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    • 专利摘要:
    SECONDARY NON-AQUEOUS ELECTROLYTE BATTERY. This secondary non-aqueous electrolyte battery has a power generating element (21) comprising a single cell layer (19) including: a positive electrode comprising a layer of the active material of the positive electrode (15) formed on the surface of a collector the positive electrode (12); a negative electrode comprising a layer of the active material of the negative electrode (13) formed on top of a negative electrode collector (11) and a separator (1) placed between the positive electrode and the negative electrode and having a non-aqueous electrolyte embedded in it . The RA value (= Rzjis (2) / Rzjis (1)) for the ratio between the surface roughness (Rzjis (1)) of the surface of the layer of the active material of the negative electrode (13) on the side in contact with the separator ( 1) and the surface roughness (Rzjis (2)) from the surface to the separator (1) on the side in contact with the active material layer of the negative electrode (13) is 0, 15 to 0.85. As a result, a high coefficient of kinetic friction can be obtained and the occurrence of misalignment of the lamination can be suppressed in one lamination step during the production of the secondary non-aqueous electrolyte battery.
    公开号:BR112014021393B1
    申请号:R112014021393-3
    申请日:2013-01-29
    公开日:2021-03-02
    发明作者:Miyuki Terado
    申请人:Envision Aesc Japan Ltd.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD:
    [001] The present invention relates to a secondary battery of non-aqueous electrolyte. PRECEDENT TECHNIQUE:
    [002] Recently, due to the greater orientation towards environmental preservation, electric vehicles (EV), hybrid electric vehicles (HEV) and fuel cell vehicles (FCV) are being developed. As a source of engine power for these vehicles, a repeatedly rechargeable secondary battery is suitable. In particular, secondary non-aqueous electrolyte batteries, such as a secondary lithium-ion battery with the expectation of high capacity and high performance, are attracting public attention.
    [003] The secondary non-aqueous electrolyte battery has, as a component part, an energy generating element comprising laminated single cell layers, each including a positive electrode, a negative electrode and an electrolyte layer disposed between the positive and negative electrodes.
    [004] Like the electrolyte layer, a structure including a separator made of a sheet of microporous resin and a non-aqueous electrolyte, such as a liquid electrolyte or gel electrolyte held in the separator is known. In the case of the secondary lithium-ion battery, the non-aqueous electrolyte contains organic solvent and lithium salt as essential components.
    [005] The separator that constitutes the electrolyte layer in each single cell layer requires both the function of maintaining the non-aqueous electrolyte to ensure an ionic conductivity between the positive and negative electrodes and the function of serving as a dividing wall between the positive and negative electrodes. In addition, in order to stop the charge / discharge reaction when the battery is at a high temperature, it is desirable that the separator has the function of stopping the migration of the ion and, until now, as such separator, a microporous film made Thermoplastic resin, such as polyolefin or the like, has been used.
    [006] However, in the case of using a separator made of a malleable material, such as polyolefin, there was a possibility that strange pieces left in the battery during the production of the battery and fragments of the active material layer of the electrode peeled from the electrodes could cross the separator to induce the undesirable internal short circuit.
    [007] In order to solve the aforementioned problem, Patent Document 1 proposed the idea in which, to suppress such an internal short circuit, a porous film made of a polyolefin or the like has at least one surface of it being a layer of breathable surface protection (heat-resistant insulating layer) including fine inorganic particles.
    [008] As a main step for the manufacture of the secondary non-aqueous electrolyte battery having the aforementioned structure, there is a process (lamination process) for producing an energy generating element by laminating a plurality of cell layers unique, each being produced by alternating lamination of the electrodes (positive electrode and negative electrode) and a separator. In this lamination process, the elements to be laminated must be precisely laminated or positioned in a lamination direction, in order to prevent misalignment of the lamination in the surface direction. If, in this lamination process, the elements are subjected to such lamination misalignment, the active materials contained in the layers of the active material cannot be adequately used for the loading / unloading reaction, resulting in a desired loading / unloading capacity not is obtained.
    [009] However, until now, a way to sufficiently suppress the above mentioned lamination misalignment is not known. According to the investigation by the inventor, it has been revealed that the misalignment of the lamination of the aforementioned type occurs remarkably at an interface between the active electrode material layer and the separator. BACKGROUND DOCUMENTS: PATENT DOCUMENTS:
    [010] Patent Document 1: Patent Application Open to Japanese Public Investigation (tokkaihei) 11-80395 SUMMARY OF THE INVENTION:
    [011] The present invention aims to present a way to effectively suppress lamination misalignment in the lamination process during the production of a secondary non-aqueous electrolyte battery.
    [012] In order to solve the problem of misalignment of the lamination mentioned above in the lamination process, a serious and intensive investigation was carried out by the inventor. As a result of this investigation, the inventor found that the problem mentioned above can be solved, in two elements that constitute an interface between the layer of active material of negative electrode in contact with the separator, by controlling a value for the ratio between the surface roughness of one of the elements and that of the other of the elements for a predetermined range.
    [013] A secondary non-aqueous electrolyte battery of an embodiment of the present invention, which has been completed in the above-mentioned manner, has a single cell layer energy generating element that includes a positive electrode including a layer of active material of positive electrode formed on a positive electrode collector surface, a negative electrode including a negative electrode active material layer formed on a negative electrode collector surface and a separator disposed between the positive electrode active material layer and the negative electrode active material layer in a way to contact the negative electrode active material layer, the separator having a non-aqueous electrolyte in it. In addition, in this secondary non-aqueous electrolyte battery, the value (which will be quoted as the surface roughness ratio) RA (= Rzjis (2) / Rzjis (1)) to the surface roughness ratio (Rzjis (1 )) of the surface of the negative electrode active material layer on the side in contact with the separator and the surface roughness (Rzjis (2)) of the separator surface on the side in contact with the negative electrode active material layer is 0, 15 to 0.85.
    [014] In the non-aqueous secondary electrolyte battery of the modality of the present invention, the dynamic friction coefficient between the active electrode material layer and the separator is controlled to a relatively large value. As a result, the misalignment of the lamination, which would occur in the lamination stage during the production of the secondary non-aqueous electrolyte battery, particularly in the lamination stage of the active electrode negative material layer and the separator, can be effectively suppressed. BRIEF DESCRIPTION OF THE DRAWINGS:
    [015] Figure 1 is a schematically illustrated sectional view of a secondary lithium ion battery which is an embodiment of the present invention.
