JP2023135371A - Positive electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery using the same, battery module, and battery system - Google Patents

Abstract

To provide a positive electrode for non-aqueous electrolyte secondary battery that can increase the energy density of the non-aqueous electrolyte secondary battery and also enhance quick charge-discharge characteristics thereof at a high current.SOLUTION: A positive electrode 1 for a non-aqueous electrolyte secondary battery has a current collector 11, and a positive electrode active material layer 12 present on the current collector 11. A current collector coating layer 15 is present on at least a portion of the surface of the current collector 11 on the positive electrode active material layer 12 side. The current collector coating layer 15 contains a conductive material. The positive electrode active material layer 12 contains positive electrode active material particles and a resin component. The content of the resin component based on the total mass of the positive electrode active material layer 15 is 0.8-3.0 mass%. With respect to the volume-based particle size distribution curve of the particles present in the positive electrode active material layer 15, the mode particle diameter is 50.0-100.0 μm, and the frequency at the mode particle diameter is 5-15%.SELECTED DRAWING: Figure 1

Description

The present invention relates to a positive electrode for a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery, a battery module, and a battery system using the same.

A non-aqueous electrolyte secondary battery generally includes a positive electrode, a non-aqueous electrolyte, a negative electrode, and a separation membrane (separator) installed between the positive electrode and the negative electrode.
As a positive electrode for a non-aqueous electrolyte secondary battery, one in which a composition consisting of a positive electrode active material containing lithium ions, a conductive agent, and a binder is fixed to the surface of a metal foil (current collector) is known. ing.
Examples of positive electrode active materials containing lithium ions include lithium transition metal composite oxides such as lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), and lithium manganate (LiMn ₂ O ₄ ), and lithium iron phosphate (lithium iron phosphate). Lithium phosphate compounds such as LiFePO ₄ ) have been put into practical use.

Patent Document 1 discloses that in a positive electrode of a non-aqueous electrolyte secondary battery, a conductive paint layer containing carbon as a conductive agent is provided between an aluminum foil current collector and a positive electrode active material layer containing a lithium-transition metal composite oxide. A method is described for improving cycle life by providing a

Japanese Patent Application Publication No. 2001-351612

However, the method of Patent Document 1 is not necessarily sufficient, and further improvement of battery characteristics is required.
An object of the present invention is to provide a positive electrode for a non-aqueous electrolyte secondary battery that not only increases the energy density of the non-aqueous electrolyte secondary battery but also improves rapid charge/discharge characteristics at large currents (large current characteristics).

The present invention has the following aspects.
[1] A current collector and a positive electrode active material layer present on the current collector, and a current collector coating layer is provided on at least a part of the surface of the current collector on the positive electrode active material layer side. the current collector coating layer contains a conductive material, the cathode active material layer contains cathode active material particles and a resin component, and the content of the resin component is 0 with respect to the total mass of the cathode active material layer. .8 to 3.0% by mass, and in the volume-based particle size distribution curve of the particles present in the positive electrode active material layer, the most frequent particle diameter is 50.0 to 100.0 μm, and the most frequent particle diameter is 50.0 to 100.0 μm. A positive electrode for a non-aqueous electrolyte secondary battery, in which the frequency is 5 to 15%.
[2] In the particle size distribution curve with frequency as the vertical axis, there are a plurality of maximum points, and the particle size at the maximum point having the largest particle size among the plurality of maximum points is the most frequent particle size. ] Positive electrode for non-aqueous electrolyte secondary batteries.
[3] The positive electrode for a non-aqueous electrolyte secondary battery according to [1] or [2], wherein in the particle size distribution curve, the distribution width obtained by subtracting the 10% diameter from the 90% diameter is 80.0 to 200.0 μm.
[4] The positive electrode for a nonaqueous electrolyte secondary battery according to any one of [1] to [3], wherein the positive electrode active material layer has a volume density of 2.00 to 2.40 g/cm ³ .
[5] The positive electrode active material particles have the general formula LiFe _x M _(1-x) PO ₄ (wherein 0≦x≦1, M is Co, Ni, Mn, Al, Ti, or Zr). The positive electrode for a non-aqueous electrolyte secondary battery according to any one of [1] to [4], which comprises the represented compound.
[6] The positive electrode active material layer contains conductive carbon, and the content of the conductive carbon is 0.5% by mass or more and less than 3.0% by mass with respect to the total mass of the positive electrode active material layer. 1] to [5], the positive electrode for a non-aqueous electrolyte secondary battery.
[7] The positive electrode for a non-aqueous electrolyte secondary battery according to any one of [1] to [6], wherein the positive electrode active material layer contains a binder, and the binder contains the resin component.
[8] The positive electrode for a non-aqueous electrolyte secondary battery according to any one of [1] to [7], wherein the positive electrode active material layer does not contain a conductive additive.
[9] A positive electrode for a non-aqueous electrolyte secondary battery according to any one of [1] to [8], a negative electrode, and a non-aqueous electrolyte present between the positive electrode for a non-aqueous electrolyte secondary battery and the negative electrode, Nonaqueous electrolyte secondary battery.
[10] A battery module or a battery system comprising a plurality of non-aqueous electrolyte secondary batteries according to [9].

According to the present invention, a positive electrode for a non-aqueous electrolyte secondary battery can be obtained that increases the energy density of the non-aqueous electrolyte secondary battery and also improves rapid charge/discharge characteristics at large currents.

1 is a cross-sectional view schematically showing an example of a positive electrode for a non-aqueous electrolyte secondary battery according to the present invention. 1 is a cross-sectional view schematically showing an example of a non-aqueous electrolyte secondary battery according to the present invention. It is a graph showing an example of particle size distribution in an example.

In the present specification and claims, "~" indicating a numerical range means that the numerical values listed before and after it are included as lower and upper limits.
FIG. 1 is a schematic cross-sectional view showing one embodiment of a positive electrode for a non-aqueous electrolyte secondary battery of the present invention, and FIG. 2 is a schematic cross-sectional view showing one embodiment of a non-aqueous electrolyte secondary battery of the present invention. .
Note that FIGS. 1 and 2 are schematic diagrams for explaining the configuration in an easy-to-understand manner, and the dimensional ratio of each component may differ from the actual one.

<Positive electrode for non-aqueous electrolyte secondary batteries>
A positive electrode for a non-aqueous electrolyte secondary battery (also simply referred to as "positive electrode") 1 of the present embodiment includes a current collector (hereinafter referred to as "positive electrode current collector") 11 and a positive electrode active material layer 12 .
The positive electrode active material layer 12 exists on at least one surface of the positive electrode current collector 11 . A positive electrode active material layer 12 may be present on both sides of the positive electrode current collector 11 .
In the example of FIG. 1, the positive electrode current collector 11 has a current collector coating layer 15 on the surface thereof on the positive electrode active material layer 12 side. That is, the positive electrode current collector 11 includes a positive electrode current collector main body 14 and a current collector coating layer 15 that covers the surface of the positive electrode current collector main body 14 on the positive electrode active material layer 12 side.

