Patent Publication Number: US-2021194043-A1

Title: Lithium ion secondary battery and method for producing same

Description:
TECHNICAL FIELD 
     The present invention relates to a lithium ion secondary battery and a method for producing the same. 
     BACKGROUND ART 
     A secondary battery used for, for example, in-vehicle use includes a lithium ion secondary battery produced by interposing a film-shaped separator between a positive electrode and a negative electrode and laminating or winding them. The positive electrode and the negative electrode are manufactured by applying mixture layers on both surfaces of electrode foils and performing drying and pressing. The separator is a porous film and manufactured by extending a sheet-shaped resin. The positive electrode and the negative electrode have roles of charge and discharge, and the separator has a role of electrically insulating the positive electrode from the negative electrode. 
     As described above, since the separator is the porous film made of resin, when an internal short-circuit occurs due to a foreign matter, nailing from outside, and the like, heat is generated to melt the separator, and a spread of a region where the internal short-circuit occurs further generates heat, thus being not preferable. 
     Therefore, there has been a proposed formation of an insulating layer made of inorganic filler on a mixture layer of a positive electrode or a negative electrode to avoid an increase in region where internal short-circuit occurs even when the separator thus melts and disappears (Patent Literature 1). The insulating layer is made of inorganic filler and therefore does not melt through heat generation. Even when the heat generation melts the separator, the insulating layer can avoid the increase in region where the internal short-circuit occurs in the positive and negative electrodes. 
     CITATION LIST 
     Patent Literature 
     Patent Literature 1: Japanese Patent No. 5112853 
     SUMMARY OF INVENTION 
     Technical Problem 
     An insulating layer formed on a mixture layer obstructs a passage through which an electrolyte moves to the mixture layer (liquid permeability is decreased). While a battery responsiveness is determined by a Li-ion amount in the electrolyte entering and exiting an active material of the positive electrode or the negative electrode, the decreased liquid permeability of the electrolyte as described above decreases a replaceability (replacement of the electrolyte after reaction with the electrolyte before reaction) of the electrolyte in the proximity of the active material of the positive electrode or the negative electrode. Thus, the Li-ion concentration is not kept constant to decrease the amount of entering and exiting of the Li-ion. As a result, there is a problem in that the battery responsiveness is deteriorated, a resistance indicating battery performance increases, and an output decreases. 
     Therefore, it is an object of the present invention to provide a lithium ion secondary battery that ensures a replaceability of an electrolyte in the proximity of an active material and is excellent in output and responsiveness, and a method for manufacturing the same. 
     Solution to Problem 
     The inventor found that the above-described problem was solved by providing holes (puddles) in an interface between an insulating layer and a mixture layer in a lithium ion secondary battery that included the insulating layer on the mixture layer. Thus, the inventor completed the invention. That is, the lithium ion secondary battery of the present invention comprises an electrode that includes an electrode foil, a mixture layer disposed on a surface of the electrode foil, and an insulating layer disposed on a surface of the mixture layer. The insulating layer contains ceramic particles. On the surface of the mixture layer facing a border between the insulating layer and the mixture layer, a plurality of holes having diameters of 2.5 μm or more are provided. 
     The description encompasses a content disclosed in Japanese Patent Application No. 2018-116217 forming a basis for priority of this application. 
     Advantageous Effects of Invention 
     According to the present invention, even when the insulating layer is formed on the mixture layer, the holes (puddles) provided in the surface of the mixture layer play a role of a buffer that stores the fresh (before reaction) electrolyte, thereby ensuring keeping the Li-ion concentration of the electrolyte in the proximity of the active material constant. Consequently, the lithium ion secondary battery excellent in output and responsiveness can be provided. Problems, configurations, and effects other than ones described above will be clarified in the following explanation of embodiments. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is an external perspective view of a square secondary battery according to one embodiment of the present invention. 
         FIG. 2  is an exploded perspective view of the square secondary battery. 
         FIG. 3  is a developed perspective view of a wound group housed in a battery can of the square secondary battery. 