    [016] Figure 2 is a schematically illustrated sectional view of a separator mounted on a heat-resistant insulating layer. MODE FOR IMPLEMENTING THE INVENTION:
    [017] In the following, an embodiment of the present invention will be described with reference to the accompanying drawings. In the drawings, the same elements are represented by the same numeral references and the repeated explanation of them will be omitted in the following description. The dimension ratio of the drawings is exaggerated for the sake of explanation and, thus, there are cases where the dimension ratio differs from an actual dimension ratio.
    [018] In the case of the classification of the non-aqueous secondary electrolyte battery with respect to the shape / structure, several types are listed which are, for example, a laminated type battery (flat type), a winding type battery ( type of cylinder), etc. Although any one of them is applicable in the invention, according to the present invention, a secondary non-aqueous electrolyte battery having a flat laminated (flat type) battery construction can exhibit the most notable effect. Thus, in the following explanation, to explain the secondary non-aqueous electrolyte battery having the construction of a flat-rolled (flat type) battery, a secondary lithium-ion battery will be described as an example of the invention.
    [019] Figure 1 is a schematically illustrated sectional view of a secondary lithium ion battery which is an embodiment of the present invention.
    [020] As seen in Figure 1, the secondary lithium-ion battery 10 of the modality has such a construction that a power generation element generally rectangular 21 that actually performs the charge / discharge reaction is hermetically sealed in a laminated sheet 29 that serves as an outer element. More specifically, by using a laminated sheet composed of polymer and metal as an outer element of the battery and joining all the peripheral portions of the outer element through thermal fusion, a construction is produced in which the power generating element 21 is hermetically wrapped in the outer element.
    [021] The power generating element 21 has such a construction that a negative electrode including a negative electrode collector 11 which has, on both of its surfaces, layers of the active material of negative electrode 13, a separator 17 and a positive electrode including a positive electrode collector 12 having, on both surfaces, layers of the positive electrode active material 15 are laminated or stacked. More specifically, the negative electrode, separator and positive electrode are laminated in that order, so that a layer of active material of negative electrode 13 and a layer of active material of positive positive electrode 15 are arranged to confront each other through the separator. 17. It should be noted that the separator 17 has a non-aqueous electrolyte (for example, liquid electrolyte) embedded in it.
    [022] Thus, the adjacent negative electrode, the separator and the positive electrode constitute a single cell layer 19. Thus, due to the lamination of a plurality of single cell layers 19, it can be said that the secondary lithium ion battery 10 of the modality has such a construction in order to establish a parallel electrical connection. The outermost negative electrode collectors arranged in the outermost layers of the power generating element 21 each have, on one surface, the layer of active material of negative electrode 13. If desired, by arrangement, in the outermost layers of the power generation element 21, of the outermost positive electrode collectors by reversing the arrangement of the negative and positive electrodes in relation to the arrangement shown in figure 1, a usable modification can be provided in which only one of the surfaces of each of the electrode collectors outermost positive has the positive electrode active material layer disposed on it. Naturally, in the case where, as shown in figure 1, the negative electrodes are arranged in the outermost layers of the power generating element 21, both surfaces of each of the outermost negative electrode collectors can be applied with the negative electrode active material layer. However, in this case, the layers of the active negative electrode material placed in the outermost layers of the power generating element are prevented from functioning.
    [023] In the collectors of the negative electrode 11 and in the collectors of the positive electrode 12, a collector plate of the negative electrode 25 and a collector plate of the positive electrode 27 are fixed respectively, which are guided to the respective electrodes (that is, positive electrode) and negative electrode). Each of these electrode collector plates 25 and 27 is extended to the outside of the laminate sheet 29 after being firmly placed between end portions of the laminate sheet 29. If desired, the collector plate of the negative electrode 25 and the collector plate of positive electrode 27 can be connected via negative and positive electrode conductors (not shown) to negative electrode collectors 11 and positive electrode collectors 12 by ultrasonic welding, resistance welding or the like. REASON FOR SURFACE Roughness
    [024] The secondary lithium-ion battery 10 of the modality is characterized in that the surface roughness ratio RA (= Rzjis (2) / Rzjis (1)), which is defined as a value for the surface roughness ratio (Rzjis (2)) of a separator surface 17 that contacts the negative electrode active material layer 13 in relation to the surface roughness (Rzjis (1)) of a surface of the negative electrode active material layer 13 that contacts the separator 17, is 0.15 to 0.85.
    [025] Now, it should be noted that the surface roughness (Rzjis) is a parameter called “average roughness of the ten points” and measured by a method that will be explained in a modality described here below. As RA, values in the aforementioned range are usable. Preferably, RA is equal to or less than 0.6, more preferably, equal to or less than 0.5, more preferably, equal to or less than 0.4, more preferably still, equal to or less than that 0.3 is most preferred, equal to or less than 0.25. Although the value of the lower limit of RA is not particularly limited, a value equal to or greater than 0.2 is usable in view of the possibility of realization.
    [026] As described here above, when the RA value is within the range of 0.15 to 0.85, the dynamic friction coefficient established between the negative electrode active material layer and the separator is controlled to a value relatively large as will be proved in a section of a modality later mentioned. As a result, in the lamination stage when the secondary non-aqueous electrolyte battery is manufactured, the occurrence of misalignment of the lamination at the moment when the layer of negative electrode active material and the separator are laminated can be effectively suppressed.
    [027] In a preferred embodiment of the present invention, in addition to the RA mentioned above, the surface roughness ratio between the positive electrode active material layer and the separator is also controlled. More specifically, in the secondary non-aqueous electrolyte battery of the present invention, the surface roughness ratio RB (= Rzjis (4) / Rzjis (3)), which is defined as the value of the surface roughness ratio (Rzjis (4 )) of a separator surface 17 that contacts the positive electrode active material layer 15 in relation to the surface roughness (Rzjis (3)) of a surface of the positive electrode active material layer 15 that contacts the separator 17, is 0.15 to 1.5.
    [028] When the RB value is within the aforementioned range, the dynamic friction coefficient established between the negative electrode active material layer and the separator and the dynamic friction coefficient established between the positive electrode active material layer and the separator has mutually close values, so that a construction is carried out, in which a similar slip is provided between the positive and negative electrodes, as will be proved in a section of a modality mentioned later. In general, in the lamination stage at the time when the secondary non-aqueous electrolyte battery is manufactured, the absolute value of the slip (ie, the dynamic friction coefficient) between the active material layer and the separator is an important factor to be considered. However, in parameters, such as the dynamic friction coefficient, it is preferable that the balance is established between the positive and negative electrodes in view of the productivity. Although the RB value is possible in the aforementioned range, preferably the value is equal to or greater than 0.5, more preferably the value is 0.5 to 1.25, more preferably, the value is 0 , 5 to 0.8 and much more preferably, the value is 0.5 to 0.6. In the other preferred embodiment, the RB value is greater than that of RA. When the battery of the invention has the aforementioned constructions, the effects of the invention can be more prominently displayed.
