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WO2008018204A1 - Accumulateur à électrolyte non aqueux - Google Patents

Accumulateur à électrolyte non aqueux Download PDF

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Publication number
WO2008018204A1
WO2008018204A1 PCT/JP2007/057891 JP2007057891W WO2008018204A1 WO 2008018204 A1 WO2008018204 A1 WO 2008018204A1 JP 2007057891 W JP2007057891 W JP 2007057891W WO 2008018204 A1 WO2008018204 A1 WO 2008018204A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
active material
winding
wound
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/057891
Other languages
English (en)
Japanese (ja)
Inventor
Akihiro Modeki
Yanko Marinov Todorov
Yoshiki Sakaguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Publication of WO2008018204A1 publication Critical patent/WO2008018204A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • 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
    • H01M4/36—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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery such as a lithium secondary battery.
  • a cylindrical type including a winding body obtained by integrally winding a positive electrode and a negative electrode with a separator interposed therebetween is known.
  • a wound body is obtained by winding a positive electrode or the like around the core for a predetermined number of times.
  • the winding body is removed from the winding core, and then a core material called a center pin is inserted into the center of the winding body, and the winding body is housed in a battery can together with the center pin (see, for example, Patent Document 1).
  • a gap is generated between the center portion of the wound body and the center pin. This gap may cause buckling of the electrode due to expansion and contraction of the wound body due to charging / discharging of the battery.
  • Patent Document 2 proposes a lithium secondary battery including an electrode winding group in which a positive electrode and a negative electrode are wound around a core member via a separator.
  • the positive electrode and the negative electrode are wound around the core material to form an electrode winding group, so that the positive electrode and the negative electrode are wound tightly.
  • An electrode winding group is obtained, and the electrode winding group is firmly fixed in the battery outer can after the electrolyte is injected, so that the electrode winding group is less likely to be displaced and the battery reliability is improved. It is supposed to be.
  • the negative electrode active material used in Patent Document 2 is a carbon-based material such as graphite. Since graphite has a small degree of expansion and contraction due to insertion and extraction of lithium, even if the negative electrode is wound tightly, the influence of expansion and contraction of the electrode winding group due to insertion and extraction of lithium of the negative electrode active material is small. .
  • silicon-based materials and tin-based materials which have been proposed as next-generation negative electrode active materials and have a larger capacity than carbon-based materials, have a volume change caused by charging / discharging more than the above-mentioned graphite. large.
  • Patent Document 1 Japanese Patent Laid-Open No. Hei 4 No.
  • Patent Document 2 JP 2001-126769 A
  • an object of the present invention is to provide a non-aqueous electrolyte secondary battery that can eliminate the various drawbacks of the above-described prior art.
  • the present invention is a laminate in which a laminate including at least a positive electrode, a negative electrode having a negative electrode active material layer containing Si or Sn, and a separator interposed therebetween is wound around a core material.
  • a non-aqueous electrolyte secondary battery provided with a rotating body,
  • the laminate is wound such that the distance between the negative electrodes in the radial direction of the wound body satisfies the following formula (1): Dissolved secondary batteries are provided.
  • the present invention also provides a method for producing a non-aqueous electrolyte secondary battery
  • Each including at least a positive electrode, a separator, and a negative electrode, each of which is in the form of a long strip, are rolled out from a roll-shaped raw fabric in this order, and wound together around a core material.
  • the winding tension is increased so that no gap is created around the core material.
  • the above-mentioned feeding tension is set lower than the feeding tension during the winding of the first circumference, and the winding is performed.
  • the wound body thus obtained is accommodated in a battery can without pulling out the core material, and a method for producing a non-aqueous electrolyte secondary battery is provided.
  • FIG. 1 is a schematic view showing a cross-sectional structure of a wound body in one embodiment of a battery of the present invention.
  • FIG. 2 is a schematic diagram showing an example of a method for manufacturing the wound body shown in FIG. 1.
  • FIG. 3 is a schematic diagram showing an arrangement state of the spacer member in plan view.
  • FIG. 4 (a) and FIG. 4 (b) are perspective views showing a wound body having a spacer member.
  • FIG. 5 is a schematic view showing another example of the method for manufacturing the wound body shown in FIG. 1.
  • FIG. 6 is a schematic diagram showing a cross-sectional structure of an embodiment of a negative electrode used in the present invention.
  • FIG. 7 (a) to FIG. 7 (d) are process diagrams showing a method for manufacturing the negative electrode shown in FIG.
  • FIG. 8 (a) and FIG. 8 (b) are CT scan images of the cross section of the battery obtained in Example 1.
  • FIG. 8 (a) and FIG. 8 (b) are CT scan images of the cross section of the battery obtained in Example 1.
  • FIG. 9 (a) and FIG. 9 (b) are CT scan images of the cross section of the battery obtained in Comparative Example 1.
  • FIG. 9 (a) and FIG. 9 (b) are CT scan images of the cross section of the battery obtained in Comparative Example 1.
  • the non-aqueous electrolyte secondary battery of the present invention (hereinafter also simply referred to as a secondary battery or a battery) has a positive electrode, a negative electrode, and a separator disposed between them as its basic constituent members.
