WO2017090219A1 - Batterie cylindrique - Google Patents

Batterie cylindrique Download PDF

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Publication number
WO2017090219A1
WO2017090219A1 PCT/JP2016/004301 JP2016004301W WO2017090219A1 WO 2017090219 A1 WO2017090219 A1 WO 2017090219A1 JP 2016004301 W JP2016004301 W JP 2016004301W WO 2017090219 A1 WO2017090219 A1 WO 2017090219A1
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WIPO (PCT)
Prior art keywords
negative electrode
active material
material layer
thickness
positive electrode
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PCT/JP2016/004301
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English (en)
Japanese (ja)
Inventor
大塚　正雄
靖志 中村
亜希子 岡部
Original Assignee
パナソニックＩｐマネジメント株式会社
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Publication of WO2017090219A1 publication Critical patent/WO2017090219A1/fr

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • 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 cylindrical battery provided with a wound electrode group.
  • Patent Document 1 in the wound electrode group of the cylindrical alkaline storage battery, a thin portion with a small thickness of the active material layer is formed in a region having a predetermined length from the outer end of the negative electrode.
  • the positive electrode and the negative electrode are wound so that the outer end of the positive electrode overlaps.
  • Patent Document 2 in the wound electrode group, a short circuit is suppressed by inserting a protective member that covers a ridge formed at the outer end of the positive electrode between the positive electrode and the separator.
  • the thickness of the negative electrode active material layer is small. Therefore, when the thin portion of the negative electrode and the outer end of the positive electrode are overlapped, the balance of the active material amount (N / P ratio balance) between the positive electrode active material layer and the negative electrode active material layer facing each other is near the outer end. Collapse and output and capacity are likely to decrease. Further, when the negative electrode region other than the thin wall portion and the outer end of the positive electrode are overlapped, the diameter of the electrode group becomes the largest at the outer end portion of the positive electrode, and it becomes difficult to insert into the battery case. Further, when an external force is applied to the case, the largest pressure is applied to the outer end portion of the positive electrode, and a short circuit is likely to occur.
  • Patent Document 2 since the protective member is disposed between the positive electrode and the separator, when the electrode is tightly wound or the number of turns is increased from the viewpoint of increasing the capacity, the step of the protective member May cause a crack in the positive electrode and cause an internal short circuit.
  • An object of the present disclosure is to provide a cylindrical battery in which an electrode group can be easily inserted into a battery case, the occurrence of an internal short circuit is suppressed, and the N / P ratio balance in the vicinity of the outer end is suppressed. It is.
  • One aspect of the present disclosure includes a strip-shaped positive electrode, a strip-shaped negative electrode, an electrode group around which a strip-shaped first separator interposed between the positive electrode and the negative electrode is wound, an electrolyte, and an opening that accommodates the electrode group and the electrolyte
  • a bottomed cylindrical battery case having a portion, and a sealing plate for sealing the opening
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on both surfaces of the negative electrode current collector,
  • the negative electrode includes a thin portion provided in a region of length L 3 from the outer end of the negative electrode, a tapered portion adjacent to the thin portion, and other body portions.
  • the thickness t 1o of the negative electrode active material layer on the outer peripheral side in the main body portion and the thickness t 3o of the negative electrode active material layer on the outer peripheral side in the thin portion satisfy t 1o > t 3o
  • the thickness t 2o of the negative electrode active material layer on the outer peripheral side of the taper portion is gradually decreased from the main body portion side toward the thin wall portion side
  • the electrode group is a cylinder, wherein the outer end of the positive electrode is disposed so as to overlap the tapered portion via the first separator, and further includes a second separator disposed between the outer end of the positive electrode and the tapered portion.
  • the present invention relates to a battery.
  • the cylindrical battery it is easy to insert the wound electrode group into the battery case, and the occurrence of an internal short circuit can be suppressed.
  • the balance of the N / P ratio in the vicinity of the outer end of the positive electrode can be suppressed.
  • FIG. 1 is a cross-sectional view schematically showing a cylindrical battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing the cylindrical battery of FIG.
  • FIG. 3 is an enlarged view of a portion surrounded by a circle indicated by III in FIG.
  • FIG. 4 is a schematic perspective view schematically showing an example of a negative electrode used in the electrode group of FIG.
  • FIG. 5 is a schematic side view of the negative electrode of FIG.
  • FIG. 6 is a schematic perspective view schematically showing another example of the negative electrode used in the electrode group in FIG. 2.
  • FIG. 7 is a schematic side view of the negative electrode of FIG.
  • a cylindrical battery according to the present invention includes a strip-shaped positive electrode, a strip-shaped negative electrode, and an electrode group wound with a strip-shaped separator (first separator) interposed between the positive electrode and the negative electrode, an electrolyte, an electrode group, A bottomed cylindrical battery case having an opening for accommodating an electrolyte, and a sealing plate for sealing the opening.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on both surfaces of the negative electrode current collector.