[Cathode active material layer]
The positive electrode active material layer 12 includes positive electrode active material particles.
The positive electrode active material layer 12 contains a resin component. Examples of the resin component in the positive electrode active material layer 12 include a binder, a dispersant, and the like.
The positive electrode active material layer 12 may further contain a conductive additive. In this specification, the term "conductive additive" refers to a conductive material having a granular, fibrous, etc. shape that is mixed with positive electrode active material particles when forming a positive electrode active material layer; Refers to a conductive material that is present in the positive electrode active material layer in a connected manner.
With respect to the total mass of the positive electrode active material layer 12, the content of the positive electrode active material particles is preferably 80.0 to 99.9% by mass, more preferably 90 to 99.5% by mass.

The thickness of the positive electrode active material layer (when positive electrode active material layers are present on both sides of the positive electrode current collector, the total thickness of both surfaces) is preferably 30 to 500 μm, more preferably 40 to 400 μm, and 50 to 500 μm. It is particularly preferred that the thickness is 300 μm. When the thickness of the positive electrode active material layer is at least the lower limit of the above range, the energy density of a battery incorporating the positive electrode tends to be high, and when it is below the upper limit of the above range, the peel strength of the positive electrode active material layer is high. , peeling can be suppressed during charging and discharging.

[Cathode active material particles]
It is preferable that an active material coating portion containing a conductive material exists on the surface of the positive electrode active material particles. That is, it is preferable that the positive electrode active material particles have a core portion made of a positive electrode active material and an active material coating portion containing a conductive material. The active material coating portion covers the surface of the core portion.
The positive electrode active material particles in the positive electrode active material layer may be single particles consisting only of positive electrode active material particles (core part), or may be single coated particles having one core part and an active material coating part, The particles may be aggregated particles that include a plurality of core portions, have active material coating portions between adjacent core portions, and are integrally aggregated, or may be a mixture of these. It is preferable that the positive electrode active material particles include aggregate particles.

(Coated particles)
In the coated particles, an active material coating portion containing a conductive material is present on the surface of the positive electrode active material particles. The presence of the active material coating portion allows the battery capacity and cycle characteristics to be further improved.
In the coated particles, the active material coating portion is formed in advance on the surface of the positive electrode active material particles, and is present on the surface of the positive electrode active material particles in the positive electrode active material layer. That is, the active material coating portion in this paper is not newly formed in a step after the step of preparing the composition for producing a positive electrode. In addition, the active material coating portion is not lost in the steps after the step of preparing the composition for producing the positive electrode.
For example, when preparing a composition for producing a positive electrode, even if the coated particles are mixed with a solvent using a mixer or the like, the active material coating portion still covers the surface of the positive electrode active material (core portion). Furthermore, even if the positive electrode active material layer is peeled off from the positive electrode and put into a solvent to dissolve the binder in the positive electrode active material layer, the active material coating part will not cover the surface of the positive electrode active material. Covered. In addition, even if an operation is performed to loosen aggregated particles when measuring the particle size distribution of particles in the positive electrode active material layer by laser diffraction/scattering method, the active material coating portion will not cover the surface of the positive electrode active material. are doing.
In the coated particles, the active material coating portion preferably exists on 50% or more, preferably 70% or more, and preferably 90% or more of the entire outer surface area of the positive electrode active material particles. .
That is, the coated particles have a core that is a positive electrode active material and an active material coating that covers the surface of the core, and the area (coverage) of the active material coating with respect to the surface area of the core is 50%. It is preferably at least 70%, more preferably at least 90%, even more preferably at least 90%.

Examples of methods for producing coated particles include sintering methods, vapor deposition methods, and the like.
Examples of the sintering method include a method in which a composition for producing an active material (for example, a slurry) containing particles of a positive electrode active material and an organic substance is fired at 500 to 1000° C. for 1 to 100 hours under atmospheric pressure. Examples of organic substances added to the composition for producing active materials include salicylic acid, catechol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, hexahydroxybenzene, benzoic acid, phthalic acid, terephthalic acid, phenylalanine, water-dispersible phenol resin, etc. , sugars such as glucose and lactose, carboxylic acids such as malic acid and citric acid, unsaturated monohydric alcohols such as allyl alcohol and propargyl alcohol, ascorbic acid, and polyvinyl alcohol. According to this sintering method, by firing the composition for producing an active material, carbon in the organic substance is sintered onto the surface of the positive electrode active material, thereby forming an active material coating portion.
Further, other sintering methods include the so-called impact sintering coating method.

In the impact sinter coating method, for example, a burner is ignited using a mixed gas of hydrocarbon fuel and oxygen in an impact sinter coating device, and the mixture is combusted in a combustion chamber to generate a flame. The flame temperature is lowered to below the equivalent of complete combustion, and a powder supply nozzle is installed behind it, and a solid-liquid consisting of the organic matter to be coated, a slurry made by melting it with a solvent, and combustion gas is passed through the nozzle. - injecting a gaseous three-phase mixture from a powder supply nozzle, increasing the amount of combustion gas maintained at room temperature, lowering the temperature of the injected fine powder and accelerating it below the transformation, sublimation, and evaporation temperatures of the powder material; Instant sintering is performed by impact to coat the particles of the positive electrode active material.
Examples of the vapor deposition method include vapor deposition methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), and liquid deposition methods such as plating.

In coated particles, to determine the area (coverage) of the active material coated portion relative to the surface area of the core, particles in the positive electrode active material layer are detected by energy dispersive X-ray spectroscopy (TEM-EDX). The outer periphery of the material particles is subjected to elemental analysis using EDX. Elemental analysis is performed on carbon to identify the carbon that coats the positive electrode active material particles. A portion where the carbon coating portion has a thickness of 1 nm or more is defined as the coating portion, and the ratio of the coating portion to the entire circumference of the observed positive electrode active material particles is determined, and this can be taken as the coverage rate. For example, the measurement can be performed on 10 positive electrode active material particles, and the average value can be taken as the average value.
Further, the active material coating portion is a layer having a thickness of 1 nm to 100 nm, preferably 5 nm to 50 nm, formed directly on the surface of the particle (core portion) composed only of the positive electrode active material, and this thickness is as described above. This can be confirmed by TEM-EDX used to measure coverage.
In the coated particles, the area of the active material coating portion relative to the surface area of the core portion is particularly preferably 100% from the viewpoint of better cycle characteristics.
Note that this coverage rate (%) is an average value for all the positive electrode active material particles present in the positive electrode active material layer, and as long as this average value is greater than or equal to the lower limit above, the positive electrode without an active material coating part This does not exclude the presence of a trace amount of active material particles.
When coated particles are used as positive electrode active material particles, if a positive electrode active material particle (single particle) without an active material coating is present in the positive electrode active material layer, the amount of positive electrode active material particles in the positive electrode active material layer is It is preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, based on the total amount of positive electrode active material particles present.