  • the battery includes a winding body formed by integrally winding a positive electrode, a negative electrode, and a separator interposed therebetween.
  • the wound body may have a circular or oval cross-sectional shape.
  • FIG. 1 shows an embodiment of a wound body 1 in a battery of the present invention.
  • the wound body 1 is a laminate including at least a positive electrode, a negative electrode, and a separator interposed therebetween.
  • the laminate 2 has a cylindrical shape wound around the core 3.
  • the laminate 2 is composed of a positive electrode, a negative electrode, and a separator, or is composed of a positive electrode, a negative electrode, a first separator, and a second separator.
  • the laminated body 2 is strongly wound around the first round, and after the second round, it is loosely wound so as to generate a gap between the laminated bodies 2.
  • Fig. 1 for the sake of convenience, the air gap is shown.
  • the core material 3 in the wound body 1 has a hollow or solid cylindrical shape.
  • the core material 3 is preferably made of a high-strength material from the viewpoint of preventing the negative electrode buckling described later.
  • the core material 3 is also preferably light in weight from the viewpoint of increasing the weight energy density of the battery. From these viewpoints, the core material 3 is preferably made of a polyolefin resin such as polyethylene or polypropylene. In that case, it is preferable to add glass fiber to improve the strength.
  • the core material 3 may be composed of a metal force such as copper.
  • the positive electrode used in the battery of the present invention has, for example, a positive electrode active material layer formed on at least one surface of a current collector.
  • the positive electrode active material layer contains an active material.
  • an active material for example, a lithium transition metal composite oxide is used.
  • Lithium transition metal complex oxides include LiCoO, LiNiO, LiMn O, LiMnO, LiCo Ni O, LiNi C
  • These positive electrode active materials can be used singly or in combination of two or more.
  • the positive electrode active material is suspended in a suitable solvent together with a conductive agent such as acetylene black and a binder such as polyvinylidene fluoride to produce a positive electrode mixture. It can be obtained by applying and drying on at least one surface of a current collector such as an aluminum foil, followed by roll rolling and pressing.
  • a conductive agent such as acetylene black
  • a binder such as polyvinylidene fluoride
  • the lithium transition metal composite oxide has an average primary particle diameter of 5 ⁇ m or more and 10 am or less. It is preferable from the combination.
  • Polyvinylidene fluoride used as a binder is An average molecular weight of 350,000 or more and 2,000,000 or less is preferable because it can improve discharge characteristics in a low temperature environment.
  • the negative electrode used in the battery of the present invention has, for example, a negative electrode active material layer formed on at least one surface of a current collector.
  • the negative electrode active material layer contains an active material.
  • the active material used in the present invention is a substance containing Si or Sn.
  • a negative electrode active material containing Si or Sn has a property of expanding when lithium is occluded and contracting when released. The degree of expansion and contraction is much greater than that of carbon-based materials that have been used as negative electrode active materials in conventional lithium secondary batteries.
  • the negative electrode active material containing Si is capable of occluding and releasing lithium ions.
  • silicon alone, an alloy of silicon and metal, silicon oxide, or the like can be used. These materials can be used alone or in combination.
  • the metal include one or more elements selected from the group force consisting of Cu, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. Of these metals, Cu, Ni, and Co are preferable. In particular, Cu and Ni are desirable because they have excellent electron conductivity and low ability to form lithium compounds. Further, lithium may be occluded in an active material made of a silicon-based material before or after the negative electrode is incorporated in the battery.
  • a particularly preferable silicon-based material is silicon or silicon oxide in view of the high occlusion amount of lithium.
  • the negative electrode active material containing Sn tin alone
  • an alloy of tin and metal, or the like can be used. These materials can be used alone or in combination.
  • the metal that forms an alloy with tin include one or more elements selected from the group consisting of Cu, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. Of these metals, Cu, Ni and Co are preferred, and Cu and Ni are particularly desirable.
  • the negative electrode active material layer includes, for example, a continuous thin film layer made of the negative electrode active material, a coating layer containing particles of the negative electrode active material, a sintered body layer containing particles of the negative electrode active material, and the like. possible . Further, it may be a layer having a structure shown in FIG.
  • a synthetic resin nonwoven fabric a polyolefin such as polyethylene-polypropylene, a porous film of polytetrafluoroethylene, etc.
  • a separator in which a polyolefin film is formed on one or both surfaces of the polyolefin microporous membrane.
  • the separator preferably has a puncture strength of 0.2 N // im thickness or more and 0.49 N / zm thickness or less, and a tensile strength in the winding axis direction of 40 MPa or more and 150 MPa or less. This is because even when a negative electrode active material that expands and contracts greatly during charging and discharging is used, damage to the separator can be suppressed and occurrence of internal short circuit can be suppressed.
  • the non-aqueous electrolyte has a solution strength in which a lithium salt as a supporting electrolyte is dissolved in an organic solvent.
  • Lithium salts include CF SO Li, (CF SO) NLi, (C F SO) NLi, LiCIO, LiAl
  • CI, LiPF, LiAsF, LiSbF, LiCl, LiBr, Lil, LiC F SO and the like are exemplified. These can be used alone or in combination of two or more.
  • CF SO Li, (CF SO) NLi, and (C F SO) NLi are preferably used from the viewpoint of excellent water decomposition resistance.