    [029] To control the surface roughness ratio (RA, RB) for the aforementioned preferable range, there is no specific limitation in the selection of the method. That is, a common general knowledge at the time when the present application is filed can be adequately cited. As an example to control the surface roughness of the surface of the active material layer, a method is exemplified in which the particle size of the active material contained in the active material layer is adjusted. In that case, if the particle size of the active material is increased, the surface roughness of the active material layer surface can be increased. As another example to control the surface roughness of the active material, there is a method in which the flattening of the surface of the active material layer is controlled by appropriately adjusting the condition of the compression treatment that can be carried out at the time of forming the active material layer. .
    [030] While, as a method to control the surface roughness of the separator surface, an example is exemplified in which, when a separator mounted on the heat-resistant insulating layer mentioned below (see figure 2), the area of specific BET surface and the particle size of the inorganic particles contained in the heat-resistant insulating layer are adjusted. In that case, when the BET-specific surface area and the particle size of the inorganic particles contained in the heat-resistant insulating layer are increased, the surface roughness of the separator surface can be increased. In addition, when elements (for example, a resin film or the like) other than the separator mounted on the heat-resistant insulating layer are used as the separator, the surface roughness of the separator surface can be controlled using a method in which a compression it is carried out by a pressure roller at a temperature below the melting point of the resin.
    [031] In the following, components of the aforementioned secondary lithium ion battery will be described. However, the present invention is not limited to the embodiment described below.
    [032] NEGATIVE ELECTRODE (NEGATIVE ELECTRODE ACTIVE MATERIAL LAYER)
    [033] The negative electrode has such a construction that a layer of active material of negative electrode 13 is formed on each surface of a negative electrode collector 11.
    [034] The negative electrode collector 11 is an element that electrically connects the layers of the active material of negative electrode 13 to an external element and is constructed of an electrically conductive material. The concrete construction of the collector is not particularly limited. A later mentioned construction of the positive electrode collector 12 is similarly usable.
    [035] The negative electrode active material layer 13 contains a negative electrode active material and can contain, when necessary, an electrically conductive material to increase its electrical conductivity and a binder. The negative electrode active material layer 13 may contain an electrolyte.
    [036] The negative electrode active material is not particularly limited, as long as it is made of a material that is capable of occluding and discharging lithium. Examples of the negative electrode active material are metals, such as Si, Sn and so on, metal oxides, such as TiO, Ti2O3, TiO2 or SiO2, SiO, SnO2 and the like, complex oxides made of lithium and transmission metal, such as such as Li4 / 3Ti5 / 3O4, Li7MnN and so on, alloys based on Li and Pb, alloys based on Li and Al, Li and carbon materials, such as natural graphite, artificial graphite, smoke grain, activated carbon , carbon fiber, coke, soft carbon, hard carbon and so on. Preferably, the negative electrode active material contains elements that can be bonded with lithium. With the use of elements that can be connected with lithium, it is possible to obtain a high capacity, high performance battery that has a high energy density when compared to a conventional battery made of carbon-based material. The aforementioned negative electrode active materials can be used individually or as a mixture of two or more of the materials.
    [037] Examples of the elements that can be linked with lithium are Si, Ge, Sn, Pb, Al, In, Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd , Hg, Ga, TI, C, N, Sb, Bi, O, S, Se, Te and CI, but in the invention, the elements are not limited to those listed. When considering an aspect of the possibility of producing a battery that is excellent in capacity and energy density, among the elements listed, it is preferable to contain at least one or more elements selected from a group consisting of carbon and / or Si material, Ge, Sn, Pb, Al, In and Zn and it is particularly preferable to contain the carbon material, Si or Sn. These elements can be used individually or two or more elements can be used simultaneously.
    [038] The average particle size of the negative electrode active material is not particularly limited. However, when considering the aspect of increasing the capacity, reactivity and durability of the negative electrode active material cycle, the average particle size is preferably 1 to 100 Dm and more preferably 1 to 20 Dm. Within such ranges, the increase in the internal resistance of the secondary battery at the time of charging / discharging under a condition of high performance is suppressed, and thus, sufficient electrical current can be obtained. When the negative electrode active material is from a secondary particle, it is preferable that the average particle size of the primary particles that make up the secondary particles is within a range of 10 nm to 1 Dm. However, in the invention, the average particle size is not necessarily limited to the aforementioned range. However, even though this depends on the production method, the negative electrode active material does not have to be the material that was formed for the secondary particle by condensation, agglomeration and so on. The particle size of the negative electrode active material and the particle size of the primary particle adopt the diameter so that it is measured by a laser diffraction / dispersion method. The shape of the negative electrode active material differs depending on the type and method of production of the material. Examples of the shape are a spherical shape (powdered shape), a tabular shape, a needle shape, a prism shape, a grain shape and so on. However, the shape is not limited to such shapes. That is, any form is usable without any problems. But, preferably, the selection should be made in the forms that are most suitable to improve the characteristics of the battery, such as charge / discharge characteristics and so on.
    [039] The electrically conductive material is contained in order to improve the electrical conductivity of the active material layer. The electrically conductive material used in this modality is not particularly limited. That is, known electrically conductive materials can be used properly. Examples of the conductive materials are carbon black, such as acetylene black, carbon black, channel black, thermal black, and so on; carbon fibers, such as steam-developed carbon fiber (VGCF) and so on, and carbon materials, such as graphite and so on. When the layer of the active material contains the electrically conductive material, electron networks are effectively produced in the layer of the active material and, thus, the performance characteristics of the battery are improved.
    [040] BINDING
    [041] Examples of the binder are not limited to those listed below. However, preferable examples are thermoplastic resins, such as polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyvinyl acetate, acrylic resin (for example, LSR and so on) and so on against; thermoset resins, such as polyimide, epoxy resin, polyurethane resin, urea resin and so on; and rubber-based materials, such as styrene butadiene rubber (SBR) and so on.
