WO2015002181A1 - 非水電解液二次電池用電極、その製造方法及び非水電解液二次電池 - Google Patents
非水電解液二次電池用電極、その製造方法及び非水電解液二次電池 Download PDFInfo
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- WO2015002181A1 WO2015002181A1 PCT/JP2014/067505 JP2014067505W WO2015002181A1 WO 2015002181 A1 WO2015002181 A1 WO 2015002181A1 JP 2014067505 W JP2014067505 W JP 2014067505W WO 2015002181 A1 WO2015002181 A1 WO 2015002181A1
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- electrode
- secondary battery
- current collector
- electrolyte secondary
- collector foil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
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- 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
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- 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 an electrode for a non-aqueous electrolyte secondary battery used for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, a manufacturing method thereof, and a non-aqueous electrolyte secondary battery.
- a nonaqueous electrolyte secondary battery such as a lithium ion secondary battery is formed by laminating a positive electrode and a negative electrode via a separator, or by laminating and laminating.
- the nonaqueous electrolyte secondary battery usually has a separator, so that insulation between the positive electrode and the negative electrode is maintained. However, if the separator contracts for some reason, the position of the separator shifts, or if foreign matter is mixed inside the battery, contact the counter electrode at the end of the electrode, especially the active material uncoated part. May cause a short circuit. In order to prevent such a problem, an insulating layer is formed at the end of one of the electrodes.
- Patent Literature 1 discloses a secondary battery having an overcoat and having a positive electrode, a negative electrode, and a separator as basic components.
- the positive electrode and the negative electrode are obtained by applying an active material to a metal foil, and are stacked via a separator.
- the overcoat is a coating provided on the surface of at least a portion of the positive electrode where the active material is not applied.
- the overcoat electrically and thermally isolates the coated part from the separator, thereby preventing the separator from melting due to abnormal heat generation of the electrode.
- resin materials such as polyimide (registered trademark: Kapton), polyphenylene sulfide resin (PPS), and polypropylene (PolyPropylene; PP) are known.
- an insulating tape may be used in addition to the overcoat.
- an insulating layer is formed at the end of the electrode in order to prevent a short circuit that occurs inside the battery.
- the insulating layer formed for the purpose of preventing a short circuit is usually an overcoat or an insulating tape, and the thickness of the electrode in the portion where the insulating layer is provided increases. For this reason, there is a possibility that the insulating layer affects the external appearance of the battery cell, or the influence of the insulating layer is not limited to the external appearance, and the volume efficiency may be reduced when the battery pack is assembled using a plurality of battery cells. is there.
- the pressing of the portion where the thickness of the electrode is increased is strong, and the pressing of the portion that is not swollen is weak. As a result, the current flow inside the battery becomes non-uniform and an overvoltage occurs, so that deterioration of the constituent members of the battery is accelerated and the battery life may be shortened.
- an object of the present invention is to provide an electrode for a non-aqueous electrolyte secondary battery that can reduce the possibility of an internal short circuit and can make the thickness of the non-aqueous electrolyte secondary battery uniform.
- An electrode for a non-aqueous electrolyte secondary battery includes a current collector foil, an electrode composite layer formed on a part of the current collector foil, and at least an electrode composite layer formed on the current collector foil. And an oxide film provided in a region extending from the boundary between the part and the non-formed part to a part of the non-formed part.
- the method for manufacturing a non-aqueous electrolyte secondary battery according to the present invention is such that the length along the first direction is longer than the length along the second direction orthogonal to the first direction.
- the electrode mixture layer is applied in a stripe shape parallel to the first direction, and at least a part of the non-formed portion from the boundary between the formed portion and the non-formed portion of the electrode mixture layer on the current collector foil
- a third step of cutting the electrode to a desired size is provided.
- the non-aqueous electrolyte secondary battery according to the present invention has a battery element in which a positive electrode and a negative electrode are laminated via a separator, and a laminate exterior that houses and seals the battery element. At least one of the positive electrode and the negative electrode is the electrode for a nonaqueous electrolyte secondary battery of the present invention.
- the oxide film provided in the non-formation part of the electrode mixture layer at least partially overlaps the end region of the separator when viewed from the stacking direction of the positive electrode and the negative electrode.
- the present invention can reduce the possibility of an internal short circuit and make the thickness of the nonaqueous electrolyte secondary battery uniform.