  • the organic solvent include ethylene carbonate, jetyl carbonate, dimethylol carbonate, propylene carbonate, butylene carbonate, and the like. In particular, 0.5 to 5% by weight of vinylene carbonate and 0.:!
  • 1,4 butanediol dimethanesulfonate based on the total amount of the non-aqueous electrolyte. It is preferable from the viewpoint of further improving the charge / discharge cycle characteristics. Although details are not clear about the reason, 1,4-butanediol dimethyl sulfonate and divinyl sulfone are decomposed stepwise to form a film on the positive electrode, so that the film containing sulfur becomes denser. It is thought that it is to become.
  • an electrolytic solution in which the high dielectric constant solvent is mixed with a low-viscosity solvent having a viscosity of SlmPa's or less, such as dimethyl carbonate, jetyl carbonate, or methyl ethyl carbonate is also preferable. This is because a higher level and ion conductivity can be obtained.
  • the content of fluorine ions in the electrolyte is 14 mass ppm or more and 1290 mass ppm or less. It is also preferable to be within the range.
  • the electrolyte solution contains an appropriate amount of fluorine ions, a coating film such as lithium fluoride derived from the fluorine ions is formed on the negative electrode, which can suppress the decomposition reaction of the electrolyte solution in the negative electrode.
  • at least one additive selected from the group consisting of acid anhydrides and derivatives thereof is contained in an amount of 0.001% to 10% by weight. This is because a film is formed on the surface of the negative electrode, and the decomposition reaction of the electrolytic solution can be suppressed.
  • the wound body 1 in the battery of the present embodiment is characterized by its wound state. Details are as follows. In the winding of the first round of the wound body 1, the laminated body 2 is wound so that a substantial gap does not occur between the laminated body 2 and the core material 3. Further, in the second and subsequent turns, the laminate 2 is wound so that the distance between the negative electrodes in the radial direction of the wound body 1 satisfies the following formula (1).
  • the winding state described here relates to the state before the battery is charged and discharged.
  • the technical significance of winding the laminated body 2 as described above in the present embodiment is as follows. First, for the winding of the first round, the stress generated due to the expansion of the negative electrode active material is obtained by winding the laminated body 2 so that no gap is generated between the laminated body 2 and the core material 3. ⁇ Even when locally applied to the center of the rotating body 1, the core material 3 can receive the stress. As a result, the negative electrode buckling is suppressed by the core material 3. If there is a gap between the laminate 2 and the core material in the first turn, the negative electrode is deformed toward the gap due to expansion of the negative electrode active material, causing buckling. End up.
  • winding the laminate so as to satisfy the above-described formula (1) means that the winding after the second round has a void in the laminate 2. It means doing as it happens. Since the laminate 2 includes the positive electrode, the negative electrode, and the separator, the formation of voids in the laminate 2 is the same as the formation of voids between these members. Therefore, in the above formula (1), the left side is the force that is the distance between the negative electrodes. Even if this is the distance between the positive electrodes or the distance between the separators, the formula on the right side is not changed. In addition, the distance between negative electrodes is the distance between the thickness direction center parts of a negative electrode. The same applies to the distance between the positive electrodes and the distance between the separators.
  • the degree of voids described above is expressed by the term [negative electrode active material layer thickness X 0.5 to 3.0] in the above formula (1).
  • the negative electrode active material force S expansion of the negative electrode due to occlusion of lithium can be mitigated by the voids.
  • expansion and deformation of the battery can be prevented.
  • the degree of void is less than [negative electrode active material layer thickness ⁇ ⁇ ⁇ 5], the expansion of the negative electrode due to the occlusion of lithium cannot be reliably relieved, and the battery will expand or deform. .
  • the degree of voids exceeds [negative electrode active material layer thickness X3.0], the winding of the laminate 2 in the wound body 1 is likely to be displaced, and the reliability of the battery is lowered.
  • the degree of voids is preferably [negative electrode active material layer thickness ⁇ 0.5 to 1.5]. . Note that the thickness of the negative electrode active material layer in the case where the active material layer is formed on each surface of the current collector is the sum of the thicknesses of the active material layers.
  • the voids exist uniformly over the entire radial direction of the wound body 1.
  • the radial direction of the wound body 1 is within the range not impairing the effects of the present invention. It is not obstructed that there is a part that does not fill the void in a part of
  • FIG. 2 schematically shows an example of a method for manufacturing a wound body in the battery of this embodiment.
  • FIG. 3 shows an enlarged view of the main part in FIG.
  • the constituent members used here are the four members of the first separator Sl, the second separator S2, the positive electrode C, and the negative electrode A. All of these members have a long strip shape.
  • the widths of the first separator S1 and the second separator S2 are wider than the widths of the positive electrode C and the negative electrode A.
  • the spacer member Pl, P2 force S which will be described later, is applied to the negative electrode A before winding.
  • the spacer members PI and P2 are not attached to the negative electrode A before winding.
  • the positive electrode C, the first separator S1, and the negative electrode A are overlapped in this order, and the second separator S2 is overlapped on the outer surface of the negative electrode A.
  • These four-membered laminates are wound around the core material.
  • adjacent members are in contact only by overlapping, and are not joined by a joining means such as an adhesive. That is, each member is only in contact so that it can be mechanically peeled off.