  • the negative electrode includes a thin portion provided in a region of the length L 3 from the outer end of the negative electrode, and a tapered portion adjacent to the thin portion, and the other body portion.
  • the thickness t 1o of the negative electrode active material layer on the outer peripheral side in the main body portion and the thickness t 3o of the negative electrode active material layer on the outer peripheral side in the thin portion satisfy t 1o > t 3o .
  • the thickness t 2o of the negative electrode active material layer on the outer peripheral side of the taper portion is gradually decreased from the main body portion side toward the thin portion portion side.
  • the electrode group further includes a separator (second separator) disposed such that the outer end of the positive electrode overlaps the tapered portion via the first separator, and is disposed between the outer end of the positive electrode and the tapered portion. Including.
  • the diameter of the electrode group is the largest at this outer end, Hard to insert into the battery case. Since burr may exist at the outer end of the positive electrode, when an external force is applied to the battery case, if a large pressure is applied to the outer end portion of the positive electrode, the burr penetrates the separator, and a short circuit is likely to occur. Become. Further, when a large pressure is applied to the outer end portion of the positive electrode, a crack may occur in the outer end portion of the positive electrode, which may cause a short circuit.
  • the number of electrode turns can be reduced, the electrode thickness can be reduced, or the electrode group can be tightly wound. It is necessary to turn. Reducing the number of turns of the electrode or reducing the thickness is disadvantageous in terms of increasing the capacity, and if the electrode group is wound tightly, the internal resistance may increase or a short circuit may occur.
  • the electrode is wound around the thin portion formed at the outer end of the negative electrode so that the outer end of the positive electrode overlaps as in Patent Document 1, an increase in the diameter of the electrode group is suppressed.
  • the amount of the negative electrode active material in the thin-walled portion is small, the balance of the active material amount is lost between the thin-walled portion and the positive electrode facing the thin-walled portion, and the output and capacity are reduced.
  • the negative electrode on the outer peripheral side extends from the main body portion to the thin wall portion between the main body portion of the negative electrode and the thin wall portion formed in the region having a predetermined length from the outer end.
  • a tapered portion where the thickness of the active material layer is reduced is formed, and the tapered portion is disposed so that the outer end of the positive electrode overlaps.
  • the thickness of the negative electrode active material layer is larger in the tapered portion than in the thin portion, the quantitative balance (N / P ratio balance) between the negative electrode active material and the positive electrode active material in the vicinity of the outer end of the positive electrode may be lost. It is suppressed. Therefore, it is possible to suppress a decrease in capacity and output.
  • a second separator is disposed between the outer end of the positive electrode and the tapered portion. Therefore, it can suppress that an internal short circuit occurs in the outer end of a positive electrode, and its periphery, or internal resistance increases and it generates heat.
  • the thin-walled portion only needs to have a thickness of the negative electrode active material layer on the outer peripheral side that is at least smaller than that of the main body portion as described above. It may be smaller than the thickness of the inner peripheral side of the main body.
  • the taper portion may be such that at least the thickness of the negative electrode active material layer on the outer peripheral side is gradually reduced from the main body portion side toward the thin wall portion side.
  • the thickness of the negative electrode active material layer of the taper portion may be gradually decreased from the main body portion side toward the thin wall portion side.
  • the length L 3 of the thin portion, the length L 1 of the main body portion described later, and the length L 2 of the tapered portion are all determined based on the negative electrode active material layer on the outer peripheral side. That is, the thin-walled portion is a region where the thickness of the negative electrode active material layer on the outer peripheral side from the outer end (end surface on the outer peripheral side) of the negative electrode is t 3o , and the tapered portion is adjacent to the thin-walled portion and the negative electrode active material on the outer peripheral side. This is a region where the thickness of the material layer changes in an inclined manner.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a cylindrical battery according to an embodiment of the present invention.
  • the cylindrical battery includes a bottomed cylindrical battery case 4 that also serves as a negative electrode terminal, an electrode group housed in the battery case 4, and an electrolyte (not shown).
  • a strip-shaped negative electrode 1, a strip-shaped positive electrode 2, and a strip-shaped separator (first separator) 3 interposed therebetween are spirally wound.
  • a sealing plate 7 including a safety valve 6 is disposed in the opening of the battery case 4 via an insulating gasket 8, and the cylindrical battery is sealed by caulking the opening end of the battery case 4 inward. .
  • the sealing plate 7 also serves as a positive electrode terminal, and is electrically connected to the positive electrode 2 via the positive electrode current collector plate 9.
