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WO2013099267A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2013099267A1
WO2013099267A1 PCT/JP2012/008396 JP2012008396W WO2013099267A1 WO 2013099267 A1 WO2013099267 A1 WO 2013099267A1 JP 2012008396 W JP2012008396 W JP 2012008396W WO 2013099267 A1 WO2013099267 A1 WO 2013099267A1
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Prior art keywords
negative electrode
silicon oxide
lithium
active material
carbon material
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English (en)
Japanese (ja)
Inventor
泰右 山本
樹 平岡
祐基 末弘
慶一 高橋
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Panasonic Corp
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Panasonic Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery containing silicon oxide and a carbon material as a negative electrode active material.
  • Non-aqueous electrolyte secondary batteries have a high voltage and a high capacity, so there are great expectations for their development.
  • a negative electrode active material of a non-aqueous electrolyte secondary battery a carbon material such as graphite capable of occluding and releasing lithium ions is mainly used.
  • an alloy-based active material having a capacity higher than that of a carbon material has been attracting attention.
  • An alloy-based active material is a material containing an element that forms an alloy with lithium, and silicon oxide is considered promising.
  • silicon oxide not only forms a reversible Si—Li bond with lithium, but also forms an irreversible Si—O—Li bond. Therefore, the irreversible capacity at the beginning of the charge / discharge cycle is large, and the initial charge / discharge cycle is large. There is a problem that the discharge efficiency is low.
  • Patent Document 1 proposes that a metal foil mainly composed of lithium is attached in advance to a negative electrode containing an oxide that can contain silicon. Thereafter, the lithium in the metal foil is occluded by the active material in the negative electrode, and the negative electrode irreversible capacity is replenished. However, at that time, the active material expands, and the negative electrode may be deformed.
  • Patent Document 2 provides a rapid reaction between silicon oxide and lithium by providing, on the surface of the negative electrode, a buffer layer that can suppress a reaction in which lithium is taken into the active material. It is proposed to suppress this.
  • the buffer layer as in Patent Document 2 when the buffer layer as in Patent Document 2 is provided on the negative electrode surface, the reaction between the active material and lithium does not proceed until the negative electrode is brought into contact with the non-aqueous electrolyte, so that the negative electrode becomes difficult to handle. This is because metallic lithium is oxidized when it is exposed to air, leading to deterioration of the negative electrode.
  • the buffer layer suppresses the reaction between lithium and the active material, there is a possibility that lithium is deposited on the surface of the buffer layer. The remaining metallic lithium causes deterioration of cycle characteristics such as promoting side reactions with the nonaqueous electrolyte.
  • one aspect of the present invention includes a positive electrode, a negative electrode, and a nonaqueous electrolyte
  • the negative electrode includes a sheet-like negative electrode current collector and a negative electrode active material layer attached to a surface of the negative electrode current collector.
  • the negative electrode active material layer includes a carbon material capable of occluding and releasing lithium and a silicon oxide represented by SiO x (0.5 ⁇ x ⁇ 1.5).
  • SiO x 0.5 ⁇ x ⁇ 1.5
  • Has a rich surface layer portion of the silicon oxide and a rich main layer of the carbon material, and the ratio of the silicon oxide in the total of the carbon material and the silicon oxide in the surface layer portion is
  • the present invention relates to a non-aqueous electrolyte secondary battery that is 50 mass% or more.
  • the negative electrode active material layer is pre-doped with an amount of lithium corresponding to at least a part of the negative electrode irreversible capacity in the battery manufacturing process.
  • Another aspect of the present invention is a step of preparing a sheet-like negative electrode current collector, and a step of forming a main layer containing, as a main component, a carbon material capable of occluding and releasing lithium on the surface of the negative electrode current collector And forming a surface layer portion containing, as a main component, a silicon oxide represented by SiO x (0.5 ⁇ x ⁇ 1.5) on the surface of the main layer, the main layer and the surface layer portion,
  • a step of obtaining a negative electrode active material layer comprising: a step of obtaining a negative electrode in which the surface layer portion is pre-doped with an amount of lithium corresponding to at least part of the negative electrode irreversible capacity; the negative electrode, the positive electrode, and a non-aqueous electrolyte; And a process for assembling a non-aqueous electrolyte secondary battery, and a method for producing a non-aqueous electrolyte secondary battery.