  • the above-described members are overlapped in the order described above and wound to obtain a wound body (not shown). As shown in Fig. 2, the winding is performed so that the positive electrode C side faces inward. By winding in this way, in the wound body, the positive electrode C, the first separator SI, the negative electrode A, and the second separator S2 are arranged in layers in this order.
  • the positive electrode C is formed by forming an active material layer (not shown) containing a positive electrode active material on each surface of a current collector (not shown).
  • the negative electrode A is formed by forming an active material layer (not shown) containing a negative electrode active material capable of occluding and releasing lithium on each surface of a current collector (not shown).
  • the first spacer member P1 Prior to the superposition of these four members, the first spacer member P1 is disposed between the first separator S1 and the negative electrode A in the longitudinal direction of these members.
  • a second spacer member P2 is disposed between the second separator S2 and the negative electrode A in the longitudinal direction of these members.
  • these spacer members PI and P2 are not arranged in the first round of winding, but are arranged in the second and subsequent rounds. In the first round of winding, these four members are placed between the core material. Wrapping around the core material so that no gaps are formed. Both spacer members PI and P2 are discontinuously arranged at a predetermined interval over the entire longitudinal direction of the negative electrode A or the like.
  • the first spacer member P1 and the second spacer member P2 may be the same shape or different shapes. Further, the same material or different materials may be used. In the present embodiment, the first spacer member P1 and the second spacer member P2 have the same shape and the same material. Both spacer members Pl and P2 are rectangular and are arranged so that their long sides coincide with the width direction of the negative electrode A or the like.
  • the long sides of the first and second spacer members Pl, P2 are larger than the width of the negative electrode A or the like.
  • the spacer members PI and P2 having such a shape are formed by connecting the negative electrode A and the separators Sl and S2 so that their longitudinal ends extend from the side edge force of the negative electrode A or the like. Arranged between.
  • the first short side Ml and the first side edge L1 of the negative electrode A, etc. meet and The end on the short side M2 side is arranged to extend from the second side edge L2 of the negative electrode A or the like.
  • the first short side N1 and the second side edge L2 of the negative electrode A, etc. meet, and the end on the second short side N2 side is the negative electrode A, etc. It is arranged to extend from the side edge L1 of 1.
  • the first spacer member P1 and the second spacer member P2 have a positional relationship in which they do not overlap each other when viewed in plan before being wound. They are arranged so that Further, the spacer members PI and P2 are arranged so that a gap G is formed between their adjacent long sides when they are viewed in plan before being wound.
  • a gap G is formed between their adjacent long sides when they are viewed in plan before being wound.
  • the wound body R in the state shown in Fig. 4 (a) is obtained.
  • the wound body R has a cylindrical shape, and the end portions of both spacer members Pl and P2 protrude from the upper and lower surfaces thereof.
  • the negative electrode A and both separators Sl and S2 are separated by the thickness of the spacer members Pl and P2. It has become.
  • the spacer members PI and P2 are removed from the wound body R in the state shown in FIG. 4 (a).
  • a means for removing the spacer members PI, P2 from the winding body R in the present embodiment, a method of pulling out and removing the spacer members Pl, P2 from the winding body R is adopted.
  • the first spacer member P1 and the second spacer member P2 are pulled out simultaneously and at the same speed in directions opposite to each other by 180 degrees. By pulling out both spacer members Pl and P2 under such conditions, the two spacer members PI and P2 can be successfully removed without impairing the winding state of the wound body R. .
  • the spacer members Pl and P2 used in the present embodiment have a material force that is not occluded by the active material of the negative electrode A.
  • both spacer members PI and P2 can be made of plastic or paper force.
  • both spacer members PI and P2 can be made of metal.
  • the spacer members PI and P2 have a short side length of 5 to 100 mm, particularly preferably 5 to 30 mm.
  • the gap G between adjacent long sides of the spacer members PI, P2 is preferably 3 to 60 mm, particularly preferably 5 to 50 mm.
  • FIG. 5 shows another example of a method for manufacturing a wound body in the battery of the present embodiment.
  • a laminate R obtained by winding the positive electrode C, the first separator Sl, the negative electrode A, and the second separator S2 is obtained.
  • the spacer members P 1 and P2 are not used.
  • the feeding tension of the positive electrode C, the first separator Sl, the negative electrode A, and the second separator S2 is controlled individually. Controls the strength of winding.
  • the rotation devices of the positive electrode C, the first separator Sl, the negative electrode A, and the second separator S2 are controlled by individual motors.
  • the positive electrode C, the first separator Sl, the negative electrode A, and the second separator S2 are not drawn out by rotation.
  • their tension is controlled individually.
  • the strength of winding of these members in the wound body R is controlled.
  • each of the positive electrode C, the first separator S1, the negative electrode A, and the second separator S2, each of which is in the shape of a long strip, is rolled out by rolling out a roll-shaped raw reaction force.
  • the winding tension is increased so that there is no gap around the core.
  • the winding tension is set lower than the winding tension when winding the first surface.
  • FIG. 6 shows a schematic diagram of a cross-sectional structure of a preferred embodiment of the negative electrode used in the present invention.
