WO2019189332A1 - Électrode pour batterie au lithium-ion, batterie au lithium-ion, et corps de rouleau d'électrode pour batterie au lithium-ion - Google Patents

Électrode pour batterie au lithium-ion, batterie au lithium-ion, et corps de rouleau d'électrode pour batterie au lithium-ion Download PDF

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WO2019189332A1
WO2019189332A1 PCT/JP2019/013136 JP2019013136W WO2019189332A1 WO 2019189332 A1 WO2019189332 A1 WO 2019189332A1 JP 2019013136 W JP2019013136 W JP 2019013136W WO 2019189332 A1 WO2019189332 A1 WO 2019189332A1
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electrode
lithium ion
ion battery
active material
material layer
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PCT/JP2019/013136
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English (en)
Japanese (ja)
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佐藤　健治
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Ｎｅｃエナジーデバイス株式会社
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Priority to JP2020509178A priority Critical patent/JP7026207B2/ja
Priority to CN201980018436.4A priority patent/CN111886720B/zh
Priority to CN202310987559.7A priority patent/CN116914078A/zh
Publication of WO2019189332A1 publication Critical patent/WO2019189332A1/fr

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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

Definitions

  • the present invention relates to an electrode for a lithium ion battery, a lithium ion battery, and an electrode roll body for a lithium ion battery.
  • Lithium ion batteries are already indispensable in modern society as a representative of secondary batteries.
  • development for further increasing the capacity, improving safety, and reducing production costs is being carried out.
  • developments such as those described in Patent Documents 1 to 4 below are being carried out.
  • Patent Document 1 discloses a composition formula: Li x (Ni y M 1-y ) O z (wherein M is Mn and Co, x is 0.9 to 1.2, and y is 0.3). To 0.9 and z is 1.8 to 2.4).
  • a positive electrode for a lithium ion battery produced by applying to the surface is described. It is described that the surface roughness (R zjis ) measured by scanning the positive electrode with a measurement length of 4 mm is 10 ⁇ m or less.
  • Patent Document 2 describes a positive electrode including a positive electrode active material capable of reversibly inserting and releasing lithium ions, a negative electrode including a negative electrode active material, and a lithium ion battery including an electrolytic solution.
  • Ra which is the arithmetic average value of the surface roughness of the positive electrode after performing the charge / discharge process, is 155 to 419 nm
  • Ra which is the arithmetic average value of the surface roughness of the negative electrode, is 183 to 1159 nm. It is described that it is.
  • Patent Document 3 discloses that a “separator” includes (i) a base material composed of a porous film, (ii) formed on at least one surface of the base material, and contains particles and a resin material.
  • a separator for a nonaqueous electrolyte battery is described that includes a porous surface layer having an uneven shape with a roughness of 1.0 ⁇ m or more and 4.0 ⁇ m or less.
  • Patent Document 4 is a document related to a “separator” as in Patent Document 3.
  • This separator is comprised from the base material containing the porous film whose main component is polyolefin, The filler is adhered to the surface of the base material, and the lubrication layer is formed. It is described that the surface roughness of the lubricating layer is 0.2 to 1.4 ⁇ m in terms of three-dimensional surface roughness.
  • An electrode (for example, positive electrode) of a lithium ion battery is usually manufactured by pressing active material particles formed on a current collector such as a metal foil.
  • a current collector such as a metal foil.
  • the electrode is stored and transported in the state of a roll wound around the winding core in a plurality of circumferences.
  • the electrode is pulled out from the roll body and processed into a predetermined shape.
  • the pressure has been increased to increase the density of electrodes and improve the energy density of lithium ion secondary batteries.
  • the pressing pressure at the time of pressing the active material particles is too large, the gap between the active material particles becomes too small, and as a result, a situation may occur in which the electrolyte does not reach the active material layer sufficiently.
  • the electrode has a low density, and improvement in rate characteristics cannot be expected. That is, it is desired to improve the rate characteristics by making appropriate gaps between the active materials by making the pressing conditions appropriate, etc., and making the density of the electrode and the permeability of the electrolyte appropriately compatible.
  • an object of the present invention is to provide a lithium ion battery electrode having good electrolyte permeability and good rate characteristics.