         FIG. 4  is a cross-sectional view in a short width direction of the wound group. 
         FIG. 5  is a cross-sectional view of a proximity of a surface of a negative electrode mixture layer. 
         FIG. 6  is a drawing illustrating a manufacturing process of the negative electrode. 
         FIG. 7  is a drawing illustrating an applying and drying step of a negative electrode mixture layer slurry and an insulating layer slurry. 
         FIG. 8  is a drawing for describing a drying behavior after applying the negative electrode mixture layer slurry and the insulating layer slurry. 
         FIG. 9  is an enlarged view of a die head and back roller portion in  FIG. 7 . 
         FIG. 10  is a developed drawing of the die head. 
         FIG. 11  is a scanning electron microscope (SEM) image of a cross-sectional surface of the negative electrode mixture layer and the insulating layer formed in accordance with the manufacturing method according to the embodiment. 
         FIG. 12  is a scanning electron microscope (SEM) image of a cross-sectional surface of a negative electrode mixture layer and an insulating layer formed in accordance with a method other than the manufacturing method according to the embodiment. 
     
    
    
     DESCRIPTION OF EMBODIMENTS 
     The following describes an embodiment of a lithium ion secondary battery according to the present invention with reference to the drawings. 
       FIG. 1  is an external perspective view of a square secondary battery  100  as one embodiment of the lithium ion secondary battery according to the present invention, and  FIG. 2  is an exploded perspective view illustrating a configuration of the square secondary battery  100 .  FIG. 3  is a developed perspective view of a wound group  3  housed in a battery can  1  of the square secondary battery  100 . While a case where a mixture layer and an insulating layer are disposed on a negative electrode foil as an electrode foil will be described in this embodiment, it should not be construed in a limiting sense. The mixture layer and the insulating layer may be disposed on a positive electrode foil, or the mixture layer and the insulating layer may be each disposed on both the negative electrode foil and the positive electrode foil. 
     As illustrated in  FIG. 1 , the square secondary battery  100  includes a battery container that includes the battery can  1  and a battery lid  6 . A material of the battery can  1  and the battery lid  6  is aluminum, an aluminum alloy, or the like. In this embodiment, a deep drawing is performed to form the battery can  1  in a flat rectangular box shape having open one end. The battery can  1  includes a bottom surface  1   d  having a rectangular flat plate shape, a pair of wide-width side surfaces  1   b  disposed on a pair of respective long side portions of the bottom surface  1   d , and a pair of narrow-width side surfaces  1   c  disposed on a pair of respective short side portions of the bottom surface  1   d.    
     The battery lid  6  has a rectangular flat plate shape and is laser-welded so as to cover the opening of the battery can  1 . That is, the battery lid  6  seals the opening of the battery can  1 . In the battery lid  6 , a positive electrode external terminal  14  and a negative electrode external terminal  12  electrically connected to a positive electrode  34  and a negative electrode  32  (see  FIG. 3 ) of the wound group  3  are disposed. Note that a positive electrode side external insulator  24  and a negative electrode side external insulator  22  to avoid short circuit are disposed between the positive electrode external terminal  14  and the battery lid  6  and between the negative electrode external terminal  12  and the battery lid  6 , respectively. 
     A flat plate-shaped busbar welding portion  142  and a flat plate-shaped busbar welding portion  152  are disposed on the positive electrode external terminal  14  and the negative electrode external terminal  12 , respectively. When a battery pack is manufactured, by bringing busbars into abutment with the busbar welding portions  142  and  152  and performing welding, the busbar is connected to the positive electrode external terminal  14  and the busbar is connected to the negative electrode external terminal  12 . 
     The battery lid  6  includes a gas discharge valve  10 . The gas discharge valve  10  is formed by partially thinning the battery lid  6  through presswork. Note that a thin-walled member may be attached to the opening of the battery lid  6  by laser welding or the like to configure the thin-walled portion as a gas discharge valve. When the square secondary battery  100  generates heat due to abnormality, such as overcharge, to generate a gas and a pressure inside the battery container increases to reach a predetermined pressure, the gas discharge valve  10  ruptures and discharges the gas from the inside to reduce the pressure inside the battery container. 