  • the negative electrode 10 of this embodiment includes a current collector 11 and an active material layer 12 formed on at least one surface thereof.
  • FIG. 6 shows a state in which the active material layer 12 is formed only on one side of the current collector 11 for convenience, but the active material layer is formed on both sides of the current collector.
  • active material layer 12 At least a part of the surface of active material particles 12 a containing Si is coated with a metal material having a low lithium compound forming ability.
  • This metal material 13 is a material different from the constituent material of the particles 12a. Voids are formed between the particles 12a coated with the metal material. That is, the metal material is coated with the surface of the particle 12a in a state where a gap is secured so that the non-aqueous electrolyte containing lithium ions can reach the particle 12a.
  • the metal material 13 is conveniently represented as a thick line surrounding the periphery of the particle 12a.
  • This figure is a schematic view of the active material layer 12 viewed two-dimensionally. Actually, each particle is in direct contact with other particles and in contact with the metal material 13.
  • “Lithium compound formation ability is low” means that lithium does not form an intermetallic compound or solid solution, or even if lithium is formed, the amount of lithium is very small or very unstable. Means.
  • the metal material 13 has conductivity, and examples thereof include copper, nickel, iron, cobalt. Or alloys of these metals.
  • the metal material 13 is preferably a highly ductile material in which even when the active material particles 12 a expand and contract, the coating on the surface of the particles 12 a is difficult to break. It is preferable to use copper as such a material.
  • the metal material 13 is preferably present on the surface of the active material particles 12 a over the entire thickness direction of the active material layer 12.
  • the active material particles 12 a are preferably present in the matrix of the metal material 13. As a result, even if the particles 12a expand and contract due to charge and discharge, even if they become fine powder, they are less likely to fall off. In addition, since the electronic conductivity of the entire active material layer 12 is ensured through the metal material 13, the electrically isolated active material particles 12 a are generated, particularly in the deep part of the active material layer 12. The formation of the active material particles 12a is effectively prevented.
  • the presence of the metal material 13 on the surface of the active material particles 12a over the entire thickness direction of the active material layer 12 can be confirmed by electron microscope mapping using the material 13 as a measurement target.
  • the metal material 13 covers the surfaces of the particles 12a continuously or discontinuously.
  • the metal material 13 continuously covers the surfaces of the particles 12a, it is preferable to form fine voids in the coating of the metal material 13 so that a nonaqueous electrolytic solution can flow.
  • the metal material 13 discontinuously covers the surface of the particle 12a, the non-aqueous electrolyte is supplied to the particle 12a through a portion of the surface of the particle 12a that is not covered with the metal material 13. .
  • the metal material 13 may be deposited on the surfaces of the particles 12a by, for example, electrolytic plating according to the conditions described later.
  • the average thickness of the metal material 13 covering the surface of the active material particles 12a is preferably 0.05-2 / im, more preferably 0.:!-0.25 ⁇ m. And that ’s a thing. That is, the metal material 13 covers the surface of the active material particles 12a with a minimum thickness. This prevents the dropout due to the particles 12a from expanding and contracting due to charge and discharge to be pulverized while increasing the energy density.
  • the “average thickness” is a value calculated based on a portion of the surface of the active material particle 12 a that is actually covered with the metal material 13. Accordingly, the portion of the surface of the active material particles 12a not covered with the metal material 13 is not used as the basis for calculating the average value.
  • the void formed between the particles 12a coated with the metal material 13 contains lithium ions. It functions as a distribution path for non-aqueous electrolyte. Since the non-aqueous electrolyte smoothly flows in the thickness direction of the active material layer 12 due to the presence of the voids, it is possible to improve the cycle characteristics. Further, the voids formed between the particles 12a also serve as a space for relieving the stress caused by the volume change of the active material particles 12a due to charge and discharge. The increase in the volume of the active material particles 12a whose volume has been increased by charging is absorbed in the voids. As a result, the fine particles of the particles 12a are less likely to occur, and the negative electrode 10 is effectively prevented from being deformed or deformed.
  • the active material layer 12 preferably has a predetermined plating bath applied to a coating film obtained by applying a slurry containing particles 12a and a binder onto a current collector and drying the slurry. It is formed by depositing the metal material 13 between the particles 12a by performing the electrolytic plating used.
  • the plating solution is sufficiently permeated into the coating film.
  • the conditions for depositing the metal material 13 by electrolytic plating using the plating solution are appropriate.
  • the plating conditions include the composition of the mating bath, the pH of the plating bath, and the current density of the electrolysis. Regarding the pH of the plating bath, it is preferable to adjust it to 7.:!-11. By keeping the pH within this range, the dissolution of the active material particles 12a is suppressed, the surface of the particles 12a is cleaned, and plating on the particle surfaces is promoted. Gaps are formed. The pH value was measured at the plating temperature.
  • the metal material 13 for plating it is preferable to use a copper pyrophosphate bath.
  • nickel used as the metal material
  • an alkaline Eckenole bath is preferably used.
  • the metal material 13 is deposited on the surface of the active material particles 12a, and the metal material 13 is less likely to be deposited between the particles 12a, so that the voids between the particles 12a are successfully formed. This is also preferable.
  • the bath composition, electrolysis conditions and pH are preferably as follows.
