WO2007032365A1 - Électrode utilisée dans une batterie - Google Patents

Électrode utilisée dans une batterie Download PDF

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Publication number
WO2007032365A1
WO2007032365A1 PCT/JP2006/318114 JP2006318114W WO2007032365A1 WO 2007032365 A1 WO2007032365 A1 WO 2007032365A1 JP 2006318114 W JP2006318114 W JP 2006318114W WO 2007032365 A1 WO2007032365 A1 WO 2007032365A1
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WO
WIPO (PCT)
Prior art keywords
active material
battery
electrode active
material layer
positive electrode
Prior art date
Application number
PCT/JP2006/318114
Other languages
English (en)
Japanese (ja)
Inventor
Kazuki Miyatake
Tamaki Miura
Tomaru Ogawa
Mikio Kawai
Original Assignee
Nissan Motor Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Motor Co., Ltd. filed Critical Nissan Motor Co., Ltd.
Publication of WO2007032365A1 publication Critical patent/WO2007032365A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a battery electrode.
  • the present invention relates to an improvement for improving the output characteristics of a battery.
  • a lithium ion secondary battery As a secondary battery for driving a motor, a lithium ion secondary battery having the highest theoretical energy is attracting attention among all batteries, and development is proceeding rapidly at present.
  • a lithium ion secondary battery uses a binder to coat a positive electrode active material or the like on both sides of a positive electrode current collector, and a binder to coat the negative electrode active material or the like on both sides of the negative electrode current collector.
  • the negative electrode is connected via an electrolyte layer and is housed in a battery case.
  • Lithium ion secondary batteries used as power sources for driving motors such as automobiles as described above have extremely high output characteristics compared to consumer lithium ion secondary batteries used in mobile phones, laptop computers, etc. At present, research and development is underway to meet the strong demands.
  • JP 2003-68299 A discloses lithium containing a Li-Mn-Ni composite oxide.
  • a positive electrode active material for a secondary battery wherein the average diameter of primary particles of Li Mn—Ni composite oxide is 2.0 m or less and the BET specific surface area is 0.4 m 2 Zg or more.
  • a featured positive electrode active material for lithium ion secondary batteries is disclosed.
  • a lithium ion secondary battery having excellent discharge capacity characteristics and cycle durability can be provided.
  • the surface area of the positive electrode active material that can be contacted with the electrolyte increases, and as a result, the charge / discharge reaction can proceed sufficiently.
  • the present inventors diligently searched for the essence of increasing the internal resistance under high output conditions. As a result, it has been found that the increase in internal resistance such as force is due to insufficient formation of a conductive network as the particle size of the active material decreases. Based on this knowledge, the present inventors examined securing the conductive network by bringing the particles of the active material into contact with each other by reducing the porosity of the active material layer of the electrode.
  • the present inventors have found that the above problems can be solved by controlling the particle diameter of the active material and the porosity of the active material layer to predetermined values. This led to the completion.
  • the battery electrode according to the first aspect of the present invention is for a battery having a current collector and a first positive electrode active material layer containing a positive electrode active material formed on the current collector.
  • An electrode is characterized in that the positive electrode active material has an average particle diameter of 5 m or less, and the porosity of the first positive electrode active material layer is 30% or more.
  • the battery electrode according to the second aspect of the present invention is a current collector. And a first negative electrode active material layer containing a negative electrode active material formed on the current collector, the average particle diameter of the negative electrode active material being 10 m or less, The negative electrode active material layer 1 has a porosity of 50% or more.
  • the method for manufacturing a battery electrode according to the present invention includes an active material slurry adjustment step of adjusting an active material slurry containing an active material by adding an active material to a solvent, and a surface of a current collector. It has a coating film forming process for forming a coating film by applying and drying an active material slurry, and a pressing process for pressing the laminate produced through the coating film forming process in the laminating direction. The combination process with the pressing process is repeated twice or more.
  • FIG. 2 is a cross-sectional view showing another embodiment (second embodiment) of the battery electrode of the present invention.
  • FIG. 3 is a cross-sectional view showing a preferred embodiment of the bipolar battery of the third embodiment.
  • Fig. 5 is a schematic view of the automobile of the fifth embodiment on which the assembled battery of the fourth embodiment is mounted.
  • FIG. 6 is a cross-sectional view showing an outline of a lithium ion secondary battery that is not bipolar.
  • FIG. 7 is a graph showing the relationship between the porosity of the positive electrode active material layer and the relative output in the battery electrode of the example of the present invention.
