JP6102442B2 - Lithium ion secondary battery - Google Patents

Description

  The present invention relates to a lithium ion secondary battery.

  In recent years, in order to cope with global warming, reduction of the amount of carbon dioxide is eagerly desired. In the automobile industry, there is a great expectation for reducing carbon dioxide emissions by introducing electric vehicles (EV) and hybrid electric vehicles (HEV). Electric devices such as secondary batteries for motor drive that hold the key to their practical application. Is being actively developed.

  As a secondary battery for driving a motor, a lithium ion secondary battery having the highest theoretical energy among all the batteries is attracting attention, and is currently being developed rapidly. Generally, a lithium ion secondary battery has a configuration in which a positive electrode and a negative electrode having an active material layer in which an active material or the like is applied to a current collector together with a binder are connected via an electrolyte layer and stored in a battery case. doing.

  The non-aqueous electrolyte secondary battery used as a motor drive power source for automobiles and the like as described above has extremely high output characteristics compared to consumer non-aqueous electrolyte secondary batteries used in mobile phones, notebook computers, etc. It is required to have. At present, research and development is underway to meet such demands.

  Patent Document 1 discloses a nonaqueous electrolyte battery having a gas adsorbing substance between the outermost layer of an exterior material made of a laminate film and a battery element.

JP 2001-155790 A

  However, in the nonaqueous electrolyte battery described in Patent Document 1, gas accumulates on the outer periphery of the electrode between the separators, and the penetration of the electrode into the electrolytic solution is inhibited. As a result, there is a problem that the heterogeneous reaction is promoted at the electrode and the electrode is deteriorated.

  Then, an object of this invention is to provide the means to suppress deterioration of an electrode.

  The present inventor has accumulated extensive research. As a result, the above problem is achieved by the lithium ion secondary battery having the gas adsorbing member between the separators and the electrode side end face of the gas adsorbing member being disposed within the distance of the electrode thickness from the outer periphery of the electrode. Found out to solve.

  When the size of the gas bubbles released to the outer periphery of the electrode increases, the gas bubbles come into contact with the gas adsorbing member and are adsorbed. Therefore, gas does not accumulate at the outer periphery of the electrode, and the penetration of the electrolyte into the electrode is not hindered and a uniform electrode reaction occurs.

1 is a schematic cross-sectional view showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat type (stacked type) bipolar type, which is an embodiment of a lithium ion secondary battery. It is the cross-sectional schematic which shows the basic composition of the bipolar lithium ion secondary battery which is other embodiment of a lithium ion secondary battery. It is the perspective view showing the external appearance of the flat lithium ion secondary battery which is another one Embodiment of a lithium ion secondary battery. 3 is a schematic diagram showing a separator produced in Example 1. FIG. 6 is a schematic diagram showing a separator produced in Example 2. FIG.

  First, although a nonaqueous electrolyte lithium ion secondary battery will be described as a preferred embodiment of a lithium ion secondary battery, it is not limited to only the following embodiments. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  There is no particular limitation when distinguished by the electrolyte form of the lithium ion secondary battery. For example, the present invention can be applied to any of a liquid electrolyte type battery in which a separator is impregnated with a nonaqueous electrolytic solution, a polymer gel electrolyte type battery also called a polymer battery, and a solid polymer electrolyte (all solid electrolyte) type battery. Regarding the polymer gel electrolyte and the solid polymer electrolyte, they are used by impregnating them in a separator.

  FIG. 1 is a schematic cross-sectional view schematically showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”) that is not a flat (stacked) bipolar type. As shown in FIG. 1, the stacked battery 10a of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside an exterior material 29 that is an exterior body. . Here, the power generation element 21 has a configuration in which a positive electrode, an electrolyte layer 17, and a negative electrode are stacked. The positive electrode has a structure in which the positive electrode active material layer 13 is disposed on both surfaces of the positive electrode current collector 11. The negative electrode has a structure in which the negative electrode active material layers 15 are disposed on both surfaces of the negative electrode current collector 12. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto face each other with the electrolyte layer 17 therebetween. . Thereby, the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10a shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.

  In addition, although the positive electrode active material layer 13 is arrange | positioned only at one side in the outermost layer positive electrode collector located in both outermost layers of the electric power generation element 21, an active material layer may be provided in both surfaces. That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector. In addition, the arrangement of the positive electrode and the negative electrode is reversed from that in FIG. 1, so that the outermost layer negative electrode current collector is positioned on both outermost layers of the power generation element 21, and the outermost layer negative electrode current collector is disposed on one or both surfaces. A negative electrode active material layer may be disposed.

  The positive electrode current collector 11 and the negative electrode current collector 12 are attached to the positive electrode current collector plate 25 and the negative electrode current collector plate 27 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between the end portions of the exterior material 29. Thus, it has a structure led out of the exterior material 29. The positive electrode current collector plate 25 and the negative electrode current collector plate 27 are ultrasonically welded to the positive electrode current collector 11 and the negative electrode current collector 12 of each electrode, respectively, via a positive electrode lead and a negative electrode lead (not shown) as necessary. Or resistance welding or the like.