  • the surface layer portion rich in silicon oxide is provided on the negative electrode, when lithium is supplied to the surface layer portion, the reaction between the silicon oxide and lithium proceeds rapidly.
  • the main layer having a small silicon oxide content is present on the base of the surface layer portion, even if silicon oxide and lithium react rapidly, the stress at that time is relaxed by the main layer. Accordingly, the negative electrode is hardly deformed.
  • metallic lithium hardly remains in the surface layer portion. Therefore, in addition to suppressing side reactions associated with the charge / discharge cycle, handling of the negative electrode during battery production is facilitated.
  • the non-aqueous electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the positive electrode and the negative electrode are disposed to face each other via a separator or a porous membrane impregnated with the non-aqueous electrolyte.
  • the negative electrode includes, for example, a sheet-like negative electrode current collector and a negative electrode active material layer formed on the surface of the negative electrode current collector.
  • the negative electrode active material layer includes a carbon material capable of occluding and releasing lithium, SiO x And a silicon oxide represented by (0.5 ⁇ x ⁇ 1.5).
  • the negative electrode active material layer has a surface layer portion rich in silicon oxide and a main layer rich in carbon material. The surface layer portion is a portion disposed on the positive electrode side in the negative electrode active material layer, and the main layer is a portion on the negative electrode current collector side. An amount of lithium corresponding to at least part of the negative electrode irreversible capacity is pre-doped from the surface layer portion into the negative electrode active material layer.
  • the ratio of silicon oxide in the total of the carbon material and silicon oxide in the surface layer is set to be as large as 50% by mass or more so that the pre-doped lithium and silicon oxide can react quickly. If the ratio of the silicon oxide in the surface layer portion is less than 50% by mass, the probability that the carbon material inhibits the reaction between the silicon oxide and lithium increases, and lithium pre-doping does not proceed rapidly. The larger the ratio of silicon oxide in the surface layer portion, the faster the lithium pre-doping proceeds, and the less lithium precipitation occurs in the surface layer portion.
  • the proportion of silicon oxide in the total of the carbon material and silicon oxide in the surface layer is preferably 60% by mass or more, or 70% by mass or more, and may be 100% by mass. .
  • the thickness of the surface layer portion is not particularly limited, for example, it is preferably 40% or less of the thickness of the negative electrode active material layer. This is because, if the thickness is about this, the stress generated in the surface layer portion when the negative electrode active material layer is predoped with lithium is sufficiently relaxed in the main layer. Although depending on the total amount of silicon oxide contained in the negative electrode active material layer, from the viewpoint of suppressing deformation of the negative electrode, it is desirable that the thickness of the surface layer is thinner, and 20% of the thickness of the negative electrode active material layer. The following is more preferable.
  • the thickness of the surface layer portion is not too thin, preferably 2% or more, more preferably 5% or more of the thickness of the negative electrode active material layer.
  • the surface layer portion may contain various materials in addition to the carbon material and silicon oxide capable of occluding and releasing lithium as the negative electrode active material. For example, 80% by mass or more of the surface layer portion may be used as the negative electrode active material. It is composed of a carbon material and silicon oxide capable of inserting and extracting lithium. For example, 20% or less of a resin component such as a binder and a thickener, or a carbon material that does not function as an active material such as carbon fiber or carbon black may be included.
  • the main layer is a part mainly composed of a carbon material capable of inserting and extracting lithium, and constitutes a main part of the negative electrode active material layer.
  • the main layer may have a configuration including only a carbon material as an active material, a configuration including a carbon material and a silicon oxide as active materials, or a configuration including another active material. That is, the ratio of silicon oxide in the main layer may be 0% by mass, for example, 1 to 5% by mass. From the viewpoint of suppressing deformation of the negative electrode when pre-doping lithium into the negative electrode active material, the ratio of silicon oxide in the total of the carbon material and silicon oxide in the main layer is preferably 30% by mass or less. 20% by mass or less is more preferable.