  • An electrode for a lithium ion battery includes a current collector and an active material layer formed on a surface of the current collector,
  • the active material layer includes active material particles and a binder resin,
  • the surface of the active material layer, the arithmetic average height S a required along with the provisions of ISO 25178 is 0.2 ⁇ 1.0 .mu.m
  • the arithmetic average roughness R a required along with the provisions of JIS B 0601-2001 is 0.1 ⁇ 1.0 .mu.m
  • a lithium-ion cell electrodes is provided a lithium-ion cell electrodes.
  • a lithium ion battery comprising the above-described lithium ion battery electrode is provided.
  • a lithium ion battery electrode roll body in which a lithium ion battery electrode is wound around a winding core, The lithium ion battery electrode includes a current collector and an active material layer formed on a surface of the current collector, The active material layer includes active material particles and a binder resin, Wherein the surface of the active material layer, the arithmetic average height S a required along with the provisions of ISO 25178 is 0.2 ⁇ 1.0 .mu.m, Wherein the surface of the active material layer, the arithmetic average roughness R a required along with the provisions of JIS B 0601-2001 is 0.1 ⁇ 1.0 .mu.m, for a lithium ion battery electrode roll body is provided.
  • an electrode of a lithium ion battery having good electrolyte permeability and high rate characteristics.
  • the notation “a to b” in the description of numerical ranges represents a to b inclusive unless otherwise specified.
  • “1 to 5 mass%” represents 1 mass% or more and 5 mass% or less.
  • the notation which does not describe substitution or non-substitution includes both those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • FIG. 1 shows an example (cross section, layer configuration) of an electrode for a lithium ion battery according to the present embodiment.
  • a lithium ion battery electrode 1 (hereinafter also referred to simply as “electrode 1”) includes at least a current collector 2 and an active material layer 3 formed on at least one surface thereof.
  • the active material layer 3 may be provided on both surfaces of the current collector 2.
  • the active material layer 3 includes active material particles and a binder resin.
  • the surface of the active material layer 3, the arithmetic average height S a required along with the provisions of ISO 25178 is 0.2 ⁇ 1.0 .mu.m.
  • the surface of the active material layer 3, an arithmetic mean roughness R a required along with the provisions of JIS B 0601-2001 is 0.1 ⁇ 1.0 .mu.m.
  • the strength of the press and the roughness of the electrode surface are considered to correlate to some extent. Specifically, when the press pressure is large, the roughness of the electrode surface tends to be small, and when the press pressure is small, the roughness of the electrode surface tends to be large. In other words, by pressing so that the roughness of the electrode surface becomes an appropriate value (a value that is not too small and not too large), an appropriate compressed state of the electrode is realized, and an appropriate amount between active materials is obtained. It is thought that there can be a gap. Then, the density of the active material particles and the permeability of the electrolytic solution are compatible, and it is considered that the rate characteristics are improved.
  • pressing is performed so that S a is 0.2 to 1.0 ⁇ m and R a is 0.1 to 1.0 ⁇ m. It is considered that the “compressed state of the electrode” has been realized.
  • the surface roughness is defined by “two” indicators of S a and R a , and it is essential that each is within a specific numerical range.
  • S a to be measured captured not only R a based on measurements along a particular one-dimensional direction (a line segment) is within a predetermined numerical range, the measurement target area as the "surface”
  • the compression state of the electrode as a whole is ensured by being within the predetermined numerical range.
  • S a and R a is out of the predetermined numerical range, it is presumed that this indicates that there is a part with an irregular roughness in the electrode.
  • S a is specifically defined in ISO 25178, and R a is defined in JIS B 0601-2001.
  • VR- 3000 can be used as a specific apparatus for measuring these.
  • the average value of the measurement results at five points may be a S a and R a in the present specification.
  • R a is, by definition, the surface of the electrode 1, which measures along a particular one-dimensional direction (a line segment). That is, the value can change depending on the measurement direction.
  • the surface of the electrode 1, at least one one-dimensional direction (a line segment), R a may if 0.1 ⁇ 1.0 .mu.m. More specifically, when the overall shape of the electrode 1 is a rectangle (often used for an electrode of a laminate-type lithium ion battery), Ra measured in two directions of the short side and the long side of the rectangle. Are preferably 0.1 to 1.0 ⁇ m.
  • S a is 0.2 to 1.0 ⁇ m, preferably 0.2 to 0.6 ⁇ m, more preferably 0.2 to 0.5 ⁇ m.