  FIG. 2 is a schematic cross-sectional view schematically showing the basic configuration of a bipolar nonaqueous electrolyte lithium ion secondary battery (hereinafter also simply referred to as “bipolar battery”) 10b. The bipolar battery 10b shown in FIG. 2 has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate film 29 that is an exterior material.

  As shown in FIG. 2, the power generation element 21 of the bipolar battery 10 b has a positive electrode active material layer 13 that is electrically coupled to one surface of the current collector 11, and is formed on the opposite surface of the current collector 11. It has a plurality of bipolar electrodes 23 in which a negative electrode active material layer 15 that is electrically coupled is formed. Each bipolar electrode 23 is laminated via the electrolyte layer 17 to form the power generation element 21. The electrolyte layer 17 has a configuration in which an electrolyte is held at the center in the surface direction of a separator as a base material. At this time, the positive electrode active material layer 13 of one bipolar electrode 23 and the negative electrode active material layer 15 of another bipolar electrode 23 adjacent to the one bipolar electrode 23 face each other through the electrolyte layer 17. The bipolar electrodes 23 and the electrolyte layers 17 are alternately stacked. That is, the electrolyte layer 17 is interposed between the positive electrode active material layer 13 of one bipolar electrode 23 and the negative electrode active material layer 15 of another bipolar electrode 23 adjacent to the one bipolar electrode 23. ing.

  The adjacent positive electrode active material layer 13, electrolyte layer 17, and negative electrode active material layer 15 constitute one unit cell layer 19. Therefore, it can be said that the bipolar battery 10b has a configuration in which the single battery layers 19 are stacked. Further, for the purpose of preventing liquid junction due to leakage of the electrolytic solution from the electrolyte layer 17, a seal portion (insulating layer) 31 is disposed on the outer peripheral portion of the unit cell layer 19. A positive electrode active material layer 13 is formed only on one side of the positive electrode outermost layer current collector 11 a located in the outermost layer of the power generation element 21. The negative electrode active material layer 15 is formed only on one surface of the outermost current collector 11b on the negative electrode side located in the outermost layer of the power generation element 21. However, the positive electrode active material layer 13 may be formed on both surfaces of the outermost layer current collector 11a on the positive electrode side. Similarly, the negative electrode active material layer 15 may be formed on both surfaces of the outermost layer current collector 11b on the negative electrode side.

  Further, in the bipolar battery 10b shown in FIG. 2, the positive electrode current collector plate 25 is disposed so as to be adjacent to the outermost layer current collector 11a on the positive electrode side, and this is extended and led out from the laminate film 29 which is an exterior material. Yes. On the other hand, the negative electrode current collector plate 27 is disposed so as to be adjacent to the outermost layer current collector 11b on the negative electrode side, and similarly, this is extended and led out from the laminate film 29 which is an exterior of the battery.

  In the bipolar battery 10 b shown in FIG. 2, a seal portion 31 is usually provided around each single cell layer 19. The purpose of the seal portion 31 is to prevent the adjacent current collectors 11 in the battery from coming into contact with each other and a short circuit caused by a slight irregularity at the end of the unit cell layer 19 in the power generation element 21. Is provided. By installing such a seal portion 31, long-term reliability and safety can be ensured, and a high-quality bipolar battery 10b can be provided.

  Note that the number of stacks of the unit cell layers 19 is adjusted according to a desired voltage. Further, in the bipolar battery 10b, the number of stacks of the single battery layers 19 may be reduced if a sufficient output can be ensured even if the battery is made as thin as possible. Even in the bipolar battery 10b, it is necessary to prevent external impact and environmental degradation during use. Therefore, the power generation element 21 is preferably sealed in a laminate film 29 that is an exterior material, and the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are taken out of the laminate film 29.

  In addition, in this specification, when describing as “current collector”, it may indicate all of the positive electrode current collector, the negative electrode current collector, and the bipolar battery current collector, or may refer to only one. is there. Similarly, when describing as “active material layer”, both the positive electrode active material layer and the negative electrode active material layer may be referred to, or only one of them may be referred to. Similarly, when describing as "active material", both a positive electrode active material and a negative electrode active material may be pointed out, and only one side may be pointed out.

  Patent Document 1 discloses a nonaqueous electrolyte battery having a gas adsorbing substance between the outermost layer of an exterior material made of a laminate film and a battery element. However, in the nonaqueous electrolyte battery described in Patent Document 1, gas accumulates on the outer periphery of the electrode between the separators, and the penetration of the electrode into the electrolytic solution is inhibited. As a result, there is a problem that the heterogeneous reaction is promoted at the electrode and the electrode is deteriorated.