  • FIG. 8 is a graph showing the relationship between the porosity of the positive electrode active material layer and the relative output in the battery electrodes of Examples and Comparative Examples of the present invention.
  • FIG. 1 is a cross-sectional view showing one embodiment of a battery electrode of the present invention.
  • the battery electrode 1 in the form shown in FIG. 1 is a bipolar electrode in which a positive electrode active material layer 13 is formed on one surface of a current collector 11 and a negative electrode active material layer 15 is formed on the other surface.
  • the average particle diameter of the positive electrode active material contained in the positive electrode active material layer 13 is 5 ⁇ m or less.
  • the average particle size is preferably 3 ⁇ m or less, more preferably 1 m or less.
  • the lower limit value of the average particle diameter of the positive electrode active material is not particularly limited, but from the viewpoint of sufficiently forming a conductive network in the electrode, the positive electrode active material.
  • the average particle diameter of is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the porosity of the positive electrode active material layer 13 is 30% or more. The porosity is preferably 33% or more, more preferably 35% or more.
  • the upper limit of the porosity of the positive electrode active material layer 13 is not particularly limited from the viewpoint of obtaining the effect of the present invention. From the viewpoint of improving the battery capacity, the porosity of the positive electrode active material layer 13 is , Preferably 50% or less, more preferably 45% or less.
  • the average particle size of the negative electrode active material contained in the negative electrode active material layer 15 is 10 ⁇ m or less.
  • the average particle size is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the lower limit of the average particle diameter of the negative electrode active material is not particularly limited, but from the viewpoint of sufficiently forming a conductive network in the electrode, the negative electrode active material
  • the average particle size of is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the porosity of the negative electrode active material layer 15 is 50% or more.
  • the porosity is preferably 52% or more, more preferably 55% or more.
  • the upper limit of the porosity of the negative electrode active material layer 15 is not particularly limited as to the viewpoint power to obtain the effects of the present invention, but the viewpoint power to improve battery capacity is not limited to the porosity of the negative electrode active material layer 15. Is preferably 80% or less, more preferably 70% or less.
  • the value measured by the particle size distribution measurement method is adopted as the value of the particle diameter of the active material.
  • the porosity of the active material layer a value calculated according to the following formula 1 shall be adopted.
  • the electrode density [ g / mL] TM ⁇ slurry_ ⁇ 3 ⁇ 4
  • the theoretical electrode density [g / mL] ⁇ (electrode constituent material true density X active material layer composition ratio).
  • the nanopolar electrode of the form shown in FIG. 1 can be employed in, for example, a bipolar lithium ion secondary battery (hereinafter also simply referred to as “bipolar battery”). Of course, it may be adopted for other batteries.
  • bipolar battery a bipolar lithium ion secondary battery
  • the average particle diameter of the active material and the voids of the active material layer are the above-described values in both the positive electrode and the negative electrode, but the technical scope of the present invention is powerful.
  • the present invention is not limited only to the form, and a form in which only one of the positive electrode and the negative electrode satisfies the predetermined value described above can also be included.
  • the configuration of the battery electrode of the present invention will be described below by taking as an example a case where it is employed in a lithium ion secondary battery.
  • the battery electrode of this embodiment is characterized in that the average particle of the active material and the porosity of the active material layer are predetermined values for each of the positive electrode and the negative electrode.
  • the selection of the current collector There is no particular limitation on the selection of the current collector, the type of active material, the binder, the supporting salt (lithium salt), the electrolyte, and other compounds added as necessary. Depending on the intended use, it may be selected by appropriately referring to known knowledge.
  • the members constituting the battery electrode of the present invention will be described in detail.
  • the current collector 11 is made of a conductive material such as aluminum foil, nickel foil, copper foil, or stainless steel (SUS) foil.
  • the typical thickness of the current collector is 1-30 m. However, a current collector having a thickness outside this range may be used.
  • the size of the current collector is determined according to the intended use of the battery. If a large electrode used for a large battery is produced, a current collector with a large area is used. If a small electrode is produced, a current collector with a small area is used.
  • active material layers (13, 15) are formed on the current collector 11.
  • the active material layers (11, 15) are layers containing an active material that plays a central role in charge / discharge reactions.
  • the average particle diameter and the porosity of the active material satisfy the above-described predetermined values for either one or both of the positive electrode active material layer 13 and the negative electrode active material layer 15.
  • the active material layers (13, 15) include an active material.
  • the active material layer contains a positive electrode active material.
  • the active material layer contains a negative electrode active material.