  • R a is 0.1 to 1.0 ⁇ m, preferably 0.1 to 0.5 ⁇ m, more preferably 0.15 to 0.5 ⁇ m.
  • the electrode 1 is a positive electrode or a negative electrode for a lithium ion battery. First, the case where the electrode 1 is a positive electrode for a lithium ion battery will be described.
  • the positive electrode current collector 2 As the positive electrode current collector 2, any conductive material can be used. For example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used. Among these, aluminum is preferable from the viewpoints of price, availability, electrochemical stability, and the like.
  • the shape of the current collector is not particularly limited, and may be a foil shape, a flat plate shape, a mesh shape, or the like.
  • the thickness of the current collector is preferably in the range of 0.001 to 0.5 mm (1 to 500 ⁇ m), more preferably 5 to 100 ⁇ m, and still more preferably 0.01 to 0.02 mm (10 to 20 ⁇ m). .
  • Active material layer 3 of positive electrode Active material layer 3, it is necessary to satisfy the requirements of S a and R a as described above for the surface, chemical materials, may be applied to the prior art as appropriate for such compositions.
  • the active material layer 3 preferably includes positive electrode active material particles. Further, it is preferable to further contain a binder resin and a conductive aid. Of course, components other than these may be included.
  • the electrode 1 is a positive electrode, the component which the active material layer 3 may contain is demonstrated.
  • the positive electrode active material particle will not be specifically limited if it is a positive electrode active material particle which can be used for the positive electrode of a lithium ion secondary battery.
  • the olivine-type lithium phosphorus oxide is, for example, at least one member selected from the group consisting of Mn, Cr, Co, Cu, Ni, V, Mo, Ti, Zn, Al, Ga, Mg, B, Nb, and Fe. It contains elements, lithium, phosphorus, and oxygen. In order to improve the characteristics of these compounds, some elements may be partially substituted with other elements. A plurality of types of positive electrode active material particles may be used in combination.
  • the positive electrode active material particles preferably include at least one compound selected from the group consisting of lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, and lithium iron phosphate.
  • lithium cobalt oxide may contain elements other than lithium, cobalt, and oxygen. The same applies to other compounds.
  • the average particle diameter (lower limit) of the positive electrode active material particles is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the average particle diameter (upper limit) is preferably 80 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 20 ⁇ m or less. From the viewpoint of input / output characteristics and electrode fabrication, an appropriate particle size is selected.
  • the average particle diameter means a particle diameter (median diameter: D 50 ) at an integrated value of 50% in a particle size distribution (volume basis) by a laser diffraction scattering method.
  • the content of the positive electrode active material particles is preferably 85 parts by mass or more and 99.4 parts by mass or less, and 90.5 parts by mass or more and 98.5 parts by mass when the entire active material layer 3 is 100 parts by mass. More preferably, it is 90.5 mass parts or more and 97.5 mass parts or less. Thereby, sufficient occlusion and release of lithium can be expected.
  • Binder resin can select a well-known thing suitably, and is not specifically limited.
  • commonly used materials such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) can be used.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • These binder resins are mixed with other components using an appropriate solvent (typically, an organic solvent such as N-methyl-pyrrolidone (NMP)).
  • NMP N-methyl-pyrrolidone
  • the content of the binder resin is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and 0.5 parts by mass or more and 5.0 parts by mass when the entire active material layer 3 is 100 parts by mass. More preferably, it is 1.0 mass part or more and 5.0 mass part or less.
  • the content of the binder resin is within the above range, the balance of electrode slurry coating properties, binder binding properties, and battery characteristics is further improved.
  • the content of the binder resin is not more than the above upper limit value because the ratio of the electrode active material is increased and the capacity per electrode mass is increased. It is preferable for the content of the binder resin to be not less than the above lower limit value because electrode peeling is suppressed.
  • a conductive support agent will not be specifically limited if the electroconductivity of an electrode is improved. Examples thereof include carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, and carbon fiber. These conductive aids may be used alone or in combination of two or more.
  • the content of the conductive assistant is preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and 1.0 part by mass or more and 4.5 parts by mass when the entire active material layer 3 is 100 parts by mass.
  • the amount is more preferably 1.5 parts by mass or less, and further preferably 1.5 parts by mass or more and 4.5 parts by mass or less.
  • the content of the conductive assistant is within the above range, the balance of electrode slurry coating property, binder binding property, and battery characteristics is further improved.