  On the other hand, the lithium ion secondary battery of this embodiment has a gas adsorbing member between the separators, and the electrode side end surface of the gas adsorbing member is disposed within the distance of the electrode thickness from the outer peripheral edge of the electrode. ing. With this configuration, when the size of the gas bubbles released to the outer periphery of the electrode increases, the gas bubbles come into contact with the gas adsorbing member and are adsorbed by the gas adsorbing member. Therefore, gas does not accumulate at the outer peripheral portion of the electrode, the permeation of the electrolyte solution into the electrode is not inhibited, and a uniform electrode reaction occurs, and the deterioration of the electrode is suppressed.

  Hereinafter, the gas adsorption member used for the lithium ion secondary battery will be described in more detail.

[Gas adsorption member]
The gas adsorbing member is provided between the separators. The gas adsorbing member preferably contains a gas adsorbing substance and other components such as an aqueous binder as necessary.

  The gas adsorbing substance is not particularly limited, but it is preferable to use a porous metal compound or a porous carbon material. Such a compound is excellent in gas adsorption performance and has a function of removing water from the electrolyte.

  Specific examples of the porous metal compound include zeolite, alumina, molecular sieve, titania, silica gel, zirconia and the like. Specific examples of the porous carbon material include activated carbon and carbon molecular sieve.

  In addition to the porous metal compound or the porous carbon material as described above, magnesium sulfate, nickel, platinum, palladium, Ca, Sr, Ba, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, calcium chloride, phosphorus pentoxide, or the like can be used. The gas adsorbing substances as described above may be used alone or in admixture of two or more.

  Moreover, it is preferable that a gas adsorption member contains an aqueous binder. Examples of the aqueous binder include, for example, an aqueous binder contained in the negative electrode active material layer, such as styrene / butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene / propylene rubber, nitrile rubber (or nitrile butadiene rubber; NBR). Rubber binders such as ethylene-propylene-diene rubber (EPDM), acrylate rubber, styrene / butadiene / styrene block copolymer and hydrogenated products thereof, styrene / isoprene / styrene block copolymer and hydrogenated products thereof You can also. Furthermore, polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polyether nitrile (PEN), polyacrylonitrile, polyimide, polyamide, cellulose, ethylene-vinyl acetate copolymer, Examples thereof include polyvinyl chloride, polyacrylate, polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, polyethylene glycol and the like. Among these, polyimide, styrene / butadiene rubber, polypropylene, polytetrafluoroethylene, polyacrylonitrile, and polyamide are more preferable. These aqueous binders may be used alone or in combination of two or more. However, the present embodiment is not limited to those exemplified above, and various conventionally known aqueous binders can be used.

  The content of the gas adsorbing substance in the gas adsorbing member is not particularly limited because it is optimized depending on the amount of gas generated in the cell used and the gas adsorbing capacity of the gas adsorbing substance. However, from the viewpoint of the adhesiveness of the gas adsorbing member, the total amount of the gas adsorbing member is preferably 90% by weight or less based on 100% by weight.

  The method for forming the gas adsorbing member is not particularly limited, and examples thereof include a method in which a slurry containing a gas adsorbing substance and, if necessary, an aqueous binder is applied on a separator and dried. The coating method is not particularly limited, and examples thereof include a bar coating method, a spray coating method, a screen printing method, and an ink jet method.

  In this embodiment, the electrode side end surface of the gas adsorbing member is disposed within a distance of the electrode thickness from the outer peripheral edge of the electrode. When the gas release amount increases, the maximum diameter of the released gas bubbles becomes the distance between the separators (distance of the electrode thickness), and when the bubbles become larger than this, the released gas bubbles have a surface tension. To grow elongated along the electrode. When the electrode-side end surface of the gas adsorbing member is disposed beyond the distance of the electrode thickness from the outer peripheral edge of the electrode, the generated gas bubbles and the gas adsorbent are not in contact with each other, so that the above effect is obtained. It becomes impossible.

  Although the installation place of said gas adsorption member will not be restrict | limited especially if it is between separators, it is preferable on the surface of the said separator. By installing in advance on the surface of the separator, a battery can be manufactured using a conventional battery manufacturing apparatus as it is. At this time, the gas adsorbing member may be installed on at least one side of the separator, but is more preferably installed on at least three sides of the separator. By adopting such a configuration, by combining with a gas discharge process such as a roll press, the gas bubbles remaining in the battery can be adsorbed to the gas adsorbing member after the electrolyte solution is injected into the separator. Moreover, it is possible to allow the electrolytic solution to permeate the entire surface of the electrode without opening the outer package.

  The thickness of the gas adsorbing member is preferably smaller than the thickness of the electrodes (positive electrode and negative electrode). When the gas adsorbing member has such a thickness, it is possible to prevent the gas adsorbing member itself from inhibiting the penetration of the electrolyte into the electrode.

  The lithium ion secondary battery described above has the following effects.

