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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
  • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
  • B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
  • B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
• • 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
  • H01M4/139—Processes of manufacture
• • 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

Definitions

• the present invention relates to a method for manufacturing an electrode layer and an apparatus for manufacturing an electrode layer.
• the production of an electrode applied to a semi-solid battery or an all-solid battery includes, for example, a step of applying an electrode material containing an electrode active material, which is a powder, onto a substrate.
• Patent Document 1 discloses a method for manufacturing an electrochemical cell, the method including the steps of coating a semi-solid cathode on a first surface of a positive current collector, coating a semi-solid anode on a first surface of a negative current collector, disposing a separator between the semi-solid cathode and the semi-solid anode, disposing the positive current collector, the negative current collector, and the separator in a pouch, and sealing the pouch to form an electrochemical cell.
• Patent document 2 discloses a method for impregnating a fibrous material with an active paste in the manufacture of electrodes for lead-acid batteries or cells, comprising moving a fibrous material having a length in the machine direction and in the main plane of the fibrous material, a width in the main plane of the fibrous sheet material and between the longitudinal edges of the fibrous sheet material, and a thickness perpendicular to the main plane of the material, and also having a fiber-to-fiber spacing of up to 100 microns, through or vice versa, a limited application zone of a paste application stage, the paste application stage also including a Pb-based paste in the limited application zone, and continuously supplying paste to the limited application zone while vibrating the paste in the limited application zone, and continuously impregnating the paste through the main surface of the moving fibrous material and through its thickness into the fibrous sheet material while maintaining pressure on the vibrating paste and preventing the paste impregnating the fibrous material from leaking out of the longitudinal edges of the fibrous sheet material.
• Patent Document 3 discloses a powder coating device that includes a drive unit that moves a member in a predetermined direction, a powder supply unit that supplies powder onto the surface of the member, and a squeegee that is positioned to form a gap between the member and the squeegee and adjusts the thickness of the powder supplied onto the surface of the member by the powder supply unit, the squeegee vibrating at a frequency of 2 kHz to 300 kHz.
• Patent Document 4 discloses a method for manufacturing a lithium-ion battery having a configuration in which a set of a positive electrode collector, a positive electrode active material layer, a separator, a negative electrode active material layer, and a negative electrode collector are stacked in order, the outer peripheries of the positive electrode active material layer and the negative electrode active material layer are sealed with a sealant, and an electrolyte is enclosed, the method comprising the steps of preparing a frame-shaped sealant and a bottom member, and manufacturing a positive electrode and/or a negative electrode by an electrode manufacturing process including a supplying step of supplying an electrode active material composition containing electrode active material particles and an electrolyte into a space surrounded by the sealant and the bottom member, and a compression step of compressing the electrode active material composition to form an electrode active material layer.
• Patent Document 1 JP-T-2017-533548 A
• Patent Document 2 JP-T-2019-503043 A
• Patent Document 3 JP-A-2021-178271
• Patent Document 4 JP-A-2021-44152 A
• the electrode active material composition of a lithium ion battery is a mixture of metal powder and electrolyte, and has strong cohesive and adhesive forces.
• the volume content of solids in such an electrode active material composition exceeds 40%, the fluidity is extremely low, and it is considered difficult to form the composition into a film or layer using the methods or devices disclosed in Patent Documents 1 to 4.
• a process includes a step A of conveying a current collecting foil having an electrode material scattered on a surface thereof in a first direction relative to a molding member provided at a position spaced a certain distance from a surface of the current collecting foil, thereby bringing the molding member into contact with the electrode material;
• the electrode material contains an electrode active material and has a solid component concentration of 40% by volume or more;
• the molding member has an ultrasonic vibration application surface to which ultrasonic waves are applied by an ultrasonic vibrator, and a rectangular vibration surface that contacts the electrode material, a distance between the ultrasonic vibration application surface and at least a part of the vibration surface is a multiple of a half wavelength of ultrasonic longitudinal vibration propagated in the molded member by the ultrasonic vibrator;
• ⁇ 2> The method for manufacturing an electrode layer according to ⁇ 1>, wherein the molding member is disposed so that a gap between the vibration surface and the surface of the current collecting foil narrows in the first direction.
• ⁇ 3> The method for producing an electrode layer according to ⁇ 1> or ⁇ 2>, wherein the molded member has a slit that is parallel to the direction of longitudinal vibration and penetrates in the thickness direction.
• ⁇ 4> The method for producing an electrode layer according to any one of ⁇ 1> to ⁇ 3>, wherein the frequency of ultrasonic waves applied to the ultrasonic vibration application surface of the molded member by the ultrasonic vibrator is 15 kHz to 120 kHz.
• ⁇ 5> The method for producing an electrode layer according to any one of ⁇ 1> to ⁇ 4>, wherein the amplitude of the longitudinal vibration on the vibration surface of the molded member is 1 ⁇ m to 100 ⁇ m at a portion where the gap between the surface of the current collecting foil and the molded member is narrowest.