     As illustrated in  FIG. 2 , the battery can  1  houses the wound group  3  (see  FIG. 3 ) held to a lid assembly  107 . The battery can  1  houses a positive electrode current collector  180  joined to the positive electrode  34  (see  FIG. 3 ) in the wound group  3 , a negative electrode current collector  190  joined to the negative electrode  32  (see  FIG. 3 ) in the wound group  3 , and the wound group  3  in a state covered with an insulating case  108 . The material of the insulating case  108  is a resin having an insulating property, such as polypropylene, and the battery can  1  is electrically insulated from the wound group  3 . The lid assembly  107  here means an integral assembly of the wound group  3 , the positive electrode current collector  180 , the positive electrode external terminal  14 , the negative electrode current collector  190 , the negative electrode external terminal  12 , and the battery lid  6 . 
     The positive electrode external terminal  14  is electrically connected to the positive electrode  34  (see  FIG. 3 ) in the wound group  3  via the positive electrode current collector  180 , and the negative electrode external terminal  12  is electrically connected to the negative electrode  32  (see  FIG. 3 ) in the wound group  3  via the negative electrode current collector  190 . In view of this, an electric power is supplied to an external device via the positive electrode external terminal  14  and the negative electrode external terminal  12 , or an electric power generated outside is supplied to be charged to the wound group  3  via the positive electrode external terminal  14  and the negative electrode external terminal  12 . 
     The positive electrode current collector  180  includes a seat portion  181  connected to the positive electrode external terminal  14 , a joining planar portion  183  connected to the positive electrode  34 , and a planar portion  182  disposed between the seat portion  181  and the joining planar portion  183 . 
     Similarly to the positive electrode current collector  180 , the negative electrode current collector  190  has a structure including a seat portion  191  connected to the negative electrode external terminal  12 , a joining planar portion  193  connected to the negative electrode  32 , and a planar portion  192  disposed between the seat portion  191  and the joining planar portion  193 . 
     As illustrated in  FIG. 2 , a liquid injection hole  9  for injecting an electrolyte into the battery container is drilled in the battery lid  6 . The liquid injection hole  9  is sealed with a liquid injection plug  11  after having injected the electrolyte. As the electrolyte, for example, a nonaqueous electrolyte produced by dissolving a lithium salt, such as lithium hexafluorophosphate (LiPF 6 ), in a carbonate ester-based organic solvent, such as ethylene carbonate, can be used. The composition of the electrolyte is not specifically limited. 
     With reference to  FIG. 3 , the wound group  3  will be described.  FIG. 3  is a perspective view illustrating the wound group  3  and illustrating a state where a winding end side of the wound group  3  is developed. The wound group  3  as a power generating element has a laminated structure formed by winding the elongated positive electrode  34  and negative electrode  32  around the winding center axis W in a flat shape while interposing separators  33  and  35 . 
     The positive electrode  34  includes a positive electrode mixture layer  34   a  formed by applying a positive electrode mixture layer slurry over both surfaces of the positive electrode foil as the positive electrode current collector and drying it, and a positive electrode foil exposed portion  34   b , over which the positive electrode mixture layer slurry is not applied, is disposed in an end portion on one side in the width direction of the positive electrode foil. 
     The negative electrode  32  includes a negative electrode mixture layer  32   a  formed by applying a negative electrode mixture layer slurry over both surfaces of the negative electrode foil as the negative electrode current collector and drying it, and a negative electrode foil exposed portion  32   b , over which the negative electrode mixture layer slurry is not applied, is disposed in an end portion on one side in the width direction of the negative electrode foil. An insulating layer  31  containing ceramic particles is disposed over the negative electrode mixture layer  32   a  and a part of the negative electrode foil exposed portion  32   b.    