  Said lithium ion secondary battery has a gas adsorption member between separators, and the electrode side end surface of the said gas adsorption member is arrange | positioned within the distance of the thickness of an electrode from the outer periphery of an electrode. With such a configuration, when the size of the gas bubbles released to the outer periphery of the electrode increases, the gas bubbles come into contact with the gas adsorbing member and are adsorbed. Therefore, gas does not accumulate at the outer peripheral portion of the electrode, the permeation of the electrolyte solution into the electrode is not inhibited, and a uniform electrode reaction occurs, and the deterioration of the electrode is suppressed.

  The lithium ion secondary battery described above is characterized by a gas adsorbing member. Hereinafter, other main components will be described.

[Active material layer]
The positive electrode active material layer or the negative electrode active material layer contains an active material, and if necessary, a conductive aid, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and a lithium salt for enhancing ion conductivity. And other additives.

(Positive electrode active material)
The positive electrode active material layer includes a positive electrode active material. The positive electrode active material has a composition that occludes ions during discharging and releases ions during charging. A preferable example is a lithium-transition metal composite oxide that is a composite oxide of a transition metal and lithium. Specifically, Li · Co-based composite oxide such as LiCoO _2, Li · Ni-based composite oxide such as LiNiO _2, Li · Mn-based composite oxide such as spinel LiMn ₂ O _4, Li · such LiFeO ₂ Fe-based composite oxides and those obtained by replacing some of these transition metals with other elements can be used. These lithium-transition metal composite oxides are excellent in reactivity and cycle characteristics, and are low-cost materials. Therefore, it is possible to form a battery having excellent output characteristics by using these materials for electrodes. In addition, examples of the positive electrode active material include transition metal oxides such as LiFePO ₄ and lithium phosphate compounds and sulfuric acid compounds; transition metal oxides such as V ₂ O ₅ , MnO ₂ , TiS ₂ , MoS ₂ , and MoO ₃ , and sulfides. Materials; PbO ₂ , AgO, NiOOH, etc. can also be used. The positive electrode active material may be used alone or in the form of a mixture of two or more.

  The average particle diameter of the positive electrode active material is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 20 μm, from the viewpoint of increasing the capacity, reactivity, and cycle durability of the positive electrode active material. Within such a range, the secondary battery can suppress an increase in the internal resistance of the battery during charging and discharging under high output conditions, and can extract a sufficient current. When the positive electrode active material is secondary particles, it can be said that the average particle diameter of the primary particles constituting the secondary particles is preferably in the range of 10 nm to 1 μm. It is not limited to. However, it goes without saying that, depending on the manufacturing method, the positive electrode active material may not be a secondary particle formed by aggregation, lump or the like. As the particle diameter of the positive electrode active material and the particle diameter of the primary particles, a median diameter obtained by using a laser diffraction method can be used. The shape of the positive electrode active material varies depending on the type and manufacturing method, and examples thereof include a spherical shape (powdered shape), a plate shape, a needle shape, a column shape, and a square shape, but are not limited thereto. Any shape can be used without any problems. It is desirable to appropriately select an optimum shape that can improve battery characteristics such as charge / discharge characteristics.

(Negative electrode active material)
The negative electrode active material layer includes a negative electrode active material. The negative electrode active material has a composition capable of releasing ions during discharge and storing ions during charging. The negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium. Examples of the negative electrode active material include metals such as Si and Sn, TiO, Ti ₂ O ₃ , TiO ₂ , or Metal oxides such as SiO ₂ , SiO, SnO ₂ , complex oxides of lithium and transition metals such as Li _4/3 Ti _5/3 O ₄ or Li ₇ MnN, Li—Pb alloys, Li—Al alloys Preferred examples include lithium-metal alloy materials such as Li, or graphite (natural graphite, artificial graphite), carbon black, activated carbon, carbon fiber, coke, soft carbon, or hard carbon.

The negative electrode active material may contain an element that forms an alloy with lithium. By using an element that forms an alloy with lithium, it is possible to obtain a battery having a high capacity and an excellent output characteristic, which has a higher energy density than conventional carbon-based materials. The negative electrode active material may be used alone or in the form of a mixture of two or more. The element alloying with lithium is not limited to the following, but specifically, Si, Ge, Sn, Pb, Al, In, Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Hg, Ga, Tl, C, N, Sb, Bi, O, S, Se, Te, Cl and the like can be mentioned. Among these, from the viewpoint of configuring a battery having excellent capacity and energy density, at least one selected from the group consisting of carbon materials and / or Si, Ge, Sn, Pb, Al, In, and Zn. It is preferable to include an element, and it is particularly preferable to include an element of a carbon material, Si, or Sn. These may be used alone or as 2
More than one species may be used in combination.