• ⁇ 6> The method for manufacturing an electrode layer according to any one of ⁇ 1> to ⁇ 5>, wherein the molded member is configured to change an area ratio between an area of an ultrasonic vibration application surface and an area of a vibration surface, thereby making a difference between an amplitude of ultrasonic waves applied to the ultrasonic vibration application surface by an ultrasonic vibrator and an amplitude of the vibration surface.
• ⁇ 7> The method for producing an electrode layer according to any one of ⁇ 1> to ⁇ 6>, wherein in step A, a thickness of the electrode material film is defined by a gap between the surface of the current collecting foil and a portion of the vibration surface of the molded member that is narrowest between the surface of the current collecting foil and the portion.
• a conveying device that conveys a current collecting foil having an electrode material scattered on a surface thereof in a first direction; a film forming apparatus including: a molding member having an ultrasonic vibration application surface to which ultrasonic waves are applied and a rectangular vibration surface that contacts an electrode material, the molding member being installed at a position maintained at a certain distance from a surface of a current collecting foil; and an ultrasonic vibrator that applies ultrasonic waves to the ultrasonic vibration application surface of the molding member; Equipped with An electrode layer manufacturing device in which the distance between the ultrasonic vibration application surface and at least a portion of the vibration surface is a multiple of half the wavelength of the ultrasonic longitudinal vibration propagated within the molded member by the ultrasonic transducer, the vibration surface resonates with the ultrasonic waves applied to the ultrasonic vibration application surface by the ultrasonic transducer, and vibrates longitudinally uniformly across the width direction of the molded member, and an electrode material on the surface of a current collecting foil transported in a first direction is brought into contact with
• the present disclosure provides an electrode layer manufacturing method and an electrode layer manufacturing device that can spread an electrode material with low fluidity scattered on a current collecting foil to form an electrode material film.
• 1 is a schematic side view showing an example of a configuration of a film forming apparatus used in a manufacturing method of an electrode layer according to the present disclosure.
• 1 is a schematic front view showing an example of a configuration of a film forming apparatus used in a manufacturing method of an electrode layer according to the present disclosure.
• 1A to 1C are schematic side views illustrating an example of a method for producing an electrode layer according to the present disclosure;
• 1A to 1C are schematic top views illustrating an example of a method for producing an electrode layer according to the present disclosure.
• 11 is a schematic front view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• FIG. 11 is a schematic side view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• FIG. 11 is a schematic side view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• FIG. 11 is a schematic side view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• FIG. 11 is a schematic side view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• a numerical range expressed using “to” means a range including the numerical values described before and after “to” as the lower and upper limits.
• the upper limit value described in a certain numerical range may be replaced with the upper limit value of another numerical range described in stages, and/or the lower limit value described in a certain numerical range may be replaced with the lower limit value of another numerical range described in stages.
• the upper limit value or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
• the term "process” includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• a combination of two or more preferred aspects or embodiments is a more preferred aspect or embodiment.
• a "solid component” means a component that is solid at 25° C. and 1 atmosphere
• a "liquid component” means a component that is liquid at 25° C. and 1 atmosphere.
• the "width direction" of the molded member refers to a direction perpendicular to the direction in which the molded member moves relatively along the surface of the current collecting foil (i.e., the film-forming direction of the electrode material film on the current collecting foil).
• the "width direction” of the molded member also corresponds to the "width direction” of the electrode material film.
• the "central portion in the width direction” of the molded member refers to the central portion in the width direction of the molded member, which is an area determined according to the width of the electrode material film to be formed on the current collecting foil.
• the electrode layer means a current collector foil having a film made of an electrode material (electrode material film) thereon.
• an electrode layer that can be used in a quasi-solid-state battery or an all-solid-state battery is an electrode layer in which an electrode material film containing an electrode active material and having a solid component concentration of 40% by volume or more is disposed on a current collecting foil.
• the electrode material film is obtained by forming an electrode material containing an electrode active material, a conductive assistant, and an electrolyte, and having a solid component concentration of 40% by volume to 80% by volume, into a film shape on a current collecting foil.
• an electrode material with a solid component concentration of 40 vol% or more is clay-like and has strong cohesive and adhesive forces, and it is difficult to spread the electrode material scattered on a current collecting foil and form it into a film. Therefore, as a result of intensive research, the inventors discovered that by using a molding member that can apply ultrasonic vibrations using a half-wavelength resonator to electrode material scattered on a current collecting foil, the scattered electrode material can be spread and formed into a film, and have developed the manufacturing method and manufacturing apparatus for an electrode layer according to the present disclosure.
• the manufacturing method of the electrode layer according to the present disclosure includes a step A of conveying the current collecting foil having an electrode material scattered on its surface in a first direction relative to a molding member installed at a position kept a certain distance from the surface of the current collecting foil, thereby bringing the molding member into contact with the electrode material,
• the electrode material contains an electrode active material and has a solid component concentration of 40% by volume or more;
• the molding member has an ultrasonic vibration application surface to which ultrasonic waves are applied by an ultrasonic vibrator, and a rectangular vibration surface that contacts the electrode material, a distance between the ultrasonic vibration application surface and at least a part of the vibration surface is a multiple of a half wavelength of ultrasonic longitudinal vibration propagated in the molded member by the ultrasonic vibrator;
• the vibration surface resonates with ultrasonic waves applied to the ultrasonic vibration application surface by an ultrasonic vibrator, vibrating longitudinally uniformly across the width direction of the molded member, and the electrode material on the surface of the current collecting foil transported in a first
• Fig. 1 is a schematic side view showing an example of the configuration of a film-forming apparatus (molding apparatus) used in the manufacturing method of an electrode layer according to the present disclosure.
