixed so as to have a volume ratio of 20: 5: 75.
  • EC ethylene carbonate
  • MEC methylethylene carbonate
  • DMC dimethyl carbonate
  • VC vinylene carbonate
  • VC 1,6-diisocyanate hexane
  • the negative electrode was punched to a predetermined size, and the negative electrode mixture layer on one side was peeled off. A Ni lead was crimped to this negative electrode, and this was used as a working electrode. In addition, a Ni lead was crimped to metallic lithium, which is sufficiently larger than the negative electrode, and this was used as the counter electrode.
  • the working electrode and the counter electrode were opposed to each other via a polyethylene separator to prepare an electrode body. This electrode body is covered with an aluminum laminate bag, the non-aqueous electrolyte is injected into the aluminum laminate bag, and then the pressure is reduced, but the opening of the aluminum laminate bag is sealed by heat welding, and the negative electrode is used as the working electrode. A polar cell was made. Further, in the same manner as described above, a unipolar cell having the positive electrode as a working electrode was produced.
  • the unipolar cell with the negative electrode as the working electrode is charged with a constant current of 0.1 C at a constant current of 0.1 C until the battery voltage reaches 0.005 V, and then the battery is charged with a constant current of 0.05 C.
  • the battery was charged with a constant current of 0.01 C until the battery voltage became 0.005 V.
  • constant current discharge with a constant current of 0.05 C until the battery voltage reaches 1 V, and then with a constant current of 0.01 C. Constant current discharge was performed until the battery voltage reached 1 V.
  • the unipolar cell with the positive electrode as the working electrode is constantly charged with a constant current of 0.1 C under a temperature environment of 25 ° C. until the battery voltage reaches 4.2 V, and then the current value of 4.2 V becomes 0. It was charged at a constant voltage until it reached 01C. Then, constant current discharge was performed with a constant current of 0.1 C until the battery voltage reached 2.5 V. Then, the charge capacity and the discharge capacity of the first time were measured, and they were applied to the above formula to calculate the charge / discharge efficiency of the first time. This was defined as the initial charge / discharge efficiency (Efc) of the positive electrode.
  • Efc initial charge / discharge efficiency
  • Example 1 the difference between the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode was calculated to be 2.7%.
  • Table 1 summarizes the results of the capacity retention rate in Example 1 and Comparative Example 1.
  • the value of the capacity retention rate is shown with the capacity retention rate of Example 1 as 100% (reference) and the capacity retention rate of Comparative Example 1 as a relative value. It should be noted that the larger the capacity retention rate value, the smaller the capacity retention rate value, the more the deterioration of the charge / discharge cycle characteristics was suppressed.
  • Efc-Efa is the same 2% in Example 1 and Comparative Example 1, but the capacity retention rate of Example 1 having both the first Si-containing material and the second Si-containing material is determined. When it was set to 100%, the capacity retention rate of Comparative Example 1 having only the first Si-containing material was 98.7%. Therefore, it can be said that the deterioration of the charge / discharge cycle characteristics of Example 1 is suppressed as compared with Comparative Example 1.
  • Example 2 In the production of the negative electrode, the graphite particles, the first Si-containing material in which the silicon particles are dispersed in the silicate phase, and the second Si-containing material in which the silicon particles are dispersed in the carbon phase are mixed in a mass ratio of 92.7: 4.3. : 3 was mixed. Then, a unipolar cell with the negative electrode as the working electrode was produced in the same manner as in Example 1 except that this mixture was used as the negative electrode active material, and the initial charge / discharge efficiency (Efa) of the negative electrode was calculated. In Example 2, the difference between the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode was 4%. Further, using the negative electrode prepared in Example 2, a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the capacity retention rate after 100 cycles was calculated.
  • Table 2 summarizes the results of capacity retention rates in Example 2 and Comparative Example 2. The value of the capacity retention rate is shown with the capacity retention rate of Example 2 as 100% (reference) and the capacity retention rate of Comparative Example 2 as a relative value.
  • Efc-Efa is the same 4% in Example 2 and Comparative Example 2, but the capacity retention rate of Example 2 having both the first Si-containing material and the second Si-containing material is determined. When it was set to 100%, the capacity retention rate of Comparative Example 2 having only the first Si-containing material was 98.5%. Therefore, it can be said that the deterioration of the charge / discharge cycle characteristics of Example 2 was suppressed as compared with Comparative Example 2.