  • the bath composition, electrolysis conditions, and pH are preferably as follows.
  • pH 25 weight 0/0 aqueous ammonia: 100 to 300 g / l in the range of pH8 ⁇ : 11 and so as to adjust.
  • the characteristics of the metal material 13 can be appropriately adjusted by adding various additives used in the electrolytic solution for producing copper foil such as protein, active sulfur compound, and cellulose to the various baths. It is.
  • the ratio of voids in the entire active material layer formed by the various methods described above, that is, the void ratio, is preferably about 15 to 45% by volume, particularly about 20 to 40% by volume. By setting the porosity within this range, it is possible to form necessary and sufficient voids in the active material layer 12 through which the non-aqueous electrolyte can flow.
  • the void amount of the active material layer 12 is measured by a mercury intrusion method (JIS R 1655).
  • the mercury intrusion method is a method for obtaining information on the physical shape of a solid by measuring the size and volume of pores in the solid.
  • the principle of the mercury intrusion method is to apply pressure to mercury and press it into the pores of the object to be measured, and measure the relationship between the pressure applied at that time and the volume of mercury that has been pushed in (intruded).
  • mercury enters the active material layer 12 in order from the large voids.
  • the void amount measured at a pressure of 90 MPa is regarded as the total void amount.
  • the porosity (%) of the active material layer 12 is obtained by dividing the void amount per unit area measured by the above method by the apparent volume of the active material layer 12 per unit area and multiplying it by 100. Ask.
  • the porosity can also be controlled by appropriately selecting the particle size of the active material particles 12a.
  • the maximum particle size of the particles 12a is preferably 30 / im or less, and more preferably 10 / im or less.
  • D value it is 0.
  • the particle size of the particles is measured by laser diffraction / scattering particle size distribution measurement and electron microscope observation (SEM observation).
  • the thickness of the active material layer is 10 to 40 ⁇ , preferably 15 to 30 ⁇ , and more preferably 18 to 25 ⁇ m.
  • a thin surface layer (not shown) may be formed on the surface of the active material layer 12.
  • the negative electrode 10 may not have such a surface layer.
  • the thickness of the surface layer is as thin as 0.25 xm or less, preferably 0.1 lzm or less. There is no limit to the lower limit of the thickness of the surface layer.
  • the negative electrode 10 When the negative electrode 10 has the thin surface layer or does not have the surface layer, a secondary battery is assembled using the negative electrode 10, and an overvoltage when the battery is initially charged is reduced. Can be lowered. This means that lithium can be prevented from being reduced on the surface of the negative electrode 10 when the secondary battery is charged. The reduction of lithium leads to the generation of dendrites that cause short circuits between the two electrodes.
  • the surface layer covers the surface of the active material layer 12 continuously or discontinuously.
  • the surface layer covers the surface of the active material layer 12 continuously, the surface layer has a large number of fine voids (not shown) that are open in the surface and communicate with the active material layer 12. It is preferable.
  • the fine voids are preferably present in the surface layer so as to extend in the thickness direction of the surface layer. The fine voids allow the non-aqueous electrolyte to flow. The role of the fine voids is to supply a non-aqueous electrolyte into the active material layer 12.
  • the fine voids are the ratio of the area covered with the metal material 13, that is, the coverage is 95% or less, particularly 80% or less, particularly 60% or less. Such a size is preferable. If the coverage exceeds 95%, it is difficult for the high-viscosity non-aqueous electrolyte to penetrate, and the range of selection of the non-aqueous electrolyte may be narrowed.
  • the surface layer is composed of a metal material having a low ability to form a lithium compound.
  • This metal material may be the same as or different from the metal material 13 present in the active material layer 12.
  • the surface layer may have a structure of two or more layers made of two or more different metal materials. Considering the ease of production of the negative electrode 10, the metal material 13 present in the active material layer 12 and the metal material constituting the surface layer are preferably the same type.
  • the resistance of the negative electrode 10 to bending is increased.
  • the MIT folding resistance measured according to JIS C 6471 is preferably 30 times or more, more preferably 50 times or more.
  • the high folding resistance is extremely advantageous since the negative electrode 10 is folded when the negative electrode 10 is folded or wound and accommodated in the battery container.
  • a film folding fatigue tester with a tank manufactured by Toyo Seiki Seisakusho (Part No. 549) is used. be able to.
  • the current collector 11 in the negative electrode 10 may be the same as that conventionally used as the current collector of the negative electrode for a non-aqueous electrolyte secondary battery.
  • the current collector 11 is preferably composed of the metal material having a low lithium compound forming ability described above. Examples of such metal materials are as already described. In particular, it is preferably made of copper, nickel, stainless steel or the like. Also, it is possible to use a copper alloy foil represented by Corson alloy foil. Further, as the current collector, a metal foil having a normal tensile strength (JIS C 2318) of preferably 500 MPa or more, for example, a copper film layer formed on at least one surface of the aforementioned Corson alloy foil can be used.
  • JIS C 2318 normal tensile strength
  • a current collector with a normal elongation CFIS C 2318) of 4% or more. This is because if the tensile strength is low, the stress is caused by the stress when the active material expands, and if the elongation is low, the current collector may crack. By using these current collectors, it is possible to further improve the folding resistance of the negative electrode 10 described above.