• Fig. 2 is a schematic front view showing an example of the configuration of a film-forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• the waveform W is shown in Fig. 1 as a schematic, but is actually a longitudinal wave.
• the film forming apparatus 10 includes an ultrasonic transducer 12 and a formed member 20 .
• the ultrasonic transducer 12 is a component that applies ultrasonic waves to the ultrasonic vibration application surface 22 of the molded member 20 to generate longitudinal vibrations, and a Langevin type transducer or the like can be used.
• the molded member 20 is a half-wavelength resonator, and is made of metal such as aluminum alloy, titanium alloy, or die steel.
• the molded member 20 is connected to the ultrasonic transducer 12 via the vibration transmission part 14 at the center in the width direction, and has an ultrasonic vibration application surface 22 to which ultrasonic waves are applied by the ultrasonic transducer 12, and a rectangular vibration surface 24 that contacts the electrode material.
• the distance between the ultrasonic vibration application surface 22 and the vibration surface 24 is set to 1 half wavelength ( ⁇ /2) of the ultrasonic longitudinal vibration propagated within the molded member 20 by the ultrasonic transducer 12.
• the molding member 20 has slits 26 in the width direction (film-forming width direction) X that are parallel to the direction of vertical vibration and penetrate in the thickness direction. By forming such slits 26 in the molding member 20, even if the molding member 20 is long, a uniform amplitude can be obtained across the width direction (film-forming width direction) X of the molding member 20.
• "uniform vertical vibration across the width direction (film-forming width direction) X of the molding member 20” means that the amplitude and phase of the vibration surface 24 vibrates vertically with high uniformity regardless of the position in the width direction X of the vibration surface 24, as shown by the arrow V in Figures 1 and 2.
• the difference in amplitude on the vibration surface 24, for example, the difference between the amplitude at the center and the amplitude at the end in the width direction X is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less.
• the number, length, width, and spacing of the slits 26 are not particularly limited, and may be set so as to achieve uniform longitudinal vibration across the width direction X depending on the material, shape, and length of the molding member 20, the ultrasonic vibration applied to the ultrasonic vibration application surface 22, and the like. Note that the molding member 20 does not necessarily need to be provided with slits 26; for example, if the width of the vibration surface 24 is relatively short, uniform longitudinal vibration across the width direction (film formation width direction) X can be achieved without providing slits 26.
• FIG. 3 is a schematic side view showing an example of a manufacturing method and an apparatus for manufacturing an electrode layer according to the present disclosure.
• Fig. 4 is a schematic top view showing an example of a manufacturing method and an apparatus for manufacturing an electrode layer according to the present disclosure. For convenience, only the top surface of the ultrasonic transducer 12 is shown in Fig. 4.
• Chunks of electrode material 40 are scattered on the surface of the current collecting foil 30, which is a support for forming the electrode material film 44. Each electrode material 40 spreads upon contact with the molding member 20 to form the electrode material film 44. It is preferable that the electrode material 40 is arranged at a predetermined interval vertically and horizontally on the surface of the current collecting foil 30, as shown in FIG. 4, so that no voids or uneven thickness are generated in the electrode material film 44. Furthermore, from the viewpoint of the uniformity of the formation of the electrode material film 44, it is preferable that the angle ⁇ between the transport direction D of the current collecting foil 30 and the width direction X of the molding member 20 is 90° ⁇ 1°.
• the current collecting foil 30 and electrode material 40 can be made of known materials. Specific materials will be described later.
• the molding member 20 is inclined with respect to the transport direction D at a position maintained at a certain distance from the surface of the current collecting foil 30, and is installed so that the gap between the vibration surface 24 and the surface of the current collecting foil 30 narrows toward the first direction (transport direction) D.
• the gap S1 between the tip 27 of the vibration surface 24 of the molding member 20 and the surface of the current collecting foil 30 in the transport direction D of the current collecting foil 30 is larger than the height of the electrode material 40 transported toward the molding member 20, and the gap S2 between the end 28 of the vibration surface 24 and the surface of the current collecting foil 30 is inclined to be smaller than the height of the electrode material 40.
• the thickness of the electrode material film 44 is determined by the gap between the surface of the current collector foil 30 and the portion (end portion 28 ) of the vibration surface 24 of the molded member 20 where the distance between the surface of the current collector foil 30 and the surface of the current collector foil 30 is narrowest.
• the amplitude of the longitudinal vibration on the vibration surface 24 of the molded member 20 is preferably 1 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 60 ⁇ m, at the portion (terminal portion) 28 where the gap with the surface of the current collecting foil 30 is narrowest.
• the vibration surface 24 resonates with the ultrasonic waves applied from the ultrasonic transducer 12 to the ultrasonic vibration application surface 22 and vibrates longitudinally in the V direction uniformly across the width direction X of the molded workpiece 20 .