(collected particles)
In this specification, "aggregated particles that are integrally aggregated" means aggregated particles that behave as one particle when measuring the particle size distribution of particles present in the positive electrode active material layer described below. .
The aggregate particles include a plurality of particles (core portions) composed only of the positive electrode active material, and an active material coating portion exists between adjacent core portions.
At least a portion of the outer surface of the aggregated particles is covered with an active material coating. Of the outer surface area of the aggregate particles, the area covered by the active material coating portion is preferably 50% or more, more preferably 70% or more, even more preferably 90% or more, and particularly preferably 100%.
The coverage rate (%) of the outer surface is the average value for all the aggregate particles present in the positive electrode active material layer, and as long as this average value is greater than or equal to the lower limit above, the active material is coated on the outer surface. This does not exclude the presence of a small amount of aggregated particles without a coating.
The aggregated particles may be secondary particles (hereinafter also referred to as "active material granules") that are granulated so that a plurality of core parts are integrated through an active material coating part, or a plurality of coated particles are aggregated. An aggregate formed by binding together with a binding material may be used, an aggregate formed by a plurality of active material granules bound together by a binding material may be used, or a mixture of these may be used.
The active material granules can be manufactured by a known method (for example, Japanese Patent No. 5509598). It is also available commercially.
The aggregate containing coated particles may contain particles other than the coated particles (for example, a conductive aid). Further, components other than the binder (for example, a dispersant) may be included.
The aggregate containing the active material granules may contain particles other than the active material granules (for example, a conductive aid). Further, components other than the binder (for example, a dispersant) may be included.

In the active material granule, the active material coating portion is formed in advance and is present between the outer surface of the aggregate particles (active material granule) and adjacent core portions in the positive electrode active material layer. That is, like the active material coating portion of the coated particles, the active material coating portion of the active material granule is not newly formed in a step subsequent to the preparation step of the positive electrode manufacturing composition. In addition, the active material coating portion is not lost in the steps after the step of preparing the composition for producing the positive electrode.
In the active material granules, the area (coverage) of the active material coating portion relative to the surface area of each core portion is preferably 50% or more, more preferably 70% or more, even more preferably 90% or more, and particularly 100%. preferable.
The core coverage rate (%) is the average value for the core present in the positive electrode active material layer, and as long as this average value is greater than or equal to the lower limit above, the core without the active material coating This does not exclude the presence of a small amount of
In the active material granules, the area and coverage of the active material coating portion that covers the surface of the core portion or the active material coating portion that covers the outer surface is the same as the active material coating portion of the coated particles. Detect particles in the layer using energy dispersive X-ray spectroscopy (TEM-EDX), and perform elemental analysis of the outer periphery of the core or the outer periphery of aggregated particles (active material granules) using EDX. I can do it.
In the active material granule, the active material coating part covering the outer surface and the active material coating part existing between adjacent core parts are directly on the surface of the particle (core part) composed only of the positive electrode active material. The formed layer has a thickness of 1 nm to 100 nm, preferably 5 nm to 50 nm, and this thickness can be confirmed by TEM-EDX used for measuring the coverage ratio described above.

In the coated particles or active material granules, the conductive material of the active material coating portion preferably contains carbon (conductive carbon). A conductive material consisting only of carbon may be used, or a conductive organic compound containing carbon and an element other than carbon may be used. Examples of other elements include nitrogen, hydrogen, and oxygen. In the conductive organic compound, the content of other elements is preferably 10 atomic % or less, more preferably 5 atomic % or less.
It is more preferable that the conductive material constituting the active material coating portion consists only of carbon.

The content of the conductive material is preferably 0.1 to 4.0% by mass, more preferably 0.5 to 3.0% by mass, and more preferably 0.7 to 3.0% by mass with respect to the total mass of the coated particles or active material granules. More preferably, it is 2.5% by mass. If the amount is too large, the conductive material may peel off from the surface of the coated particles or active material granules and remain as independent conductive aid particles, which is not preferable.

The particle diameter of the positive electrode active material particles is the most frequent particle diameter (hereinafter also referred to as "mode diameter") in the particle size distribution curve of particles present in the positive electrode active material layer described below, and the frequency in the mode diameter is within a preferable range. It is preferable to design it as follows.
The average particle diameter of the positive electrode active material particles (single particles) consisting only of the positive electrode active material (core) is preferably 1.0 to 20.0 μm, more preferably 5.0 to 15.0 μm. When using two or more types of positive electrode active material particles (single particles), the average particle diameter of each may be within the above range.
The average particle diameter of the coated particles is preferably 0.1 to 5.0 μm, more preferably 0.5 to 3.0 μm. When using two or more types of coated particles, the average particle diameter of each coated particle may be within the above range.
The average particle diameter of the active material granules is preferably 5.0 to 30.0 μm, more preferably 10.0 to 20.0 μm. When using two or more types of active material granules, the average particle size of each may be within the above range.
Unless otherwise specified, the average particle diameter of the positive electrode active material particles in this specification is a volume-based median diameter measured using a particle size distribution analyzer using a laser diffraction/scattering method.

The positive electrode active material particles preferably contain a compound having an olivine crystal structure as a positive electrode active material.
The compound having an olivine crystal structure is preferably a compound represented by the general formula LiFe _x M _(1-x) PO ₄ (hereinafter also referred to as "general formula (I)"). In general formula (I), 0≦x≦1. M is Co, Ni, Mn, Al, Ti or Zr. A small amount of Fe and M (Co, Ni, Mn, Al, Ti, or Zr) can also be replaced with other elements to the extent that the physical properties do not change. Even if the compound represented by the general formula (I) contains trace amounts of metal impurities, the effects of the present invention are not impaired.
The compound represented by the general formula (I) is preferably lithium iron phosphate (hereinafter also simply referred to as "lithium iron phosphate") represented by LiFePO ₄ .

The positive electrode active material particles may include one or more other positive electrode active material particles containing a positive electrode active material other than a compound having an olivine crystal structure.
The other positive electrode active material is preferably a lithium transition metal composite oxide. For example, lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium nickel cobalt aluminate (LiNix _{Co y} Al _z O ₂ , where x+y+z=1), lithium nickel cobalt manganate (LiNix _{Co y} Mn _{zO 2} , where x+y+z=1), lithium manganate (LiMn ₂ O ₄ ), lithium cobalt manganate (LiMnCoO ₄ ), lithium manganese chromate (LiMnCrO ₄ ), lithium vanadium nickelate (LiNiVO ₄ ), nickel-substituted manganese Examples include lithium oxide (for example, LiMn _1.5 Ni _0.5 O ₄ ), lithium vanadium cobalt oxide (LiCoVO ₄ ), and non-stoichiometric compounds in which a portion of these compounds is replaced with a metal element. Examples of the metal element include one or more selected from the group consisting of Mn, Mg, Ni, Co, Cu, Zn, and Ge.
The other positive electrode active material particles may be single particles consisting only of the positive electrode active material (core part), or may be single coated particles with one core part, or multiple core parts may be connected through the active material coating part. Secondary particles granulated so as to be integrated (active material granulation) may be used, or these may be mixed.