  • Examples of the positive electrode active material include lithium transition metal oxides, lithium transition metal phosphate compounds, and lithium transition metal sulfate compounds. In some cases,
  • Two or more positive electrode active materials may be used in combination.
  • Examples of the negative electrode active material include carbon materials, lithium transition metal compounds, metal materials, and lithium metal alloy materials. In some cases, two or more negative electrode active materials may be used in combination.
  • the active material layers (13, 15) may contain other materials if necessary.
  • the active material layers (13, 15) may contain other materials if necessary. For example
  • Conductive aids such as, binders, supporting salts (lithium salts), ion conductive polymers, and the like.
  • a polymerization initiator for polymerizing the polymer may be included! / ⁇ .
  • the conductive auxiliary agent is an additive blended to improve the conductivity of the active material layer.
  • conductive assistants include carbon black such as acetylene black, carbon powder such as graphite, and various carbon fibers such as vapor grown carbon fiber (VGCF (registered trademark)). I can get lost.
  • the average particle diameter of the active material in the positive electrode active material layer 13 of the battery electrode and the porosity of the active material layer 13 are the predetermined values described above.
  • the positive electrode active material layer 13 desirably contains 5% by mass or more, more preferably 10% by mass or more of the conductive auxiliary with respect to the total mass of the positive electrode active material layer 13.
  • the negative electrode active material layer 15 preferably contains 1% by mass or more, more preferably 5% by mass or more of a conductive additive with respect to the total mass of the negative electrode active material layer 15.
  • Examples of the noinder include polyvinylidene fluoride (PVdF), a synthetic rubber binder, and the like.
  • the supporting salt includes Li (C F SO) N, LiPF, LiBF, LiAsF, LiCF
  • Examples of the ion conductive polymer include a polyethylene oxide (PEO) -based polymer and a polypropylene oxide (PPO) -based polymer.
  • the polymer may be the same as or different from the ion conductive polymer used in the electrolyte layer of the battery in which the electrode of the present invention is employed. preferable.
  • the polymerization initiator is blended so as to act on the crosslinkable group of the ion conductive polymer to advance the crosslinking reaction. Depending on the external factors to act as an initiator, it is classified into photopolymerization initiator, thermal polymerization initiator, etc.
  • the polymerization initiator include azobisisoptyl-tolyl (AIBN), which is a thermal polymerization initiator, and benzyl dimethyl ketal (BDK), which is a photopolymerization initiator.
  • the mixing ratio of the components contained in the active material layers (13, 15) is not particularly limited.
  • the blending ratio can be adjusted by appropriately referring to known knowledge about lithium ion secondary batteries.
  • the thickness of the active material layer (13, 15) is not particularly limited can be appropriately referred to.
  • the thickness of the active material layer (13, 15) is preferably about 10 to about L00 m, and more preferably about 20 to 50 m. Life If the material layers (13, 15) are about 10 / zm or more, the battery capacity can be sufficiently secured. On the other hand, if the active material layer (13, 15) is about 100 ⁇ m or less, the problem of increased internal resistance due to diffusion of lithium ions to the electrode deep part (current collector side) is suppressed. Can be.
  • the active material layers (13, 15) of the battery electrode of the present invention may comprise two or more layers.
  • the electrode of the present invention will be described with reference to the drawings, taking as an example the case where each of the positive electrode active material layer 13 and the negative electrode active material layer 15 is composed of two layers.
  • FIG. 2 is a cross-sectional view showing another embodiment of the battery electrode of the present invention.
  • the positive electrode active material layer 13 is formed on one surface of the current collector 11 and the negative electrode active material is formed on the other surface, similarly to the electrode having the form shown in FIG. This is a bipolar electrode in which the layer 15 is formed.
  • the battery electrode 1 having the form shown in FIG. 2 includes the current collector 11, the average particle diameter of the active material and the porosity of the active material layer described above in each of the positive electrode active material layer 13 and the negative electrode active material layer 15.
  • the second active material layer (13b, 1a) having a lower porosity than the first active material layer (13a, 15a) between the first positive electrode active material layer (13a, 15a) that satisfies the above requirements 5b) is characterized by intervening.
  • the second active material layer (13b, 15b) is located on the current collector 11 side, and the first active material layer Material layers (13a, 15a) are located on the electrolyte side of the battery. According to such a configuration, by disposing an active material layer with a higher porosity on the electrolyte side, it is possible to diffuse lithium ions deep into the entire electrode active material layer (current collector 11 side). Become.
  • the internal resistance of the battery (mainly due to the diffusion resistance of lithium ions) can be reduced.