• the angle ⁇ between the vibration surface 24 and the transport direction D is preferably 0° ⁇ 90°, more preferably 10° ⁇ 80°, and even more preferably 20° ⁇ 60°.
• the frequency of the ultrasonic waves applied by the ultrasonic vibrator 12 to the ultrasonic vibration application surface 22 of the molded member 20 is, from the viewpoint of the film formation of the electrode material film 44 by the longitudinal vibration of the vibration surface 24, 15 kHz to 120 kHz.
• a known transport means can be used as the transport device 50 for the current collecting foil 30.
• a belt conveyor, a linear motion guide, a cross roller table, etc. can be used.
• the method of dotting the electrode material 40 on the surface of the current collector foil 30 is not particularly limited, and any known method can be used. There are no particular limitations on the method of dotting the electrode material 40 on the current collector foil 30, i.e., the method of dispersing and arranging the electrode material 40, but from the viewpoints of easily adjusting the size of the electrode material lumps, easily adjusting the dispersion of the lumps, and stabilizing the supply amount, a method of scattering and supplying multiple lumps of the electrode material on the current collector foil can be mentioned. In other words, by scattering and supplying multiple lumps of the electrode material that have been prepared in advance onto the current collector foil, multiple lumps of the electrode material can be dispersed and arranged on the current collector foil.
• the plurality of lumps of electrode material used for the sprinkling supply can be produced by a known granulation means capable of granulating the electrode material.
• the granulation method include extrusion granulation, pulverization granulation, compression granulation, wet (agglomeration) granulation, and granulation using a dicer.
• the lumps obtained by the granulation means are spread and supplied onto the current collector foil by known conveying means and supplying means.
• the scattering supply can be performed by moving the supplying means relatively along the surface of the current collecting foil.
• the diameter of the electrode material 40 dispersedly disposed on the current collector foil is, for example, preferably 0.1 mm to 20 mm, more preferably 0.5 mm to 10 mm, and even more preferably 1 mm to 5 mm.
• a known method for determining a circle-equivalent diameter is used to measure the diameter of the electrode material 40. That is, the diameter of the electrode material means the circle-equivalent diameter of the electrode material 40.
• the average height of the electrode material 40 dispersed on the current collecting foil is, for example, preferably 0.1 mm to 10 mm, more preferably 0.5 mm to 10 mm, and even more preferably 1 mm to 5 mm.
• the distance between the area centers of gravity of adjacent electrode materials 40 is preferably 0.1 mm to 50 mm, more preferably 1 mm to 20 mm, and even more preferably 5 mm to 10 mm.
• the current collecting foil 30, on whose surface the electrode material 40 is dotted, is transported in a first direction D relative to the molding member 20, which is disposed at an angle with respect to the transport direction D of the current collecting foil 30 and whose vibration surface 24 is vertically vibrating, to bring the molding member 20 into contact with the electrode material 40.
• the electrode materials 40 on the transported current collecting foil 30 come into contact with the vertically vibrating vibration surface 24, for example, in the case of a semi-solid, the clay-like electrode materials 40 become fluidized, their height decreases, and they spread over the current collecting foil 30, and an integrated electrode material film 44 is formed by passing through the end portion 28 of the vibration surface 24.
• the conveying speed of the current collector foil 30 in the first direction D is not particularly limited, but if the conveying speed is too slow, productivity will decrease, and the electrode material 40 will be subjected to excessive treatment by the vertical vibration, which may affect the electrolyte and the conductive assistant. On the other hand, if the conveying speed is too fast, the electrode material 40 will be subjected to insufficient treatment by the vertical vibration, which may result in a lack of uniformity in the thickness of the electrode material film 44 and poor coating. From this viewpoint, the conveying speed of the current collector foil 30 is preferably 1 to 50 m/min, more preferably 10 to 40 m/min, and even more preferably 20 to 30 m/min. From the viewpoint of the uniformity of the thickness of the electrode material film 44, it is preferable that the variation in the conveying speed of the current collector foil 30 is ⁇ 5% or less.
• FIG. 5 is a schematic front view showing another example of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• film forming apparatuses 10A having the same configuration of ultrasonic transducer 12 and shaping member 20 are arranged side by side in the film forming width direction X.
• a gap is provided between the two shaping members 20.
• 6, 7, and 8 are schematic side views showing other examples of the configuration of a film forming apparatus used in the manufacturing method of an electrode layer according to the present disclosure.
• the distance between the ultrasonic vibration application surface 22 and the vibration surface 24B is twice the half wavelength of the ultrasonic longitudinal vibration propagating through the molded member 20B by the ultrasonic transducer 12.
• the vibration surface 24B resonates with the ultrasonic waves applied from the ultrasonic transducer 12 to the ultrasonic vibration application surface 22, longitudinally vibrating to the maximum extent, and contacts with the electrode material, thereby forming an electrode material film.
• the molded member 20C shown in FIG. 7 has rounded ends 27C, 28C of the vibration surface 24C.