     The positive electrode foil exposed portion  34   b  and the negative electrode foil exposed portion  32   b  are regions where metal surfaces of the electrode foils are exposed and wound so as to be disposed at respective positions on one side and the other side in the winding center axis W direction (width direction in  FIG. 3 ). 
       FIG. 4  schematically illustrates a cross-sectional surface in a short width direction of the wound group  3  in which the positive electrode  34 , the separator  33 , and the negative electrode  32  are laminated. The positive electrode  34  includes the positive electrode mixture layer  34   a  formed on both surfaces of the positive electrode foil, and includes the positive electrode foil exposed portion  34   b  in one end portion. The negative electrode  32  includes the negative electrode mixture layer  32   a  formed on both surfaces of the negative electrode foil, and includes the negative electrode foil exposed portion  32   b  in one end portion. The insulating layer  31  is formed over the negative electrode mixture layer  32   a  and a part of the negative electrode foil exposed portion  32   b . The separator  33  is interposed between the positive electrode  34  and the negative electrode  32 . 
       FIG. 5  schematically illustrates a cross-sectional surface near the surface of the negative electrode mixture layer  32   a . The negative electrode mixture layer  32   a  is formed by laminating negative electrode active material particles  32   p  and other particulate matters containing one or more selected from conductive materials and binders (not illustrated). The insulating layer  31  is formed by laminating ceramic particles  31   p . The thickness of the insulating layer  31  is preferably in a range of 1 μm or more and 10 μm or less while not limited to this. Here, in a surface of the negative electrode mixture layer  32   a  facing a border between the negative electrode mixture layer  32   a  and the insulating layer  31 , a plurality of holes  30  are provided. Specifically, the plurality of holes  30  are formed so as to be surrounded by a plurality of particulate matters, such as the negative electrode active material particles  32   p , and the insulating layer  31  (hatched portion in  FIG. 5 ). 
     The hole  30  functions as a puddle that holds the electrolyte to allow keeping a Li-ion concentration in the proximity of the negative electrode active material particles  32   p  constant, thereby ensuring improvement of the output and the responsiveness of the lithium ion secondary battery. In this embodiment, to provide the effect of the improved output and responsiveness, it is necessary to provide a plurality of holes having the diameter of 2.5 μm or more. Here, the hole  30  means a void portion formed on the surface of the negative electrode mixture layer  32   a  opening toward the interface between the negative electrode mixture layer  32   a  and the insulating layer  31  in a scanning electron microscope (SEM) image of a cross-sectional surface of a laminated body of the negative electrode mixture layer  32   a  and the insulating layer  31 . The diameter of the hole  30  means a diameter of a circle circumscribing the hole  30  similarly in the SEM image of the cross-sectional surface. Furthermore, “to provide a plurality of holes having the diameter of 2.5 μm or more” means that a plurality of holes having the diameter of 2.5 μm or more are present on a straight line having a length of 100 μm along the interface between the negative electrode mixture layer  32   a  and the insulating layer  31  similarly in the SEM image of the cross-sectional surface. 
     The diameter of the hole  30  is preferably 0.5 times or more of the thickness of the insulating layer  31 . Accordingly, a large amount of electrolyte exceeding the amount of the electrolyte held by the insulating layer  31  can be held by the holes  30 , thereby ensuring maximally providing the buffer function of the holes  30 . Here, the diameter of the hole  30  compared with the thickness of the insulating layer  31  means an average value of the diameters of the plurality of holes  30  having the diameter of 2.5 μm or more present on a straight line having a length of 100 μm along the interface between the negative electrode mixture layer  32   a  and the insulating layer  31  in a scanning electron microscope (SEM) image of a cross-sectional surface of the laminated body of the negative electrode mixture layer  32   a  and the insulating layer  31 . 