  The average particle size of the negative electrode active material is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 20 μm from the viewpoint of increasing the capacity, reactivity, and cycle durability of the negative electrode active material. Within such a range, the secondary battery can suppress an increase in the internal resistance of the battery during charging and discharging under high output conditions, and can extract a sufficient current. In addition, when the negative electrode active material is secondary particles, it can be said that the average particle diameter of primary particles constituting the secondary particles is desirably in the range of 10 nm to 1 μm. It is not limited to. However, it goes without saying that, depending on the manufacturing method, the negative electrode active material may not be a secondary particle formed by aggregation, lump or the like. As the particle size of the negative electrode active material and the particle size of the primary particles, the median diameter obtained using a laser diffraction method can be used. The shape of the negative electrode active material varies depending on the type and manufacturing method, and examples thereof include a spherical shape (powdered shape), a plate shape, a needle shape, a column shape, and a square shape, but are not limited thereto. Any shape can be used without any problems. Preferably, an optimal shape that can improve battery characteristics such as charge / discharge characteristics is appropriately selected.

  The positive electrode active material layer and the negative electrode active material layer can include a binder.

  Although it does not specifically limit as a binder used for an active material layer, For example, the following materials are mentioned. Polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC), ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR), isoprene Rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and its hydrogenated product, styrene / isoprene / styrene block copolymer and its hydrogenated product, etc. Thermoplastic polymer, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Tet Fluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), polyfluorinated Fluorine resin such as vinyl (PVF), vinylidene fluoride-hexafluoropropylene-based fluororubber (VDF-HFP-based fluororubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based fluororubber (VDF-HFP-TFE-based fluorine) Rubber), vinylidene fluoride-pentafluoropropylene-based fluoro rubber (VDF-PFP-based fluoro rubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene-based fluoro rubber (VDF-PFP-TFE fluorine rubber), vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene fluorine rubber (VDF-PFMVE-TFE fluorine rubber), vinylidene fluoride-chlorotrifluoroethylene fluorine rubber (VDF) Vinylidene fluoride fluororubbers such as (-CTFE fluororubber) and epoxy resins. Among these, polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, and polyamide are more preferable. These suitable binders are excellent in heat resistance, have a very wide potential window, are stable at both the positive electrode potential and the negative electrode potential, and can be used for the active material layer. These binders may be used independently and may use 2 or more types together.

  Examples of other additives that can be included in the active material layer include a conductive additive, an electrolyte, and an ion conductive polymer.

  The conductive assistant refers to an additive that is blended in order to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer. Examples of the conductive auxiliary agent include carbon materials such as carbon black such as acetylene black, graphite, and carbon fiber. When the active material layer contains a conductive additive, an electronic network inside the active material layer is effectively formed, which can contribute to improvement of the output characteristics of the battery.

Examples of the electrolyte salt (lithium salt) include Li (C ₂ F ₅ SO ₂ ) ₂ N, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO _{3 and the} like.

  Examples of the ion conductive polymer include polyethylene oxide (PEO) -based and polypropylene oxide (PPO) -based polymers.

  The compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer is not particularly limited. The mixing ratio can be adjusted by appropriately referring to known knowledge about the non-aqueous solvent secondary battery. The thickness of each active material layer is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to. For example, the thickness of each active material layer is about 2 to 100 μm.

[Current collector]
There is no particular limitation on the material constituting the current collector, but a metal is preferably used.

  Specifically, examples of the metal include aluminum, nickel, iron, stainless steel, titanium, copper, and other alloys. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used. Moreover, the foil by which aluminum is coat | covered on the metal surface may be sufficient. Of these, aluminum, stainless steel, and copper are preferable, and aluminum is more preferable from the viewpoint of electron conductivity and battery operating potential.

  The size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used. There is no particular limitation on the thickness of the current collector. The thickness of the current collector is usually about 1 to 100 μm.

[Electrolyte layer]
The electrolyte layer includes an electrolyte and a separator formed by impregnating or holding the electrolyte in pores. The electrolyte layer having a separator functions as a spatial partition (spacer) between the positive electrode and the negative electrode. In addition, it also has a function of holding an electrolyte that is a lithium ion transfer medium between the positive and negative electrodes during charging and discharging. Furthermore, the separator may have a function of holding the gas adsorption member.

  There is no restriction | limiting in particular in the electrolyte which comprises an electrolyte layer, Polymer electrolytes, such as a liquid electrolyte and a polymer gel electrolyte and a polymer solid electrolyte, can be used suitably.

[Liquid electrolyte]
The liquid electrolyte is obtained by dissolving a lithium salt as a supporting salt in a solvent. Examples of the solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propionate (MP), methyl acetate (MA), and methyl formate (MF). 4-methyldioxolane (4MeDOL), dioxolane (DOL), 2-methyltetrahydrofuran (2MeTHF), tetrahydrofuran (THF), dimethoxyethane (DME), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) , And γ-butyrolactone (GBL). These solvent may be used individually by 1 type, and may be used in combination of 2 or more type. As the supporting salt (lithium salt) is not particularly _{limited, LiPF 6, LiBF 4, LiClO} 4, LiAsF 6, LiTaF 6, LiSbF 6, LiAlCl 4, Li 2 B 10 Cl 10, LiI, LiBr, LiCl Inorganic acid anion salts such as LiAlCl, LiHF ₂ , LiSCN, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiBOB (lithium bisoxide borate), LiBETI (lithium bis (perfluoroethylenesulfonylimide); And organic acid anion salts such as Li (C ₂ F ₅ SO ₂ ) ₂ N). These electrolyte salts may be used alone or in the form of a mixture of two or more.