• the rounded ends 27C, 28C of the vibration surface 24C in this way, damage to the ends 27C, 28C of the molded member 20C can be suppressed.
• the shaped member 20D shown in Fig. 8 has a shape in which the vibration surface 24D is inclined. Since the vibration surface 24D is an inclined surface, the vibration surface 24D can be inclined without inclining the shaped member 20D with respect to the conveying direction D of the current collector foil 30, that is, with the shaped member 20D perpendicular to the surface of the current collector foil 30.
• the distance between the ultrasonic vibration application surface 22 and the vibration surface 24C shown in Figure 7 and the distance between the ultrasonic vibration application surface 22 and the vibration surface 24D shown in Figure 8 are not multiples of half the wavelength of the ultrasonic longitudinal vibration propagating within each molded member 20C, 20D in parts of the vibration surfaces 24C, 24D, respectively, and the amplitude is reduced by the amount of deviation from the resonating distance as shown by arrow V.
• the distance between the ultrasonic vibration application surface 22 and the entire vibration surface 24 be a multiple of half the wavelength of the ultrasonic longitudinal vibration propagated within the molded member 20 by the ultrasonic vibrator 12 of the molded member 20, as shown in FIG.
• the current collecting foil 30 is not particularly limited, and any known current collecting foil (positive electrode current collecting foil and negative electrode current collecting foil) can be used.
• the positive electrode current collector foil examples include foils (i.e., metal layers) of aluminum, aluminum alloys, stainless steel, nickel, and titanium.
• the positive electrode current collector foil is preferably aluminum or an aluminum alloy.
• the positive electrode current collector foil may be aluminum having a coating layer on the surface that includes one or more of carbon, nickel, titanium, silver, gold, platinum, and vanadium oxide.
• Examples of the negative electrode current collector foil include foils (i.e., metal layers) of aluminum, copper, copper alloy, stainless steel, nickel, and titanium.
• the negative electrode current collector foil is preferably aluminum, copper, copper alloy, or stainless steel, and more preferably copper or a copper alloy.
• the negative electrode current collector foil may be copper or stainless steel having a coating layer on the surface that contains one or more of carbon, nickel, titanium, silver, and lithium.
• the current collector foil is preferably aluminum foil (including aluminum foil having the above-mentioned coating layer on its surface) or copper foil (including copper foil having the above-mentioned coating layer on its surface).
• Aluminum foil is usually used as a positive current collector foil.
• Copper foil is usually used as a negative current collector foil.
• the current collecting foil may have a resin film attached thereto.
• the resin film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, a cyclic olefin polymer (COP, COC) film, a triacetyl cellulose (TAC) film, a polyimide (PI) film, and a polyamide (PA) film.
• the thickness of the current collector foil (including the case of a laminate) is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more. From the viewpoints of flexibility and light weight, the thickness of the current collector foil is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
• the thickness of the current collector foil is defined as the arithmetic average value of the thicknesses measured at three points by cross-sectional observation. A known microscope (e.g., a scanning electron microscope) can be used for cross-sectional observation.
• the electrode material 40 contains an electrode active material and has a solid content of 40% by volume or more.
• the electrode material 40 may contain, for example, a conductive assistant and an electrolyte solution, and may further contain an additive, as necessary.
• the electrode material 40 may contain an electrolyte without containing a solvent.
• the electrode active material is a material capable of inserting and releasing ions of a metal element belonging to Group 1 or Group 2 of the periodic table.
• the electrode active material is included in the solid component. Examples of the electrode active material include a positive electrode active material and a negative electrode active material.
• Positive electrode active material is not limited, and any known electrode active material used for a positive electrode can be used.
• the positive electrode active material is preferably a positive electrode active material that can reversibly insert and release lithium ions.
• the positive electrode active material include transition metal oxides and elements that can be composited with lithium (e.g., sulfur).
• the positive electrode active material is preferably a transition metal oxide.
• the transition metal oxide is preferably a transition metal oxide containing at least one transition metal element (hereinafter referred to as "element Ma”) selected from the group consisting of Co (cobalt), Ni (nickel), Fe (iron), Mn (manganese), Cu (copper), and V (vanadium).
• element Ma transition metal element selected from the group consisting of Co (cobalt), Ni (nickel), Fe (iron), Mn (manganese), Cu (copper), and V (vanadium).
• the molar ratio of Li to Ma (Li/Ma) is preferably 0.3 to 2.2.
• the transition metal oxide may also contain at least one transition metal element (hereinafter referred to as "element Mb") selected from the group consisting of Group 1 elements other than lithium, Group 2 elements, Al (aluminum), Ga (gallium), In (indium), Ge (germanium), Sn (tin), Pb (lead), Sb (antimony), Bi (bismuth), Si (silicon), P (phosphorus), and B (boron).
• element Mb transition metal element selected from the group consisting of Group 1 elements other than lithium, Group 2 elements, Al (aluminum), Ga (gallium), In (indium), Ge (germanium), Sn (tin), Pb (lead), Sb (antimony), Bi (bismuth), Si (silicon), P (phosphorus), and B (boron).
• element Mb transition metal element
• the content of element Mb is preferably 0 mol% to 30 mol% with respect to the amount of substance of element Ma.