The content of the compound having an olivine crystal structure is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more with respect to the total mass of the positive electrode active material particles. It may be 100% by mass.

[Binder]
The binder contained in the positive electrode active material layer 12 is an organic substance, and examples thereof include polyacrylic acid, lithium polyacrylate, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene rubber, polyvinyl alcohol, and polyvinyl. Examples include resins such as acetal, polyethylene oxide, polyethylene glycol, carboxymethyl cellulose, polyacrylonitrile, and polyimide. One type of binder may be used, or two or more types may be used in combination.
The content of the binder relative to the total mass of the positive electrode active material layer is preferably designed so that the content of the resin component for the positive electrode active material layer, which will be described later, falls within a preferable range.

[Conductivity aid]
Examples of the conductive additive included in the positive electrode active material layer 12 include carbon materials such as graphite, graphene, hard carbon, Ketjen black, acetylene black, and carbon nanotubes (CNT). One type of conductive aid may be used, or two or more types may be used in combination.
The content of the conductive aid in the positive electrode active material layer is, for example, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, based on 100 parts by mass of the total mass of the positive electrode active material. It is particularly preferable that the conductive agent is not contained, and it is desirable that there be no independent conductive agent particles (for example, independent carbon particles).
When blending a conductive support agent into the positive electrode active material layer, the lower limit of the content of the conductive support agent is appropriately determined depending on the type of the conductive support agent, and is, for example, 0.0% relative to the total mass of the positive electrode active material layer. It is considered to be more than 1% by mass.
Note that the expression that the positive electrode active material layer "does not contain a conductive additive" means that it does not substantially contain it, and does not exclude that it contains it to the extent that it does not affect the effects of the present invention. For example, if the content of the conductive additive is 0.1% by mass or less with respect to the total mass of the positive electrode active material layer, it can be determined that the conductive additive is not substantially contained.

[Dispersant]
The dispersant contained in the positive electrode active material layer 12 is an organic substance, and examples thereof include resins such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and polyvinyl formal (PVF). One type of dispersant may be used, or two or more types may be used in combination.
The content of the dispersant relative to the total mass of the positive electrode active material layer is preferably designed so that the content of the resin component for the positive electrode active material layer, which will be described later, falls within a preferable range.

[Positive electrode current collector body]
The positive electrode current collector body 14 is made of a metal material. Examples of the metal material include conductive metals such as copper, aluminum, titanium, nickel, and stainless steel.
The thickness of the positive electrode current collector body 14 is, for example, preferably 8 to 40 μm, more preferably 10 to 25 μm.
The thickness of the positive electrode current collector main body 14 and the thickness of the positive electrode current collector 11 can be measured using a micrometer. An example of a measuring device is Mitutoyo's product name "MDH-25M."

[Current collector coating layer]
A current collector coating layer 15 is present on at least a portion of the surface of the positive electrode current collector body 14 . Current collector coating layer 15 includes a conductive material.
Here, "at least a portion of the surface" means 10% to 100%, preferably 30% to 100%, more preferably 50% to 100% of the surface area of the positive electrode current collector body.
The conductive material in the current collector coating layer 15 preferably contains carbon (conductive carbon). A conductive material consisting only of carbon is more preferable.
The current collector coating layer 15 is preferably a coating layer containing carbon particles such as carbon black and a binder. Examples of the binding material for the current collector coating layer 15 include those similar to those for the positive electrode active material layer 12.
The positive electrode current collector 11 in which the surface of the positive electrode current collector body 14 is coated with a current collector coating layer 15 is prepared by, for example, applying a slurry containing a conductive material, a binder, and a solvent using a known coating method such as a gravure method. It can be manufactured by coating the surface of the positive electrode current collector body 14 using a solvent and drying to remove the solvent.

The thickness of the current collector coating layer 15 is preferably 0.1 to 4.0 μm.
The thickness of the current collector coating layer can be measured by a method of measuring the thickness of the coating layer in a transmission electron microscope (TEM) image or a scanning electron microscope (SEM) image of a cross section of the current collector coating layer. The thickness of the current collector coating layer does not have to be uniform. It is preferable that a current collector coating layer with a thickness of 0.1 μm or more exists on at least a part of the surface of the positive electrode current collector main body 14, and the maximum value of the thickness of the current collector coating layer is 4.0 μm or less. .

[Particle size distribution curve]
In this specification, the particle size distribution curve of particles present in the positive electrode active material layer 12 (hereinafter also referred to as "particle size distribution curve of the positive electrode active material layer") refers to the volume measured by a particle size distribution measuring device using a laser diffraction/scattering method. This is a standard particle size distribution curve.
The particle size distribution curve is a frequency distribution curve where the horizontal axis is the particle diameter and the vertical axis is the frequency (unit: %), or an integrated distribution curve where the horizontal axis is the particle diameter and the vertical axis is the integrated value of the frequency (unit: %). It can be displayed as
In the frequency distribution curve, the particle diameter at which the frequency becomes the maximum value is the most frequent particle diameter (mode diameter).
The particle size that shows the maximum point (peak) in the frequency distribution curve is hereinafter also referred to as "peak diameter." The maximum point of the frequency distribution curve means the point where the slope of the tangent changes from positive to negative.
In the integrated distribution curve, the particle size at a frequency integrated value of 10% from the small particle size side is the 10% diameter (D10), and the particle size at a frequency integrated value of 90% from the small particle size side is the 90% diameter (D90).

As a sample for measuring the particle size distribution, the positive electrode active material layer 12 is peeled off from the positive electrode 1, and an aqueous dispersion in which particles present in the positive electrode active material layer 12 are dispersed in water is used. For example, the sample is an aqueous dispersion in which powder obtained by peeling off the outermost surface of the positive electrode active material layer at a depth of several micrometers with a spatula or the like is dispersed in water.
The aqueous dispersion is treated with ultrasonic waves to sufficiently disperse the particles, and the particle size distribution is then measured.

In the positive electrode of this embodiment, the mode diameter in the particle size distribution curve of the positive electrode active material layer is 50.0 to 100.0 μm, and the frequency in the mode diameter is 5 to 15%.
The mode diameter is preferably 60.0 to 100.0 μm, more preferably 80.0 to 100.0 μm.
The frequency in the mode diameter is preferably 6 to 14%, more preferably 8 to 12%.
When the mode diameter is at least the lower limit of the above range, it is easy to increase large current characteristics, and when it is at most the upper limit, it is easy to increase the weight energy density.
When the frequency in the mode diameter is at least the lower limit of the above range, it is easy to increase large current characteristics, and when it is at most the upper limit, it is easy to increase the weight energy density.
The mode diameter and the frequency in the mode diameter in the particle size distribution curve of the positive electrode active material layer can be adjusted by adjusting the particle diameter of the positive electrode active material particles used for manufacturing the positive electrode, the amount of binder added, the amount of dispersant added, and the like.
For example, when a binder is added to the composition for producing a positive electrode to bind the positive electrode active material particles, the mode diameter increases. The mode diameter can be adjusted by adjusting the amount of binder added. Furthermore, when the particles in the composition for producing a positive electrode are more uniformly dispersed using a dispersant, the uniformity of the particle diameter increases, and the frequency in the mode diameter tends to increase.