  • the electrode group is accommodated in the battery case 4, the electrolyte is injected, the sealing plate 7 is disposed in the opening of the battery case 4 via the insulating gasket 8, and the battery case 4 The opening end can be obtained by caulking and sealing.
  • the negative electrode 1 of the electrode group is preferably electrically connected by contacting the battery case 4 on the outermost periphery.
  • the cylindrical battery is not particularly limited, and may be a primary battery or a secondary battery. Since an increase in resistance due to the occurrence of an internal short circuit or a crack in the positive electrode can be suppressed, the cylindrical battery is suitable as a secondary battery that repeats charging and discharging.
  • Cylindrical batteries are particularly suitable for alkaline storage batteries such as nickel metal hydride storage batteries.
  • the alkaline storage battery includes a nickel cadmium storage battery and a nickel zinc storage battery in addition to the nickel metal hydride storage battery.
  • nickel-metal hydride storage batteries use electrodes having a relatively large thickness compared to other secondary batteries, and thus problems such as ease of insertion of an electrode group into a battery case and occurrence of internal short-circuits are likely to become obvious.
  • the configuration of the cylindrical battery of the present invention in which the thin portion and the tapered portion are provided is particularly suitable for application to a nickel metal hydride storage battery.
  • oxygen gas is generated during overcharge, but by providing a negative electrode active material layer that does not face the positive electrode on the outer peripheral side of the thin portion, oxygen gas generated during overcharge can be absorbed. it can. From this point of view, it is advantageous to apply the configuration of the cylindrical battery of the present invention to a nickel metal hydride storage battery.
  • FIG. 2 is a cross-sectional view schematically showing the cylindrical battery of FIG.
  • the present invention is characterized in the vicinity of the outer end of the positive electrode of the wound electrode group.
  • FIG. 3 shows an enlarged view of the vicinity of the outer end of the positive electrode (that is, a portion surrounded by a circle indicated by III in FIG. 2).
  • FIG. 4 is a schematic perspective view schematically showing an example of a negative electrode used in the electrode group of FIG.
  • FIG. 5 is a schematic side view of the negative electrode of FIG.
  • the negative electrode 1 includes a main body portion 1a located on the inner peripheral side in the electrode group, a thin portion 1c formed on the outer end side, and a tapered portion 1b located between the main body portion 1a and the thin portion 1c.
  • Thin portion 1c is an area of a length L 3 from the outer end of the negative electrode 1, the taper portion 1b is a region of length L 2 adjacent to the thin portion 1c.
  • Body portion 1a, of the negative electrode 1, a region other than the thin portion 1c and the tapered portion 1b, has a length L 1.
  • the outermost periphery of the positive electrode 2 is covered with a thin portion 1 c of the negative electrode 1 through the first separator 3, and the thin portion 1 c is in contact with the inner wall of the battery case 4.
  • the negative electrode 1 includes a strip-shaped negative electrode current collector 11 and a negative electrode active material layer 12 formed on the surface of the negative electrode current collector 11.
  • the negative electrode active material layer 12 includes a negative electrode active material layer 12 a formed on the outer peripheral surface of the negative electrode current collector 11 and a negative electrode active material layer 12 b formed on the inner peripheral surface of the negative electrode current collector 11. Contains.
  • the thickness t 3o of the negative electrode active material layer 12a of the outer peripheral side of the thin portion 1c of the negative electrode 1 is smaller than the thickness t 1o of the negative electrode active material layer 12a of the outer periphery of the main body 1a (t 1o> t 3o) .
  • thickness t2o of the negative electrode active material layer 12a of the outer peripheral side of the taper part 1b is decreasing gradually toward the thin part 1c from the main-body part 1a side.
  • the electrode group is arranged so that the outer end of the positive electrode 2 overlaps the tapered portion 1b with the first separator 3 interposed therebetween. And the 2nd separator 3a is distribute
  • the wound electrode group can be easily inserted into the battery case, the occurrence of an internal short circuit can be suppressed, and the balance of the N / P ratio in the vicinity of the outer end can be suppressed. can do.
  • the second separator 3 a is disposed between the tapered portion 1 b and the first separator 3 in contact with the outer end of the positive electrode 2.
  • the second separator 3a may be disposed so as to overlap at least the outer end of the positive electrode 2 and its periphery so as to support the outer end of the positive electrode 2.
  • FIG. 6 is a schematic perspective view schematically showing another example of the negative electrode used in the electrode group of FIG.
  • FIG. 7 is a schematic side view of the negative electrode of FIG.
  • the thickness of the negative electrode active material layer on the inner peripheral side is small in the thin-walled portion of the negative electrode, as in the negative electrode active material layer on the outer peripheral side, and the negative electrode active material layer on the inner peripheral side is also in the tapered portion. The thickness gradually decreases from the main body portion side toward the thin wall portion side.
  • the example is the same as the example of FIGS.