- FIG. 1 is a diagram for explaining an example of a nonaqueous electrolyte secondary battery electrode 1 according to an embodiment of the present invention.
- FIG. 1A shows a plan view
- FIG. 1B shows a cross-sectional view taken along line AA ′ in FIG. 1A.
- 2A and 2B are diagrams of a lithium ion secondary battery having a stacked structure according to an embodiment of the present invention.
- FIG. 2C shows a cross-sectional view of a lithium ion secondary battery having a stacked structure according to an embodiment of the present invention.
- FIG. 3 shows a diagram of a lithium ion secondary battery having a wound structure in the first embodiment.
- a lithium ion secondary battery as a nonaqueous electrolyte secondary battery will be described as an example.
- the battery element 11 is formed by laminating the positive electrode 7 and the negative electrode 8 with a separator 9 interposed therebetween.
- this battery element 11 is housed in an aluminum laminate outer package 12 to produce a lithium ion secondary battery 13.
- a non-aqueous electrolyte is injected into the battery.
- a battery element of the lithium ion secondary battery in addition to the battery element 11 as described above, as shown in FIG. 3, a laminate in which a positive electrode 22 and a negative electrode 23 are sandwiched with a separator 24 interposed therebetween is wound in a spiral shape.
- a battery element 25 or a battery element obtained by forming a spiral wound body into a flat shape may be used.
- the lithium ion secondary battery 13 having a laminated structure will be mainly described, but the present invention is not limited to this.
- the electrode of the present embodiment is formed of a current collector foil 10, an electrode mixture layer 2 applied to the current collector foil 10, and a tab 21.
- the current collector foil 10 is a metal foil also called a current collector.
- the electrode mixture layer 2 is a mixture containing an active material, as will be described later.
- the active material plays a central role in the battery reaction, and is a substance that performs an oxidation / reduction reaction by sending and receiving electrons.
- a lithium transition metal oxide such as lithium cobaltate is used for the positive electrode, and carbon is used for the negative electrode.
- the tab 21 is a connection terminal for inputting and outputting power.
- the tab may be welded to one end of the current collector foil 10 or may function as a tab by extending one end of the current collector foil 10.
- nonaqueous electrolytic solution for example, an organic solvent such as ethylene carbonate or diethyl carbonate mixed with a lithium salt such as lithium hexafluorophosphate is used.
- the separator 9 functions to maintain insulation between the positive electrode 7 and the negative electrode 8.
- the separator 9 may have a characteristic called “shutdown characteristic”. “Shutdown characteristic” refers to the fuse function of the separator 9. That is, when a short-circuit or the like occurs and a large short-circuit current flows between the positive electrode 7 and the negative electrode 8 and the internal temperature of the battery rises, the separator 9 softens and melts, thereby closing the hole of the separator 9 Is done. Thereby, the permeability
- a film of polyolefin such as polypropylene or polyethylene is typically used as the separator 9.
- the electrode mixture layer 2 described above is formed by mixing an active material, a dispersant, a leveling agent, a conductive additive, and a binder.
- the dispersant is for preventing and dispersing the active material.
- the leveling agent brings the electrode mixture layer 2 into good contact with the electrolyte and maintains wettability.
- a conductive support agent is for improving the electroconductivity of an electrode compound-material layer.
- the binder is a binding material that binds solid particles to each other. The leveling agent and the conductive additive may not be mixed in the binder.
- the electrode 1 for a non-aqueous electrolyte secondary battery includes a current collector foil 10 and an electrode mixture layer 2 formed on a part of the current collector foil 10.
- the region on the current collector foil 10 includes a forming portion 3 where the electrode mixture layer 2 is formed and a non-forming portion 4 where the electrode mixture layer 2 is not formed.
- an oxide film 6 is provided at least in a region extending from the boundary 5 between the formation part 3 and the non-formation part 4 to a part of the non-formation part 4.
- the oxide film 6 is formed on the other electrode. It does not matter whether or not is formed.
- the oxide film 6 is formed only on one surface of both the positive electrode and the negative electrode, the oxide film 6 is provided on the same surface side of both electrodes. This is to prevent the surfaces of both electrodes that do not have the oxide film 6 from facing each other when the positive electrode and the negative electrode are laminated.