Further, it is preferable that the positive electrode of this embodiment has a plurality of maximum points (peaks) in the frequency distribution curve, and the particle diameter at the maximum point having the largest particle diameter among the plurality of maximum points is the mode diameter.
That is, in the frequency distribution curve, it is preferable that the number of peak diameters is two or more and that the peak (frequency) at the largest peak diameter is the highest.
For example, if some of the positive electrode active material particles are bound using a binder, particles with large particle diameters and particles with small particle diameters will be mixed, and the number of peaks will increase. When the amount of binder added is increased, the peak (frequency) at the maximum peak diameter tends to increase.
When particles with large particle diameters and particles with small particle diameters coexist, when the positive electrode active material layer is pressurized, the thickness of the positive electrode active material layer tends to become small and the volume density tends to increase. As a result, the weight energy density tends to increase.
When the maximum peak diameter is the mode diameter, there are many particles in which the positive electrode active material particles are bound together, that is, particles that contribute to improving the conductive path, and the large current characteristics are likely to be improved.

Further, in the positive electrode of this embodiment, the distribution width obtained by subtracting the 10% diameter from the 90% diameter is preferably 80.0 to 200.0 μm, more preferably 90.0 to 180.0 μm, and more preferably 100.0 to 180.0 μm. More preferably, the thickness is 160.0 μm.
For example, when a portion of the positive electrode active material particles are bound using a binder in an appropriate amount, particles with large particle diameters and particles with small particle diameters are mixed, and the distribution width becomes large.
Further, by adjusting the dispersibility of particles in the composition for producing a positive electrode using a dispersant, the uniformity of the particle diameter can be adjusted and the distribution width can be adjusted.
When particles with large particle diameters and particles with small particle diameters coexist, when the positive electrode active material layer is pressurized, the thickness of the positive electrode active material layer tends to become small and the volume density tends to increase. As a result, the weight energy density tends to increase.

[Content of resin component]
The content of the resin component is 0.8 to 3.0% by mass, preferably 1.0 to 2.9% by mass, and 1.2 to 2.8% by mass with respect to the total mass of the positive electrode active material layer. is more preferable, and even more preferably 1.4 to 2.7% by mass.
When the content of the resin component in the positive electrode active material layer is at least the lower limit of the above range, the large current characteristics tend to improve, and when it is at most the upper limit, the volume density tends to increase, and as a result, the weight energy density decreases. Easy to raise.
The content of the resin component with respect to the total mass of the positive electrode active material layer is determined by the following <<Content of resin component It can be measured using the measurement method≫.
For example, a powder obtained by peeling off the outermost surface of the positive electrode active material layer at a depth of several micrometers using a spatula or the like can be vacuum-dried in a 120° C. environment and used as a measurement target.

When the positive electrode active material layer contains a binder that is a resin component, the content of the binder relative to the total mass of the positive electrode active material layer is preferably 0.70 to 2.90% by mass, and 0.90 to 2.70% by mass. The amount is more preferably 1.10 to 2.50% by weight, and even more preferably 1.10 to 2.50% by weight.
When the positive electrode active material layer contains a dispersant which is a resin component, the content of the literary agent is preferably 0.10 to 0.50% by mass, and 0.15 to 0.45% by mass with respect to the total mass of the positive electrode active material layer. is more preferable, and even more preferably 0.20 to 0.40% by mass.

[Conductive carbon content]
In this embodiment, it is preferable that the positive electrode active material layer 12 contains conductive carbon. Examples of embodiments in which the positive electrode active material layer contains conductive carbon include embodiments 1 to 3 below.
Embodiment 1: An embodiment in which the positive electrode active material layer contains a conductive additive, and the conductive additive contains conductive carbon.
Aspect 2: The positive electrode active material layer contains a conductive additive, and the positive electrode active material particles have an active material coating portion containing a conductive material, and one or both of the conductive material of the active material coating portion and the conductive additive Embodiment containing conductive carbon.
Embodiment 3: An embodiment in which the positive electrode active material layer does not contain a conductive aid, the positive electrode active material particles have an active material coating portion containing a conductive material, and the conductive material of the active material coating portion contains conductive carbon.
Embodiment 3 is more preferable in terms of increasing the weight energy density.

With respect to the total mass of the positive electrode active material layer, the content of conductive carbon is preferably 0.5% by mass or more and less than 3.0% by mass, more preferably 1.0 to 2.8% by mass, and 1.2 to 2.8% by mass. 2.6% by mass is more preferred.
When the content of conductive carbon in the positive electrode active material layer is at least the lower limit of the above range, it is sufficient to form a conductive path in the positive electrode active material layer, and when it is at most the upper limit, it is excellent in improving dispersibility.

The content of conductive carbon with respect to the total mass of the positive electrode active material layer is determined by peeling off the positive electrode active material layer from the positive electrode and vacuum-drying the dried material (powder) in a 120°C environment as the measurement target. Quantity measurement method≫
For example, a powder obtained by peeling off the outermost surface of the positive electrode active material layer at a depth of several micrometers using a spatula or the like can be vacuum-dried in a 120° C. environment and used as a measurement target.
The conductive carbon content measured by the following <Method for Measuring Conductive Carbon Content> includes carbon in the active material coating and carbon in the conductive aid. Carbon in the binder is not included. Carbon in the dispersant is not included.