  • the content of the conductive assistant is not more than the above upper limit value because the ratio of the electrode active material is increased and the capacity per electrode mass is increased. It is preferable that the content of the conductive auxiliary is not less than the above lower limit value because the conductivity of the electrode becomes better.
  • the density of the active material layer 3 is not particularly limited, but is typically 2.0 g / cm 3 or more, preferably 3.0 g / cm 3 or more, more preferably 3.4 g / cm 3. That's it. Further, from the viewpoint of ease of production, etc., it is typically 4.0 g / cm 3 or less, preferably 3.5 g / cm 3 or less. Within this numerical range, the discharge capacity at the time of use at a high discharge rate is improved, which is preferable.
  • the thickness of the active material layer 3 is not specifically limited, It can set suitably according to a desired characteristic. For example, it can be set thick from the viewpoint of energy density, and can be set thin from the viewpoint of output characteristics.
  • the thickness of the active material layer 3 per side of the current collector can be appropriately set, for example, in the range of 10 to 250 ⁇ m, preferably 20 to 200 ⁇ m, more preferably 50 to 150 ⁇ m, and still more preferably 50 to 100 ⁇ m.
  • the active material layer 3 may be provided not only on one side of the current collector 2 but also on both sides. Therefore, the thickness of the active material layer 3 is described as “per side” for the sake of safety.
  • the manufacturing method is not limited. By any of the methods may be you get an electrode that satisfies the S a and R a above. For example, (i) First, an electrode slurry in which positive electrode active material particles, a binder resin, and a conductive additive are dispersed or dissolved in an appropriate solvent (typically an organic solvent such as N-methylpyrrolidone) is prepared, and (ii) ) Next, the electrode slurry is applied to one side or both sides of the current collector 2 and dried to provide an active material layer 3. (iii) Thereafter, the active material layer 3 formed on the current collector 2 is By pressing together with the current collector 2 (roll press or the like), the lithium ion battery electrode of this embodiment can be obtained.
  • an appropriate solvent typically an organic solvent such as N-methylpyrrolidone
  • FIG. 2 schematically shows an example of a pressing process (roll press).
  • the electrode 1 (not shown in the figure, but including the current collector 2 and the active material layer 3) is sandwiched by two rolls 10 disposed so as to face each other with the buffer film 5 interposed therebetween. Is done.
  • the sandwiched electrode 1 and buffer film 5 are fed from the left to the right in FIG. 2 by the force of rotation of two rolls 10 (indicated by arrows in FIG. 2).
  • the active material layer 3 on the surface of the electrode 1 is compressed and / or flattened by being pressed by the roll 10 through the buffer film 5.
  • the buffer film 5 exists on the “both sides” of the electrode 1, but this is not essential.
  • the buffer film 5 may exist only on the current collector 2 side.
  • a film that is soft to some extent and has deformability is selected from the viewpoint of stress relaxation described above.
  • an aluminum film is selected as the buffer film 5.
  • the “aluminum film” does not only refer to a film made of pure aluminum but also includes an alloy film of aluminum and other trace metal elements.
  • a synthetic resin film is preferably selected from the viewpoint of softness and deformability.
  • a polyester film PET film or the like
  • a polyolefin film polyethylene film, polypropylene film
  • other known synthetic resin films can be applied.
  • the buffer film 5 made of a softer material based on the hardness of the positive electrode active material particles contained in the active material layer 3.
  • the buffer film 5 preferably has a surface that is flat to some extent (a surface in contact with the electrode 1).
  • the arithmetic average roughness of the surface of the buffer film 5 that contacts the electrode 1 is, for example, 0.1 to 2.0 ⁇ m, preferably 0.5 to 1.5 ⁇ m, and more preferably 0.6 to 0.8 ⁇ m. It is considered that the surface of the active material layer 3 can be made even more smooth by satisfying this numerical range.
  • the thickness of the buffer film 5 is not particularly limited, but is 10 to 100 ⁇ m, preferably 10 to 50 ⁇ m, and more preferably 15 to 25 ⁇ m from the viewpoint of handling properties.
  • the conveying speed of the electrode 1 (corresponding approximately to the linear speed of rotation of the roll 10) is not particularly limited, but is typically 1 to 100 m / min, preferably 2 to 50 m / min.