• transition metal oxides include transition metal oxides having a layered rock salt structure, transition metal oxides having a spinel structure, lithium-containing transition metal phosphate compounds, lithium-containing transition metal halide phosphate compounds, and lithium-containing transition metal silicate compounds.
• transition metal oxides having a layered rock salt structure examples include LiCoO2 (lithium cobalt oxide [LCO]), LiNi2O2 (lithium nickel oxide ) , LiNi0.85Co0.10Al0.05O2 (lithium nickel cobalt aluminate [ NCA]), LiNi1 /3Co1 / 3Mn1 / 3O2 ( lithium nickel manganese cobalt oxide [NMC]), and LiNi0.5Mn0.5O2 (lithium manganese nickel oxide ) .
• LiCoO2 lithium cobalt oxide [LCO]
• LiNi2O2 lithium nickel oxide
• LiNi0.85Co0.10Al0.05O2 lithium nickel cobalt aluminate [ NCA]
• LiNi1 /3Co1 / 3Mn1 / 3O2 lithium nickel manganese cobalt oxide [NMC]
• LiNi0.5Mn0.5O2 lithium manganese nickel oxide
• transition metal oxides having a spinel structure examples include LiCoMnO4 , Li2FeMn3O8 , Li2CuMn3O8 , Li2CrMn3O8 , and Li2NiMn3O8 .
• lithium-containing transition metal phosphate compounds include olivine-type iron phosphate salts (e.g., LiFePO4 and Li3Fe2 ( PO4 ) 3 ), iron pyrophosphate salts (e.g., LiFeP2O7 ), cobalt phosphate salts (e.g., LiCoPO4 ), and monoclinic Nasicon-type vanadium phosphate salts (e.g., Li3V2(PO4)3 ( lithium vanadium phosphate)).
• olivine-type iron phosphate salts e.g., LiFePO4 and Li3Fe2 ( PO4 ) 3
• iron pyrophosphate salts e.g., LiFeP2O7
• cobalt phosphate salts e.g., LiCoPO4
• monoclinic Nasicon-type vanadium phosphate salts e.g., Li3V2(PO4)3 ( lithium vanadium phosphate)
• lithium-containing transition metal halophosphate compounds include iron fluorophosphates (eg, Li 2 FePO 4 F), manganese fluorophosphates (eg, Li 2 MnPO 4 F), and cobalt fluorophosphates (eg, Li 2 CoPO 4 F).
• iron fluorophosphates eg, Li 2 FePO 4 F
• manganese fluorophosphates eg, Li 2 MnPO 4 F
• cobalt fluorophosphates eg, Li 2 CoPO 4 F
• lithium - containing transition metal silicate compounds examples include Li2FeSiO4 , Li2MnSiO4 , and Li2CoSiO4 .
• the transition metal oxide is preferably a transition metal oxide having a layered rock salt structure, and more preferably at least one compound selected from the group consisting of LiCoO2 (lithium cobalt oxide [LCO]), LiNi0.85Co0.10Al0.05O2 (lithium nickel cobalt aluminum oxide [NCA]), and LiNi1 /3Co1 / 3Mn1 / 3O2 (lithium nickel manganese cobalt oxide [ NMC]).
• LiCoO2 lithium cobalt oxide [LCO]
• LiNi0.85Co0.10Al0.05O2 lithium nickel cobalt aluminum oxide [NCA]
• LiNi1 /3Co1 / 3Mn1 / 3O2 lithium nickel manganese cobalt oxide [ NMC]
• the positive electrode active material may be a commercially available product or a synthetic product produced by a known method (e.g., a calcination method).
• the positive electrode active material obtained by the calcination method may be washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
• the positive electrode active material may have a carbon coating on its surface.
• the shape of the positive electrode active material is not limited, but from the viewpoint of ease of handling, it is preferable that it be in particulate form.
• the volume average particle diameter of the positive electrode active material is not limited and may be, for example, 0.1 ⁇ m to 50 ⁇ m.
• the volume average particle diameter of the positive electrode active material is preferably 0.3 ⁇ m to 40 ⁇ m, and more preferably 0.5 ⁇ m to 30 ⁇ m.
• the volume average particle size of the positive electrode active material is measured by the following method.
• a dispersion liquid containing 0.1% by mass or less of the positive electrode active material is prepared by mixing the positive electrode active material with a solvent (e.g., pure water, ethanol, heptane, octane, toluene, or xylene).
• the dispersion liquid irradiated with 1 kHz ultrasonic waves for 10 minutes is used as a measurement sample.
• a laser diffraction/scattering type particle size distribution measuring device e.g., LA-960 manufactured by Horiba, Ltd.
• data is taken 50 times under a temperature of 25°C, and the volume average particle size is obtained from the volume frequency particle size distribution.
• a quartz cell is used as the measurement cell.
• the above measurement is performed using five samples, and the average of the measured values is the volume average particle size of the positive electrode active material.
• JIS Z 8828:2013 refers the volume average particle size of the positive electrode
• Methods for adjusting the particle size of the positive electrode active material include, for example, a method using a grinder, a crusher, or a classifier.