     Furthermore, an opening width of the hole  30  on the surface of the negative electrode mixture layer  32   a  is preferably equal to or more than a particle diameter of the ceramic particle  31   p . The ceramic particles  31   p  mutually bind to form bridges on the negative electrode mixture layer  32   a , and the holes  30  are formed adjacent to the bridge portions. Therefore, the opening width of the hole  30  equal to or more than the particle diameter of the ceramic particle  31   p  forms the hole  30  having the sufficient size. The particle diameter of the ceramic particle here means a value of a median diameter in a particle size distribution (volume basis) obtained by a measurement using a laser diffraction particle size analyzer. The opening width of the hole  30  means an average value of the widths of the holes  30  opening toward the interface relating to all the holes  30  having the diameter of 2.5 μm or more present on a straight line having a length of 100 μm along the interface between the negative electrode mixture layer  32   a  and the insulating layer  31  in a scanning electron microscope (SEM) image of a cross-sectional surface of the laminated body of the negative electrode mixture layer  32   a  and the insulating layer  31 . 
     Next, a method for manufacturing the lithium ion secondary battery according to the embodiment will be described.  FIG. 6  illustrates a manufacturing process of the negative electrode  32 . 
     For the negative electrode mixture layer slurry, for example, 10 parts by weight of polyvinylidene fluoride (hereinafter referred to as PVDF) as a binder is added to 100 parts by weight of an amorphous carbon powder as a negative electrode active material, and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a first solvent is added thereto and mixing it. Thus, the negative electrode mixture layer slurry can be prepared. While the case of using the amorphous carbon as the negative electrode active material has been described, the material is not limited to this. Natural graphite, various kinds of artificial graphite materials, a carbonaceous material, such as coke, a compound of Si, Sn, and the like (for example, SiO and TiSi 2 ), or a composite material of these substances into which lithium ions can be intercalated or from which lithium ions can be desorbed may be used. Their particle shapes include a scaly shape, a spherical shape, a fiber shape, a lump shape, and the like, and the shapes are not especially limited. When various kinds of graphite are especially used as the negative electrode active material and in the similar case, water or a mixture of water and the NMP is selectable as the first solvent in addition to the NMP, thus ensuring reduction in environmental load. An example of aqueous negative electrode mixture layer slurry includes a negative electrode mixture layer slurry produced by adding 1 part by weight of styrene-butadiene rubber (hereinafter, SBR) as a binder and 1 part by weight of carboxymethylcellulose sodium (hereinafter, CMC) as a thickening agent to 100 parts by weight of natural graphite powder. 
     For the insulating layer slurry, for example, 3 parts by weight of SBR as a binder is added to 100 parts by weight of alumina as ceramic particles, and a solvent having a boiling point equal to or less than a boiling point of the first solvent is used as a second solvent to it. Preferably, the boiling point of the second solvent is less than the boiling point of the first solvent, and for example, preferably lower than the boiling point of the first solvent by 10° C. or more. The boiling point has a correlation with a steam pressure. Accordingly, as described later, the drying behaviors of the first solvent and the second solvent are mutually different, and the holes are easily formed on the surface of the negative electrode mixture layer. Specifically, the example of the second solvent includes an alcohol-based solvent, a ketone-based solvent, a mixture thereof, a mixture of those and water, or water. The alcohol-based solvent includes methanol, ethanol, isopropanol, or the like, and the ketone-based solvent includes acetone, methyl ethyl ketone, or the like. 
     The insulating layer slurry can be prepared by mixing using the second solvent. While the case where alumina (Al 2 O 3 ) is used as the ceramic particles is described above, this should not be construed in a limiting sense. For example, the one or more of ceramic particles selected from silica, zirconia (ZrO 2 ), magnesia (MgO), lithium carbonate, boehmite (Al 2 O 3 .H 2 O), and the like may be used, and their particle shapes are not especially limited while including a plate shape, a scaly shape, a spherical shape, a fiber shape, a lump shape, and the like. Especially, when the ceramic particles have the plate shapes, the bridges are formed on the surface of the mixture layer when the ceramic particles mutually bind to form the insulating layer. This is preferable because the holes having the sufficient sizes can be formed without the ceramic particles falling into the holes. Here, having the plate shapes means that the ceramic particles having the thicknesses of 0.5 μm to 2 μm and their major axes of 1 μm to 5 μm are included by 90 mass % or more of in whole. 