  • the ratio of silicon oxide to the total of the carbon material and silicon oxide is preferably 1 to 30% by mass in total. In such a range, the stress due to the expansion and contraction of the silicon oxide can be sufficiently relaxed while achieving high capacity of the negative electrode, so that not only when lithium is pre-doped, but also the charge / discharge cycle When repeating the above, deformation of the negative electrode is difficult to occur. Further, gas generation due to the reaction between the silicon oxide and the nonaqueous electrolyte is also suppressed.
  • the main component of the negative electrode active material is a carbon material
  • silicon oxide has an extremely large capacity compared to the carbon material, so the amount of silicon oxide in the entire negative electrode active material is relatively small as described above. However, it can greatly contribute to the improvement of the negative electrode capacity.
  • the ratio of silicon oxide to the total of the carbon material and silicon oxide contained in the entire negative electrode active material layer is 30 in total. % By mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is particularly preferable.
  • the total proportion of silicon oxide is preferably 3% by mass or more, and more preferably 5% by mass or more. These upper and lower limits can be arbitrarily combined.
  • the range of the ratio of silicon oxide to the total of the carbon material and silicon oxide contained in the entire negative electrode active material layer may be, for example, 10 to 20% by mass in total.
  • the thickness of the negative electrode active material layer that is, the total thickness of the main layer and the surface layer portion is not particularly limited, but is preferably, for example, 10 ⁇ m or more and 150 ⁇ m or less from the viewpoint of ensuring a balance between capacity and rate characteristics. .
  • the negative electrode active material layer is predoped with an amount of lithium corresponding to at least part of the negative electrode irreversible capacity.
  • the amount of pre-doped lithium may be equal to the negative electrode irreversible capacity at the beginning of charge / discharge, and may be greater or less than the irreversible capacity.
  • the irreversible capacity of silicon oxide is about 30 to 50% of the charge capacity (theoretical capacity), and even when the ratio of silicon oxide to the total of the carbon material and silicon oxide is about 10% by mass, a considerable amount is obtained.
  • the amount of lithium to be pre-doped may be controlled to about 30 to 200% of the irreversible capacity ⁇ Cn of the negative electrode.
  • the relationship between the theoretical capacity and the irreversible capacity is a numerical value when the battery is charged / discharged at 25 ° C. with a current value of 0.1 C / hour.
  • the lithium pre-doping may be performed by any method.
  • a metal lithium foil may be attached to the surface layer portion of the negative electrode active material layer.
  • a vapor deposition method is preferable at the point from which lithium is rapidly taken in into a negative electrode active material from a surface layer part.
  • Lithium can be deposited using, for example, a resistance heating deposition apparatus in a vacuum atmosphere. Specifically, lithium is loaded into the vapor deposition source in the resistance heating vapor deposition apparatus, the negative electrode is fixed so that the negative electrode active material layer faces the vapor deposition source, and current is passed through the container of the vapor deposition source for vapor deposition.
  • the negative electrode is a long hoop, the negative electrode is unwound at a constant speed from the hoop, passed over the vapor deposition source, and then wound on the negative electrode with a take-up roll to continuously deposit lithium. It can be carried out.
  • silicon oxide and carbon material is not limited, but silicon oxide has poor conductivity. Therefore, in order to ensure output characteristics and cycle characteristics, contact with a carbon material having conductivity is ensured, and active material It is necessary to form a conductive network in the layer. Therefore, it is desirable that the silicon oxide and the carbon material are filled in the main layer or the surface layer part in a mixed or compounded state.
  • the mixed or compounded state is not particularly limited. For example, (i) a state where a gap formed by a carbon material is filled with silicon oxide, or (ii) a gap formed by silicon oxide And (iii) a state in which the carbon material and silicon oxide are granulated to form composite particles. Further, the surface of the silicon oxide may be coated with a carbon material.
