WO2007097172A1 - 角形扁平二次電池の製造方法 - Google Patents
角形扁平二次電池の製造方法 Download PDFInfo
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- WO2007097172A1 WO2007097172A1 PCT/JP2007/051702 JP2007051702W WO2007097172A1 WO 2007097172 A1 WO2007097172 A1 WO 2007097172A1 JP 2007051702 W JP2007051702 W JP 2007051702W WO 2007097172 A1 WO2007097172 A1 WO 2007097172A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode group
- secondary battery
- rectangular flat
- core member
- plate
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 238000004804 winding Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 abstract description 3
- 239000011162 core material Substances 0.000 description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000011149 active material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 nickel metal hydride Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012404 LiSnO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910005790 SnSiO Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- H01M10/0436—Small-sized flat cells or batteries for portable equipment
-
- 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
-
- 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
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0468—Compression means for stacks of electrodes and separators
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—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
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M50/147—Lids or covers
-
- 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/4911—Electric battery cell making including sealing
Definitions
- the present invention relates to a method for producing a high-capacity rectangular flat secondary battery excellent in stability of battery characteristics.
- Non-aqueous electrolyte secondary batteries such as nickel cadmium batteries, nickel metal hydride batteries, or sealed small lead-acid batteries have begun to be used as power sources for driving these electronic devices as electronic devices become smaller and lighter.
- a nonaqueous electrolyte secondary battery in order to realize high-efficiency charging / discharging, it is common to form an electrode group by winding a positive electrode plate and a negative electrode plate through a separator.
- the shape of the secondary battery is also flattened from the viewpoint of effective use of the space of the electronic device, and the outer can is made of a lightweight alloy such as aluminum. Is used.
- Patent Document 1 proposes a technique for forming a recess on the long side surface of an outer can. That is, by forming a recess on the long side surface of the outer can, the internal pressure applied to the long side surface is made uniform, thereby preventing the long side surface of the outer can from being swollen.
- the swelling of the electrode group caused by repeating the charge / discharge cycle of the battery causes another problem of increasing the internal resistance of the battery. This is because a gap (core hole) after the core is removed remains at the center of the wound electrode group, and due to swelling of the electrode group, a part of the electrode plate is inserted into the core hole. As a result, the distance between the electrode plates has increased. It is thought to be the cause.
- Patent Document 2 proposes a method of inserting an elastic body into the core hole after the core is extracted.
- the elastic body inserted into the core hole exerts a pressure on the electrode group, thereby preventing the electrode group from being squeezed into the core hole, thereby preventing an increase in internal resistance. It is what.
- the member inserted into the core hole is an elastic body, it exerts an action of absorbing the swelling of the electrode group, so that the outer can can be prevented from being swollen together.
- Patent Document 1 Japanese Patent Laid-Open No. 2002-042741
- Patent Document 2 Japanese Patent Laid-Open No. 08-055637
- the method of inserting an elastic body into the core hole described in Patent Document 2 inserts an elastic body that is superior in terms of preventing an increase in internal resistance due to stagnation of the electrode plate. Even so, in the rectangular flat battery, the internal resistance may increase or the dispersion of the internal resistance may increase. In particular, when a compound such as Si or Sn (for example, SiO, TiSi, etc.) is used as the active material of the negative electrode, the problem may be noticeable.
- Si or Sn for example, SiO, TiSi, etc.
- Active materials that also have compound power such as Si have a larger theoretical capacity than carbon materials such as graphite, and are therefore suitable for high-capacity batteries.
- these active materials are charged and discharged.
- the expansion and contraction of the volume accompanying this is large. Therefore, the increase or variation in the above-mentioned internal resistance is expected to cause the problem of electrode plate stagnation again as a result of the degree of swelling of the electrode group.
- the present invention has been made in view of an energetic problem, and its main object is to provide a method for manufacturing a high-capacity rectangular flat secondary battery in which an increase in the internal resistance of the battery is suppressed. .
- the inventors of the present application have focused on the process of assembling a rectangular flat battery as a cause of an increase in internal resistance and variations despite insertion of an elastic body into the core hole of the electrode group. .
- a positive electrode plate and a negative electrode plate are wound around a separator to form a circular or oval electrode group, and then the electrode group is compressed to be deformed into a flat electrode group. After that, the electrode group deformed into a flat shape is accommodated in a rectangular flat-shaped bottomed outer can. Assembled. If the spiral state of the electrode group is not uniform due to variations in the winding pressure in the winding process, the compression pressure applied to each part of the electrode group may vary in the next compression pressure process. . In this case, excessive compression pressure is locally applied to the electrode group, which may cause stagnation in the electrode group at the site where the force is applied.