     When the particle diameters of the ceramic particles are excessively small, the ceramic particles easily fall into the holes on the surface of the negative electrode mixture layer due to a capillarity to make the formation of the holes having the appropriate sizes difficult in some cases. Meanwhile, in the case of excessively large, the function as the insulating layer is impaired in some cases while the falling into the holes due to the capillarity does not occur. Therefore, the particle diameters of the ceramic particles are appropriately set considering them. For example, the particle diameters of the ceramic particles are preferably in a range of 0.5 μm or more and 3.0 μm or less. Here, the particle diameter means a value of a median diameter in a particle size distribution (volume basis) obtained by a measurement using a laser diffraction particle size analyzer. 
     While the case where 3 parts by weight of the SBR as the binder is added is described above, since the binder generally interferes with ion movements that occur in the reactions in the positive electrode and the negative electrode, the additive amount is preferably a less amount and not specifically limited. The negative electrode mixture layer slurry and the insulating layer slurry are applied over the negative electrode foil, such as a copper foil, and dried to form the negative electrode mixture layer  32   a  and the insulating layer  31  in accordance with the manufacturing process illustrated in  FIG. 6 , thus manufacturing the negative electrode  32 . 
     Next, the applying and drying step of the negative electrode mixture layer slurry and the insulating layer slurry will be described based on  FIG. 7 . A coating dryer  38  illustrated in  FIG. 7  includes a die head  40  and a back roller  46  to apply each slurry and a drying furnace  41  to volatilize and dry solvent during coating. Additionally, conveyance rollers  43  are disposed to sequentially convey a negative electrode foil  45  of a copper foil or the like to the applying step portion and the drying step portion in the coating dryer  38 . An unwind roller  42  and a roll-up roller  44  are each disposed to unwind and roll up the negative electrode foil  45 . The negative electrode foil  45  of a copper foil or the like is conveyed along the conveyance rollers  43  from the unwind roller  42 . 
     Over the negative electrode foil  45 , the negative electrode mixture layer slurry is applied with the thickness of 50 μm to 200 μm, and the insulating layer slurry is applied thereover with the thickness of 2 μm to 20 μm. Subsequently, through the conveyance to the drying furnace  41 , the solvent components in the negative electrode mixture layer slurry and the insulating layer slurry are volatilized and dried by circulating hot wind at 60 to 100° C., thus forming the negative electrode mixture layer  32   a  and the insulating layer  31 . The respective film thicknesses after the drying are reduced to about the halves. After the drying, the roll-up roller  44  rolls up it with the negative electrode foil  45  in a roll shape. The rolled-up roll is again conveyed from the unwind roller  42 , and the back surface is similarly formed to manufacture the negative electrode  32 . 
     Here, the drying behavior after applying the negative electrode mixture layer slurry and the insulating layer slurry will be described based on  FIG. 8 . Immediately after the applying (before drying), the applied negative electrode mixture layer slurry and insulating layer slurry include a first solvent  28  and a second solvent  29 , respectively. In the respective dispersing solvents, the particulate matter, such as the negative electrode active material particles  32   p , and the ceramic particle  31   p  are dispersedly present. When the drying starts, the second solvent  29 , whose boiling point is low and therefore the steam pressure having correlation with the boiling point is small, in the insulating layer slurry on the outermost surface volatilizes at first. By the volatilization of the second solvent  29 , the ceramic particles  31   p  are mutually secured by the binder. When the drying further proceeds, the first solvent  28  in the negative electrode mixture layer slurry volatilizes. At this time, since the ceramic particles  31   p  are mutually secured to form the bridges on the outermost surface of the negative electrode mixture layer, the ceramic particles  31   p  do not fall into the voids of the particulate matters, such as the negative electrode active material particles  32   p . Consequently, as illustrated in  FIG. 8  (after drying), the holes  30  are formed in the voids of the negative electrode active material particles  32   p  on the outermost surface of the negative electrode mixture layer. 