- a connection terminal (tab 21) for inputting / outputting electric power is formed at one end of the current collector foil 10 by extending the current collector foil 10.
- one side of the nonaqueous electrolyte secondary battery electrode 1 on which the tab 21 is provided is the opposite side (A of the broken line AA ′).
- the electrode mixture layer 2 is formed from the other end of the “side”.
- the electrode mixture layer 2 extends from the other end of the current collector foil 10 to the boundary 5, but does not extend to the region of the tab 21.
- the oxide film 6 extends from the region including the boundary 5 to a part of the region of the tab 21.
- the oxide film 6 in the first embodiment is formed by oxidizing only a part adjacent to the boundary 5, but may be formed by oxidizing the entire surface of the non-formed part 4. .
- a method of forming the oxide film 6 a method of forming by heating is used, and examples thereof include heating using IH (Induction Heating) (IH heating), heating using a heater, and heating using a laser.
- IH heating Induction Heating
- a method for forming the oxide film 6 there is a method of performing chemical treatment such as boehmite treatment.
- the formation method of the oxide film 6 is not limited to these.
- the oxide film 6 only needs to be formed to a thickness that reduces the conductivity compared to the portion where the oxide film 6 is not formed.
- the oxide film 6 was formed on the current collector foil 10 by heating the non-formation part 4 of the positive electrode as shown in FIG. 1 using a heater.
- the oxide film 6 was formed by heating to such an extent that the color of the surface of the current collector foil 10 changes.
- heat is also transmitted to a portion below the region (formation portion 3) where the electrode mixture layer 2 is applied.
- FIG. 1B an oxide film 6 is also formed on a part of the forming part 3 in the same manner as the non-forming part 4.
- FIG. 2A shows a battery element 11 formed by laminating the positive electrode 7 and the negative electrode 8 through the separator 9 using the positive electrode 7 shown in FIG.
- FIG. 2B shows a lithium ion secondary battery 13 produced by housing the battery element 11 in the aluminum laminate sheath 12.
- the insulating portion is only the oxide film 6 and the thickness of the positive electrode 7 hardly changes. Therefore, as shown in FIG. 2B, a lithium ion secondary battery 13 in which the appearance corresponding to the battery element 11 is smooth was obtained.
- the thickness of the battery cell formed by stacking a plurality of lithium ion secondary batteries 13 can be made uniform, so that the performance of the battery cell, the safety can be improved, and the volume efficiency (volume energy density) of the battery pack can be improved. Can be planned.
- a laminate exterior (exterior material formed by a metal laminate sheet in which a metal layer and a resin layer are laminated).
- the present invention is not limited to the laminate exterior, and a film-like exterior material made only of a resin material may be used.
- the oxide film 6 provided on the non-formed portion 4 at least partially overlaps the end region of the separator 9 when viewed from the electrode stacking direction.
- the oxide film 6 is formed on the non-forming portion 4 of the positive electrode 7 so as to partially overlap the end portion of the separator 9 in a cross section parallel to the electrode stacking direction.
- the oxide film 6 functions as an insulating protective film. Therefore, in the unlikely event, it is possible to prevent heat generation, smoke generation, and ignition due to a short circuit caused by contraction or displacement of the separator 9 and the entry of foreign matter into the battery. This is because even when the separator 9 as the insulating film is contracted or displaced, the oxide film 6 that at least partially overlaps the end region of the separator 9 has an effect of functioning as the insulating film. .
- a safety test was performed using the lithium ion battery cell 13 described above.
- An overcharge test was performed as a safety test item.
- the overcharge test since the thickness of the electrode is uniform and the battery elements 11 are uniformly laminated, the heat transfer during overcharging is uniform.
- the overcharge test in the present embodiment, the shutdown of the separator 9 proceeded uniformly, the current was reduced, and the test was completed without the battery cell 13 bursting or firing.
- the battery element 11 described above is formed by laminating the positive electrode 7 and the negative electrode 8 with the separator 9 interposed therebetween, but is not limited to the structure of the battery element 11. As shown in FIG. 3, even when a lithium ion secondary battery is manufactured using a battery element 25 formed by spirally winding a laminate of a positive electrode 22 and a negative electrode 23 with a separator 24 in between. The same effect can be obtained.
- a battery pack was assembled using ten lithium ion battery cells 13 of the first embodiment.