- electrode stagnation during the charge / discharge When electrode plate stagnation (hereinafter referred to as “initial electrode plate stagnation”) due to compression of the electrode group occurs, the initial electrode plate stagnation starts when charging / discharging the battery. Therefore, it is considered that the sag of the electrode plate is promoted and the internal resistance increases or varies due to this. In such a situation, it is considered that the conventional means for inserting the elastic body into the core hole cannot suppress the stagnation of the electrode plate. However, the increase in internal resistance due to the sag of the conventional electrode plate or the variation did not take into account the initial sag of the electrode plate at all.
- the inventors of the present application consider that it is indispensable to prevent the occurrence of initial electrode plate stagnation in order to reduce the increase or variation in internal resistance.
- the electrode group is compressed in a state where the core member that applies pressure (force acting in the direction of expanding the core hole) to the electrode group is inserted into the core hole of the electrode group, A method of forming a flat electrode group was adopted.
- the method for manufacturing a rectangular flat secondary battery according to the present invention includes a step (a) of forming a circular or oval electrode group by winding a positive electrode plate and a negative electrode plate through a separator.
- the core member that applies pressure to the electrode group is inserted into the core hole of the electrode group. It is possible to prevent initial electrode plate stagnation that sometimes occurs, thereby suppressing increase in internal resistance due to repeated charge / discharge cycles or variations. [0017] The above-described effect is particularly prominent in a rectangular flat secondary battery in which the negative electrode active material formed on the negative electrode plate has a compound power containing at least one of S and Sn. .
- the core member is composed of a plate-like elastic body having a Young's modulus of 2.0 X 10 _3 GPa or more. It is preferable that
- the electrode group is compressed and deformed into a flat shape in a state where the core member that applies pressure to the electrode group is inserted into the core hole of the electrode group. It is possible to prevent initial electrode plate stagnation that occurs during compression, thereby realizing a high-capacity rectangular flat secondary battery that suppresses an increase in the internal resistance of the battery.
- FIG. 1 (A) is a schematic diagram showing the configuration of an electrode group in an embodiment of the present invention
- (B) is a configuration of a rectangular flat secondary battery in which the electrode group is inserted into an outer can.
- the schematic diagram shown, (C), is a cross-sectional view along aa in (B).
- FIG. 2 is a cross-sectional view showing an example of a configuration of a core member in the present embodiment.
- FIG. 3 is a schematic view showing another example of the configuration of the core member in the present embodiment.
- FIG. 4 is a table showing the evaluation results of internal resistance in Examples of the present invention.
- FIG. 1 (A) is a schematic diagram showing the electrode group 3 deformed into a flat shape in the present embodiment, and Fig. 1 (B) shows the electrode group 3 shown in Fig. 1 (A) as an outer can.
- FIG. 1 (C) is a cross-sectional view taken along line aa in FIG. 1 (B).
- the rectangular flat secondary battery is manufactured by the following process. First, a positive electrode plate and a negative electrode plate are wound through a separator to form a circular or oval electrode group 3. Next, the core member 2 that applies pressure to the electrode group 3 is inserted into the core hole 6 of the electrode group 3. Thereafter, the electrode group 3 is compressed to deform the electrode group 3 into a flat shape. Then, the flat electrode group 3 is accommodated in the rectangular flat bottomed outer can 4, and finally, the opening of the outer can 4 is sealed to complete the rectangular flat secondary battery.
- the positive electrode plate 3 and the negative electrode lead 3b are connected to the positive electrode plate and the negative electrode plate of the electrode group 3, and either the positive electrode lead 3a or the negative electrode lead 3b is connected.
- One of them is joined to the terminal 5 of the outer can 4 as shown in FIG. 1 (B), and the other is joined to the outer can 4.
- an electrolytic solution is injected from the injection hole la, and then the opening of the outer can 4 is sealed by the sealing plate 1.
- the method for manufacturing a rectangular flat secondary battery in the present embodiment when the formed electrode group 3 wound in a circular shape or an oval shape is compressed and deformed into a flat shape, the electrode group 3 Since the core member 2 that applies pressure to the electrode group 3 is inserted into the core hole 6, the initial electrode plate stagnation that occurs during compression can be prevented. As a result, increase in internal resistance due to repeated charge / discharge cycles or variations can be effectively suppressed.
- the negative electrode active material formed on the negative electrode plate is composed of a compound containing S or at least one of Sn, and the volume expansion and contraction due to charge / discharge is large, Internal prevention of electrode plate stagnation during charge / discharge because it prevents the occurrence of initial plate stagnation The effect of the present invention that suppresses an increase or variation in resistance can be exhibited more remarkably.