     The step of applying the negative electrode mixture layer slurry and the insulating layer slurry over the negative electrode foil will be described based on  FIG. 9 .  FIG. 9  is a schematically enlarged view of the die head  40  and the back roller  46  portion in  FIG. 7 . The die head  40  includes an outlet-side block  47 , a three-dimensional shim  48 , and an inlet-side block  49 , and internally includes an insulating layer slurry manifold  50  and a negative electrode mixture layer slurry manifold  51 . The two kinds of slurries are vertically discharged from the respective manifolds toward the negative electrode foil  45  at the same time, thereby performing a simultaneous applying of the two layers. 
       FIG. 10  is a developed drawing of the die head  40 . The three-dimensional shim  48  is interposed between the outlet-side block  47  and the inlet-side block  49 , and grooves  52  as flow passages of the slurries are formed on both surfaces of the three-dimensional shim  48 . Thus, the die head  40  includes the flow passages configured to apply the two kinds of slurries, the negative electrode mixture layer slurry and the insulating layer slurry, and simultaneously forms the negative electrode mixture layer  32   a  and the insulating layer  31  on the negative electrode foil  45  by simultaneously discharging those slurries. 
     While viscosities of the negative electrode mixture layer slurry and the insulating layer slurry in the applying are not specifically limited, for the insulating layer slurry, an excessively low viscosity causes the insulating layer slurry to easily fill the voids of the negative electrode active material particles  32   p , thus making the hole formation difficult. Therefore, the viscosity is preferably high to some extent. Specifically, the viscosity at 25° C. is preferably 300 mPa·s or more, and more preferably 500 mPa·s or more. 
     After the applying and drying, a presswork is performed by a roll press machine. Specifically, the laminated body in which the negative electrode mixture layer and the insulating layer are formed on the negative electrode foil is sandwiched between rollers heated to 60 to 120° C. and a pressure is applied, thus performing the presswork. After the presswork, slitting is performed to have a predetermined width, thereby ensuring obtaining the negative electrode  32  as illustrated in  FIG. 3 . 
       FIG. 11  illustrates a scanning electron microscope (SEM) image of a cross-sectional surface of the negative electrode mixture layer and the insulating layer formed in accordance with the manufacturing method according to the embodiment. In  FIG. 11 , it was confirmed that the thickness of the insulating layer  31  was 4 μm and a plurality of holes  30  having the diameters of 2.5 μm were formed on the surface of the negative electrode mixture layer  32   a  facing the border between the insulating layer  31  and the negative electrode mixture layer  32   a . In contrast,  FIG. 12  illustrates a cross-sectional surface when the negative electrode mixture layer slurry is applied and dried to form the negative electrode mixture layer  32   a , and subsequently, the insulating layer slurry is applied thereon and dried to form the insulating layer  31 . In  FIG. 12 , the ceramic particles included in the insulating layer  31  invade between the negative electrode active material particles due to the capillarity in the negative electrode mixture layer  32   a , resulting in a state where the voids of the negative electrode active material particles are clogged with the ceramic particles. The distances in the lateral direction in  FIG. 11  and  FIG. 12  are 200 μm. 
     For the positive electrode  34 , for example, 10 parts by weight of scaly graphite as a conductive material and 10 parts by weight of PVDF as a binder are added to 100 parts by weight of lithium manganate (chemical formula: LiMn 2 O 4 ) as a positive electrode active material, and NMP as a dispersing solvent is added thereto and mixing it. Thus, the positive electrode mixture layer slurry is prepared, and this positive electrode mixture layer slurry is applied over both surfaces of the aluminum foil (positive electrode foil) excluding the weld portion (positive electrode foil exposed portion  34   b ) and dried. Subsequently, through the presswork and the slitting step similarly to the negative electrode described above, the positive electrode  34  as illustrated in  FIG. 3  in which the thickness of the positive electrode mixture layer excluding the aluminum foil is 100 μm to 200 μm can be obtained. 