  • the state (i) can be more easily achieved by, for example, making the average particle size of the silicon oxide particles smaller than the average particle size of the carbon material.
  • the state (ii) can be achieved more easily by, for example, making the average particle size of the carbon material smaller than the average particle size of the silicon oxide.
  • the state (iii) is a state in which, for example, at least part of the silicon oxide and at least part of the carbon material are aggregated to form composite particles.
  • Composite particles for example, be or the SiO x powder and a carbon material, or by stirring with stirrer and fluidized bed shear force can be applied, such as a ball mill, then spray drying the slurry comprising a SiO x powder and a carbon material Is obtained.
  • As the carbon material before being combined with SiO x particulate materials such as graphite, graphitizable carbon, non-graphitizable carbon, and amorphous carbon can be used.
  • the precursor may be carbonized or graphitized by combining the SiO x powder and the precursor of the carbon material and then heating the composite material.
  • the precursor For example, pitch, tar, or the like can be used as the precursor.
  • (Silicon oxide) SiO x (0.5 ⁇ x ⁇ 1.5) is preferably microcrystalline or amorphous.
  • a microcrystalline or amorphous silicon oxide By using a microcrystalline or amorphous silicon oxide, it becomes easy to suppress the pulverization of the silicon oxide.
  • x By setting the molar ratio of oxygen to silicon element: x to be 0.5 ⁇ x ⁇ 1.5, it becomes easy to suppress pulverization of silicon oxide while securing a high capacity.
  • the use of such a silicon oxide is easier to suppress the expansion and contraction, and is advantageous for improving the cycle characteristics.
  • the silicon oxide as described above is considered to be composed of an amorphous SiO 2 matrix and microcrystalline or amorphous silicon dispersed in the matrix.
  • the silicon oxide contained in the negative electrode active material layer is preferably a granular material having an average particle size of 0.2 to 20 ⁇ m, more preferably 1 to 15 ⁇ m.
  • the silicon oxide has such a particle size range, it becomes easy to suppress the pulverization, and since the specific surface area is sufficient, it is easy to ensure the active material utilization rate and rate characteristics. Moreover, since the specific surface area is sufficiently small, gas generation is also suppressed.
  • Carbon material examples of the carbon material capable of inserting and extracting lithium ions include artificial graphite, natural graphite, non-graphitizable carbon, graphitizable carbon, and amorphous carbon. These may be used independently and may use multiple types together.
  • the carbon material contained in the negative electrode active material layer preferably contains a particulate material having an average particle diameter of 1 to 30 ⁇ m, more preferably 5 to 20 ⁇ m, from the viewpoint of increasing the capacity.
  • the particulate material of the carbon material is preferably at least one selected from the group consisting of graphite, non-graphitizable carbon, and graphitizable carbon, and more preferably contains at least graphite. When such a carbon material is used, it becomes easy to obtain a high capacity.
  • the proportion of the particulate matter in the carbon material is preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% from the viewpoint of increasing the capacity.
  • Examples of the carbon material other than the particulate material include a carbon material that covers the surface of the silicon oxide.
  • the sheet-like negative electrode current collector 10 is prepared.
  • the negative electrode collector 10 is not specifically limited, For example, a copper foil, a copper alloy foil, etc. are used preferably.
  • Step (ii) a main layer containing, as a main component, a carbon material capable of inserting and extracting lithium is formed on the surface of the negative electrode current collector 10.
  • a first slurry containing a carbon material as an essential component and containing silicon oxide, a binder, a thickener and the like as optional components is prepared.
  • a dispersion medium for the slurry water, an organic solvent such as N-methyl-2-pyrrolidone is preferably used.
  • the 1st slurry is apply
  • the dried main layer 20 may be rolled with a roller or the like.
  • Fluorine resin, acrylic resin, polyolefin, rubber particles, etc. are used as the binder.
  • the fluororesin include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and examples of the polyolefin include polyethylene and polypropylene.