≪Measurement method for conductive carbon content≫
[Measurement method A]
The object to be measured is mixed uniformly, a sample (mass w1) is weighed, and a thermogravimetric differential thermal analysis (TG-DTA) measurement is performed according to the following steps A1 and A2 to obtain a TG curve. The following first weight loss amount M1 (unit: mass %) and second weight loss amount M2 (unit: mass %) are determined from the obtained TG curve. The content of conductive carbon (unit: mass %) is obtained by subtracting M1 from M2.
Step A1: In an argon stream of 300 mL/min, the temperature is raised from 30 °C to 600 °C at a temperature increase rate of 10 °C / min, and from the mass w2 when held at 600 °C for 10 minutes, according to the following formula (a1) A first weight reduction amount M1 is determined.
M1=(w1-w2)/w1×100...(a1)
Step A2: Immediately after step A1, the temperature was lowered from 600°C at a rate of 10°C/min, and after being held at 200°C for 10 minutes, the measurement gas was completely replaced with oxygen from argon, and an oxygen stream of 100 mL/min was added. The second weight loss amount M2 ( Unit: mass %).
M2=(w1-w3)/w1×100...(a2)

[Measurement method B]
Mix the measurement object uniformly, weigh 0.0001 mg of the sample accurately, burn the sample under the following combustion conditions, quantify the generated carbon dioxide with a CHN elemental analyzer, and calculate the total carbon content M3 ( Unit: mass%). Further, the first weight loss amount M1 is determined by the procedure of step A1 of the measuring method A. The conductive carbon content (unit: mass %) is obtained by subtracting M1 from M3.
[Combustion conditions]
Combustion furnace: 1150℃
Reduction furnace: 850℃
Helium flow rate: 200mL/min Oxygen flow rate: 25-30mL/min

[Measurement method C]
The total carbon content M3 (unit: mass %) contained in the sample is measured in the same manner as the measurement method B above. Further, the content M4 of carbon derived from the binder (unit: mass %) is determined by the following method. The content of conductive carbon (unit: mass %) is obtained by subtracting M4 from M3.
When the binder is polyvinylidene fluoride (PVDF: the molecular weight of the monomer (CH ₂ CF ₂ ) is 64), the content of fluoride ions (F ^- ) measured by combustion ion chromatography using the tubular combustion method ( (unit: mass %), the atomic weight of fluorine (19) of the monomer constituting PVDF, and the atomic weight (12) of carbon constituting PVDF using the following formula.
PVDF content (unit: mass %) = fluoride ion content (unit: mass %) × 64/38
PVDF-derived carbon content M4 (unit: mass %) = fluoride ion content (unit: mass %) × 12/19
The fact that the binder is polyvinylidene fluoride can be confirmed by Fourier transform infrared spectroscopy (FT-IR) measurement of the sample or the liquid extracted from the sample with N,N-dimethylformamide (DMF) solvent, and it can be determined that the origin of the C-F bond is This can be confirmed by checking the absorption of Similarly, it can be confirmed by ^19F -NMR measurement.
If the binder is identified as other than PVDF, the binder content (unit: mass %) and carbon content (unit: mass %) corresponding to the molecular weight can be determined to determine the origin of the binder. The carbon amount M4 can be calculated.
When a dispersant is included, the conductive carbon content (unit: mass %) can be obtained by subtracting M4 from M3 and further subtracting the amount of carbon derived from the dispersant.
These techniques are described in the following several known documents.
Toray Research Center The TRC News No. 117 (Sep. 2013) pp. 34-37, [Retrieved February 10, 2021], Internet <https://www.toray-research.co.jp/technical-info/trcnews/pdf/TRC117(34- 37).pdf＞
Tosoh Analysis Center Technical Report No. T1019 2017.09.20, [Retrieved February 10, 2021], Internet <http://www.tosoh-arc.co.jp/techrepo/files/tarc00522/T1719N.pdf>

≪Analysis method of conductive carbon≫
The conductive carbon that constitutes the active material coating portion of the positive electrode active material and the conductive carbon that is a conductive aid can be distinguished by the following analysis method.
For example, when particles in a positive electrode active material layer are detected by transmission electron microscopy electron energy loss spectroscopy (TEM-EELS), particles with a carbon-derived peak around 290 eV only near the particle surface are found to be positive electrode active material particles (coated particles). (particles), and particles in which carbon-derived peaks exist even inside the particles can be determined to be conductive aids. Here, "near the particle surface" means a region up to a depth of approximately 100 nm from the particle surface, and "inside the particle" means a region inside the vicinity of the particle surface.
Another method is to perform mapping analysis of particles in the positive electrode active material layer by Raman spectroscopy, and particles in which the peaks of carbon-derived G-band and D-band and oxide crystals derived from the positive electrode active material are simultaneously observed are Particles that are positive electrode active material particles and in which only G-band and D-band are observed can be determined to be conductive additives.
Another method is to observe the cross section of the positive electrode active material layer using a scanning spread resistance microscope (SSRM), and if there is a part on the particle surface with a lower resistance than the inside of the particle, the part with low resistance is determined. It can be determined that this is conductive carbon present in the active material coating portion. A portion that exists independently other than such particles and has a low resistance can be determined to be a conductive aid.
Note that trace amounts of carbon that can be considered as impurities and trace amounts of carbon that are unintentionally peeled off from the surface of the positive electrode active material during manufacturing are not determined to be conductive additives.
Using these methods, it can be confirmed whether or not a conductive additive made of a carbon material is included in the positive electrode active material layer.

≪Method for measuring the content of resin components≫
The mass w2 obtained in the measurement method A can be detected as a resin component. The resin component composition ratio in the positive electrode active material layer can be determined as w2/w1×100 (wt%).

[Volume density of positive electrode active material layer]
In this embodiment, the volume density of the positive electrode active material layer 12 is preferably 2.00 to 2.40 g/cm ³ , more preferably 2.10 to 2.30 g/cm ³ .
The volume density of the positive electrode active material layer can be measured, for example, by the following measuring method.
The thicknesses of the positive electrode 1 and the positive electrode current collector 11 are each measured using a microgauge, and the thickness of the positive electrode active material layer 12 is calculated from the difference. The thickness of the positive electrode 1 and the positive electrode current collector 11 is an average value of values measured at five or more arbitrary points. As the thickness of the positive electrode current collector 11, the thickness of the positive electrode current collector exposed portion 13, which will be described later, may be used.
The mass of a measurement sample obtained by punching out the positive electrode 1 to have a predetermined area is measured, and the mass of the positive electrode current collector 11 measured in advance is subtracted to calculate the mass of the positive electrode active material layer 12.
The volume density of the positive electrode active material layer 12 is calculated based on the following formula (1).
Volume density (unit: g/cm ³ ) = mass of positive electrode active material layer (unit: g) / [(thickness of positive electrode active material layer (unit: cm) x area of measurement sample (unit: cm ² )]・...(1)

When the volume density of the positive electrode active material layer is at least the lower limit of the above range, it is easy to increase the energy density of the nonaqueous electrolyte secondary battery. When it is below the upper limit, cracks due to press load are unlikely to occur in the positive electrode active material layer, and an excellent conductive path can be formed.
The volume density of the positive electrode active material layer can be adjusted by, for example, the content of the positive electrode active material, the particle size of the positive electrode active material, the thickness of the positive electrode active material layer, and the like. When the positive electrode active material layer has a conductive additive, it can also be adjusted by the type of conductive additive (specific surface area, specific gravity), the content of the conductive additive, and the particle size of the conductive additive.