  • the pressure of the roll press is not particularly limited, but is typically 0.7 to 2.0 [t / cm], preferably 1.3 to 1.7 [t / cm]. By setting the pressure appropriately, it is easy to manufacture the electrode 1 having S a and R a having appropriate values.
  • a roll press is preferable from the viewpoint of ease of applying a large pressure and ease of continuous production.
  • the electrode 1 is a positive electrode for a lithium ion battery has been described above. Next, the case where the electrode 1 is a negative electrode for a lithium ion battery will be described. For the drawings, refer to the same as the positive electrode (FIG. 1 and the like).
  • the current collector 2 can be made of any conductive material.
  • the material copper, stainless steel, nickel, titanium, alloys thereof, and the like can be used. The thickness and the like are as described for the current collector 2 as the positive electrode.
  • the active material layer 3 as the negative electrode preferably includes negative electrode active material particles. Moreover, you may contain binder resin and a conductive support agent as needed.
  • the negative electrode active material particles include graphite, amorphous carbon, silicon, silicon oxide, metallic lithium, and the like. However, the negative electrode active material particles are not limited to these as long as they can occlude and release lithium.
  • the average particle diameter (lower limit) of the negative electrode active material particles is preferably 1 ⁇ m, more preferably 2 ⁇ m, and even more preferably 5 ⁇ m from the viewpoint of input / output characteristics and electrode production. Moreover, as an average particle diameter (upper limit), 80 micrometers is preferable and 40 micrometers is more preferable.
  • the average particle diameter means a particle diameter (median diameter: D 50 ) at an integrated value of 50% in a particle size distribution (volume basis) by a laser diffraction scattering method. By setting it as this numerical range, the side reaction at the time of charging / discharging can be suppressed and the fall of charging / discharging efficiency can be suppressed.
  • the binder resin and conductive additive that may be included in the active material layer 3 as the negative electrode the same materials as those that can be used for the active material layer 3 as the positive electrode described above can be used.
  • the binder resin styrene / butadiene rubber or the like can be used.
  • water can also be used as a solvent at the time of application instead of an organic solvent.
  • the amount of each component in the negative electrode is appropriately adjusted from the viewpoint of battery performance, manufacturability, adhesion to the current collector, and the like.
  • An electrode roll body can be manufactured by winding the long electrode 1 around a winding core. Specifically, the electrode roll body can be manufactured by fixing one end of the long electrode 1 to the winding core and winding up the electrode 1 over a plurality of circumferences around the winding core. In order to prevent the electrode 1 from sagging and the electrode 1 from shifting in a direction parallel to the axis of the winding core, it is preferable to take up the electrode 1 by applying tension. Industrially, the electrode 1 is usually stored and transported in the form of an electrode roll.
  • the lithium ion battery of this embodiment includes the above-described electrode for a lithium ion battery.
  • a lithium ion battery includes a positive electrode and a negative electrode.
  • at least one is comprised of the electrode satisfying such provisions of the above S a and R a.
  • one of the S a and R a of the positive electrode and the negative electrode is the within a specific number, even if the other S a and R a a lithium ion battery is a specific numerical value outside, lithium of the battery in this embodiment It can be an ion battery.
  • at least a positive electrode satisfies the provisions of the above S a and R a.
  • the lithium ion battery of the present embodiment includes, as one aspect, an electrolyte, a separator, an outer container, and the like in addition to a positive electrode and a negative electrode. These will be described.
  • a non-aqueous electrolyte containing a lithium salt is usually used as the electrolytic solution.
  • the lithium salt for example, LiClO 4, LiBF 6, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5 ) 4 , CF 3 SO 3 Li, CH 3 SO 3 Li, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, and a lower fatty acid lithium carboxylate.
  • the solvent for dissolving the lithium salt known ones can be used without particular limitation.
  • carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), vinylene carbonate (VC);
  • ⁇ Lactones such as butyrolactone and ⁇ -valerolactone
  • ethers such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran
  • sulfoxides such as dimethyl sulfoxide
  • Oxolanes such as 4-methyl-1,3-dioxolane
  • nitrogen-containing solvents such as acetonitrile, nitromethane, formamide, dimethylformamide; methyl formate, methyl acetate, ethyl acetate
  • the separator is made of, for example, a resin porous film, a woven fabric, a non-woven fabric, or the like.