  On the other hand, the polymer electrolyte is classified into a gel electrolyte containing an electrolytic solution and a polymer solid electrolyte containing no electrolytic solution.

[Gel electrolyte]
The gel electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer having lithium ion conductivity. Examples of the matrix polymer having lithium ion conductivity include a polymer having polyethylene oxide in the main chain or side chain (PEO), a polymer having polypropylene oxide in the main chain or side chain (PPO), polyethylene glycol (PEG), poly Acrylonitrile (PAN), polymethacrylic acid ester, polyvinylidene fluoride (PVdF), copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), poly (methyl acrylate) (PMA), poly (Methyl methacrylate) (PMMA) etc. are mentioned. In addition, mixtures of the above-described polymers, modified products, derivatives, random copolymers, alternating copolymers, graft copolymers, block copolymers, and the like can also be used. Among these, it is desirable to use PEO, PPO and their copolymers, PVdF, PVdF-HFP. In such a matrix polymer, an electrolyte salt such as a lithium salt can be well dissolved.

[Polymer solid electrolyte]
The polymer solid electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the above matrix polymer and does not contain an organic solvent. Therefore, when the electrolyte layer is composed of a polymer solid electrolyte, there is no fear of liquid leakage from the battery, and the battery reliability can be improved.

  A matrix polymer of a polymer gel electrolyte or a polymer solid electrolyte can exhibit excellent mechanical strength by forming a crosslinked structure. In order to form a crosslinked structure, thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte, using an appropriate polymerization initiator. A polymerization treatment may be performed. In addition, the said electrolyte may be contained in the active material layer of an electrode.

[Separator]
The separator is not particularly limited, and conventionally known separators can be appropriately used. For example, a porous sheet separator or nonwoven fabric separator made of a polymer or fiber that absorbs and holds the electrolyte can be used.

  As the separator of the porous sheet made of the polymer or fiber, for example, a microporous (microporous film) can be used. Specific examples of the porous sheet made of the polymer or fiber include polyolefins such as polyethylene (PE) and polypropylene (PP); a laminate in which a plurality of these are laminated (for example, three layers of PP / PE / PP) And a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.

  The thickness of the microporous (microporous membrane) separator cannot be uniquely defined because it varies depending on the intended use. For example, in applications such as secondary batteries for driving motors such as electric vehicles (EV), hybrid electric vehicles (HEV), and fuel cell vehicles (FCV), it is 4 to 60 μm in a single layer or multiple layers. Is desirable. The microporous (microporous membrane) separator preferably has a fine pore diameter of 1 μm or less (usually a pore diameter of about several tens of nanometers) and a porosity (porosity) of 20 to 80%. .

  As the nonwoven fabric separator, cotton, rayon, acetate, nylon, polyester; polyolefins such as PP and PE; conventionally known ones such as polyimide and aramid are used alone or in combination. The bulk density of the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated polymer gel electrolyte.

  The nonwoven fabric separator preferably has a porosity (porosity) of 45 to 90%. Furthermore, the thickness of the nonwoven fabric separator may be the same as that of the electrolyte layer, preferably 5 to 200 μm, particularly preferably 10 to 100 μm. When the thickness is less than 5 μm, the electrolyte retention deteriorates, and when it exceeds 200 μm, the resistance increases.

[Seal part]
The seal part 31 is a member peculiar to the bipolar battery 10 b shown in FIG. 2, and is disposed on the outer peripheral part of the single battery layer 19 for the purpose of preventing leakage of the electrolyte layer 17. In addition to this, it is possible to prevent current collectors adjacent in the battery from coming into contact with each other and a short circuit due to a slight unevenness at the end of the laminated electrode. In the form shown in FIG. 2, the seal portion 31 is sandwiched between the respective current collectors 11 constituting the two adjacent single battery layers 19 so as to penetrate the outer peripheral edge portion of the separator that is the base material of the electrolyte layer 17. Further, it is arranged on the outer peripheral portion of the unit cell layer 19. Examples of the constituent material of the seal portion 31 include polyolefin resins such as polyethylene and polypropylene, epoxy resins, rubber, and polyimide. Of these, polyolefin resins are preferred from the viewpoints of corrosion resistance, chemical resistance, film-forming properties, economy, and the like.