  • Example 3 In the production of the negative electrode, the graphite particles, the first Si-containing material in which the silicon particles are dispersed in the silicate phase, and the second Si-containing material in which the silicon particles are dispersed in the carbon phase are mixed in a mass ratio of 90.2: 6.8. : 3 was mixed. Then, a unipolar cell with the negative electrode as the working electrode was produced in the same manner as in Example 1 except that this mixture was used as the negative electrode active material, and the initial charge / discharge efficiency (Efa) of the negative electrode was calculated. In Example 3, the difference between the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode was 6%. Further, using the negative electrode prepared in Example 3, a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the capacity retention rate after 100 cycles was calculated.
  • Table 3 summarizes the results of capacity retention rates in Example 3 and Comparative Example 3. The value of the capacity retention rate is shown with the capacity retention rate of Example 3 as 100% (reference) and the capacity retention rate of Comparative Example 3 as a relative value.
  • Example 3 having both the first Si-containing material and the second Si-containing material is 6%, which is the same as that of Example 3 and Comparative Example 3.
  • the capacity retention rate of Comparative Example 3 having only the first Si-containing material was 98.3%. Therefore, it can be said that the deterioration of the charge / discharge cycle characteristics of Example 3 was suppressed as compared with Comparative Example 3.
  • Example 4 In the production of the negative electrode, the graphite particles, the first Si-containing material in which the silicon particles are dispersed in the silicate phase, and the second Si-containing material in which the silicon particles are dispersed in the carbon phase are mixed in a mass ratio of 93.2: 1.5. : The mixture was mixed so as to be 5.3. Then, a unipolar cell with the negative electrode as the working electrode was produced in the same manner as in Example 1 except that this mixture was used as the negative electrode active material, and the initial charge / discharge efficiency (Efa) of the negative electrode was calculated. In Example 4, the difference between the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode was 3%. Further, using the negative electrode prepared in Example 4, a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the capacity retention rate after 100 cycles was calculated.
  • Table 4 summarizes the results of capacity retention rates in Example 4 and Comparative Example 4. The value of the capacity retention rate is shown with the capacity retention rate of Example 4 as 100% (reference) and the capacity retention rate of Comparative Example 4 as a relative value.
  • Efc-Efa is the same 6% in Example 4 and Comparative Example 4, but the capacity retention rate of Example 4 having both the first Si-containing material and the second Si-containing material is determined. When it was set to 100%, the capacity retention rate of Comparative Example 4 having only the second Si-containing material was 98.0%. Therefore, it can be said that the deterioration of the charge / discharge cycle characteristics of Example 4 is suppressed as compared with Comparative Example 4.
  • Example 5 In the production of the negative electrode, the graphite particles, the first Si-containing material in which the silicon particles are dispersed in the silicate phase, and the second Si-containing material in which the silicon particles are dispersed in the carbon phase are mixed in a mass ratio of 90.7: 4: 5. It was mixed so as to be 0.3. Then, a unipolar cell with the negative electrode as the working electrode was produced in the same manner as in Example 1 except that this mixture was used as the negative electrode active material, and the initial charge / discharge efficiency (Efa) of the negative electrode was calculated. In Example 5, the difference between the initial charge / discharge efficiency (Efc) of the positive electrode and the initial charge / discharge efficiency (Efa) of the negative electrode was 6%. Further, using the negative electrode prepared in Example 4, a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the capacity retention rate after 100 cycles was calculated.
  • Table 5 summarizes the results of capacity retention rates in Example 5 and Comparative Example 5. The value of the capacity retention rate is shown with the capacity retention rate of Example 5 as 100% (reference) and the capacity retention rate of Comparative Example 5 as a relative value.
  • Example 5 As shown in the results of Table 5, the capacity retention rate of Example 5 having both the first Si-containing material and the second Si-containing material is 6%, which is the same as that of Example 5 and Comparative Example 5. When it was set to 100%, the capacity retention rate of Comparative Example 5 having only the first Si-containing material was 98.1%. Therefore, it can be said that the deterioration of the charge / discharge cycle characteristics of Example 5 is suppressed as compared with Comparative Example 5.
  • Table 6 summarizes the results of capacity retention rates in Comparative Example 6 and Comparative Example 7. The value of the capacity retention rate is shown with the capacity retention rate of Comparative Example 6 as 100% (reference) and the capacity retention rate of Comparative Example 7 as a relative value.
  • Table 7 summarizes the results of capacity retention rates in Comparative Example 8 and Comparative Example 9. The value of the capacity retention rate is shown with the capacity retention rate of Comparative Example 8 as 100% (reference) and the capacity retention rate of Comparative Example 9 as a relative value.
  • non-aqueous electrolyte secondary battery 11 positive electrode, 12 negative electrode, 13 separator, 14 electrode body, 15 battery case, 16 case body, 17 sealing body, 18, 19 insulating plate, 20 positive electrode lead, 21 negative electrode lead, 22 overhang , 23 filter, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cap, 28 gasket.

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