  • the negative electrode 21 includes a main body portion 21a located on the inner peripheral side of the electrode group, a thin portion 21c formed on the outer end side, and a tapered portion 21b located therebetween.
  • the negative electrode 21 includes a strip-shaped negative electrode current collector 31 and a negative electrode active material layer 32 formed on the surface of the negative electrode current collector 31.
  • the negative electrode active material layer 32 includes a negative electrode active material layer 32 a formed on the outer peripheral surface of the negative electrode current collector 31 and a negative electrode active material layer 32 b formed on the inner peripheral surface.
  • the relationship of the thickness of the negative electrode active material layer 32a on the outer peripheral side is the same as in the examples of FIGS.
  • the thickness t 3i of the inner peripheral negative electrode active material layer 32b in the thin portion 21c of the negative electrode 21 is smaller than the thickness t 1i of the inner peripheral negative electrode active material layer 32b in the main body 21a (t 1i > t 3i ). Further, the thickness t 2i of the negative electrode active material layer 32b on the inner peripheral side in the taper portion 21b is gradually reduced from the main body portion 21a side toward the thin portion 21c.
  • the negative electrode has a main body part, a taper part, and a thin part in which the thickness of the negative electrode active material layer on the outer peripheral side of the electrode group is different.
  • the thickness t 3o of the negative electrode active material layer on the outer peripheral side is smaller than the thickness t 1o of the negative electrode active material layer on the outer peripheral side of the main body portion. Therefore, it is advantageous to provide a thin portion in a region where the negative electrode active material layer on the outer peripheral side does not face the positive electrode because the amount of the negative electrode active material that is not used for the electrode reaction can be reduced and the volume required for it can be reduced.
  • the thickness t 3o is small, by forming a negative electrode active material layer that does not face the positive electrode in the thin wall portion, the nickel hydrogen storage battery can absorb oxygen gas generated during overcharge.
  • the thickness of the negative electrode active material layer on the inner peripheral side is not particularly limited and may be the same.
  • the thickness may be varied as necessary. May be.
  • this thickness may be the same as t 1o , for example.
  • the thickness of the negative electrode active material layer on the inner peripheral side may be changed similarly to the thickness of the negative electrode active material layer on the outer peripheral side.
  • the thickness gradient of the negative electrode active material layer is not necessarily the same between the outer peripheral side and the inner peripheral side, and may be different.
  • the position where the thickness of the negative electrode active material layer on the inner peripheral side starts to decrease from the main body side toward the thin wall side is not necessarily between the main body portion and the tapered portion (that is, the thickness of the negative electrode active material layer on the outer peripheral side is the main body). It does not need to coincide with the position where the portion starts to decrease from the portion side toward the thin portion side, and may overlap with either the main body portion or the tapered portion.
  • the position at which the decrease in the thickness of the negative electrode active material layer on the inner peripheral side converges does not necessarily coincide with the end point of the tapered portion (between the tapered portion and the thin portion), and the tapered portion and the thin portion. It may overlap with any of the above.
  • the length L 3 of the thin portion is, for example, 50% or more and 115% or less, and preferably 70% or more and 110% or less, or 80% or more and 105% or less of the length of the outermost periphery of the negative electrode.
  • the main body part is a region that is located on the center side (or inner peripheral side) of the electrode group, and that both surfaces face the positive electrode, and are mainly responsible for electrode reactions.
  • the entire region of the negative electrode on the center side excluding the thin-walled portion and the tapered portion on the outer peripheral side is referred to as a main body portion, but in the main body portion, the region that does not face the innermost positive electrode of the negative electrode Then, if necessary, the thickness of the negative electrode active material layer may be partially reduced.
  • the thicknesses t 1o and t 1i of the negative electrode active material layers on the outer peripheral side and the inner peripheral side in the main body can be determined in consideration of the type of the battery, the balance with the amount of the positive electrode active material in the positive electrode, and the like.
  • Each of t 1o and t 1i is, for example, from 0.01 mm to 0.3 mm, or from 0.1 mm to 0.2 mm.
  • the difference (t 1o -t 3o ) between the thickness t 1o of the negative electrode active material layer and the thickness t 3o of the negative electrode active material layer is preferably 0.01 mm or more and 0.2 mm or less, or 0.02 mm or more and 0 It may be 1 mm or less.
  • the thickness t 1i of the negative electrode active material layer, also the difference between the thickness t 3i of the negative electrode active material layer (t 1i -t 3i), can be selected from the same range as (t 1o -t 3o). When the thickness difference is in such a range, it is easy to give a gradient of the thickness of the negative electrode active material layer in the tapered portion, and it becomes easier to ensure the ease of inserting the electrode group into the battery case. Moreover, even if the second separator is provided, the periphery of the outer end of the positive electrode is not easily affected by the step due to the second separator.