  • the thickness of the current collector 11 is preferably 9 to 35 ⁇ considering the balance between maintaining the strength of the negative electrode 10 and improving the energy density.
  • a copper foil is used as the current collector 11, it is preferable to perform a chromate treatment or an antifungal treatment using an organic compound such as a triazole compound or an imidazole compound.
  • a coating film is formed on the current collector 11 using a slurry containing active material particles and a binder, and then the coating is electrolyzed.
  • a current collector 11 is prepared as shown in FIG. 7 (a). Then, a slurry containing active material particles 12 a is applied onto the current collector 11 to form a coating film 15.
  • the surface roughness of the coating film forming surface of the current collector 11 is preferably 0.5 to 4 / m as the maximum height of the contour curve. When the maximum height exceeds 4 zm, the accuracy of forming the coating film 15 is reduced, and current concentration tends to occur at the protrusions. When the maximum height is less than 0.5 zm, the adhesion of the active material layer 12 tends to be lowered.
  • the active material particles 12a those having the above-described particle size distribution and average particle size are preferably used.
  • the slurry contains a binder and a diluting solvent in addition to the particles of the active material.
  • the slurry may also contain a small amount of conductive carbon material particles such as acetylene black and graphite.
  • the conductive carbon material is contained in an amount of:! To 3% by weight with respect to the weight of the active material particles 12a.
  • the content of the conductive carbon material is less than 1% by weight, the viscosity of the slurry is lowered and the sedimentation of the active material particles 12a is promoted, so that it is difficult to form a good coating film 15 and a uniform void.
  • plating nuclei concentrate on the surface of the conductive carbon material, and it becomes difficult to form a good coating.
  • binder styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), polyethylene (PE), ethylene propylene monomer (EPDM), or the like is used.
  • diluting solvent N-methylpyrrolidone, cyclohexane or the like is used.
  • the amount of the active material particles 12a in the slurry is preferably about 30 to 70% by weight.
  • the amount of the binder is preferably about 0.4 to 4% by weight. Diluting solvent is added to these to form a slurry.
  • the formed coating film 15 has a large number of minute spaces between the particles 12a.
  • the current collector 11 on which the coating film 15 is formed is immersed in a plating bath containing a metal material having a low lithium compound forming ability. By dipping in the plating bath, the plating solution enters the minute space in the coating film 15 and reaches the interface between the coating film 15 and the current collector 11. Under this condition, electrolytic plating is performed to deposit metal species on the surface of the particles 12a (hereinafter, this plating is also referred to as penetration plating). The penetration is performed by using the current collector 11 as a force sword, immersing the counter electrode as the anode in the plating bath, and connecting both electrodes to the power source.
  • Precipitation of the metal material by penetration adhesion is preferably caused to proceed from one side of the coating film 15 to the other side. Specifically, as shown in FIGS. 7 (b) to (d), the electrolysis is performed so that the deposition of the metal material 13 proceeds from the interface between the coating film 15 and the current collector 11 toward the surface of the coating film. Make a mess. By precipitating the metal material 13 in this way, the surface of the active material particles 12a can be successfully coated with the metal material 13, and a void is successfully formed between the particles 12a coated with the metal material 13. can do.
  • the surface of the coating film is shown from the interface between the coating film 15 and the current collector 11.
  • the fine particles 13a consisting of the nuclei of the metal material 13 are present in a layered manner with a substantially constant thickness at the forefront of the precipitation reaction. is doing.
  • the adjacent fine particles 13a are combined to form larger particles, and when the deposition proceeds further, the particles are combined to continuously cover the surface of the active material particles 12a. It becomes like this.
  • the penetration staking is terminated when the metal material 13 is deposited in the entire thickness direction of the coating film 15.
  • the end point of the plating it is possible to form a surface layer (not shown) on the upper surface of the active material layer 12. In this manner, the target negative electrode is obtained as shown in FIG. 7 (d).
  • the negative electrode 10 is also preferably subjected to antifouling treatment.
  • anti-bacterial treatment include organic anti-bacterials using triazole compounds such as benzotriazole, carboxybenzotriazole, tolyltriazole and imidazole, and inorganic anti-bacterials using cobalt, nickel, chromate and the like.
  • a current collector made of an electrolytic copper foil having a thickness of 18 zm was acid washed at room temperature for 30 seconds. After the treatment, it was washed with pure water for 15 seconds.
  • a slurry containing particles made of silicon was applied on both sides of the current collector to a thickness of 20 zm to form a coating film.
  • the average particle diameter D of the particles was 2 ⁇ m.
  • the average particle size D was measured using a Microtrac particle size distribution measuring device (No. 9320-XI00) manufactured by Nikkiso Co., Ltd.
  • the current collector on which the coating film was formed was immersed in a copper pyrophosphate bath having the following bath composition, and by electrolysis, copper penetrated into the coating film to form an active material layer. did.
  • the electrolysis conditions were as follows. DSE was used for the anode. A DC power source was used as the power source.
  • LiCoNiMnO was used as the positive electrode active material. This is acetylene black and
  • Both the polyvinylidene fluoride and the polybutylpyrrolidone solvent were suspended to obtain a positive electrode mixture.