[Positive electrode current collector and negative electrode current collector]
The material which comprises a current collector plate (25, 27) is not restrict | limited in particular, The well-known highly electroconductive material conventionally used as a current collector plate for lithium ion secondary batteries can be used. As a constituent material of the current collector plate, for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable. Note that the positive electrode current collector plate 25 and the negative electrode current collector plate 27 may be made of the same material or different materials. Further, as shown in FIG. 2, the outermost layer current collector (11a, 11b) may be extended to form a current collector plate, or a separately prepared tab may be connected to the outermost layer current collector.

[Positive lead and negative lead]
Moreover, although illustration is abbreviate | omitted, you may electrically connect between the collector 11 and the current collector plates (25, 27) via a positive electrode lead or a negative electrode lead. As a constituent material of the positive electrode and the negative electrode lead, materials used in known lithium ion secondary batteries can be similarly employed. In addition, heat-shrinkable heat-shrinkable parts are removed from the exterior so that they do not affect products (for example, automobile parts, especially electronic devices) by touching peripheral devices or wiring and causing leakage. It is preferable to coat with a tube or the like.

[Exterior material]
As the exterior material 29, a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can seal the power generation element inside can be used. For example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto. A laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.

  In addition, said lithium ion secondary battery can be manufactured with a conventionally well-known manufacturing method.

[Appearance structure of lithium ion secondary battery]
FIG. 3 is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of the secondary battery.

  As shown in FIG. 3, the flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive electrode tab 58 and a negative electrode tab 59 for taking out electric power are drawn out from both sides thereof. Yes. The power generation element 57 is encased in an exterior material 52 of the lithium ion secondary battery 50, and the periphery thereof is heat-sealed. The power generation element 57 is sealed with the positive electrode tab 58 and the negative electrode tab 59 pulled out to the outside. ing. Here, the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery 10 shown in FIGS. 1 and 2 described above. The power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 13, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 15.

  The lithium ion secondary battery is not limited to a stacked flat shape. The wound lithium ion secondary battery may have a cylindrical shape, or may have a shape that is a flattened rectangular shape by deforming such a cylindrical shape. There is no particular limitation. In the said cylindrical shape thing, a laminate film may be used for the exterior material, and the conventional cylindrical can (metal can) may be used, for example, It does not restrict | limit. Preferably, the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.

  Also, the removal of the tabs 58 and 59 shown in FIG. 3 is not particularly limited. The positive electrode tab 58 and the negative electrode tab 59 may be drawn from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, as shown in FIG. It is not limited to things. Further, in a wound type lithium ion battery, instead of a tab, for example, a terminal may be formed using a cylindrical can (metal can).

  The lithium ion secondary battery is used as a power source for driving a vehicle or an auxiliary power source that requires a high volume energy density and a high volume output density as a large capacity power source for an electric vehicle, a hybrid electric vehicle, a fuel cell vehicle, and a hybrid fuel cell vehicle It can be suitably used.

  Although the said lithium ion secondary battery is demonstrated still in detail using a following example and a comparative example, it is not necessarily limited to a following example.

Example 1
LiMn ₂ O ₄ as a positive electrode active material, ketjen black as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder were prepared in an amount such that the composition ratio was 85: 5: 10. These were mixed and a positive electrode slurry was prepared using N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent.

  An aluminum foil (thickness: 20 μm) was prepared as a positive electrode current collector. The positive electrode slurry prepared above was applied to one side of an aluminum foil using a doctor blade, vacuum dried and pressed, and a positive electrode having a thickness of 80 μm was completed.

  Next, graphite as a negative electrode active material, ketjen black as a conductive auxiliary agent, and PVdF as a binder were prepared in amounts such that the composition ratio was 90: 5: 5 by weight. These were mixed, and negative electrode slurry was prepared using N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent.

  A copper foil (thickness: 20 μm) was prepared as a negative electrode current collector. The negative electrode slurry prepared above was applied to one side of a copper foil using a doctor blade, vacuum dried and pressed to complete a negative electrode having a thickness of 60 μm.

[Production of separator with gas adsorbing member]
A polyethylene porous film (thickness: 25 μm) having a porosity of 55% was punched into a square having a side of 6 cm. On one side of the punched film, a slurry in which 90% by weight of carbon molecular sieve and 10% by weight of an aqueous binder (styrene / butadiene rubber) were mixed as a gas adsorbing substance was applied by a bar coating method. Thereafter, vacuum drying was performed to produce a separator having a gas adsorbing member on one side having a width of 4.9 mm from the end of the separator and a thickness of 0.1 mm (see FIG. 4).