- Si-containing materials Si, SiOx (0. 05 ⁇ ⁇ 1.95), or any of these forces include B, Mg, Ni, Ti, Mo, Co, Ca, Cr Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N, an alloy or a compound in which a part of Si is substituted with an element, or a solid solution can be used.
- Sn Ni Sn, Mg Sn, SnO (0 ⁇ x ⁇ 2),
- SnO, SnSiO, LiSnO, etc. can be used.
- the core member 2 inserted into the core hole 6 of the electrode group 3 is 2.0 X 10 _3 GPa It is preferable to be made of a plate-like elastic body having the above Young's modulus.
- the shape, material, and the like of the core member 2 to be inserted into the core hole 6 of the electrode group 3 can be appropriately selected as long as the operational effects of the present invention are not particularly limited.
- the core member 2 having the following shape or material the effects of the present invention can be suitably exhibited.
- a plate-like elastic body that absorbs an electrolyte solution and swells for example, polyvinylidene fluoride (PVDF), styrene butadiene copolymer (SBR), acrylonitrile butadiene styrene copolymer, etc.)
- PVDF polyvinylidene fluoride
- SBR styrene butadiene copolymer
- acrylonitrile butadiene styrene copolymer etc.
- a plate-like elastic body may be formed into a wedge shape! If the core member 2 has such a wedge shape, it can be easily inserted into the core hole 6.
- the length of the wedge-shaped straight portion L (acting in the direction of expanding the core hole 6 of the relevant part force electrode group 3) is the total length of the core member 2 (of the core hole 6). (Axial direction) is preferably 50% or more.
- the Young's modulus of the elastic body preferably does not exceed 210 GPa. If the Young's modulus exceeds 210 GPa, the action of absorbing the swelling of the electrode group is not exerted, so that the outer can may swell, which is not preferable.
- the core member 2 not having a plate shape for example, as shown in FIG. 1 (C)
- the core member 2 may be formed of an elastic body formed in a C shape.
- the core member 2 may be formed of a member provided with a spring 2 a that applies pressure to the electrode group 3. Since these core members 2 also act in the direction in which the core holes 6 of the electrode group 3 are widened, the effects of the present invention can be exhibited.
- the width of the core member 2 is preferably 80% or more with respect to the width of the core hole 6 of the electrode group 3 in the flat direction.
- a positive electrode mixture consisting of lithium cobaltate as an active material, PVDF as a binder, and acetylene black as a conductive agent is applied and dried on an aluminum foil as a current collector. Cut to 5 mm width to obtain a hoop of the positive electrode plate.
- a negative electrode mixture consisting of artificial graphite as an active material, SBR as a binder, and carboxymethyl cellulose as a thickener is applied and dried on a copper foil as a current collector. Cut to a width of 6 mm to obtain a hoop of the negative electrode plate.
- LiPF 1M LiPF was dissolved in a non-aqueous mixed solvent (volume ratio 3: 5: 2) consisting of ethylene carbonate, ethylmethyl carbonate, and jetinole carbonate to prepare an electrolyte solution.
- a non-aqueous mixed solvent volume ratio 3: 5: 2 consisting of ethylene carbonate, ethylmethyl carbonate, and jetinole carbonate to prepare an electrolyte solution.
- the positive electrode plate hoop and the negative electrode plate hoop were each cut to a predetermined length to obtain a positive electrode plate and a negative electrode plate.
- the electrode layer mixture layer is partially peeled to connect the positive electrode lead 3a and the negative electrode lead 3b, and a separator made of a polyethylene resin microporous membrane sheet having a thickness of 20 m between the positive electrode plate and the negative electrode plate.
- a separator made of a polyethylene resin microporous membrane sheet having a thickness of 20 m between the positive electrode plate and the negative electrode plate.
- an ellipsoidal spiral electrode group 3 (theoretical capacity) with a length of 33.5 mm, a width of 32.7 mm, and a thickness of 4.25 mm as shown in Fig. 1 (a). 700 mAh) was formed.
- a 0.1 mm thick panel steel (SUP) is formed into a substantially C-shaped core member 2 (length 30 mm, width 26.4 mm, thickness 0. 3mm, Young's modulus 210GPa) was inserted, and the structure shown in Fig. 1 (C) was obtained.
- the electrode group 3 is compressed and accommodated in an aluminum case 4 having a length of 34.6 mm, a width of 33. lmm, and a thickness of 4.6 mm, and the case 4 and the sealing plate 1 are welded by laser.