  • the rubber particles styrene butadiene rubber is preferable.
  • the thickener for example, carboxymethyl cellulose (CMC) is used.
  • Step (iii) a surface layer portion containing silicon oxide as a main component is formed on the surface of the main layer.
  • a second slurry containing silicon oxide as an essential component and containing a carbon material, a binder, a thickener and the like as optional components is prepared.
  • the dispersion medium of the slurry may be the same as or different from the first slurry.
  • the surface layer portion 30 rich in silicon oxide is formed by applying the second slurry to the surface of the main layer 20 and drying it.
  • the dried surface layer 30 is preferably rolled with a roller or the like together with the main layer 20 to adjust the density of the active material layer 40 that is a laminate of the main layer 20 and the surface layer 30.
  • Step (iv) lithium is pre-doped with an amount corresponding to at least a part of the negative electrode irreversible capacity by depositing metallic lithium on the surface layer portion.
  • a predetermined amount of lithium vapor may be supplied to the negative electrode active material using a resistance heating vapor deposition apparatus in a vacuum atmosphere.
  • a nonaqueous electrolyte secondary battery is assembled using the negative electrode 50 obtained in the above manner, a positive electrode prepared in advance, and a nonaqueous electrolyte prepared in advance.
  • a positive electrode and a negative electrode are laminated or wound with a separator interposed therebetween to constitute an electrode group.
  • the obtained electrode group is housed in a battery case together with a non-aqueous electrolyte, and the battery case is sealed to complete the battery.
  • FIG. 2 is an example of a rectangular non-aqueous electrolyte secondary battery, and is shown in a perspective view with a part cut away.
  • the battery 100 is a rectangular battery in which the flat electrode group 1 and a nonaqueous electrolyte are accommodated in a rectangular battery case 4.
  • the electrode group 1 is obtained by winding a positive electrode and a negative electrode with a separator interposed therebetween, and press-molding the wound body into a flat shape.
  • the positive electrode and the sealing plate 5 having a function as a positive electrode terminal are connected by the positive electrode lead 2, and the negative electrode and the negative electrode terminal 6 provided at the center of the sealing plate 5 are connected by the negative electrode lead 3.
  • the sealing plate 5 and the negative electrode terminal 6 are insulated by a gasket 7.
  • the electrode group 1 is accommodated in the battery case 4. Then, the opening of the battery case 4 is closed by the sealing plate 5, and the sealing plate 5 is joined to the opening end of the battery case by welding. Since the injection hole (not shown) is formed in the sealing plate 5, the non-aqueous electrolyte is injected into the battery case 4 from the injection hole, and finally the injection hole is closed with the plug 8 to complete the battery. To do.
  • the positive electrode is composed of a sheet-like positive electrode current collector and a positive electrode active material layer attached to the surface of the positive electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material and a binder as essential components, and may include a conductive material, a thickener, and the like as optional components.
  • the positive electrode active material layer is obtained by applying a slurry obtained by mixing a positive electrode active material, a binder, and a liquid component as a dispersion medium to one or both surfaces of the positive electrode current collector, and drying the coating film. Is obtained. The thickness and density of the coating film are controlled by rolling.
  • a lithium-containing transition metal oxide is preferably used as the positive electrode active material.
  • the lithium-containing transition metal oxide include lithium cobaltate (LiCoO 2 ) having a layered structure and a material having a crystal structure similar to this, lithium manganate having a spinel structure (LiMn 2 O 4 ), and the same Materials having a crystal structure are known.
  • known materials can be used without particular limitation.
  • a fluororesin is used preferably.
  • it does not specifically limit as a electrically conductive material of a positive electrode Carbon black, carbon nanofiber, graphite, etc. are used.
  • Nonaqueous electrolyte As the non-aqueous electrolyte, it is desirable to use a non-aqueous solvent in which a lithium salt is dissolved.
  • Nonaqueous solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
  • Chain carbonates such as (EMC), cyclic carboxylic acid esters such as ⁇ -butyrolactone and ⁇ -valerolactone are used.