- a battery pack was configured by stacking and arranging ten battery cells 13.
- the surface of each battery cell 13 is smooth, the battery cells 13 could be stacked without any gap.
- the life evaluation of the battery pack of the second embodiment configured as described above was performed.
- the surface of each battery cell 13 is smooth, and each battery cell 13 is uniformly pressed.
- FIG. 4A and 4B are diagrams of a lithium-ion secondary battery having a stacked structure according to the first comparative embodiment.
- the insulating tape 14 was pasted on the non-formed portion 4 of the positive electrode 7.
- the insulating tape 14 was made of polypropylene as a main component.
- two insulating tapes 14 were attached to the front and back of the positive electrode for each positive electrode.
- a lithium ion secondary battery 15 was fabricated under the same conditions as in the first embodiment except that such a positive electrode was used.
- the insulating layer is made of the insulating tape 14, and even if the individual insulating tapes 14 are thin, the thickness of the insulating tape 14 is overlapped by twice the number of stacked positive electrodes.
- a bulge 16 is generated in the portion where the insulating tape 14 is applied, and the bulge 16 appears prominently when the surface of the lithium ion secondary battery 15 is viewed from the outside.
- a secondary battery 15 was constructed.
- a safety test was performed using the lithium ion battery cell 15 described above.
- An overcharge test was performed as a safety test item.
- the thickness of the electrodes is non-uniform and the battery elements are laminated non-uniformly, so that the heat transfer during overcharging is non-uniform.
- the overcharge test even when the separator 9 of a part of the battery was shut down, the current continued to flow because the separator 9 of the other part was not shut down. As a result, the first comparative form ignited.
- a battery pack was assembled using 10 lithium ion battery cells 15 of the first comparative embodiment.
- a battery pack was configured by stacking and arranging 10 battery cells 15.
- the portion of the surface of each battery cell 15 to which the insulating tape 14 is applied bulges, a gap is created between the battery cells 15 when the battery cells 15 are stacked, and the battery pack The overall thickness has also increased.
- the life evaluation of the battery pack of the second comparative embodiment configured as described above was performed. As a result of the life evaluation, the battery pack of the second comparative form has a reduced life compared to the second embodiment.
- the swollen portion is strongly pressed and the unswollen portion is weakly pressed. For this reason, in the second comparative embodiment, it is considered that the deterioration of the constituent members of the battery cell 15 was accelerated due to the influence of an overvoltage due to the non-uniform flow of the internal current of the battery.
- FIG. 5 is a perspective view of a lithium ion secondary battery according to the third embodiment.
- the second length along the first direction D1 is perpendicular to the first direction D1.
- the electrode mixture layer 2 was applied in a stripe shape parallel to the first direction D1 on a strip-shaped current collector foil much longer than the length along the direction D2 (stripe coating).
- the oxide film 19 was formed by IH heating the vicinity of the boundary part of the formation part 17 and the non-formation part 18.
- the oxide film 19 was formed at least in a region extending from the boundary between the formation part 17 and the non-formation part 18 to a part of the non-formation part 18.
- the oxide film 19 was formed by heating to such an extent that the aluminum foil was colored.
- An electrode roll as shown in FIG. 5 was formed by winding the current collector foil thus processed around an axis parallel to the second direction. Even if the oxide film 19 is formed, the thickness of the electrode hardly changes, so even when the winding operation is performed using a long current collecting foil of 4000 m or more, the roll shape of the electrode roll is not affected. The electrode roll was able to be manufactured efficiently. According to the third embodiment, when the current collector foil is wound, the electrode roll can be prevented from being partially raised, and the electrode roll can be made longer and the productivity can be improved.
- the electrode for a lithium ion secondary battery as shown in FIG. 1 is obtained by cutting an electrode having a size corresponding to a desired lithium ion secondary battery from an electrode roll as shown in FIG.
- FIG. 6 the perspective view of the electrode roll of the lithium ion secondary battery in the 3rd comparative form is shown.
- the third comparative embodiment in the manufacturing process of the positive electrode for a lithium ion secondary battery, after stripe coating is performed on the strip-shaped current collector foil, insulation is formed at the boundary between the formed portion 17 and the non-formed portion 18.