  • an active material layer having a smaller porosity on the current collector 11 side it is possible to ensure the filling rate of the active material in the entire electrode active material layer. As a result, the capacity characteristics and output characteristics of the battery can be sufficiently secured.
  • the specific form of the first active material layer (13a, 15a) is as described above, and thus detailed description thereof is omitted here.
  • the second active material layer (13b, 15b) is connected to the first active material layer (second positive electrode active material layer 13b) corresponding to each porosity.
  • the first positive electrode active material layer 13a; the second negative electrode active material layer 15b has a lower porosity than the first negative electrode active material layer 13a)! /
  • the form is not particularly limited.
  • FIG. 2 illustrates a form in which each of the active material layers (13, 15) is composed of two layers.
  • the technical scope of the present invention is not limited to such a form, and either It is also possible to include a form in which the active material layer is composed of one layer or a form in which three or more layers of force are present.
  • the electrode of the present invention for example, prepares an active material slurry by adding an active material to a solvent (active material slurry preparation step), applies the active material slurry to the surface of the current collector, It can be produced by forming a coating film by drying (coating film forming process) and pressing the laminate produced through the coating film forming process in the laminating direction (pressing process).
  • active material slurry preparation step When an ion conductive polymer is added to the active material slurry and a polymerization initiator is further added for the purpose of cross-linking the ion conductive polymer, at the same time as drying in the coating film forming process or before the drying.
  • a polymerization treatment may be performed later (polymerization step).
  • the desired active material and other components are mixed in a solvent as necessary.
  • an active material slurry is prepared.
  • the specific form of each component blended in the active material slurry is as described in the column of the configuration of the electrode of the present invention, and a detailed description is omitted here.
  • the type of solvent and the mixing means are not particularly limited, and conventionally known knowledge about electrode production can be appropriately referred to.
  • the solvent N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide and the like can be used.
  • NMP N-methyl-2-pyrrolidone
  • PVdF polyvinylidene fluoride
  • the porosity of the active material layer of the produced electrode is adjusted by adjusting the mixing ratio of the solid content and the solvent in the active material slurry prepared in the active material slurry preparation step. It is also possible to control. Specifically, when it is desired to reduce the porosity of the formed active material layer, the amount of solid content in the active material slurry should be increased. On the other hand, when it is desired to increase the porosity of the active material layer to be formed, the blending amount of the solid content in the active material slurry is preferably decreased. However, the porosity of the active material layer may be controlled in a coating process and a pressing process described later.
  • a current collector is prepared, and the active material slurry prepared above is applied to the surface of the current collector and dried. As a result, a coating film made of the active material slurry is formed on the surface of the current collector. This coating film becomes an active material layer through a pressing step described later.
  • the application means for applying the active material slurry is not particularly limited.
  • a commonly used means such as a self-propelled coater can be adopted.
  • an ink jet method as a coating unit because finer adjustment is possible and the porosity of the active material layer can be more easily controlled.
  • the coating film is formed according to a desired arrangement of the current collector and the active material layer in the manufactured electrode. For example, in the case of a manufactured electrode force S bipolar electrode, a coating film containing a positive electrode active material is formed on one surface of the current collector, and a coating film containing a negative electrode active material is formed on the other surface. . On the other hand, when manufacturing a non-polar electrode, a coating film containing either the positive electrode active material or the negative electrode active material is formed on both surfaces of one current collector.
  • the coating film formed on the surface of the current collector is dried. Thereby, the solvent in the coating film is removed.
  • the drying means for drying the coating film is not particularly limited, and conventionally known knowledge about electrode production can be appropriately referred to. For example, heat treatment is exemplified.
  • the drying conditions (drying time, drying temperature, etc.) are suitable for the amount of active material slurry applied and the volatilization rate of the solvent in the slurry. Can be set appropriately.
  • the coating film contains a polymerization initiator
  • the ion conductive polymer in the coating film is cross-linked by a crosslinkable group by further performing a polymerization step.
  • the polymerization treatment in the polymerization step is not particularly limited, and conventionally known knowledge may be referred to as appropriate.
  • the coating film contains a thermal polymerization initiator (AIBN, etc.)
  • the coating film is heat treated.
  • the coating film contains a photopolymerization initiator (BDK, etc.)
  • light such as ultraviolet light is irradiated.
  • the heat treatment for thermal polymerization may be performed at the same time as the above drying step, or may be performed before or after the drying step.
  • the laminated body produced through the said coating-film formation process is pressed to the lamination direction. Thereby, the battery electrode of the present invention is completed.