  • the thickness t 2o of the negative electrode active material layer on the outer peripheral side is gradually reduced from the main body portion side toward the thin portion portion side. That is, the thickness t 2o varies in an inclined manner within a range of t 3o ⁇ t 2o ⁇ t 1o . Further, when the thickness t 2i of the negative electrode active material layer on the inner peripheral side is decreased from the main body portion side toward the thin wall portion side, the thickness t 2i may be changed in an inclined manner within the range of t 3i ⁇ t 2i ⁇ t 1i. Good.
  • the taper portion When the length (L 2 ) of the taper portion is short, the taper portion has a steep gradient, and stress is easily applied to the outer end of the positive electrode disposed in the taper portion and the periphery thereof. That is, it is preferable that the length L 2 has a certain size. From this point of view, the length L 2 of the tapered portion, the length of the outermost periphery of the negative electrode, longer is favored over 1/6, may be 1/5 or more or 1/4 or more. The length L 2 of the tapered portion is preferably equal to or less than half of the length of the outermost periphery of the negative electrode.
  • the positive electrode and the negative electrode may be arranged so that the outer end of the positive electrode overlaps at least the taper portion, but the position of the end surface of the outer end of the positive electrode is near the center in the length direction of the taper portion. It is preferable to arrange a positive electrode and a negative electrode in For example, the end face of the outer end of the positive electrode is located in a region of ⁇ 0.2 ⁇ L 2 (preferably a region of ⁇ 0.1 ⁇ L 2 ) across the center in the length direction of the taper portion. It is preferable to overlap the outer end of the positive electrode with the tapered portion.
  • the stress applied to the outer end of the positive electrode can be reduced by the taper portion and the second separator, even if the number of turns of the negative electrode is increased or the thickness is increased, the outer end of the positive electrode and the periphery thereof are increased. Generation of internal short circuit can be suppressed.
  • the number of turns of the negative electrode can be selected according to the size of the cylindrical battery. For example, when the outer diameter of the cylindrical battery is 6 mm or more and 24 mm or less, it can be 2 or more and 10 or less, and can be 3 or more and 6 or less. Also good.
  • the negative electrode includes a negative electrode current collector (core material) and a negative electrode active material layer formed on both surfaces of the negative electrode current collector.
  • a negative electrode current collector a known material and / or current collector can be used depending on the type of battery.
  • a porous substrate such as a punching metal or a lath body, or a non-porous substrate such as a metal foil may be used.
  • a negative electrode active material layer a negative electrode active material layer containing a known component can be adopted depending on the type of battery.
  • the negative electrode active material layer only needs to contain at least a negative electrode active material, and may be a negative electrode mixture layer including a negative electrode active material, a binder, a conductive agent, and / or a thickener. These components may be appropriately selected according to the type of battery.
  • the nickel hydride storage battery will be described as an example.
  • the material of the negative electrode current collector include stainless steel, nickel, or an alloy thereof.
  • the negative electrode active material include known hydrogen storage alloys such as A 2 B 7 type (or Ce 2 Ni 7 type), AB 5 type (CaCu 5 type or MmNi 5 type (Mm represents Misch metal)), Those having a crystal structure such as AB 3 type (or CeNi 3 type) and / or AB 2 type (MgCu 2 type or the like) can be used without particular limitation.
  • a resin material for example, a rubber-like material such as styrene-butadiene copolymer rubber (SBR), a polyolefin resin, a fluororesin such as polyvinylidene fluoride, and / or an acrylic resin (including its Na ion crosslinked product) And the like.
  • the thickener include carboxymethyl cellulose (CMC) and a salt thereof, polyvinyl alcohol, and / or polyethylene oxide.
  • the conductive agent include carbon black, conductive fibers, and / or organic conductive materials.
  • the negative electrode may be formed, for example, by attaching a negative electrode active material to a negative electrode current collector. Moreover, you may form a negative electrode by apply
  • the thickness of the negative electrode (main body part) may be determined in consideration of the type of battery and the balance with the positive electrode, but is preferably 0.1 mm or more and 0.6 mm or less, for example.
  • the length of the region facing the tapered portion is, for example, 1% to 15% of the length of the positive electrode. % Or more and 5% or less is preferable.
  • the positive electrode a known positive electrode is used according to the type of battery.
  • the positive electrode only needs to contain at least a positive electrode active material, and may be one obtained by molding and sintering a positive electrode mixture containing a positive electrode active material.
  • a positive electrode active material or a positive electrode mixture supported on a positive electrode current collector (core material) may be used.
  • the positive electrode mixture may include a conductive agent, a binder, and / or a thickener in addition to the positive electrode active material.
  • the positive electrode can be obtained by a known method.
  • the positive electrode current collector a current collector of a known material and / or form can be used depending on the type of battery.