<Manufacturing method of positive electrode>
The method for manufacturing the positive electrode 1 of the present embodiment includes a composition preparation step of preparing a positive electrode manufacturing composition containing positive electrode active material particles, and a coating step of coating the positive electrode manufacturing composition onto the positive electrode current collector 11. has.
For example, the positive electrode 1 can be manufactured by a method in which a positive electrode manufacturing composition containing positive electrode active material particles and a solvent is applied onto the positive electrode current collector 11, dried, and the solvent is removed to form the positive electrode active material layer 12. . The composition for producing a positive electrode may include a conductive additive. The composition for producing a positive electrode may include a binder. The composition for producing a positive electrode may also contain a dispersant.
The thickness of the cathode active material layer 12 is determined by sandwiching the laminate in which the cathode active material layer 12 is formed on the cathode current collector 11 between two flat jigs and applying pressure uniformly in the thickness direction. Can be adjusted. For example, a method of applying pressure using a roll press machine can be used.

The solvent for the composition for producing a positive electrode is preferably a non-aqueous solvent. Examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; linear or cyclic amides such as N-methylpyrrolidone and N,N-dimethylformamide; and ketones such as acetone. One type of solvent may be used, or two or more types may be used in combination.

In a preferred embodiment, the composition preparation step includes a step of mixing positive electrode active material particles and a binder to form aggregate particles in which the positive electrode active material particles are bound together.
Specifically, the positive electrode active material particles and the binder are mixed to form aggregate particles such that the mode diameter and the frequency of the mode diameter in the particle size distribution curve of the positive electrode active material layer fall within the above-mentioned preferred range. The positive electrode active material particles and the binder may be mixed in a solvent. The positive electrode active material particles and the binder may be mixed in the presence of a dispersant.

<Nonaqueous electrolyte secondary battery>
A non-aqueous electrolyte secondary battery 10 of this embodiment shown in FIG. 2 includes a positive electrode 1 for a non-aqueous electrolyte secondary battery of this embodiment, a negative electrode 3, and a non-aqueous electrolyte. Furthermore, a separator 2 may be provided. Reference numeral 5 in the figure is an exterior body.
In this embodiment, the positive electrode 1 includes a plate-shaped positive electrode current collector 11 and positive electrode active material layers 12 provided on both surfaces thereof. The positive electrode active material layer 12 exists on a part of the surface of the positive electrode current collector 11 . The edge of the surface of the positive electrode current collector 11 is a positive electrode current collector exposed portion 13 where the positive electrode active material layer 12 does not exist. A terminal tab (not shown) is electrically connected to an arbitrary location on the positive electrode current collector exposed portion 13 .
The negative electrode 3 includes a plate-shaped negative electrode current collector 31 and negative electrode active material layers 32 provided on both surfaces thereof. The negative electrode active material layer 32 exists on a part of the surface of the negative electrode current collector 31 . The edge of the surface of the negative electrode current collector 31 is a negative electrode current collector exposed portion 33 where the negative electrode active material layer 32 does not exist. A terminal tab (not shown) is electrically connected to an arbitrary location on the negative electrode current collector exposed portion 33 .
The shapes of the positive electrode 1, negative electrode 3, and separator 2 are not particularly limited. For example, it may have a rectangular shape in plan view.

[Negative electrode]
The negative electrode active material layer 32 contains a negative electrode active material. It may further contain a binding material. Furthermore, a conductive aid may be included. The shape of the negative electrode active material is preferably particulate.
For example, the negative electrode 3 is prepared by preparing a negative electrode manufacturing composition containing a negative electrode active material, a binder, and a solvent, coating this on the negative electrode current collector 31, drying it, and removing the solvent to form the negative electrode active material. It can be manufactured by a method of forming layer 32. The composition for producing a negative electrode may also contain a conductive additive.

Examples of the negative electrode active material and conductive aid include carbon materials, lithium titanate (LTO), silicon, and silicon monoxide. Examples of the carbon material include graphite, graphene, hard carbon, Ketjen black, acetylene black, carbon nanotube (CNT), and the like. The negative electrode active material and the conductive aid may be used alone or in combination of two or more.

Examples of the material of the negative electrode current collector 31 include those similar to the materials of the positive electrode current collector 11 described above.
As the binder in the negative electrode manufacturing composition, polyacrylic acid (PAA), polylithium acrylate (PAALi), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-propylene hexafluoride copolymer (PVDF-HFP) ), styrene-butadiene rubber (SBR), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyethylene glycol (PEG), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyimide (PI), and the like. The binder may be used alone or in combination of two or more.
Examples of the solvent in the composition for producing a negative electrode include water and organic solvents. Examples of organic solvents include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; linear or cyclic amides such as N-methylpyrrolidone (NMP) and N,N-dimethylformamide (DMF); and ketones such as acetone. I can give an example. The solvent may be used alone or in combination of two or more.

With respect to the total mass of the negative electrode active material layer 32, the total content of the negative electrode active material and the conductive additive is preferably 80.0 to 99.9% by mass, more preferably 85.0 to 98.0% by mass.

[Separator]
A separator 2 is placed between the negative electrode 3 and the positive electrode 1 to prevent short circuits and the like. The separator 2 may hold a non-aqueous electrolyte, which will be described later.
The separator 2 is not particularly limited, and examples thereof include porous polymer membranes, nonwoven fabrics, glass fibers, and the like.
An insulating layer may be provided on one or both surfaces of separator 2. The insulating layer is preferably a layer having a porous structure in which insulating fine particles are bound with a binder for an insulating layer.

The separator 2 may contain various plasticizers, antioxidants, and flame retardants.
As antioxidants, phenolic antioxidants such as hindered phenolic antioxidants, monophenolic antioxidants, bisphenol antioxidants, and polyphenol antioxidants; hindered amine antioxidants; phosphorus antioxidants Sulfur-based antioxidants; benzotriazole-based antioxidants; benzophenone-based antioxidants; triazine-based antioxidants; salicylic acid ester-based antioxidants, and the like. Phenol-based antioxidants and phosphorus-based antioxidants are preferred.

[Nonaqueous electrolyte]
The non-aqueous electrolyte fills the space between the positive electrode 1 and the negative electrode 3. For example, known nonaqueous electrolytes can be used in lithium ion secondary batteries, electric double layer capacitors, and the like.
As the non-aqueous electrolyte, a non-aqueous electrolyte in which an electrolyte salt is dissolved in an organic solvent is preferred.
It is preferable that the non-aqueous electrolyte further contains an additive. The non-aqueous electrolyte secondary battery 10 after manufacture (after initial charging) contains an organic solvent and an electrolyte salt, and may further contain residues or traces derived from additives.

The organic solvent preferably has resistance to high voltage. For example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, γ-butyrolactone, sulfolane, dimethyl sulfoxide, acetonitrile, dimethylformamide, dimethylacetamide, 1,2-dimethoxyethane, 1,2-diethoxyethane, Examples include polar solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, and methyl acetate, and mixtures of two or more of these polar solvents.

The electrolyte salt is not particularly limited, and includes, for example, LiClO ₄ , LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₆ , LiCF ₃ CO ₂ , LiPF ₆ SO ₃ , LiN(SO ₂ F) ₂ , LiN(SO ₂ CF ₃ ). ₂ , Li( _{SO2CF2CF3 ) 2 , LiN} ( _COCF3 ) ₂ , LiN( _COCF2CF3 ) ₂ , or a mixture of two or more of these salts.