• a known milling method may be used as a method for adjusting the particle size of the positive electrode active material.
• the positive electrode active material may be used alone or in combination of two or more kinds. Even when one type of positive electrode active material is used, positive electrode active materials having different particle sizes may be used in combination.
• the content of the positive electrode active material relative to the total volume of the electrode material is preferably 30% by volume to 60% by volume, more preferably 35% by volume to 55% by volume, and even more preferably 40% by volume to 50% by volume.
• the amount of the positive electrode active material used is determined so that the content in the electrode material film falls within the above-mentioned range.
• Negative electrode active material is not limited, and any known electrode active material used for a negative electrode can be used.
• the negative electrode active material is preferably a negative electrode active material that can reversibly insert and release lithium ions.
• the negative electrode active material examples include carbonaceous materials, metal oxides (e.g., tin oxide), silicon oxide, metal composite oxides, lithium alone, lithium alloys (e.g., lithium aluminum alloys), and metals capable of forming alloys with lithium (e.g., Sn, Si, and In).
• the negative electrode active material is a carbonaceous material or a lithium composite oxide.
• a carbonaceous material is a material that consists essentially of carbon.
• Examples of carbonaceous materials include petroleum pitch, carbon black (e.g., acetylene black), graphite (e.g., natural graphite and artificial graphite (e.g., vapor-grown graphite)), hard carbon, and carbonaceous materials obtained by firing synthetic resins (e.g., polyacrylonitrile (PAN) and furfuryl alcohol resin).
• PAN polyacrylonitrile
• furfuryl alcohol resin e.g., polyacrylonitrile (PAN) and furfuryl alcohol resin
• carbonaceous materials include carbon fibers (e.g., polyacrylonitrile-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers).
• carbon fibers e.g., polyacrylonitrile-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers.
• graphite include mesophase microspheres, graphite whiskers, and tabular graphite.
• "flat" means a shape having two major planes facing in opposite directions.
• the metal composite oxide is preferably a metal composite oxide capable of absorbing and releasing lithium.
• the metal composite oxide capable of absorbing and releasing lithium preferably contains at least one element selected from the group consisting of titanium and lithium.
• the metal oxides and metal composite oxides are preferably amorphous oxides.
• the metal oxides and metal composite oxides are also preferably chalcogenides.
• Chalcogenides are reaction products between metal elements and elements of Group 16 of the periodic table.
• amorphous oxides and chalcogenides of semimetallic elements are preferred, and oxides and chalcogenides containing at least one element selected from the group consisting of elements of groups 13 to 15 in the periodic table, Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi are more preferred.
• the negative electrode active material further contains titanium.
• the negative electrode active material containing titanium is preferably Li 4 Ti 5 O 12 (lithium titanate [LTO]).
• the negative electrode active material may be a commercially available product or a synthetic product produced by a known method (e.g., a calcination method).
• the negative electrode active material obtained by the calcination method may be washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
• the negative electrode active material is available, for example, as CGB20 (Nippon Graphite Industries Co., Ltd.).
• the composition of the negative electrode active material is measured using inductively coupled plasma (ICP) optical emission spectroscopy.
• ICP inductively coupled plasma
• the shape of the negative electrode active material is not limited, but it is preferable that it be particulate, as this makes it easier to handle and makes it easier to control uniformity during mass production.
• the volume average particle size of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m, more preferably 0.3 ⁇ m to 50 ⁇ m, and particularly preferably 0.5 ⁇ m to 40 ⁇ m.
• the volume average particle diameter of the negative electrode active material is measured by a method similar to the method for measuring the volume average particle diameter of the positive electrode active material.
• Methods for adjusting the particle size of the negative electrode active material include, for example, using a grinder or a classifier.
• the negative electrode active material may be used alone or in combination of two or more kinds. Even when one type of negative electrode active material is used, negative electrode active materials having different particle sizes may be used in combination.
• the content of the negative electrode active material relative to the total volume of the electrode material is preferably 30 vol % to 60 vol %, more preferably 35 vol % to 57 vol %, and further preferably 45 vol % to 55 vol %.
• the amount of the negative electrode active material used is determined so that the content in the electrode material film falls within the above-mentioned range.
• the surfaces of the positive electrode active material and the negative electrode active material may each be coated with a surface coating agent.
• the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Si, or Li.
• the metal oxides include titanate spinel, tantalum-based oxides, niobium-based oxides, and lithium niobate-based compounds.
• the electrode material film contains a conductive assistant from the viewpoint of improving the electronic conductivity of the electrode active material.
• the conductive assistant is not limited, and any known conductive assistant can be used.
• the conductive assistant is included in the solid component.
• Conductive additives include, for example, graphite (e.g., natural graphite and artificial graphite), carbon black (e.g., acetylene black, ketjen black, and furnace black), amorphous carbon (e.g., needle coke), carbon fibers (e.g., vapor-grown carbon fibers and carbon nanotubes), other carbonaceous materials (e.g., graphene and fullerene), metal powders (e.g., copper powder and nickel powder), metal fibers (e.g., copper fibers and nickel fibers), and conductive polymers (e.g., polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives).