  • 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy Methane, sulfolane, 3-methyl-2-oxazolidinone, diethyl ether, 1,3-propane sultone and the like can also be used. These are preferably used in combination.
  • LiPF 6 for example, LiPF 6 , LiBF 4 , LiClO 4 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 or the like may be used. It can. These may be used individually by 1 type and may use multiple types together. Among them, LiPF 6 is preferably used from the viewpoint of obtaining a high capacity, and LiN (C 3 F 5 SO 2 ) 2 and / or LiBF 4 is further changed to LiPF 6 from the viewpoint of enhancing the effect of improving the cycle characteristics. Alternatively, they may be used in a proportion of 1 to 50 mol%.
  • the concentration of the lithium salt in the nonaqueous electrolyte is, for example, 0.5 to 2 mol / L.
  • an unsaturated cyclic carbonate is preferably added to the nonaqueous electrolyte.
  • the unsaturated cyclic carbonate include vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, and the like.
  • the nonaqueous electrolyte secondary battery includes a separator or a porous membrane between the positive electrode and the negative electrode.
  • a separator The microporous film and nonwoven fabric made from polyolefin are used preferably.
  • the microporous membrane is a resin sheet produced by uniaxial stretching or biaxial stretching, and the thickness thereof is, for example, 5 to 30 ⁇ m, and preferably 10 to 20 ⁇ m.
  • porous membrane for example, an organic porous membrane containing at least one heat-resistant resin selected from the group consisting of polyamide, polyimide and polyamideimide, or an inorganic system containing inorganic oxide particles and a resin binder A porous membrane is mentioned.
  • the organic porous film may contain 25 to 80% by mass of inorganic oxide particles in addition to the heat resistant resin. However, the inorganic oxide contained in the organic porous membrane does not have fluidity. Of the heat resistant resins, polyamide is preferable, and aromatic polyamide (aramid) is more preferable because of a good balance between strength and flexibility.
  • the thickness of the organic porous membrane is preferably from 0.5 to 15 ⁇ m, more preferably from 0.5 to 10 ⁇ m.
  • the inorganic porous film is a film mainly composed of inorganic oxide particles, and the content of the inorganic oxide particles is, for example, 90 to 99% by mass.
  • the inorganic oxide particles are bonded to each other by a resin binder and are also bonded to the electrode surface and the separator.
  • the inorganic oxide contained in the inorganic porous membrane has fluidity.
  • the resin binder fluorine resin (for example, polyvinylidene fluoride or polytetrafluoroethylene), acrylic resin, rubber particles (for example, styrene butadiene rubber), and the like can be used, but the resin binder is not limited thereto.
  • the thickness of the inorganic porous membrane is preferably 0.5 to 10 ⁇ m, more preferably 2 to 7 ⁇ m.
  • alumina, titania, magnesia, silica and the like having an average particle diameter of 0.05 to 5 ⁇ m, for example, 0.1 to 2 ⁇ m, are inexpensive, And it is preferable at the point which is excellent in chemical stability.
  • the average particle diameter of the active material, inorganic oxide, etc. is the median diameter at which the cumulative volume in the volume-based particle size distribution is 50%, and is measured by, for example, a laser diffraction particle size distribution measuring device. can do.
  • SBR styrene butadiene rubber
  • SiO parts Y (50 ⁇ Y ⁇ 100) parts by mass, graphite particles (100-Y) parts by mass, 7 parts by mass of polyamideimide resin as a binder, and an appropriate amount of NMP were mixed with a mixer, A second slurry was prepared. The second slurry was applied onto the main layer and dried to form a silicon oxide rich surface layer.
  • Lithium was deposited on the negative electrode active material layer in a vacuum atmosphere using a resistance heating vapor deposition apparatus.
  • the amount of lithium deposition was estimated by irreversible capacity from the theoretical capacity of the negative electrode and matched with the irreversible capacity.
  • the negative electrode thus obtained was cut into a shape having a size of 21 mm ⁇ 21 mm and having a lead attachment portion at the end.