     While the case of using lithium manganite as the positive electrode active material is described above, another lithium manganate having a spinel crystal structure, a lithium manganese composite oxide partially replaced by or doped with a metallic element, a lithium cobaltate or a lithium titanate having a layered crystal structure, or a lithium-metal composite oxide produced by replacing or doping a part of these substances by/with a metallic element may be used. 
     While the embodiment has described the case of using the PVDF as a binder of the mixture layer in the positive electrode  34  and the negative electrode  32 , for example, a polymer, such as polytetrafluoroethylene (PTFE), polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene-butadiene rubber, polysulfide rubber, nitrocellulose, cyanoethyl cellulose, various kinds of latexes, acrylonitrile, vinyl fluoride, vinylidene fluoride, propylene fluoride, chloroprene fluoride, and acrylic-based resin, and a mixture of these substances may be used. 
     Among both end portions in the width direction of the wound group  3 , that is, in the winding center axis W direction perpendicular to the winding direction, one is configured as the laminated portion of the positive electrode  34 , and the other is configured as the laminated portion of the negative electrode  32 . In the laminated portion of the positive electrode  34  disposed on the one end, the positive electrode foil exposed portion  34   b  where the positive electrode mixture layer  34   a  is not formed is laminated. In the laminated portion of the negative electrode  32  disposed on the other end, the negative electrode foil exposed portion  32   b  where the negative electrode mixture layer  32   a  is not formed is laminated. The laminated portion of the positive electrode foil exposed portion  34   b  and the laminated portion of the negative electrode foil exposed portion  32   b  are each preliminarily squashed and connected to the positive electrode current collector  180  and the negative electrode current collector  190 , respectively by ultrasonic joining, and the obtained lid assembly  107  is housed in the battery can  1 , thus ensuring the manufacture of the lithium ion secondary battery. 
     According to the manufacturing method of this embodiment, the electrode structure that includes the holes (puddles) in the interface between the insulating layer and the mixture layer can be obtained, and the lithium ion secondary battery excellent in output and responsiveness can be provided. 
     While the embodiment of the present invention has been described in detail, the specific configuration is not limited to the embodiment. Design changes and the like within a scope not departing from the gist of the present invention are included in the present invention. 
     REFERENCE SIGNS LIST 
     
         
           1  Battery can 
           1   b  Wide-width side surface 
           1   c  Narrow-width side surface 
           1   d  Bottom surface 
           3  Wound group 
           6  Battery lid 
           9  Liquid injection hole 
           10  Gas discharge valve 
           11  Liquid injection plug 
           12  Negative electrode external terminal 
           14  Positive electrode external terminal 
           22  Negative electrode side external insulator 
           24  Positive electrode side external insulator 
           28  First solvent 
           29  Second solvent 
           30  Hole 
           31  Insulating layer 
           31   p  Ceramic particle 
           32  Negative electrode 
           32   a  Negative electrode mixture layer 
           32   b  Negative electrode foil exposed portion 
           32   p  Negative electrode active material particle 
           33  Separator 
           34  Positive electrode 
           34   a  Positive electrode mixture layer 
           34   b  Positive electrode foil exposed portion 
           35  Separator 
           38  Coating dryer 
           40  Die head 
           41  Drying furnace 
           42  Unwind roller 
           43  Conveyance roller 
           44  Roll-up roller 
           45  Negative electrode foil 
           46  Back roller 
           47  Outlet-side block 
           48  Three-dimensional shim 
           49  Inlet-side block 
           50  Insulating layer slurry manifold 
           51  Negative electrode mixture layer slurry manifold 
           52  Groove 
           100  Square secondary battery 
           107  Lid assembly 
           108  Insulating case 
           142  Busbar welding portion 
           152  Busbar welding portion 
           180  Positive electrode current collector 
           181  Seat portion 
           182  Planar portion 
           183  Joining planar portion 
           190  Negative electrode current collector 
           191  Seat portion 
           192  Planar portion 
           193  Joining planar portion 
       
    
     Every published material, patent, and patent application referred in this description are incorporated herein directly by reference.