[Production of battery]
The positive electrode produced above was punched into a square with a side of 5 cm, and an Al tab was welded to the surface opposite to the electrode application surface. Next, the negative electrode was punched into a square having a side of 5.5 cm, and a Ni tab was welded to the surface opposite to the electrode application surface. Next, the positive electrode and the negative electrode were dried in a vacuum oven at 70 ° C. for 8 hours. The positive electrode, the separator, and the negative electrode were laminated in this order so that the gas adsorption member coated on the separator was opposed to the positive electrode side. At this time, the gas adsorption member coated on the separator was installed so as to be in the opposite direction to the tab. The obtained laminate is put in an aluminum laminate film outer packaging, dried again at 70 ° C., and then the electrolyte for the total amount of vacancies in the laminated contents is injected and vacuum sealed to produce a battery. did. Incidentally, the _{electrolyte, 1M LiPF 6 / (EC:} DEC) (EC: DEC = 1: 1 volume ratio) was used.

(Example 2)
A battery was produced in the same manner as in Example 1 except that the separator and the battery provided with the gas adsorbing member were produced by the following method.

[Production of separator with gas adsorbing member]
A polyethylene porous film having a porosity of 55% (thickness: 25 μm) was punched into a square having a side of 6 cm. A slurry obtained by mixing 90% by weight of carbon molecular sieve as a gas adsorbing substance and 10% by weight of an aqueous binder (styrene / butadiene rubber) as a gas adsorbing substance was applied to three sides of the punched film by a bar coating method. Then, vacuum drying was performed to produce a separator having gas adsorbing members on three sides having a width of 4.9 mm from the end of the separator and a thickness of 0.1 mm (see FIG. 5).

[Production of battery]
The produced positive electrode was punched into a square having a side of 5 cm, and an Al tab was welded on the surface opposite to the electrode application surface. Further, the negative electrode was punched into a square having a side of 5.5 cm, and a Ni tab was welded to the surface opposite to the electrode application surface. Next, the positive electrode and the negative electrode were dried in a vacuum oven at 70 ° C. for 8 hours. Subsequently, the positive electrode, the separator, and the negative electrode were laminated in this order so that the gas adsorbing member applied to the separator was opposed to the positive electrode side. At this time, the side where the tabs of the positive electrode and the negative electrode protrude was placed in the center of the separator so that the end surface overlaps the end surface of the separator. Further, the coated gas adsorbing member was laminated so as to be installed on the side other than the side where the tab is protruding. The obtained laminate was put into an aluminum laminate film outer package, dried at 70 ° C., and then an electrolyte solution corresponding to the total amount of vacancies in the laminated contents was injected and vacuum sealed to produce a battery. Incidentally, the _{electrolyte, 1M LiPF 6 / (EC:} DEC) (EC: DEC = 1: 1 volume ratio) was used.

(Comparative example)
A battery was fabricated in the same manner as in Example 1 except that the gas adsorbing member was not provided.

(Evaluation method)
The batteries of the above Examples and Comparative Examples were subjected to initial charge / discharge at 0.1 C for 24 hours (upper limit voltage 4.2V, lower limit voltage 2.5V). Next, a charge / discharge cycle test of 500 cycles at 1C was performed at 25 ° C, and a capacity measurement after the cycle test was measured by a charge / discharge measurement of 0.1C.

(Evaluation results)
The evaluation results obtained using the battery are shown in Table 1. Capacity maintenance rate is
Capacity maintenance rate (%) = 500 cycles after discharge capacity / initial discharge capacity.

  From Table 1, the batteries of Example 1 and Example 2 were superior in cycle characteristics as compared with the battery of Comparative Example 1 having no gas adsorption layer, and the effectiveness of the above embodiment could be confirmed.

  Moreover, it was confirmed from Table 1 that the cycle performance was improved in Example 2 with a large amount of the gas adsorbent as compared with Example 1. This result is considered to indicate that the capacity retention rate after the cycle is improved by removing the gas bubbles generated by the charging / discharging of the cell by the gas adsorbent provided in the cell.

10a, 10b, 50 lithium ion secondary battery,
11 positive electrode current collector,
12 negative electrode current collector,
13 positive electrode active material layer,
15 negative electrode active material layer,
17 electrolyte layer,
19 cell layer,
21, 57 power generation element,
22 separator,
23 Gas adsorption member,
25 positive current collector,
27 negative current collector,
29, 52 Exterior material,
31 seal part,
58 positive electrode tab,
59 Negative electrode tab.

Claims (4)

A power generation element in which an electrode and a separator are repeatedly laminated;
An exterior material that seals the power generation element inside;
A gas adsorbing member between the separators;
Have
Lithium ion secondary , wherein the electrode side end surface of the gas adsorbing member is disposed within a distance of the electrode thickness from the outer peripheral edge of the electrode, and the gas adsorbing member is disposed on the surface of the separator battery.   The lithium ion secondary battery according to claim 1, wherein a thickness of the gas adsorbing member is smaller than a thickness of the electrode. The lithium ion secondary battery according to claim 1 or 2 , wherein the gas adsorption member is installed on at least three sides of the separator. The lithium ion secondary battery according to any one of claims 1 to 3 , wherein the gas adsorbing substance contained in the gas adsorbing member is a porous metal compound or a porous carbon-based material.

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