  • the active material layer of the lead attachment part was peeled, and a nickel lead having a polypropylene (PP) tab was joined to the peeled part by resistance welding.
  • PP polypropylene
  • Positive electrode 100 parts by mass of LiNi 0.80 Co 0.15 Al 0.05 O 2 , 2 parts by mass of acetylene black, 2 parts by mass of polyvinylidene fluoride, and an appropriate amount of NMP are mixed with a mixer to prepare a positive electrode mixture slurry. did. This slurry was applied to one side of a current collector sheet made of an Al foil having a thickness of 15 ⁇ m, dried and rolled to obtain a positive electrode. The thickness of the positive electrode was 70 ⁇ m.
  • the obtained positive electrode was cut into a shape having a lead attachment part at the end with a size of 20 mm ⁇ 20 mm, the active material layer of the lead attachment part was peeled off, and an aluminum lead having a polypropylene (PP) tab was superposed on the peeled part. Joined by sonic welding.
  • PP polypropylene
  • the ratio of the reversible capacity of the positive electrode / negative electrode was designed to be 1.1.
  • Non-aqueous electrolyte LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent having a volume ratio of EC / EMC of 2/8 to prepare a non-aqueous electrolyte.
  • Electrode group The above-mentioned positive electrode and negative electrode were opposed to a positive electrode active material layer and a negative electrode active material layer through a separator made of a polyethylene microporous film having a thickness of 20 ⁇ m to constitute an electrode group.
  • the obtained electrode group was inserted into a cylindrical body made of an Al laminate sheet, and the opening end was sealed by aligning and thermally welding a PP tab to one opening end of the cylindrical body. Thereafter, 0.4 ml of nonaqueous electrolyte was added to the battery case from the other opening end, and the opening end was sealed by heat welding under vacuum.
  • the laminated batteries 10 to 16 were completed through the steps as described above, and the following evaluations were performed. The results are shown in Table 1.
  • the ratio of the thickness t of the surface layer portion to the thickness T of the X, Y and negative electrode active material layers was adjusted as shown in Table 1.
  • Table 1 also shows the ratio Z (mass%) of SiO in the total of graphite and SiO in the entire negative electrode active material layer.
  • Comparing batteries 10, 13, and 15 with batteries 11, 12, 14, and 16 suppresses negative electrode deformation when the amount of silicon oxide in the surface layer is large even if the total amount of silicon oxide is the same. It was confirmed that the cycle characteristics were improved. Furthermore, it was also confirmed that when the amount of silicon oxide in the surface layer portion was larger, lithium was smoothly occluded in the negative electrode active material layer when lithium was predoped.
  • the nonaqueous electrolyte secondary battery of the present invention has a high capacity and excellent cycle characteristics, it can be applied to a power source for portable electronic devices, a hybrid vehicle (HEV), an electric vehicle, a household power storage device, and the like.
  • a power source for portable electronic devices a hybrid vehicle (HEV), an electric vehicle, a household power storage device, and the like.
  • HEV hybrid vehicle
  • electric vehicle a household power storage device, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention fournit une batterie dans laquelle la contrainte lors d'une réaction étant atténuée par une couche principale, une électrode négative est peu susceptible de se déformer, une partie couche superficielle riche en oxyde de silicium et un lithium réagissant directement et rapidement, des réactions secondaires liées à un cycle charge-décharge sont inhibées, et en outre la manipulation de l'électrode négative lors de la fabrication de la batterie est facilitée. Plus précisément, l'invention concerne une batterie secondaire à électrolyte non aqueux munie d'une électrode positive, de l'électrode négative et d'un électrolyte non aqueux. L'électrode négative contient une matière active d'électrode négative en adhésion sur la surface d'un collecteur d'électrode négative. Une couche de matière active d'électrode négative contient un matériau de carbone capable de stocker et rejeter un lithium, et un oxyde de silicium représenté par SiOx (0,5<x<1,5). Cette couche de matière active d'électrode négative possède la partie couche superficielle riche en oxyde de silicium, et la couche principale qui est riche en matériau de carbone. La proportion d'oxyde de silicium comprise dans la somme du matériau de carbone et dans l'oxyde de silicium dans la partie couche superficielle, est supérieure ou égale à 50% en masse.