  • resin component polyolefin resin such as polypropylene and polyethylene, polyester resin, acrylic resin, styrene resin, nylon resin, or the like can be used.
  • a polyolefin-based microporous membrane is preferable because of its excellent ion permeability and performance of physically separating the positive electrode and the negative electrode.
  • the layer containing an inorganic particle may be formed in the separator as needed.
  • the inorganic particles include insulating oxides, nitrides, sulfides, and carbides. Among these, it is preferable to contain TiO 2 and / or Al 2 O 3 .
  • An exterior container A well-known member can be used for an exterior container. From the viewpoint of reducing the weight of the battery, it is preferable to use a flexible film.
  • a flexible film what provided the resin layer on the front and back of the metal layer used as a base material can be used.
  • the metal layer a metal layer having a barrier property such as preventing leakage of the electrolytic solution or entry of moisture from the outside can be selected, and aluminum, stainless steel, or the like can be used.
  • Preparation of slurry for forming active material layer (1) Preparation of positive electrode slurry 1 First, the following materials were uniformly mixed at the indicated ratio. ⁇ Positive electrode active material: lithium nickel oxide particles (D 50 : 8 ⁇ m) and lithium manganese oxide particles (D 50 : 12 ⁇ m) mixed at a mass ratio of 3: 7: 93% by mass -Conductive auxiliary agent: carbon black ... 3% by mass -Binder resin: PVDF (polyvinylidene fluoride) ... 4% by mass
  • This mixture was further mixed with a solvent NMP (N-methyl-2-pyrrolidone) to prepare a positive electrode slurry 1.
  • NMP N-methyl-2-pyrrolidone
  • a positive electrode slurry 2 was prepared in the same manner as in the above (1) except that lithium nickel oxide and lithium manganese oxide were mixed at a mass ratio of 7: 3 as a positive electrode active material.
  • a positive electrode slurry 3 was produced in the same manner as in the above (1) except that only lithium nickel oxide was used as the positive electrode active material.
  • Each positive electrode slurry produced in (1) was applied to both sides of an aluminum base (thickness: about 15 ⁇ m) serving as a current collector and dried to obtain a positive electrode with an uncompressed active material layer.
  • This positive electrode with the active material layer uncompressed was pressed at 1.6 t / cm from both sides through a buffer film as described in FIG. 2 using a roll press device (roll diameter: ⁇ 300, transported) Speed: 3 m / min).
  • an aluminum substrate was used as the buffer film.
  • a lithium ion battery electrode (positive electrode) having an active material layer formed of the positive electrode slurry 1, 2 or 3 was obtained.
  • the density of the active material layer was 3.4 g / cm 2 or more.
  • the thickness of the active material layer per one side of the current collector was 70 ⁇ m.
  • the positive electrode obtained using the positive electrode slurry 1 was “positive electrode of Example 1”
  • the positive electrode obtained using the positive electrode slurry 2 was “positive electrode of Example 2”
  • the positive electrode obtained using the positive electrode slurry 3 was “ This is referred to as the positive electrode of Example 3.
  • Comparative Example 1 A positive electrode of Comparative Example 1 was obtained in the same manner as the positive electrode of Example 1 except that the slurry was pressed at 2.4 t / cm in “2. Application of slurry onto current collector, roll press, etc.”.
  • Comparative example 2 A positive electrode of Comparative Example 2 was obtained in the same manner as the positive electrode of Example 1 except that the roll pressing was not performed in “2. Application of slurry onto current collector, roll press, etc.”.
  • a lithium ion secondary battery was produced using the positive electrode produced in step 1 and the following negative electrode, electrolytic solution, separator, and the like. That is, the positive electrode obtained above and the following negative electrode were stacked via the following separators to produce a laminate, and accommodated in a laminate outer package. Thereafter, the following electrolytic solution was injected to produce a laminated lithium ion secondary battery.
  • Negative electrode produced by the following method A negative electrode slurry was prepared by adding 97% by mass of graphite as a negative electrode active material, 2% of styrene-butadiene rubber and 1% of carboxymethyl cellulose as binders and adding ion exchange water. This was applied to both sides of a copper foil serving as a current collector, dried, and roll pressed to create a negative electrode. The coating amount of the negative electrode active material layer was adjusted to 16 mg / cm 2 and the density was adjusted to 1.5 g / cm 3 .