  • the positive electrode active material, the conductive agent, the binder, and the thickener may be appropriately selected according to the type of battery.
  • a nickel metal hydride storage battery will be described as an example.
  • the positive electrode current collector include a nickel foam, and a porous substrate formed of nickel or a nickel alloy such as a sintered nickel plate.
  • the positive electrode active material for example, nickel compounds such as nickel hydroxide and / or nickel oxyhydroxide are used.
  • the conductive agent, binder and thickener may be appropriately selected from those exemplified for the negative electrode.
  • conductive cobalt oxide such as cobalt hydroxide and / or ⁇ -type cobalt oxyhydroxide may be used.
  • the first separator and the second separator for example, a microporous film, a nonwoven fabric, or a laminate thereof can be used depending on the type of battery.
  • the material of the microporous membrane or the nonwoven fabric may be appropriately selected from known materials according to the type of battery and the operating temperature of the battery. For example, a resin or inorganic fiber is used.
  • the nickel hydride storage battery will be described as an example.
  • the resin include polyolefin resins such as polyethylene and polypropylene, fluorine resins, and / or polyamide resins.
  • the separator may be subjected to hydrophilization treatment such as corona discharge treatment, plasma treatment, and / or sulfonation treatment as necessary.
  • each separator can be appropriately selected from the range of 10 ⁇ m to 300 ⁇ m, for example, and may be 15 ⁇ m to 200 ⁇ m, for example.
  • the second separator may be disposed between the outer end of the positive electrode and the tapered portion of the negative electrode, or may be disposed between the outer end of the positive electrode and the first separator in contact with the tapered portion of the negative electrode. Further, the second separator may be disposed between the taper portion of the negative electrode and the first separator in contact with the outer end of the positive electrode. In this case, the step at the end of the second separator is relaxed by the first separator, and the effect of suppressing the occurrence of an internal short circuit at the outer end of the positive electrode and its periphery can be enhanced.
  • the length of the second separator, the L 2, for example, 200% or less than 50%, may be 100% or less than 80%.
  • the second separator only needs to protect the outer end of the positive electrode and its periphery. Therefore, a sufficient effect can be obtained even if the length of the second separator is shorter than the length L 2 of the tapered portion.
  • the length of the second separator, the L 2 for example, less than 50% to 100%, and preferably less than 80% or more 100%.
  • the width of the second separator may be made smaller than the width of the positive electrode and / or the negative electrode.
  • the width of the second separator is preferably larger than the width of the positive electrode, and even larger than the width of the negative electrode. Good. Further, the width of the second separator may be approximately the same as the width of the first separator.
  • the length of the second separator is the length of the second separator in the direction parallel to the length direction of the electrode, and the width of the second separator is the second length in the direction perpendicular to the length direction of the electrode. The length of the separator.
  • the electrolyte includes a solute and a solvent that dissolves the solute.
  • solute and the solvent known materials can be used depending on the type of battery.
  • concentration of the solute and the specific gravity of the electrolyte can also be selected as appropriate.
  • an alkaline electrolyte such as an aqueous solution containing an alkali is used as the electrolyte.
  • the alkali include alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and / or sodium hydroxide.
  • the specific gravity of the alkaline electrolyte is, for example, 1.03 or more and 1.55 or less.
  • components such as a battery case and a sealing plate
  • known components can be used depending on the type of the battery.
  • Example 1 An AA cylindrical nickel-metal hydride storage battery having a capacity of 2500 mAh was manufactured by the following procedure.
  • the obtained negative electrode mixture slurry was applied to both surfaces of an iron punching metal (thickness 60 ⁇ m, hole diameter 1 mm, hole area ratio 42%) having a nickel plating on the surface as a negative electrode current collector.
  • the coating amount of the negative electrode mixture slurry was changed in the length direction of the negative electrode current collector so that the thicknesses of the negative electrode active material layers on both sides were different between the main body part, the tapered part, and the thin part.
  • the coating film of the negative electrode mixture slurry was dried at 95 ° C. for 10 minutes, and then the negative electrode was formed by pressing the coating film together with the negative electrode current collector with a roller.
  • the taper portion was formed in a region between the main body portion and the thin portion, and the length L 2 of the taper portion was 12 mm.
  • nickel hydroxide powder containing 2.5% by mass of zinc and 1.0% by mass of cobalt as a coprecipitation component was added to an aqueous cobalt sulfate solution. While stirring the resulting mixture, an aqueous sodium hydroxide solution (sodium hydroxide concentration: 1 mol / L) was gradually added dropwise to adjust the pH to 11, followed by further stirring for a predetermined time. The precipitate was filtered off from the resulting mixture. The precipitate separated by filtration was washed with water and vacuum-dried to obtain a powder in which the surface of nickel hydroxide particles was coated with 5% by mass of cobalt hydroxide.