- 1.9 g of electrolyte solution was injected from the injection hole la of the sealing plate 1, and the injection hole was sealed, and a rectangular lithium ion secondary as shown in FIG. The battery was completed.
- the electrode leads 5a and 5b were welded to the sealing plate 1 and the terminal 5, respectively, before laser sealing.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the core member 2 was polypropylene (Young's modulus: 4.5 GPa).
- the material of the core member 2 is PVDF (Young's modulus: 2. OX 10-3GPa), and the dimensions (length 30mm, width 26.4mm, thickness 0.3mm) are the same and have the same shape.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except that the plate shape was used.
- a lithium ion secondary battery was fabricated in the same manner as in Example 1 except that the size of the core member 2 was not changed and the structure using the spring 2a as shown in FIG.
- Example 3 Compared to Example 3, the maximum dimension of the core member 2 is not changed, and the structure shown in FIG. 3 (the wedge portion has a diameter of 22.7 mm and a thickness of 0.1 mm) is the same as Example 1. Similarly, a lithium ion secondary battery was fabricated.
- a lithium ion secondary battery was prepared in the same manner as in Example 1 except that SiO coated with carbon fiber was used as the negative electrode active material and polyacrylic acid was used as the binder for the negative electrode plate.
- Example 1 TiSi was used as the negative electrode active material, and the binder for the negative electrode plate was made of polyacrylic acid.
- a lithium ion secondary battery was produced in the same manner as in Example 1 except for the above.
- a lithium ion secondary battery was fabricated in the same manner as in Example 1, except that the core member 2 was not inserted into the first example.
- a lithium ion secondary battery was produced in the same manner as in Example 1, except that a bag having a laminated resin film strength was used instead of the outer can 4 and heat sealed by sealing.
- Lithium ion secondary batteries were produced in the same manner as in Examples 7 and 8, except that the core member 2 was not inserted into Examples 7 and 8.
- each example of the present invention resulted in suppression of an increase in battery internal resistance as compared with Comparative Examples 1, 3, and 4 that did not include the core member 2.
- Examples 7 and 8 in which an active material containing at least one of Si and Sn as an element was used for the negative electrode plate, the difference in resistance value was remarkable with Comparative Examples 3 and 4 that did not include the core member 2. It turns out that the implementation effect of invention is high.
- Example 3 in which PVDF having a low Young's modulus was used for the core member 2, the internal resistance of the battery was slightly increased due to a decrease in the effect of the present invention.
- PVDF is a material that swells in the electrolyte solution, and the increase in the internal resistance of the battery is thought to have been significant due to the action of expanding the core hole of the electrode group 3 due to the swelling.
- the structure of the core member 2 is a wedge shape that acts in the direction in which the core hole of the electrode group 3 is widened. As a result, the secondary effect was confirmed.
- Example 1 having a Young's modulus of 210 GPa is A slight deformation was seen in the outer can 4 after the electric cycle. The reason for this is that if the tang ratio of the core member 2 is large, it is difficult to deform it to absorb electrode plate stagnation.
- the present invention has been described with reference to the preferred embodiments, but such description is not a limitation, and various modifications can be made.
- the same effect can be obtained even when the present invention is applied to other nonaqueous electrolyte secondary batteries such as the power nickel hydride storage battery described with the lithiumion secondary battery as an example.
- the “square flat secondary battery” in the present invention refers to a battery formed by storing a wound electrode group that has been deformed into a flat shape by compression in an outer can. It is not defined by the shape itself. Industrial applicability
- the present invention is useful for a high-capacity rectangular flat secondary battery that suppresses an increase in the internal resistance of the battery.
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Abstract
Description
Claims
Priority Applications (2)
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JP2007539385A JPWO2007097172A1 (ja) | 2006-02-21 | 2007-02-01 | 角形扁平二次電池の製造方法 |
US11/919,505 US8129048B2 (en) | 2006-02-21 | 2007-02-01 | Method for producing rectangular flat secondary battery |
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JP2006-043367 | 2006-02-21 | ||
JP2006043367 | 2006-02-21 |
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US (1) | US8129048B2 (ja) |
JP (1) | JPWO2007097172A1 (ja) |
KR (1) | KR20080095166A (ja) |
CN (1) | CN101356685A (ja) |
WO (1) | WO2007097172A1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
US8129048B2 (en) | 2012-03-06 |
US20090077794A1 (en) | 2009-03-26 |
CN101356685A (zh) | 2009-01-28 |
KR20080095166A (ko) | 2008-10-28 |
JPWO2007097172A1 (ja) | 2009-07-09 |
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