    [042] The concrete value of the surface roughness (Rzjis (1)) of the negative electrode active material layer 13 that contacts the separator 17 is not particularly limited. That is, the surface roughness can be adjusted accordingly, as long as it meets the above mentioned rules. Preferably, however, Rzjis (1) is 3.0 to 10.0 Dm and, more preferably, 3.0 to 6.0 Dm.
    [043] POSITIVE ELECTRODE (POSITIVE ELECTRODE ACTIVE MATERIAL LAYER)
    [044] The positive electrode has such a construction that a layer of active material of positive electrode 15 is formed on each surface of a positive electrode collector 12.
    [045] The positive electrode collector 12 is an element that electrically connects the layers of the positive electrode active material 15 to an external element and is constructed of an electrically conductive material. The concrete construction of the collector is not particularly limited. The collector material is not particularly limited, as long as the material has an electrical conductivity. That is, known conductive materials that have been used in ordinary lithium-ion secondary batteries can be used. As a collector material, electrically conductive metals and polymers can be used. More specifically, examples of the material are iron, chromium, nickel, manganese, titanium, molybdenum, vanadium, niobium, copper, silver, platinum, stainless steel, carbon and so on. These materials can be used individually or as an alloy or complex type. It should be noted that a structure having such a construction that an electrically conductive filler is dispersed in a base material made of non-conductive polymer can be used as an example of the collectors. The thickness of the collector is not particularly limited, but the thickness is usually 1 to 100 Dm. The size of the collector is decided according to the planned use of the secondary lithium-ion battery.
    [046] The positive electrode active material layer 15 contains a positive electrode active material and can contain, when necessary, an electrically conductive material to increase its electrical conductivity and a binder. The positive electrode active material layer 15 may contain an electrolyte.
    [047] The active material of the positive electrode is not particularly limited, as long as it is made of a material that is capable of occluding and discharging lithium. Positive electrode active materials commonly used in the secondary lithium ion battery can be used. More specifically, lithium transition metal compound oxides are preferable and examples of them are compound oxides based on Li and Mn, such as LiMn2O4 and so on, compound oxides based on Li and Ni, such as LiNiO2 and so on. on and compound oxides based on Li, Ni and Mn, such as LiNi0.5Mn0.5O2 and so on. In some cases, two or more of the above mentioned examples of the positive electrode active material are usable together.
    [048] The average particle size of the positive electrode active material is not particularly limited. However, when considering an aspect of increased capacity, reactivity and durability of the positive electrode active material cycle, the average particle size is preferably 1 to 100 μm and more preferably, 1 to 20 μm. Within such ranges, the increase in the internal resistance of the secondary battery at the time of charging / discharging under a condition of high performance is suppressed, and thus, sufficient electrical current can be obtained. When the positive electrode active material is of a secondary particle, it is preferable that the average particle size of the primary particles that constitute the secondary particles is within a range of 10 nm to 1 μm. However, in the invention the average particle size is not necessarily limited to the aforementioned range. However, even though this depends on the production method, the negative electrode active material does not have to be the material that was formed for the secondary particles by condensation, agglomeration and so on. The particle size of the negative electrode active material and the particle size of the primary particle adopt the diameter so that it is measured by a laser diffraction / dispersion method. The shape of the negative electrode active material differs depending on the type and method of production of the material. Examples of the shape are a spherical shape (powdered shape), a tabular shape, a needle shape, a prism shape, a grain shape and so on. However, the shape is not limited to such shapes. That is, any form is usable without any problems. But, preferably, the selection should be made in the forms that are most suitable to optimize the characteristics of the battery, such as charge / discharge characteristics and so on.
    [049] Since examples of the electrically conductive material and the binder that may be contained in the positive electrode active material layer 15 are those explained in the negative electrode active material layer 13 section, their detailed explanation will be omitted.
    [050] The concrete value of the surface roughness (Rzjis (3)) of the positive electrode active material layer 15 that contacts the separator 17 is not particularly limited. That is, the surface roughness can be suitably adjustable, as long as it meets the above mentioned rules. However, preferably, Rzjis (3) is 1.5 to 3.5 μm and, more preferably, 2.0 to 3.0 μm. SEPARATOR
    [051] The separator 17 acts as a spatial dividing wall (spacer) that is supplied between the negative electrode active material layer 13 and the positive electrode active material layer 15. In addition to this function, the separator can function as a resource that holds in it a non-aqueous electrolyte or medium through which the lithium ion moves between the positive and negative electrodes at the time of charging / discharging.
    [052] As mentioned above, the separator 17 keeps the non-aqueous electrolyte in it. The concrete shape of the non-aqueous electrolyte maintained in the separator 17 is not particularly limited. That is, how non-aqueous electrolyte, liquid electrolyte and polymer gel electrolyte can be used.
    [053] Liquid electrolyte is obtained by dissolving the lithium salt in an organic solvent. Examples of the organic solvent are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propionate (MP), methyl acetate (MA), methyl formate (MF), 4-methyldioxolane (4MeDOL), dioxolane (DOL), 2-methyltetrahydrofuran (2MeTHF), tetrahydrofuran (THF), dimethoxyethane (DME), ethylene carbonate (EC), propylene carbonate (PC), carbonate butylene (BC), y-butyrolactone (GBL) and so on. These solvents can be used individually or as a mixture of two or more of the solvents.
    [054] The type of lithium salt is not particularly limited. However, examples of the lithium salt are anionic salts of inorganic acid, such as LiPF6, LiBF4, LiClO4, LiAsF6, LiTaF6, LiSbF6, LiAlCl4, Li2B10Cl10, Lil, LiBr, LiCl, LiAlCl, LiHF2, LiSCN and so on and anionic salts of organic acid, such as LiCF3SO3, Li (CF3SO2) 2N, LiBOB (lithiobisoxydeborate), LiBETI (lithiobis perfluoroethylenesulfonylamide); which is also represented by Li (C2F6SO2) 2N) and so on. These lithium salts can be used individually or as a mixture of two or more of the lithium salts.