  • This positive electrode mixture was applied to a current collector made of aluminum foil, dried, and then rolled and pressed to obtain a positive electrode.
  • the total thickness of the positive electrode including the current collector and the active material layer was 160 ⁇ m.
  • a polypropylene porous film having a thickness of 20 ⁇ m was used as the first and second separators.
  • the negative electrode, the positive electrode, and the first and second separators were formed in a long strip shape having a width of 60 mm.
  • the battery can was sealed to obtain a lithium secondary battery.
  • the battery had a diameter of 18mm and a height of 65mm (type 18650).
  • CT scan of battery cross section When the distance between the negative electrodes in the wound body was measured, it was 280 ⁇ m.
  • Example 2 Using the same positive electrode and negative electrode as in Example 1 and the first and second separators, these members were wound around the same core material as in Example 1 to obtain a wound body. The winding was performed so that there was no gap between these members. After completing the winding, the cylindrical body was also pulled out. The wound body after the cylindrical tube was pulled out was housed in a battery can in the same manner as in Example 1 to obtain a lithium secondary battery.
  • the batteries obtained in the examples and comparative examples were charged and discharged for 50 cycles.
  • the charging conditions were 0.5C, final voltage 4.2V, constant current / constant voltage (CCCV).
  • the discharge conditions were 0.5C, final voltage 2.7V, and constant current (CC).
  • charge / discharge at the first cycle is 0.05C
  • charge / discharge at the second to fourth cycle is 0.1C
  • charge / discharge at the fifth to seventh cycle is 0.5C
  • 8-: charge / discharge at the tenth cycle is 1C.
  • the cross-section of the battery was CT scanned to observe the state of the wound body in a non-destructive manner. The results are shown in FIG. 8 (Example 1) and FIG. 9 (Comparative Example 1). 8 and 9 also show a CT scan image of the battery before charging and discharging.
  • the negative electrode and the like are hardly deformed after 50 cycles of charge / discharge, whereas in the battery of the comparative example, It can be seen that after 50 cycles of charging and discharging, the iron, the negative electrode, etc. are squeezed and buckled. Since the core material used in Example 1 is made of polypropylene, the core material appears in FIG. 8 which is the CT scan image.
  • the wound body composed of the positive electrode and the negative electrode is not in a state of being strongly wound, and has a void in the wound body.
  • the voids can alleviate the expansion of the negative electrode caused by the negative electrode active material storing lithium. As a result, expansion and deformation of the battery can be prevented.
  • the core of the wound body is provided with a core material, even if a stress caused by the expansion of the negative electrode is locally applied to the center of the wound body, the buckling of the negative electrode is caused by the core. Suppressed by the material.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un accumulateur à électrolyte non aqueux comprenant un élément enroulé (1) dans lequel un stratifié (2), comprenant une anode, une cathode comptant une couche de substance d'activation de cathode contenant du Si ou du Sn et un séparateur disposé entre les deux, est enroulé autour d'un noyau (3). À partir du deuxième enroulement, le stratifié (2) est enroulé de telle sorte que la distance entre les cathodes dans la direction radiale de l'élément enroulé (1) peut satisfaire la formule (1) suivante. Au premier enroulement de l'élément enroulé (1), le stratifié (2) est de préférence enroulée sans laisser d'espace entre le stratifié (2) et le noyau (3). Distance de la cathode = (Épaisseur de l'anode) + (Épaisseur du séparateur) + (Épaisseur de la cathode) + (Épaisseur de la couche de substance d'activation de la cathode) x 0,5 à 3,0 (1)
PCT/JP2007/057891 2006-08-10 2007-04-10 Accumulateur à électrolyte non aqueux Ceased WO2008018204A1 (fr)

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CN102318122B (zh) 2009-02-09 2015-08-19 瓦尔达微电池有限责任公司 纽扣电池和用于产生该纽扣电池的方法
DE102009060800A1 (de) 2009-06-18 2011-06-09 Varta Microbattery Gmbh Knopfzelle mit Wickelelektrode und Verfahren zu ihrer Herstellung
JP2014179221A (ja) * 2013-03-14 2014-09-25 Sanyo Electric Co Ltd 非水電解質二次電池
WO2017190364A1 (fr) * 2016-05-06 2017-11-09 深圳先进技术研究院 Batterie secondaire et procédé de préparation de celle-ci
EP3605697B1 (fr) * 2018-07-31 2025-04-23 VARTA Microbattery GmbH Procédé de fabrication d'une bobine d'électrodes-séparateur, bobine d'électrodes-séparateur et pile bouton dotée d'une telle bobine
JPWO2022209601A1 (fr) * 2021-03-30 2022-10-06
JP7638836B2 (ja) * 2021-09-15 2025-03-04 株式会社東芝 二次電池、電池モジュール、及び車両
JPWO2023189937A1 (fr) * 2022-03-30 2023-10-05

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JP2001189167A (ja) * 1999-10-22 2001-07-10 Sony Corp 非水電解質二次電池
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JP2001189167A (ja) * 1999-10-22 2001-07-10 Sony Corp 非水電解質二次電池
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US12388072B2 (en) 2021-03-17 2025-08-12 Ningde Amperex Technology Limited Electrochemical apparatus and electronic apparatus

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