  • the porosity of the active material layer can be controlled by adjusting the pressing conditions.
  • Specific means and press conditions for the press treatment are not particularly limited, and can be appropriately adjusted so that the porosity of the active material layer after the press treatment becomes a desired value.
  • Specific examples of the press process include a hot press machine and a calendar roll press machine.
  • pressing conditions temperature, pressure, etc.
  • conventionally known knowledge in which pressing conditions (temperature, pressure, etc.) are particularly limited, can be referred to as appropriate.
  • the present application provides a method of manufacturing a battery electrode of a preferred form shown in FIG. That is, the battery electrode manufacturing method according to the present invention includes an active material slurry preparation step of preparing an active material slurry containing an active material by adding the active material to a solvent, and the active material on the surface of the current collector.
  • a coating film forming process for forming a coating film by applying slurry and drying; a pressing process for pressing the laminate produced through the coating film forming process in the stacking direction; and the coating film forming process and the press It is characterized by repeating the combination process with the process twice or more.
  • the manufacturing method repeats the combination step of the coating film forming step and the pressing step twice or more for the purpose of controlling the porosity of each layer of the active material layer having two or more layers. It has the characteristics.
  • a coating film is formed on the surface of the current collector 11 (first coating film forming process) and pressed (first pressing process).
  • first coating film forming process a coating film is formed on the surface of the current collector 11 (first coating film forming process) and pressed (first pressing process).
  • first pressing process As a result, the second shown in FIG. Active material layers (13b, 15b) are formed.
  • a coating film is formed again on the surface of the second active material layer (second coating film forming process) and pressed (second pressing process).
  • the first active material layers (13a, 15a) shown in FIG. 2 are formed, and the battery electrode having the configuration shown in FIG. 2 is completed.
  • the press pressure in the (n + 1) th press process (n ⁇ 1) is set smaller than the press pressure in the nth press process. If the manufacturing method described above is taken as an example, the pressing pressure in the second pressing step should be made smaller than the pressing pressure in the first pressing step. In this way, the porosity of the first active material layer (13a, 15a) formed by the second pressing process is changed to the second active material layer (13b, 15b) formed by the first pressing process. 2), the battery electrode having the configuration shown in FIG. 2 can be produced.
  • a lithium ion secondary battery is configured using the battery electrode of the first embodiment or the second embodiment. That is, a third aspect of the present invention is a lithium-ion secondary battery including at least one single battery layer laminated in this order, the positive electrode, the electrolyte layer, and the negative electrode force S, and at least one of the positive electrode or the negative electrode is It is a lithium ion battery which is an electrode for a battery of the present invention.
  • the electrode of the present invention can be applied to any of a positive electrode, a negative electrode, and a bipolar electrode.
  • a lithium ion secondary battery including the electrode of the present invention as at least one electrode belongs to the technical scope of the present invention. However, preferably, all of the electrodes constituting the lithium ion secondary battery are the electrodes of the present invention. By adopting such a configuration, the output characteristics of the lithium ion secondary battery can be effectively improved.
  • the battery of the present invention may be a bipolar lithium ion secondary battery (hereinafter also referred to as a bipolar battery).
  • FIG. 3 is a cross-sectional view showing a third lithium ion secondary battery of the present invention, which is a bipolar battery.
  • the bipolar battery shown in FIG. 3 will be described in detail as an example.
  • the technical blade of the present invention is not limited to only a powerful form.
  • the bipolar battery 10 of the present embodiment shown in FIG. 3 has a structure in which a substantially rectangular battery element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior.
  • the battery element 21 of the bipolar battery 10 of the present embodiment includes a bipolar element in which a positive electrode active material layer 13 and a negative electrode active material difference 15 are formed on each surface of a current collector 11. It has a plurality of electrodes (bipolar electrodes of the form shown in FIG. 1). Each bipolar electrode is laminated via an electrolyte layer 17 to form a battery element 21.
  • each of the bipolar electrodes and the positive electrode active material layer 13 of one bipolar electrode and the negative electrode active material layer 15 of another bipolar electrode adjacent to the one bipolar electrode face each other through the electrolyte layer 17.
  • the electrolyte layer 1 is laminated.
  • the bipolar battery 10 has a configuration in which the unit cell layers 19 are laminated.
  • an insulating layer 31 for insulating the adjacent current collectors 11 is provided on the outer periphery of the unit cell layer 19.
  • the current collector (outermost layer current collector) (11a, ib) positioned on the outermost layer of the battery element 21 has a positive electrode active material layer 13 (positive electrode side outermost layer current collector 1) on only one side. la) or negative electrode active material layer 15 (negative electrode side outermost layer current collector 1 lb) is formed!