    [055] Meanwhile, the gel electrolyte is obtained by pouring the aforementioned liquid electrolyte into a matrix polymer that has a lithium ion conductivity. Examples of the lithium ion conduction matrix polymer are polymers (PEO) that have polyethylene oxide in a main or secondary chain, polymers (PPO) that have polypropylene oxide in a main or secondary chain, polyethylene glycol (PEG) , polyacrylonitrile (PAN), polymethacryl ester, polyvinylidene fluoride (PVdF), polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), poly (methylacrylate) (PMA), poA, poA methyl methacrylate) (PMMA) and so on. In addition to the aforementioned polymers, a mixture of the polymers, modified, derivative, random copolymer, alternating cup-polymer, graft copolymer, block copolymer and so on can be used. Among them, the use of PEO, PPO, PEO copolymer and PPO, PVdF or PVdF-HFP is preferable. Lithium salts are well dissolved in such matrix polymers. The electrolyte matrix polymers of the polymer gel can exhibit excellent mechanical strength when having a cross-linked structure. In order to provide matrix polymers with such a cross-linked structure, it is only necessary that, with the help of a suitable polymerization initiator, a polymerizable polymer (eg PEO and PPO) prepared to produce a polymer electrolyte is subjected to a polymerization treatment, such as thermal polymerization, ultraviolet ray polymerization, radiation polymerization, electronic beam polymerization or the like. The non-aqueous electrolyte mentioned above may be contained in the active material layer of the electrodes.
    [056] Meanwhile, a concrete element used to form the separator 17 is a thin porous membrane constructed of, for example, polyolefin, such as polyethylene, polypropylene or the like, hydrocarbon, such as polyvinylidene and hexafluoropropylene fluoride (PVdF- HFP) or similar or fiberglass.
    [057] According to the inventor's investigation, it has been revealed that the misalignment of the lamination that appears at an interface between the layer of active material of negative electrode and the separator in the lamination stage during the production of the secondary electrolyte battery does not aqueous is notable when a separator with a heat resistant insulating layer (which will be referred to as the “heat resistant insulating layer separator” below for ease of explanation) revealed in the above mentioned Patent Document 1 is practically used and has been verified that such misalignment of the lamination, which occurred when the separator mounted on the heat resistant insulating layer was practically used, is effectively suppressed when a construction according to the present invention is used practically. Thus, in a preferred embodiment of the present invention, as a separator 17 that forms part of the secondary non-aqueous electrolyte battery, a so-called separator mounted on the heat-resistant insulating layer is used. In the following, the preferred embodiment in the case where the separator 17 is the separator mounted on the heat resistant insulating layer will be described.
    [058] In figure 2, a schematic illustrated sectional view of the separator mounted on the heat-resistant insulating layer that is used in the modality is shown. The separator mounted on the heat resistant insulating layer 1 shown in figure 2 comprises a porous base layer 3 which forms on both surfaces from which the heat resistant insulating layers (5a, 5b) are formed. The porous base layer 3 is a thin porous membrane constructed of, for example, polyethylene. The heat-resistant insulating layers (5a, 5b) each have such a construction that particles of alumina (Al2O3) are connected or bonded through the binder which is, for example, carboxymethyl cellulose (CMC). Since the heat-resistant insulating layers (5a, 5b) each have a porous structure due to the presence of spaces or gaps produced by the bonded alumina particles, the separator 1 with the heat-resistant insulating layers has a porous construction as one all. In this way, the separator 1 with the heat-resistant insulating layers functions as a separator that has a lithium ion conductivity as a whole. In the following, elements of construction of the separator mounted on the heat-resistant insulating layer shown in figure 2 will be described. POROUS BASE LAYER
    [059] As seen in figure 2, the porous base layer 3 serves as a base element at the time of the formation of the heat-resistant insulating layers (5a, 5b). Although the material of the porous base layer 3 is not particularly limited, resin materials such as thermoplastic resin, thermoset resin and so on, metallic materials and cellulosic materials can be used. When considering an aspect of the need to provide the separator mounted on the heat-resistant insulating layer with a stopping function, it is preferable to use a porous base element made of resin material (the element of which will be called “porous resin base layer” Next).
    [060] Examples of the resin material that forms the resinous porous base layer are polyethylene (PE), polypropylene (PP), copolymer obtained by copolymerizing ethylene and propylene (copolymer of ethylene and propylene), copolymer obtained by copolymerizing the ethylene or propylene with a monomer other than ethylene and propylene, polystyrene (PS), polyvinyl acetate (PVAc), polyethylene terephthalate (PET), polyvinylidene fluoride (PFDV), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyethersulfone (PES ), polyetheretherketone (PEEK), polyimide (PI), polyamide (PAI), phenol resin (PF), epoxy resin (EP), melamine resin (MF), urea resin (UF), alkyd resin , polyurethane (PUR) and so on. These resins can be used individually or as a mixture of two or more of the resins.
    [061] In order to provide the separator mounted on the heat-resistant insulating layer with a standstill function in a temperature range of 120 to 200 ° C, it is preferred that the resin material to form the resinous porous base layer contains a resin whose melting temperature is 120 to 200 ° C. More specifically, it is preferable to use a layer of resinous porous base containing polyethylene (PE), polypropylene (PP), copolymer obtained by copolymerizing ethylene and propylene (copolymer of ethylene and propylene), copolymer obtained by copolymerizing ethylene or propylene with monomer other than ethylene and propylene or similar. When the resin material to form the resinous base layer contains a resin of which the melting temperature is 120 to 200 ° C, a thermoplastic resin or thermoset resin of which the melting temperature exceeds 200 ° C can be used together. In that case, the ratio of the amount of resin from which the melting temperature is 120 to 200 ° C to the total amount of the resinous porous base layer is preferably equal to or greater than 50% weights, more preferable equal to or greater than 70 pesos%, much more preferable equal to or greater than 90 pesos%, particularly preferable equal to or greater than 95 pesos%, more preferably 100 pesos%.
    [062] In addition, a laminated sheet produced by laminating two or more of the aforementioned or other resin materials can be used as the resinous porous base layer. An example is a layer of porous resinous base that has a three-layer structure of PP / PE / PP. Since the PE melting temperature is 130 ° C, the resinous porous base layer of the three-layer structure can exhibit the standstill function when the battery temperature reaches 130 ° C. Even if the battery temperature were to increase further, the entire surface short circuit can be suppressed because the melting temperature of the PP is 170 ° C and thus the separator has an optimized safety.
    [063] The shape of the resinous porous base layer is not particularly limited and woven cloth, non-woven cloth, fine porous membrane and so on are usable. Among them, the thin porous membrane is preferable when considering from an aspect of the need to obtain a high conductivity of the lithium ion. In addition, the porosity of the resinous porous base layer is preferably 40 to 85%, more preferably 50 to 70%, much more preferably 55 to 60%. By adjusting the porosity in the above mentioned ranges, sufficient lithium ion conductivity and resistance can be obtained.