- Tape 20 was affixed. Although the individual insulating tapes 20 are thin, the thickness of the insulating tape 20 is integrated as the current collector foil is wound up in a roll shape. Therefore, as shown in FIG. When the current collector foil was further wound, the current collector foil was cut at the rising portion. For this reason, in the 3rd comparative form, it was difficult to wind up current collection foil 1000m or more.
- Electrode for nonaqueous electrolyte secondary batteries 2 Electrode compound layer 3 Forming part 4 Non-forming part 5 Boundary 6 Oxide film 7 Positive electrode 8 Negative electrode 9 Separator 10 Current collection foil 11 Battery element 12 Aluminum laminate exterior 13 Lithium ion secondary battery
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Abstract
Description
電極の端部に絶縁層を形成するためには、オーバーコートに加えて、絶縁テープが用いられることもある。
図1に、本発明の実施形態における非水電解液二次電池用電極1の一例を説明するための図を示す。図1Aに平面図を示し、図1Bに図1AにおけるA-A’線に沿って切断した断面図を示す。図2A及び図2Bに、本発明の実施形態における積層型構造のリチウムイオン二次電池の図を示す。図2Cに、本発明の実施形態における積層型構造のリチウムイオン二次電池の断面図を示す。図3に、第1の実施形態における捲回型構造のリチウムイオン二次電池の図を示す。
図1Aに示すように、集電箔10の一端には、電力を入出力するための接続端子(タブ21)が、集電箔10を延ばして形成されている。集電箔10上には、非水電解液二次電池用電極1のうちタブ21が設けられた一端側(破線A-A’のA側)とは逆側(破線A-A’のA’側)の他端から電極合材層2が形成されている。電極合材層2は、集電箔10の他端から境界5まで延ばされているが、タブ21の領域まで延ばされていない。一方、酸化皮膜6は、境界5を含む領域から、タブ21の領域の一部まで延びている。
第1の実施形態のリチウムイオン電池セル13を10個用いて、電池パックを組み立てた。10個の電池セル13を積み重ねて配置することで電池パックを構成した。第2の実施形態は、それぞれの電池セル13の表面が平滑であるので、電池セル13を隙間なく積み重ねることができた。このように構成された第2の実施形態の電池パックの寿命評価を行った。第2の実施形態は、それぞれの電池セル13の表面が平滑であり、各電池セル13が均一に押さえられているので、良好な寿命性能を示した。
図4A及び図4Bに、第1の比較形態における積層型構造のリチウムイオン二次電池の図を示す。積層型のリチウムイオン二次電池を作製するにあたって、図4Bに示すように、正極7の非形成部4の上に絶縁テープ14を貼り付けた。絶縁テープ14は、ポリプロピレンを主成分として形成されたものを用いた。絶縁テープ14に関し、1枚の正極あたり、2枚の絶縁テープ14を正極の表裏にそれぞれ貼り付けた。このような正極を使用することを除いて、第1の実施形態と同一条件でリチウムイオン二次電池15を作製した。このようにして得られた電池は、絶縁層が絶縁テープ14からなり、個々の絶縁テープ14が薄くても、正極の積層数の2倍分だけ絶縁テープ14の厚みが重なることになる。その結果、図4Bに示すように、絶縁テープ14を貼り付けた部分に膨らみ16が生じ、リチウムイオン二次電池15の表面を外側から見たときに、その膨らみ16が顕著に現れたリチウムイオン二次電池15が構成された。