  • Electrolyte solution Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 30:70, and LiPF 6 as a lithium salt was dissolved so as to be 1.0 mol / L. , VC) to which 1% by mass was added was used.
  • the electrolyte solution penetration time was measured as follows. First, the electrode was cut out to 5 cm ⁇ 5 cm and placed on a horizontal test bench. From the height of 1 mm, 1 ⁇ L of propylene carbonate solvent (simulated electrolyte) was dropped from the tip of the dispenser nozzle onto the surface of the electrode for evaluation. The time from the time of dropping until the time when the entire dropping solution soaked into the electrode active material layer (when it disappeared) was measured (dry air atmosphere at 25 ° C., dew point temperature: ⁇ 40 ° C. or lower). This time was defined as the penetration time.
  • the time when the dropping liquid disappears is the time when it is visually confirmed that the dropping liquid has disappeared from the electrode surface in one direction arbitrarily determined from the base point on the electrode. Considered the time.
  • the base point on the electrode was directly below the tip of the discharge port of the dispenser.
  • the case where the permeation time exceeded 800 seconds was evaluated as x (defect), and the case where the permeation time was shorter than 800 seconds was evaluated as good (good).
  • Examples 1-3 of the positive electrode (S a is 0.2 ⁇ 1.0 .mu.m, and, R a is a positive electrode is 0.1 ⁇ 1.0 .mu.m) Lithium Ion using The secondary battery showed good results in rate characteristics and permeability.
  • the lithium ion secondary battery using the positive electrode of Comparative Example 1 had bad results in both rate characteristics and permeability.
  • the positive electrode of Comparative Example 1 has a small surface roughness, but is too compressed, so the permeability of the electrolytic solution is poor, the ionic resistance between the electrolytic solution and the active material is high, and good rate characteristics cannot be obtained. Estimated. Further, it can be seen from Comparative Example 1 that the smaller the surface roughness is, the better, and that there is an appropriate surface roughness from the viewpoint of rate characteristics and electrolyte permeability.
  • the lithium ion secondary battery using the positive electrode of Comparative Example 2 had good permeability, but had poor rate characteristics.
  • the positive electrode of Comparative Example 2 has good electrolyte permeability, it is presumed that good rate characteristics could not be obtained because the adhesion between the active materials was low and the electronic resistance through the conductive material was high.

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Abstract

L'invention concerne une électrode pour une batterie au lithium-ion, et une batterie au lithium-ion équipée de cette électrode, l'électrode étant équipée d'un collecteur de courant et d'une couche de matériau actif formée sur la surface du collecteur de courant, la couche de matériau actif contenant des particules de matériau actif et une résine liante, une hauteur moyenne arithmétique Sa, qui est obtenue conformément aux réglementations de la norme ISO 25178, de la surface de la couche de matériau actif étant de 0,2 à 1,0 µm, et une rugosité moyenne arithmétique Ra, qui est obtenue conformément aux réglementations de la norme JIS B 0601-2001, de la surface de la couche de matériau actif étant de 0,1 à1,0 μm. Cette électrode peut être fabriquée, par exemple, par pression de rouleau par l'intermédiaire d'un film tampon lorsque l'électrode est pressée par rouleau.
PCT/JP2019/013136 2018-03-28 2019-03-27 Électrode pour batterie au lithium-ion, batterie au lithium-ion, et corps de rouleau d'électrode pour batterie au lithium-ion WO2019189332A1 (fr)

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CN201980018436.4A CN111886720B (zh) 2018-03-28 2019-03-27 锂离子电池用电极、锂离子电池以及锂离子电池用电极卷筒体
CN202310987559.7A CN116914078A (zh) 2018-03-28 2019-03-27 锂离子电池用电极的制造方法

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JP7149437B1 (ja) 2022-03-24 2022-10-06 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム
JP2023507719A (ja) * 2020-02-20 2023-02-27 エルジー エナジー ソリューション リミテッド 二次電池圧延装置
EP4358168A1 (fr) * 2022-09-23 2024-04-24 II-VI Delaware, Inc. Revêtement double face pour applications de dispositif électrochimique

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CN112103471A (zh) * 2020-09-08 2020-12-18 东莞维科电池有限公司 一种极片及锂离子电池
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EP4358168A1 (fr) * 2022-09-23 2024-04-24 II-VI Delaware, Inc. Revêtement double face pour applications de dispositif électrochimique

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