• graphite e.g., natural graphite and artificial graphite
• carbon black e.g., acetylene black, ketjen black, and furnace black
• amorphous carbon e.g., needle coke
• carbon fibers e.g.
• the conductive additive may be used alone or in combination of two or more types.
• the content of the conductive assistant relative to the total volume of the electrode material is preferably 0.05 to 5% by volume, more preferably 0.1 to 4% by volume, and even more preferably 0.5 to 3% by volume.
• the amount of the conductive assistant used is determined so that the content in the electrode material film falls within the above-mentioned range.
• the electrolyte is not particularly limited, and a known electrolyte can be used.
• the electrolyte includes an electrolyte containing an electrolyte and a solvent.
• a specific electrolyte includes an electrolyte containing a lithium salt compound as an electrolyte and a carbonate compound as a solvent.
• lithium salt compound is lithium hexafluorophosphate.
• the electrolyte may contain a single lithium salt compound, or may contain two or more lithium salt compounds.
• carbonate compounds examples include linear carbonate compounds such as ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC), and cyclic carbonate compounds such as ethylene carbonate (EC) and propylene carbonate (PC).
• EMC ethyl methyl carbonate
• DMC dimethyl carbonate
• DEC diethyl carbonate
• cyclic carbonate compounds such as ethylene carbonate (EC) and propylene carbonate (PC).
• the electrolyte may contain one type of carbonate compound alone, may contain two or more types of carbonate compounds, or may contain one or more linear carbonate compounds and one or more cyclic carbonate compounds in combination.
• known inorganic solid electrolytes can be used as the electrolyte contained in the electrolytic solution.
• an ionic liquid may be used as a component of the electrolyte.
• the ionic liquid may be used as either an electrolyte or a solvent.
• the content of the electrolyte solution relative to the total volume of the electrode material is preferably 70% by volume or less, and may be 50% by volume or less, or may be 40% by volume or less.
• the lower limit of the content of the electrolyte solution relative to the total volume of the electrode material is not limited, and may be 20% by volume or more, or may be 30% by volume or more.
• the content of the electrolyte relative to the total volume of the electrode material may be, for example, 30% by volume to 50% by volume.
• the electrode material film may contain, as a liquid component, a solvent (hereinafter, simply referred to as "solvent”) other than the solvent contained as a component of the electrolyte solution.
• solvent include alcohol compound solvents, ether compound solvents, amide compound solvents, amino compound solvents, ketone compound solvents, aromatic compound solvents, aliphatic compound solvents, and nitrile compound solvents.
• the electrode material film may contain a binder, a dispersant, other additives, etc.
• the electrode material film preferably has a low binder (also referred to as a resin component) content, preferably 1 mass % or less, and particularly preferably does not contain any binder (0 mass %).
• the binder refers to components called rheology adjusters and dispersants in known electrode material films, in addition to binders, and examples thereof include fluorine-containing resins, hydrocarbon-based thermoplastic resins, acrylic resins, and urethane resins.
• the dispersant may be any known dispersant capable of dispersing the object to be dispersed.
• known additives that are added to electrodes can be used.
• LiPF 6 electrolyte
• EC ethylene carbonate
• PC propylene carbonate
• DEC diethyl carbonate
• VC vinylene carbonate
• 64 g of the resulting mixed solution was taken out and used as electrolyte solution X1.
• 2 g of a conductive additive (Ketjen black) and 174 g of a positive electrode active material (lithium iron phosphate) were stirred in a mixer (Awatori Rentaro ARE-310, manufactured by Thinky Corporation) at 1,500 rpm (revolutions per minute) for 30 seconds to prepare a kneaded material Y1 (176 g).
• the positive electrode material (P1) was extruded using a mincer (Bonny Co., Ltd.) to obtain a mass (P1) containing cylindrical granules (diameter: 3 mm to 5 mm).
• Example 1 Agglomerates (P1) prepared in advance were scattered and supplied onto the continuously conveyed current collector foil, so that a plurality of lumps of electrode material were dispersed and arranged on the current collector foil.
• the multiple lumps dispersed on the current collector foil had an average height of 6 mm, a diameter of 3 mm to 5 mm, a distance between the area centers of gravity of adjacent lumps of 10 mm, and an area ratio of 15%. As shown in Fig. 3 and Fig.
• the forming member 20 was arranged so that the angle ⁇ between the vibration plane and the surface of the current collector foil was 20°, the gap S1 between the surface of the current collector foil 30 and the tip end 27 of the forming member (half-wave resonator) 20 was 15 mm, and the gap S2 between the surface of the current collector foil 30 and the end end 28 of the forming member (half-wave resonator) 20 was 0.3 mm.
• the current collector foil 30 was transported in the direction of the arrow D at 6 m/min, and a plurality of lumps (P1) of the electrode material 40 distributed on the current collector foil 30 were brought into contact with the forming member 20 and passed through.
• an electrode material film 44 which is a continuous film, was formed on the current collector foil 30 along the transport direction (direction of the arrow D) of the current collector foil 30.
• the film thickness of the obtained electrode material film 44 was 0.3 mm.

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