  • the positive electrode side outermost layer current collector 11a is extended to form a positive electrode tab 25, which is led out from a laminate sheet 29 which is an exterior.
  • 1 lb of the negative electrode side outermost layer current collector is extended to form a negative electrode tab 27, which is similarly led out from the laminate sheet 29.
  • electrolyte constituting the electrolyte layer 17 a liquid electrolyte or a polymer electrolyte can be used.
  • the liquid electrolyte has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer.
  • the organic solvent that can be used as the plasticizer include carbonates such as ethylene carbonate (EC) and propylene carbonate (PC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • support As the supported salt (lithium salt), a compound that can be added to the active material layer of the electrode, such as LiBETI, can be similarly employed.
  • polymer electrolytes are classified into gel electrolytes containing an electrolytic solution and authentic polymer electrolytes containing no electrolytic solution.
  • the gel electrolyte has a configuration in which the above-described liquid electrolyte is injected into a matrix polymer having ion-conductive polymer power.
  • the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.
  • Electrolyte salts such as lithium salts can be well dissolved in such polyalkylene oxide polymers.
  • the electrolyte layer 17 is composed of a liquid electrolyte or a gel electrolyte
  • a separator may be used for the electrolyte layer 17.
  • a specific form of the separator for example, a microporous film that is also a polyolefin linker such as polyethylene or polypropylene can be cited.
  • the intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the above matrix polymer, and does not contain a plastic organic solvent. Therefore, when the electrolyte layer 17 is made of an intrinsic polymer electrolyte, the reliability of the battery can be improved without worrying about the leakage of liquid from the battery.
  • a supporting salt lithium salt
  • the matrix polymer of the gel electrolyte or the intrinsic polymer electrolyte can exhibit excellent mechanical strength by forming 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 polyelectrolyte using an appropriate polymerization initiator.
  • the polymerization process may be performed.
  • an insulating layer 31 is usually provided around each unit cell layer 19. This insulating layer 31 is intended to prevent the adjacent current collectors 11 in the battery from contacting each other and short-circuiting due to slight unevenness at the end of the cell layer 19 in the battery element 21 or the like. Provided. The installation of a strong insulating layer 31 ensures long-term reliability and safety, and can provide a high-quality bipolar battery 10.
  • the insulating layer 31 has an insulating property, a sealing property against falling off of the fixed electrolyte, and water from the outside.
  • urethane resin, epoxy resin, polyethylene resin, polypropylene resin, polyimide resin can be used as long as they have a sealing property against moisture permeation (sealing property) and heat resistance under battery operating temperature. Fats, rubbers and the like can be used.
  • urethane resin and epoxy resin are preferred from the viewpoints of corrosion resistance, chemical resistance, ease of production (film forming property), and economical efficiency.
  • the material of the tabs is not particularly limited, and a known material conventionally used as a tab for a bipolar battery can be used.
  • a known material conventionally used as a tab for a bipolar battery can be used.
  • aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are exemplified.
  • the positive electrode tab 25 and the negative electrode tab 27 may be made of the same material or different materials.
  • the outermost layer current collector (l la, ib) may be extended to form tabs (25, 27), or may be connected to a separately prepared outermost layer current collector. It's good.
  • the battery element 21 is preferably housed in an exterior such as a laminate sheet 29 in order to prevent external impact and environmental degradation during use.
  • the exterior is not particularly limited, and a conventionally known exterior can be used. From the viewpoint of efficiently transferring heat from a heat source of an automobile and quickly heating the inside of the battery to the battery operating temperature, a polymer metal composite laminate sheet having excellent heat conductivity can be preferably used.
  • an assembled battery is configured by connecting a plurality of the bipolar batteries of the above-described third embodiment in parallel and Z or in series.
  • FIG. 4 is a perspective view showing the assembled battery of this embodiment.
  • the assembled battery 40 is the bipolar battery described in the second embodiment. It is configured by connecting a plurality. Each bipolar battery 10 is connected by connecting the positive electrode tab 25 and the negative electrode tab 27 of each bipolar battery 10 using a bus bar. On one side surface of the assembled battery 40, electrode terminals (42, 43) are provided as electrodes of the assembled battery 40 as a whole.
  • connection method for connecting the plurality of bipolar batteries 10 constituting the assembled battery 40 is not particularly limited, and a conventionally known method can be appropriately employed. For example, a method using welding such as ultrasonic welding or spot welding, or a method of fixing using rivets or caulking can be employed. According to the powerful connection method, the long-term reliability of the assembled battery 40 can be improved.