  • a positive electrode mixture slurry was prepared.
  • the mass ratio of the composite particles and zinc oxide in the mixed powder was 100: 2.
  • the obtained positive electrode mixture slurry was filled in pores of a nickel foam (surface density (unit weight) of about 325 g / m 2 , thickness of about 1.2 mm) as a positive electrode current collector and dried.
  • the dried product was rolled to a thickness of 0.66 mm to obtain a positive electrode (length 118 mm, width 44.7 mm, thickness 0.66 ⁇ m).
  • maintain an active material was provided in the one end part of the length direction of a positive electrode collector, and the positive electrode lead was connected to this exposed part.
  • the first separator (length 325 mm, width 46.7 mm, thickness 0.082 ⁇ m)
  • the electrode group was prepared by winding these in a spiral shape. At this time, winding was performed so that the main body portion of the negative electrode was the inner peripheral side, the thin portion was the outer peripheral side, and the outer end of the positive electrode was overlapped with the tapered portion of the negative electrode.
  • a second separator (length 10 mm, width 46.7 mm, thickness 0.082 ⁇ m) was disposed between the outer end of the positive electrode and the tapered portion, and between the tapered portion and the first separator. .
  • the second separator was arranged so that the end face on the outer peripheral side of the positive electrode came near the center in the length direction.
  • a sulfonated polypropylene nonwoven fabric (thickness 82 ⁇ m, basis weight 50 g / m 2 , and sulfonation degree 1.90 ⁇ 10 ⁇ 3 ) was used.
  • the number of turns of the negative electrode in the electrode group was 6.
  • the obtained electrode group was inserted into an AA bottomed cylindrical metal battery case (outer diameter 14.60 mm) having a ring-shaped groove on the opening side, and the outermost negative electrode (thin wall portion) was inserted.
  • the battery case was brought into contact with the inner surface.
  • the positive electrode lead connected to the positive electrode was welded to the inner bottom surface of the cover plate of the sealing body.
  • the sealing body is arranged so as to close the gas vent hole at the center of the top plate of the lid plate having a circular vent hole at the center, the insulating packing attached to the periphery of the lid plate, and the lid plate. And a cap-like positive electrode terminal having a protrusion that covers the valve body.
  • an alkaline electrolyte was poured into the battery case, the opening of the battery case was covered with a sealing body, and sealed by insulating caulking. The diameter was reduced by pressing the peripheral surface of the battery case from the outside. And the groove part formed in the opening part side of the battery case was crimped
  • an aqueous solution containing sodium hydroxide at a concentration of 7.5 mol / L was used as the alkaline electrolyte.
  • the donut-shaped insulating member was arranged on the upper part of the sealing body with the protruding portion of the positive electrode terminal protruding from the central hole of the insulating member.
  • an exterior label so as to cover the peripheral part of the sealing body (peripheral part of the insulating member disposed on the sealing body), the peripheral surface of the battery case, and the peripheral part of the bottom surface of the battery case.
  • a nickel metal hydride storage battery (A1) was obtained.
  • a total of 50 batteries A1 were produced in the same procedure.
  • the battery was charged at a current value of 1 It in a 40 ° C. environment until the state of charge (SOC) reached 120% of full charge, and the battery internal pressure at this time was measured.
  • SOC state of charge
  • the battery of Example 1 and Comparative Example described below were evaluated with the battery internal pressure of Example 1 being 100.
  • Example 2 The length L 2 of the taper portion of the negative electrode was changed from 12 mm to 6 mm. That is, the length of the taper portion is shorter than the length (10 mm) of the second separator. Except for these, 50 nickel-metal hydride storage batteries (A2) were produced and evaluated in the same manner as in Example 1.
  • Example 3 The 2nd separator was arrange
  • Comparative Example 1 The length L 1 of the main body part was changed to 120 mm, the length L 2 of the taper part was changed to 12 mm, and the length L 3 of the thin part was changed to 23 mm so that the outer end of the positive electrode overlaps the main body part of the negative electrode ( That is, the thickness of the negative electrode active material layer in each part was adjusted so that the lengths of the main body part and the thin-walled part would have such values).
  • the second separator was disposed between the outer end of the positive electrode and the main body of the negative electrode and between the main body and the first separator. Except these, it carried out similarly to Example 1, produced 50 nickel-metal hydride storage batteries (B1), and evaluated.
  • Comparative Example 2 The length L 1 of the main body is 88 mm and the length L 2 of the taper is 12 mm so that the outer end of the positive electrode overlaps with the thin part of the negative electrode (thin part facing the inner peripheral side of the outer end of the positive electrode).
  • the length L 3 of the thin portion was changed to 55 mm (that is, the thickness of the negative electrode active material layer in each portion was adjusted so that the lengths of the main body portion and the thin portion had such values).