    [064] The thickness of the resinous porous base layer is not particularly limited. Preferably, however, the thickness is 1 to 200 μm, more preferably 5 to 100 μm, much more preferably 7 to 30 μm, particularly preferably 10 to 20 μm. When this thickness is equal to or greater than 5 μm, the electrolyte has a satisfied retention property. Meanwhile, when the thickness is equal to or less than 200 μm, an excessive increase in strength does not occur easily. HEAT RESISTANT INSULATING LAYER
    [065] The heat-resistant insulating layer (5a, 5b) is arranged on one surface or both surfaces of the porous base layer mentioned above and has the function of re-energizing the separator resistance. Particularly, in the case of the resinous porous base layer of which the porous base layer is made of resin material, the heat-resistant insulating layer acts as a part to facilitate the internal tension that would be produced when the battery temperature rises and acts as a part of suppressing the deformation of the separator that would be caused by thermal contraction. The heat-resistant insulating layer contains inorganic particles and a binder.
    [066] Inorganic particles contribute to increase the mechanical strength and the effect of suppressing the thermal contraction of the heat-resistant insulating layer. The materials used as inorganic particles are not particularly limited. Examples of the materials are oxides of silicon, aluminum, zirconium, and titanium (SiO2, Al2O3, ZrO2, TiO2), hydroxides, nitrides, and complexes made from these materials. These inorganic particles can be based on mineral resources, such as boemite, zeolite, apatite, kaolin, mullite, spinel, olivine, mica and so on, or they can be artificially produced. In addition, one type of these inorganic particles can be used individually or two or more of them can be used together. Among them, the use of silica (SiO2) or alumina (Al2O3) is preferable when considering a cost aspect and the use of alumina (Al2O3) is more preferable.
    [067] The binder acts as a part to bond the inorganic particles, as well as to bond the inorganic particles and the resinous porous base layer. Due to the binder, the heat resistant insulating layer is formed stably and the separation between the porous base layer and the heat resistant insulating layer is eliminated.
    [068] Binders used for the heat-resistant insulating layer are not particularly limited. That is, binders generally used are appropriately adopted by those skilled in the art. Examples of binders are compounds, such as carboxymethyl cellulose (CMC), polyacrylonitrile, cellulose, ethylene and vinyl acetate copolymer, polyvinyl chloride, styrene butadiene rubber (SBR), isoprene rubber, butadiene rubber, polyvinyl fluoride - deno (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), methyl acrylate and so on. Among them, the use of carboxymethyl cellulose (CMC), methyl acrylate or polyvinylidene fluoride (PVDF) is preferable. One type of these compounds can be used individually or two or more of them can be used together.
    [069] Preferably, the content of the binder in the heat-resistant insulating layer is 2 to 20% pesos compared to 100 pesos% of the heat-resistant insulating layer. When the content of the binder is equal to or greater than 2 weights%, the peeling resistance between the heat-resistant insulating layer and the porous base layer can be increased and the vibration resistance of the separator can be improved. Meanwhile, when the content of the binder is equal to or less than 20 wt%, the spaces or gaps between the inorganic particles can be adequately maintained and, thus, sufficient conductivity of the lithium ion can be obtained.
    [070] The thickness of each heat-resistant insulating layer is preferably 1 to 20 μm, more preferably 2 to 10 μm, much more preferably 3 to 7 μm. When the heat resistant insulating layer is of such thickness, the separator mounted on the heat resistant insulating layer is provided with sufficient mechanical strength and prevented from having an excessive volume and weight and, therefore, such thickness is desirable.
    [071] In the case where the heat resistant insulating layer is provided on both surfaces of the porous base layer, the components of the two heat resistant insulating layers can be the same or different. However, when considering the aspect of easy handling in production, it is preferable that the components are the same.
    [072] The thickness of the entire construction of the separator mounted on the heat-resistant insulating layer is not particularly limited, as long as the construction guarantees sufficient strength. However, when considering an aspect of reducing the size of the battery, it is preferable that the thickness is not too large. More specifically, the thickness of the separator mounted on the heat-resistant insulating layer is preferably 10 to 50 μm, more preferably 15 to 30 μm.
    [073] The production method of the separator mounted on the heat-resistant insulating layer is not particularly limited. That is, the separator can be produced using and referring appropriately to known techniques. In the following, a method of producing a separator mounted on the heat resistant insulating layer in the case of using the porous resinous base layer as the porous base layer will be described.
    [074] In the case of producing a thin porous polyolefin membrane as a porous resin based element, the polyolefin is first dissolved in a solvent, such as paraffin, liquid paraffin, paraffin oil, tetralin, ethylene glycol, glycerin, decalin or the like. Then, it is extruded into a sheet-like object, the solvent is removed from the object, and then the object is subjected to uniaxial and biaxial stretching (simultaneously or successively) to produce the fine porous membrane.
    [075] In the following, the method of forming the heat-resistant insulating layer on the resinous porous base element will be described. First, inorganic particles and binder are dispersed in a solvent to prepare the liquid for the dispersion. Then, the dispersion liquid is applied to one surface or both surfaces of the resinous porous base element and the base element applied with the dispersion liquid is dried to form the heat resistant insulating layer.
    [076] As the solvent for the dispersion liquid, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, cyclohexane, hexane, water or the like can be used. In the case of using polyvinylidene fluoride as the binder (PVDF), it is preferable to use NMP as a solvent.
    [077] Then, the aforementioned dispersion liquid is coated on the resinous porous base element. The method of this coating is not particularly limited. For example, the knife coating method, engraving coating method, screen printing method, Meyer-bar method, matrix coating method, reverse roller coating method, inkjet method, spray method or similar can be used. By adjusting the amount of the coated dispersion liquid in the resinous porous base element, the aforementioned coating ratio can be controlled over a predetermined range. An example is to adjust the amount of the coated dispersion liquid in the base element, so that the coated amount of the heat-resistant insulating layer shows approximately 5 to 20 g / m2.
    [078] Like the solvent, the temperature is preferably 50 to 70 ° C. However, if NMP is used as the solvent, the temperature is preferably 70 to 90 ° C. If necessary, the solvent can be dried under decompression. In addition, if necessary, part of the solvent can remain without removing the entire amount of the solvent.
    [079] In the above, the separator mounted on the heat-resistant insulating layer which is a preferable example of separator 17 has been explained in detail. However, the technical range of the invention is not limited to such an example. In other words, even though a separator has a different construction than the separator mounted on the heat-resistant insulating layer, the separator can exhibit effects of the present invention, as long as the separator satisfies the required conditions defined by the claims.