  • the individual bipolar batteries 10 constituting the assembled battery 40 are excellent in output characteristics, and therefore an assembled battery excellent in output characteristics can be provided.
  • all of the bipolar batteries 10 constituting the assembled battery 40 may be connected in parallel, or all of the plurality of bipolar batteries 10 may be connected in series. You may combine the connection.
  • the bipolar battery 10 of the third embodiment or the assembled battery 40 of the fourth embodiment is mounted as a motor driving power source to constitute a vehicle.
  • Vehicles that use the bipolar battery 10 or the assembled battery 40 as a motor power source include, for example, gasoline! /, Fully electric vehicles, hybrid vehicles such as series hybrid vehicles and parallel hybrid vehicles, and fuel cell vehicles.
  • One example is an automobile that drives a vehicle by a motor.
  • FIG. 5 shows a schematic diagram of an automobile 50 in which the assembled battery 40 is mounted.
  • the assembled battery 40 mounted on the automobile 50 has the characteristics as described above. Therefore, the automobile 50 equipped with the assembled battery 40 has excellent output characteristics and can provide sufficient output even under high output conditions.
  • FIG. 6 shows a cross-sectional view showing an outline of a non-bipolar lithium ion secondary battery 60.
  • a cathode active material spinel-type lithium manganate (average particle size: 0. ⁇ ⁇ ⁇ ) (80 wt%)
  • acetylene black as a conductive aid (10 mass 0/0)
  • polyvinylidene fluoride A suitable amount of N-methyl-2-pyrrolidone (NMP), which is a slurry viscosity adjusting solvent, was added to the solid content of PVdF) (10% by mass) to prepare a positive electrode active material slurry.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode active material slurry prepared above was placed on an aluminum foil (thickness: 2 O / zm) as a positive electrode current collector, with a basis weight of 12.0 mgZcm 2 , a film thickness of 46 / zm was applied and dried to obtain a laminate.
  • the obtained laminate was pressed using a press so that the porosity of the positive electrode active material layer was 32%, and a tab was connected to the current collector to produce a test positive electrode.
  • Hard carbon as a negative electrode active material (average particle diameter: 10 m) (90 mass%), and by Sunda a is polyvinylidene Kapi - isopropylidene (PVdF) to (10 mass 0/0) solids consisting slurry viscosity An appropriate amount of N-methyl-2-pyrrolidone (NMP) as a adjusting solvent was added to prepare a negative electrode active material slurry.
  • NMP N-methyl-2-pyrrolidone
  • the negative electrode active material slurry prepared above was applied to a copper foil (thickness: 10 m) as a negative electrode current collector using a self-propelled die coater and a basis weight of 3 mg / cm 2 and a film thickness of 30 ⁇ m. And dried to obtain a laminate. Next, the obtained laminate was pressed using a press so that the porosity of the negative electrode active material layer was 55%, and a tab was connected to the current collector to prepare a test negative electrode. [0094] ⁇ Preparation of electrolyte solution>
  • Ethylene carbonate (EC) and jetyl carbonate (DEC) were mixed at a volume ratio of 1: 1 to obtain a plasticizer (organic solvent) for the electrolytic solution.
  • LiPF which is a lithium salt, was added to the plasticizer so as to have a concentration of 1M to prepare an electrolytic solution.
  • a polyethylene porous membrane (thickness: 25 m) as a separator for a lithium ion battery was sandwiched between the test positive electrode and the test negative electrode produced above.
  • the sandwiched body obtained in (1) was inserted into an aluminum laminate bag, which was a three-side sealed exterior material. Thereafter, the electrolyte prepared above was injected into the aluminate bag, and the pack was vacuum-sealed so that the tabs were also exposed to complete the laminated battery.
  • a laminated battery was produced in the same manner as in Example 1 except that the thickness of the positive electrode active material slurry was 49 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 35%. .
  • a laminated battery was produced in the same manner as in Example 1 except that the thickness of the positive electrode active material slurry was 52 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 39%. .
  • a laminated battery was produced in the same manner as in Example 1 except that the thickness of the positive electrode active material slurry was 58 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 45%. .
  • a laminated battery was produced in the same manner as in Example 1 except that the thickness of the positive electrode active material slurry was 61 ⁇ m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 48%. did.
  • Average particle of spinel type lithium manganate which is solid content of the positive electrode active material slurry A laminated battery was produced in the same manner as in Example 1 except that the diameter was 5 ⁇ m and the thickness of the positive electrode active material slurry was 47 ⁇ m.