  • the second separator was disposed between the outer end of the positive electrode and the thin portion of the negative electrode (thin portion facing the inner peripheral side of the outer end of the positive electrode) and between the thin portion and the first separator. Except these, it carried out similarly to Example 1, produced 50 nickel-metal hydride storage batteries (B2), and evaluated.
  • Table 1 shows the results of Examples and Comparative Examples.
  • the short-circuit test result is shown by the number of batteries in which a short circuit occurs in 50 batteries, and the battery internal pressure is shown as a ratio when the battery internal pressure of Example 1 is 100.
  • Examples 1 to 3 are A1 to A3, and Comparative Examples 1 and 2 are B1 and B2.
  • the cylindrical battery according to the present invention can be used for various batteries (primary battery, secondary battery) having a wound electrode group.
  • the cylindrical battery is particularly suitable for an alkaline storage battery such as a nickel hydride storage battery whose battery characteristics are easily affected by the N / P ratio.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Primary Cells (AREA)

Abstract

Cette batterie cylindrique est pourvue : d'un groupe d'électrodes obtenu par enroulement d'une électrode positive, d'une électrode négative, et d'un premier séparateur intercalé entre celles-ci, qui présentent tous une forme de ceinture ; d'un électrolyte ; d'un boîtier de batterie cylindrique à fond ; et d'une plaque d'étanchéité d'ouverture. L'électrode négative comporte un collecteur d'électrode négative et des couches de matière active d'électrode négative formées sur les deux surfaces du collecteur d'électrode négative. L'électrode négative présente une partie mince au niveau d'une zone à l'intérieur d'une longueur L3 à partir de l'extrémité extérieure de l'électrode négative ; une partie conique adjacente à la partie mince ; et une partie de corps autre que ces parties. L'épaisseur de la couche de matière active d'électrode négative sur le côté périphérique extérieur de la partie conique est progressivement réduite du côté partie de corps au côté partie mince. Le groupe d'électrodes est formé de telle sorte que l'extrémité extérieure de l'électrode positive recouvre la partie conique via le premier séparateur, et comprend en outre un second séparateur intercalé entre la partie conique et l'extrémité extérieure de l'électrode positive.
PCT/JP2016/004301 2015-11-27 2016-09-21 Batterie cylindrique WO2017090219A1 (fr)

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JP2015232240A JP2019016423A (ja) 2015-11-27 2015-11-27 円筒形電池
JP2015-232240 2015-11-27

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CN110007245A (zh) * 2019-03-19 2019-07-12 合肥国轩高科动力能源有限公司 一种三电极检测锂离子电池n/p比设计合理性的方法
CN113328064A (zh) * 2021-05-31 2021-08-31 珠海冠宇电池股份有限公司 一种负极片及电池
CN113328133A (zh) * 2021-05-31 2021-08-31 珠海冠宇电池股份有限公司 一种电池
US20220294025A1 (en) * 2021-03-10 2022-09-15 Fdk Corporation Electrode for alkaline secondary battery and alkaline secondary battery
WO2022198682A1 (fr) * 2021-03-26 2022-09-29 宁德时代新能源科技股份有限公司 Ensemble électrode, élément de batterie, batterie, et procédé et dispositif de fabrication d'ensemble électrode

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KR20210103745A (ko) * 2020-02-14 2021-08-24 삼성에스디아이 주식회사 전극 조립체 및 이를 포함하는 이차전지

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JPH09213361A (ja) * 1996-01-30 1997-08-15 Furukawa Battery Co Ltd:The 渦巻状極板群の製造方法
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Publication number Priority date Publication date Assignee Title
CN110007245A (zh) * 2019-03-19 2019-07-12 合肥国轩高科动力能源有限公司 一种三电极检测锂离子电池n/p比设计合理性的方法
CN110007245B (zh) * 2019-03-19 2021-08-06 合肥国轩高科动力能源有限公司 一种三电极检测锂离子电池n/p比设计合理性的方法
US20220294025A1 (en) * 2021-03-10 2022-09-15 Fdk Corporation Electrode for alkaline secondary battery and alkaline secondary battery
CN115084455A (zh) * 2021-03-10 2022-09-20 Fdk株式会社 碱性充电电池用电极和碱性充电电池
WO2022198682A1 (fr) * 2021-03-26 2022-09-29 宁德时代新能源科技股份有限公司 Ensemble électrode, élément de batterie, batterie, et procédé et dispositif de fabrication d'ensemble électrode
CN113328064A (zh) * 2021-05-31 2021-08-31 珠海冠宇电池股份有限公司 一种负极片及电池
CN113328133A (zh) * 2021-05-31 2021-08-31 珠海冠宇电池股份有限公司 一种电池

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