PCT/JP2012/008396 2011-12-29 2012-12-27 Batterie secondaire à électrolyte non aqueux Ceased WO2013099267A1 (fr)

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JP2011290282A JP2015046220A (ja) 2011-12-29 2011-12-29 非水電解質二次電池

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US20140356723A1 (en) * 2011-12-28 2014-12-04 Panasonic Corporation Negative electrode for nonaqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the same
WO2015166622A1 (fr) * 2014-04-28 2015-11-05 ソニー株式会社 Batterie, électrode négative, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage d'électricité et système d'alimentation électrique
WO2016035289A1 (fr) * 2014-09-05 2016-03-10 三洋電機株式会社 Electrode négative pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
JP2017537449A (ja) * 2014-12-01 2017-12-14 スリーエム イノベイティブ プロパティズ カンパニー リチウムイオン電池用アノード材料並びにその製造方法及び使用方法
US10770717B2 (en) 2017-12-28 2020-09-08 Jnc Corporation Composition for secondary battery negative electrode and negative electrode for secondary battery using the same and secondary battery
EP3618161A4 (fr) * 2017-05-25 2021-01-13 Murata Manufacturing Co., Ltd. Batterie rechargeable à électrolyte non aqueux et procédé de production d'une batterie rechargeable à électrolyte non aqueux
CN115039252A (zh) * 2020-01-31 2022-09-09 松下知识产权经营株式会社 非水电解质二次电池用负极和非水电解质二次电池
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EP3667774A4 (fr) 2017-10-16 2021-03-17 LG Chem, Ltd. Électrode au lithium et batterie rechargeable au lithium la comprenant
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US20140356723A1 (en) * 2011-12-28 2014-12-04 Panasonic Corporation Negative electrode for nonaqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the same
US10050262B2 (en) * 2011-12-28 2018-08-14 Panasonic Intellectual Property Mangement Co., Ltd. Negative electrode for nonaqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the same
WO2015166622A1 (fr) * 2014-04-28 2015-11-05 ソニー株式会社 Batterie, électrode négative, bloc-batterie, dispositif électronique, véhicule électrique, dispositif de stockage d'électricité et système d'alimentation électrique
CN106797020A (zh) * 2014-09-05 2017-05-31 三洋电机株式会社 非水电解质二次电池用负极和非水电解质二次电池
JPWO2016035289A1 (ja) * 2014-09-05 2017-06-15 三洋電機株式会社 非水電解質二次電池用負極及び非水電解質二次電池
WO2016035289A1 (fr) * 2014-09-05 2016-03-10 三洋電機株式会社 Electrode négative pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
US10263252B2 (en) 2014-09-05 2019-04-16 Sanyo Electric Co., Ltd. Negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
CN106797020B (zh) * 2014-09-05 2019-05-10 三洋电机株式会社 非水电解质二次电池用负极和非水电解质二次电池
JP2017537449A (ja) * 2014-12-01 2017-12-14 スリーエム イノベイティブ プロパティズ カンパニー リチウムイオン電池用アノード材料並びにその製造方法及び使用方法
EP3618161A4 (fr) * 2017-05-25 2021-01-13 Murata Manufacturing Co., Ltd. Batterie rechargeable à électrolyte non aqueux et procédé de production d'une batterie rechargeable à électrolyte non aqueux
US10770717B2 (en) 2017-12-28 2020-09-08 Jnc Corporation Composition for secondary battery negative electrode and negative electrode for secondary battery using the same and secondary battery
CN115039252A (zh) * 2020-01-31 2022-09-09 松下知识产权经营株式会社 非水电解质二次电池用负极和非水电解质二次电池
WO2023145443A1 (fr) * 2022-01-31 2023-08-03 パナソニックＩｐマネジメント株式会社 Batterie au lithium-ion

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