第2の比較形態では、第1の比較形態のリチウムイオン電池セル15を10個用いて、電池パックを組み立てた。10個の電池セル15を積み重ねて配置することで電池パックを構成した。第2の比較形態は、それぞれの電池セル15の表面の、絶縁テープ14を貼った部分が膨出しているので、電池セル15を積み重ねたときに電池セル15の間に隙間が生じ、電池パック全体の厚みも厚くなった。このように構成された第2の比較形態の電池パックの寿命評価を行った。寿命評価の結果、第2の比較形態の電池パックは、第2の実施形態に比べて寿命が低下した。第2の比較形態では、電池セル15の、絶縁テープ14を貼った部分が膨らんでいるので、膨らんだ部分の押さえが強く、膨らんでいない部分の押さえが弱くなる。このため、第2の比較形態は、電池の内部電流の流れが不均一となって過電圧がかかるなどの影響により、電池セル15の構成部材の劣化が早められたものと考えられる。
図5に、第3の実施形態におけるリチウムイオン二次電池の斜視図を示す。第3の実施形態では、リチウムイオン二次電池用の正極の製造工程にて、図5に示すように、第1の方向D1に沿った長さが第1の方向D1に直交する第2の方向D2に沿った長さよりもはるかに長い帯状の集電箔上に、電極合材層2を第1の方向D1に平行なストライプ状に塗布した(ストライプ塗工)。ストライプ塗工後に、形成部17と非形成部18との境界部分の近傍をIH加熱することによって酸化皮膜19を形成した。このとき、酸化皮膜19は、少なくとも形成部17と非形成部18との間の境界から非形成部18の一部にわたる領域に形成した。酸化皮膜19は、アルミニウム箔に色が付く程度に加熱して形成した。
このように加工された集電箔を第2の方向に平行な軸回りに巻き付けることで、図5に示すような電極ロールを形成した。酸化皮膜19が形成されても電極の厚みはほとんど変わらないので、4000m以上の長尺の集電箔を用いて巻き付け作業を行った場合であっても、電極ロールのロール形状に影響がなく、電極ロールを効率良く製造することができた。第3の実施形態によれば、集電箔の巻き付け時に、電極ロールの部分的な盛り上がりが生じることを防止でき、電極ロールの長尺化、生産性の向上を図ることが可能となる。
図6に、第3の比較形態におけるリチウムイオン二次電池の電極ロールの斜視図を示す。第3の比較形態では、リチウムイオン二次電池用の正極の製造工程にて、帯状の集電箔上にストライプ塗工を行った後、形成部17と非形成部18との境界部分に絶縁テープ20を貼付した。個々の絶縁テープ20は薄いが、集電箔をロール状に巻き取ってゆくに従って絶縁テープ20の厚みが積算されるので、図6に示すように、絶縁テープ20を貼った部分が盛り上がった。集電箔を更に巻き続けたときに、盛り上がり部分で集電箔に切れ目が生じた。このため、第3の比較形態では、集電箔を1000m以上巻き取ることが困難であった。
この出願は、2013年 7月 1日に出願された日本出願特願2013-138358を基礎とする優先権を主張し、その開示の全てをここに取り込む。
2 電極合材層
3 形成部
4 非形成部
5 境界
6 酸化皮膜
7 正極
8 負極
9 セパレータ
10 集電箔
11 電池要素
12 アルミニウムラミネート外装
13 リチウムイオン二次電池
Claims (6)
- 集電箔と、
前記集電箔上の一部に形成された電極合材層と、
前記集電箔上における、少なくとも前記電極合材層の形成部と非形成部との間の境界から前記非形成部の一部にわたる領域に設けられた酸化皮膜と、
を有する、非水電解液二次電池用電極。 - 前記酸化皮膜は、前記集電箔の表面を酸化させてなる、請求項1に記載の非水電解液二次電池用電極。
- 第1の方向に沿った長さが前記第1の方向に直交する第2の方向に沿った長さよりも長い集電箔上に、電極合材層を前記第1の方向に平行なストライプ状に塗布し、前記集電箔上における、少なくとも前記電極合材層の形成部と非形成部との間の境界から前記非形成部の一部にわたる領域に、酸化皮膜を設ける第1の工程と、
前記第1の工程後、前記第2の方向に平行な軸回りに前記集電箔を巻き付けて電極ロールを形成する第2の工程と、
前記電極ロールから所望の大きさに電極を切り取る第3の工程と、
を有する、非水電解液二次電池用電極の製造方法。 - 前記第1の工程では、前記酸化皮膜を、前記集電箔の表面を酸化させることによって形成する、請求項3に記載の非水電解液二次電池用電極の製造方法。
- 正極と負極とをセパレータを介して積層してなる電池要素と、前記電池要素を収容して封止する前記ラミネート外装と、を有し、
前記正極及び前記負極の少なくとも一方が、請求項1または2に記載の非水電解液二次電池用電極であり、
前記電極合材層の前記非形成部に設けられた前記酸化皮膜は、前記正極及び負極の積層方向から見たときに前記セパレータの端部領域と少なくとも部分的に重なっている、非水電解液二次電池。 - 前記電池要素は、渦巻き状に巻回された状態で前記ラミネート外装に収容されている、請求項5に記載の非水電解液二次電池。
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