    [080] The concrete value of the surface roughness (side of the negative electrode active material layer: Rzjis (2), side of the positive electrode active material layer: Rzjis (4)) of the separator surface 17 is not particularly limited . That is, the surface roughness can be adjusted accordingly to meet the above mentioned rules. However, Rzjis (2) and Rzjis (4) are each preferably 1.0 to 4.0 μm, more preferably 1.0 to 3.0 μm. Although Rzjis (2) and Rzjis (4) can be identical or different, it is preferable that they are identical. POSITIVE ELECTRODE COLLECTOR PLATE AND NEGATIVE ELECTRODE COLLECTOR PLATE
    [081] The materials for the collector plates (25, 27) are not particularly limited. That is, high conductivity materials known until now used as the materials for the collector plates of the secondary lithium ion battery can be used. The preferred material for the collector plates is, for example, aluminum, copper, titanium, nickel, stainless steel (SUS), alloys of these metals or the like. When considering a low weight, corrosion resistance and high conductivity aspect, the most preferable material is aluminum and / or copper and the most preferable material is still aluminum. For the positive electrode collector plate 27 and the negative electrode collector plate 25, the same or different materials can be used. POSITIVE ELECTRODE CONDUCTOR AND NEGATIVE ELECTRODE CONDUCTOR
    [082] Although not shown in the drawings, each electrode collector 11 and each collector plate (25, 27) can be electrically connected via a positive electrode conductor or negative electrode conductor. Materials for the positive and negative electrode conductors can use materials that are generally used in a known secondary lithium-ion battery. Preferably, portions of the conductors that are exposed to an external cover are covered with heat-shrinkable tubes and heat-resistant insulators in order to prevent short-circuiting with a peripheral device and wiring. In fact, such a short circuit affects products (for example, auto parts, particularly electronic devices). EXTERNAL COVERAGE
    [083] As seen in figure 1, a laminated sheet 29 can be used as the outer covering. The laminated sheet has a three-layer structure including, for example, a polypropylene film, an aluminum film and a nylon film which are laminated or placed on top of one another in that order. In some cases, a known conventionally used metal can be used as the outer covering. MODALITIES:
    [084] In the following, modalities of the present invention will be described concretely. However, it should be noted that the technical range of the present invention is not limited to the following modalities. VARIOUS MEASUREMENT METHODS
    [085] In the comparative modalities and examples, the following methods were used to measure the surface roughness (Rzjis) of a surface of an element and the dynamic friction coefficient of the element. SURFACE HARDNESS MEASUREMENT (Rzjis)
    [086] Using a laser microscope, the surface roughness of an element (ie, separator or layer of the active material) was measured. Specifically, a surface of a part with the size of 128 μm x 100 μm was observed and the surface roughness (Rzjis) of the 128 μm range was measured from a line cut profile at an arbitrary point. MEASUREMENT OF THE DYNAMIC FRICTION COEFFICIENT
    [087] Following the method of measuring the friction coefficient defined in JIS No. k7125, an electrode (positive electrode or negative electrode) was placed in a separator and a slide piece (200 g) was placed on the electrode. Then, the displacement of the charge was measured at the moment when one end of the electrode was pulled at a speed of 100 mm / min by a tensile strength tester. The average (ie average load value) of the loads appeared at positions 20 to 100 mm from a measurement start position that was made as a dynamic friction energy and the dynamic friction energy was divided by the normal energy of the slide piece to calculate the dynamic friction coefficient. FIRST MODE OF NEGATIVE ELECTRODE PRODUCTION
    [088] 96.5% weights of artificial graphite (average particle size: 15 μm) as a negative electrode active material and 3.5% weights of polyvinylidene fluoride as a binder were dispersed in N-methyl-2 -pyrrolidone (NMP) to produce a slurry.
    [089] With the help of a matrix coating device, the slurry was coated on a surface of a 10 μm thick copper sheet and after being dried at 120 ° C for 3 minutes, the coated copper sheet with the slurry the compression was molded by a roller press machine. For this process, the amount of coating of the slurry and the condition of the press were adjusted, so that the amount of application of the solid content (active and binding material) of the negative electrode was 106 g / m2 and the mass density of the layer of the active material was 1.35 g / cm3.
    [090] The surface roughness (Rzjis (1)) of the negative electrode active material layer surface of the negative electrode produced in the above-mentioned manner was 5.91 μm. POSITIVE ELECTRODE PRODUCTION
    [091] 92.2 wt% oxide composed of lithium and cobalt (LiCoO2) as the positive electrode active material, 4.6 wt% acetylene black as the electrically conductive material and 3.2 wt% polyvinylidene fluoride as a binder they were dispersed in N-methyl-2-pyrrolidone (NMP) to produce a slurry.
    [092] With the help of a matrix coating device, the slurry was coated on a surface of 20 μm thick aluminum foil and, after being dried at 130 ° C for 3 minutes, the foil coated with slurry was molded to compression by a roller press machine. For this process, the amount of coating of the slurry and the condition of the press were adjusted, so that the amount of application of the solid content (active material, electrically conductive and binding material) of the positive electrode was 250 g / m2 and the density mass of the active material layer was 3.00 g / cm3.
    [093] The surface roughness (Rzjis (3)) of the surface of the positive electrode active material layer of the positive electrode produced in the aforementioned manner was 2.46 μm. PREPARATION OF NON AQUEOUS ELECTROLYTE
    [094] In a mixed solvent of “ethylene carbonate: ethyl carbonate = 1: 2 (volume ratio)”, LiPF6 as a solute was dissolved by an amount that indicates a concentration of 1.0 mol / L. With this process, the non-aqueous electrolyte was prepared. SEPARATOR PRODUCTION
    [095] A separator mounted on the heat-resistant insulating layer was produced that comprises a porous polyolefin resin membrane (thickness: 30 μm) obtained by performing a biaxial stretching and heat-resistant insulating layers (thickness in each layer: 5 μm) arranged respectively on both surfaces of the porous membrane. Specifically, firstly, 95% weights of alumina particles (BET specific surface: 5 m2 / g, average particle size: 0.48 μm) as inorganic particles and 5%% polyethylene as a binder were dispersed in water to prepare a fluid paste. Then, with the help of an engraving coating device, the slurry was coated on the porous polyolefin resin membrane (thickness: 16 μm) and then the slurry-coated porous membrane was dried at 60 ° C to remove the Water. With this process, the separator mounted on the heat-resistant insulating layer was produced.