  • a laminated battery was produced in the same manner as in Example 6 except that the thickness of the positive electrode active material slurry was 52 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 39%. .
  • a laminated battery was produced in the same manner as in Example 6 except that the thickness of the positive electrode active material slurry was 58 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 45%. .
  • the mass ratio of spinel type lithium manganate, acetylene black, and PVdF, which are solids in the positive electrode active material slurry, is 70:20:10, and the basis weight and film thickness of the positive electrode active material slurry are 13.7 mgZcm 2 and A laminated battery was produced in the same manner as in Example 1 except that the length was 56 m.
  • a laminated battery was produced in the same manner as in Example 9 except that the thickness of the positive electrode active material slurry was 59 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 35%. .
  • a laminated battery was produced in the same manner as in Example 9 except that the thickness of the positive electrode active material slurry was 63 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 39%. .
  • a laminated battery was produced in the same manner as in Example 9 except that the thickness of the positive electrode active material slurry was 74 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 45%. .
  • Example 13 A laminated battery was produced in the same manner as in Example 9 except that the thickness of the positive electrode active material slurry was 85 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 55%. .
  • a laminated battery was produced in the same manner as in Comparative Example 1 except that the thickness of the positive electrode active material slurry was 52 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 39%. .
  • a laminated battery was produced in the same manner as in Comparative Example 1 except that the thickness of the positive electrode active material slurry was 60 m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 45%. .
  • a laminated battery was produced in the same manner as in Comparative Example 6 except that the thickness of the positive electrode active material slurry was 61 ⁇ m and the positive electrode active material layer was pressed so that the porosity of the positive electrode active material layer was 48%. did.
  • each laminate battery was initially charged at a constant current of 0.2 C, discharged at a constant current of 0.5 C, and then charged and discharged at 10 cycles at a constant current of 1 C. Went.
  • the average particle diameter of the positive electrode active material is as large as about 10 m, even if the porosity of the positive electrode active material layer increases, the diffusion resistance in the positive electrode active material layer is almost the same. Unaffected and relative output does not change.
  • the average particle diameter of the positive electrode active material is extremely small, the diffusion resistance in the positive electrode active material layer decreases corresponding to the increase in the porosity of the positive electrode active material layer, and the relative Output increases. Therefore, by combining the small particle size of the electrode active material and the increase in the porosity of the electrode active material, a battery capable of exhibiting excellent output characteristics even under a high output condition of 100 C can be provided. Is suggested.

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Abstract

La présente invention concerne une électrode utilisée dans une batterie comprenant un collecteur et un premier matériau actif positif disposé sur le collecteur et contenant un matériau actif positif, caractérisée en ce que la taille moyenne de particules du matériau actif positif est inférieure ou égale à 5µm, et en ce que la porosité du premier matériau actif positif est d'au moins 30%. Ou bien elle concerne une électrode utilisée dans une batterie comprenant un collecteur et un premier matériau actif négatif disposé sur le collecteur et contenant un matériau actif négatif, caractérisée en ce que la taille moyenne de particules du matériau actif négatif est inférieure ou égale à 10µm, et en ce que la porosité du premier matériau actif négatif est d'au moins 50%. Par conséquent, une batterie secondaire à l'ion lithium peut présenter un moyen de prévention de l'augmentation de la résistance interne de la batterie pendant la charge/la décharge sous une condition de forte sortie tout en fournissant un courant suffisant.
PCT/JP2006/318114 2005-09-14 2006-09-13 Électrode utilisée dans une batterie WO2007032365A1 (fr)

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JP2005267457 2005-09-14
JP2006239219A JP2007109636A (ja) 2005-09-14 2006-09-04 電池用電極
JP2006-239219 2006-09-04

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JP5391630B2 (ja) * 2008-10-03 2014-01-15 日産自動車株式会社 電池用電極の製造方法
KR20100044087A (ko) * 2008-10-20 2010-04-29 삼성전자주식회사 잉크젯 프린트용 전극 조성물, 이를 사용하여 제조된 전극 및 이차 전지
JP5333184B2 (ja) * 2009-03-16 2013-11-06 トヨタ自動車株式会社 全固体二次電池
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JP5854285B2 (ja) 2010-11-12 2016-02-09 トヨタ自動車株式会社 二次電池
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JP6418560B2 (ja) * 2014-03-05 2018-11-07 パナソニックＩｐマネジメント株式会社 薄型電池および電池搭載デバイス
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