    [096] The surface roughness of the separator surface produced in the aforementioned manner was 1.38 μm on both surfaces (Rzjis (2) and Rzjis (4)). That is, the ratio of the surface roughness (RA) between the separator surface and the surface of the negative electrode active material layer was represented by RA = Rzjis (2) / Rzjis (1) = 1.38 / 5.91 = 0.23 and the surface roughness ratio (RB) between the separator surface and the surface of the positive electrode active material layer was represented by RB = Rzjis (4) / Rzjis (3) = 1.38 / 2 , 46 = 0.56. And the dynamic friction coefficient between the separator surface and the negative electrode active material layer surface was 0.27 and the dynamic friction coefficient between the separator surface and the positive electrode active material layer surface was 0. , 35. SECOND MODE
    [097] To produce a separator mounted on the heat-resistant insulating layer of this second modality, substantially the same production process as that of the first aforementioned modality was performed, except that to produce the heat-resistant insulating layers, alumina particles from which the specific BET surface is 15 m2 / g of which the average particle size is 0.55 μm were used as inorganic particles.
    [098] The surface roughness of the separator surface produced in the aforementioned manner was 1.48 μm on both surfaces (Rzjis (2) and Rzjis (4)). That is, the ratio of the surface roughness (RA) between the separator surface and the surface of the negative electrode active material layer was represented by RA = Rzjis (2) / Rzjis (1) = 1.48 / 5.91 = 0.25 and the surface roughness ratio (RB) between the separator surface and the surface of the positive electrode active material layer was represented by RB = Rzjis (4) / Rzjis (3) = 1.48 / 2 , 46 = 0.60. And the dynamic friction coefficient between the separator surface and the negative electrode active material layer surface was 0.23 and the dynamic friction coefficient between the separator surface and the positive electrode active material layer surface was 0. , 35. THIRD MODE
    [099] To produce the separator mounted on the heat-resistant insulating layer of this third modality, substantially the same production process as that of the first modality mentioned above was performed, except that to produce the heat-resistant insulating layers, alumina particles from which the specific BET surface is 52 m2 / g of which the average particle size is 2.8 μm were used as inorganic particles.
    [0100] The surface roughness of the separator surface produced in the aforementioned manner was 2.97 μm on both surfaces (Rzjis (2) and Rzjis (4)). That is, the surface roughness ratio (RA) between the separator surface and the surface of the negative electrode active material layer was represented by RA = Rzjis (2) / Rzjis (1) = 2.97 / 5.91 = 0.50 and the surface roughness ratio (RB) between the separator surface and the surface of the positive electrode active material layer was represented by RB = Rzjis (4) / Rzjis (3) = 2.97 / 2 , 46 = 1.21. And the dynamic friction coefficient between the separator surface and the negative electrode active material layer surface was 0.22 and the dynamic friction coefficient between the separator surface and the positive electrode active material layer surface. was 0.44. COMPARATIVE EXAMPLE
    [0101] To produce this comparative example, substantially the same production process as that of the third modality mentioned above was performed, except that as the negative electrode active material contained in the negative electrode active material layer, a material of which the size particle average is 12 μm was used.
    [0102] The surface roughness (Rzjis (1)) of the surface of the negative electrode active material layer of the negative electrode produced in the aforementioned manner was 3.34 μm. That is, the surface roughness (RA) ratio between the separator surface and the surface of the negative electrode active material layer was represented by RA = Rzjis (2) / Rzjis (1) = 2.97 / 3.34 = 0.89 and the surface roughness ratio (RB) between the separator surface and the surface of the positive electrode active material layer was represented by RB = Rzjis (4) / Rzjis (3) = 2.97 / 2 , 46 = 1.21. And the dynamic friction coefficient between the separator surface and the negative electrode active material layer surface was 0.19 and the dynamic friction coefficient between the separator surface and the positive electrode active material layer surface was 0. , 47. TABLE-1


    [0103] As will be understood by Table-1, when the surface roughness (RA) ratio between the active electrode negative material layer and the separator is within a predetermined range, the dynamic friction coefficient between the material layer negative electrode active and the separator can be controlled to a high value. Thus, in accordance with the present invention, it is expected that the occurrence of misalignment of the lamination can be effectively suppressed in a lamination step during the production of the secondary non-aqueous electrolyte battery.
    权利要求:
    Claims (4)
    [0001]
    1. Secondary battery of non-aqueous electrolyte having a power generation element with a single cell layer, FEATURED by the fact that it includes: a positive electrode including a layer of positive electrode active material formed on a surface of an electrode collector positive, a negative electrode including a layer of active negative electrode material formed on a negative electrode collector surface; and a separator disposed between the positive electrode active material layer and the negative electrode active material layer in a way to contact the negative electrode active material layer, the separator having a non-aqueous electrolyte in it, in which the RA value (= Rzjis (2) / Rzjis (1)) for the ratio between the surface roughness (Rzjis (1)) of the surface of the negative electrode active material layer on the side in contact with the separator and the surface roughness (Rzjis (2)) the separator surface on the side in contact with the negative electrode active material layer is 0.15 to 0.85, where the separator is disposed between the positive electrode active material layer and the material layer negative electrode active in a way to contact the positive electrode active material layer, where the RB value (= Rzjis (4) / Rzjis (3)) for the ratio of the surface roughness (Rzjis (3)) of surface of the positive electrode active material layer on the side in contact with the eparator and the surface roughness (Rzjis (4)) of the separator surface on the side in contact with the positive electrode active material layer is greater than 0.15 and less than or equal to 1.5, where the RB value is greater than the RA value.
    [0002]
    2. Secondary non-aqueous electrolyte battery, according to claim 1, CHARACTERIZED by the fact that the separator is a separator mounted on the heat-resistant insulating layer comprising: a porous base layer; and a heat-resistant insulating layer that is formed on one or both surfaces of the porous base layer and includes inorganic particles and a binder.
    [0003]
    3. Secondary non-aqueous electrolyte battery, according to claim 1, CHARACTERIZED by the fact that the RB value is equal to or greater than 0.5.
    [0004]
    4. Secondary non-aqueous electrolyte battery, according to claim 2, CHARACTERIZED by the fact that the RB value is equal to or greater than 0.5.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-10-29| B25A| Requested transfer of rights approved|Owner name: ENVISION AESC JAPAN LTD. (JP) |
    2020-12-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012042134A|JP5910164B2|2012-02-28|2012-02-28|Nonaqueous electrolyte secondary battery|
    JP2012-042134|2012-02-28|
    PCT/JP2013/051886|WO2013129009A1|2012-02-28|2013-01-29|Non-aqueous electrolyte secondary battery|
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