Examples of the additive include compound A containing one or both of a sulfur atom and a nitrogen atom. The additives may be used alone or in combination of two or more.
Examples of compound A include lithium bis(fluorosulfonyl)imide (LiN(SO ₂ F) ₂ , hereinafter also referred to as "LiFSI"), lithium bis(trifluoromethanesulfonyl)imide (LiN(SO ₂ CF ₃ ) ₂ , (hereinafter also referred to as "LiTFSI").

<Method for manufacturing non-aqueous electrolyte secondary battery>
The method for manufacturing the non-aqueous electrolyte secondary battery of this embodiment includes a method of assembling a positive electrode, a separator, a negative electrode, a non-aqueous electrolyte, an exterior body, etc. by a known method to obtain a non-aqueous electrolyte secondary battery.
An example of the method for manufacturing the non-aqueous electrolyte secondary battery of this embodiment will be described. For example, an electrode laminate in which positive electrodes 1 and negative electrodes 3 are alternately laminated with separators 2 in between is produced. The electrode laminate is enclosed in an exterior body (casing) 5 such as an aluminum laminate bag. Next, a non-aqueous electrolyte (not shown) is injected into the outer shell, and the outer shell 5 is sealed to form a non-aqueous electrolyte secondary battery.

The nonaqueous electrolyte secondary battery of this embodiment can be used as a lithium ion secondary battery for various uses such as industrial use, consumer use, automobile use, and residential use.
The usage form of the non-aqueous electrolyte secondary battery of this embodiment is not particularly limited. For example, it can be used in a battery module configured by connecting a plurality of non-aqueous electrolyte secondary batteries in series or in parallel, a battery system including a plurality of electrically connected battery modules and a battery control system, and the like.
Examples of battery systems include battery packs, stationary storage battery systems, automotive power storage battery systems, automotive auxiliary storage battery systems, emergency power storage battery systems, and the like.

The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

<Measurement method>
[Method of measuring particle size distribution]
A sample was prepared by peeling off the outermost surface of the positive electrode active material layer at a depth of several micrometers using a spatula, and dispersing the obtained powder in water.
For the measurement, a laser diffraction particle size distribution analyzer (Horiba, Ltd. product name: LA-960V2) was used, and a flow cell was used. The sample was circulated, stirred, and irradiated with ultrasonic waves (for 10 minutes), and the particle size distribution was measured after the dispersion state was sufficiently stable.
A volume-based particle size distribution curve was obtained, and the most frequent diameter (mode diameter), frequency in the mode diameter, number of maximum points (number of peaks), and distribution width (D90-D10) were determined.

[Method of measuring volume density]
Using a micrometer, the thickness of the positive electrode sheet and the thickness of the exposed portion of the positive electrode current collector were measured. Each was measured at five arbitrary points and the average value was calculated. The thickness of the positive electrode active material layer was calculated by subtracting the thickness of the exposed portion of the positive electrode current collector from the thickness of the positive electrode sheet.
Five measurement samples were prepared by punching out a positive electrode sheet into a circular shape with a diameter of 16 mm.
The mass of each measurement sample was weighed using a precision balance, and the mass of the positive electrode active material layer in the measurement sample was calculated by subtracting the mass of the positive electrode current collector measured in advance from the measurement result. The volume density of the positive electrode active material layer was calculated from the average value of each measured value based on the above formula (1).

<Evaluation method>
[Gravimetric energy density]
Evaluation of gravimetric energy density was performed according to the following procedures (1) to (3).
(1) A cell was prepared with a rated capacity of 1 Ah, and the weight of the cell was measured.
(2) The obtained cell was charged at a constant current of 0.2C rate (i.e. 200mA) at a final voltage of 3.6V in an environment of 25°C (normal temperature), and then charged at a constant voltage of 3.6V. After charging was carried out with 1/10 of the charging current as the final current (ie, 20 mA), the battery was rested in an open circuit state for 30 minutes.
(3) Discharge was performed at a constant current at a rate of 0.2C with a final voltage of 2.5V. At this time, the gravimetric energy density (Wh/kg) was calculated by dividing the total discharge power (Wh) measured from the start of discharge to the end of discharge by the weight (kg) of the cell measured in (1). .

[Large current characteristics]
Evaluation of large current characteristics was performed according to the following procedures (1) to (5).
(1) The obtained cell was charged at a constant current at a rate of 0.2C (i.e. 200mA) at a final voltage of 3.6V in an environment of 25°C (normal temperature), and then charged at a constant voltage at a final voltage of 3.6V. After charging was carried out with 1/10 of the charging current as the final current (ie, 20 mA), the battery was rested in an open circuit state for 30 minutes.
(2) Discharge was carried out at a constant current at a rate of 0.2C with a final voltage of 1.5V. At this time, the total discharge capacity (Ah) measured from the start of discharge to the end of discharge was defined as 0.2C discharge capacity.
(3) After charging again at a constant current at a 0.2C rate (i.e., 200 mA) with a final voltage of 3.6 V, 1/10 of the charging current is set as a final current (i.e., 20 mA) at a constant voltage. After charging, the battery rested in an open circuit state for 30 minutes.
(4) Discharge was carried out at a constant current at a rate of 20C with a final voltage of 1.5V. At this time, the total discharge capacity (Ah) measured from the start of discharge to the end of discharge was defined as the 20C discharge capacity.
(5) The large current characteristics were evaluated by calculating the value (unit: %) obtained by dividing the 20C discharge capacity (Ah) by the 0.2C discharge capacity (Ah). The closer this value is to 100%, the better the large current characteristics are.

<Manufacture example 1: Manufacture of negative electrode>
100 parts by mass of artificial graphite as a negative electrode active material, 1.5 parts by mass of styrene-butadiene rubber as a binder, 1.5 parts by mass of carboxymethyl cellulose Na as a thickener, and water as a solvent, A composition for producing a negative electrode with a solid content of 50% by mass was obtained.
The obtained composition for producing a negative electrode was applied on both sides of a copper foil (thickness: 8 μm), vacuum dried at 100° C., and then pressed under a load of 2 kN to obtain a negative electrode sheet. The obtained negative electrode sheet was punched out to form a negative electrode.

<Production Example 2: Production of a current collector having a current collector coating layer>
A slurry was obtained by mixing 100 parts by mass of carbon black, 40 parts by mass of polyvinylidene fluoride as a binder, and N-methylpyrrolidone (NMP) as a solvent. The amount of NMP used was the amount necessary to coat the slurry.
The obtained slurry was coated on both the front and back sides of a 15 μm thick aluminum foil (positive electrode current collector body) using a gravure method so that the thickness of the dried current collector coating layer (total of both sides) was 2 μm. Then, it was dried and the solvent was removed to obtain a positive electrode current collector. The current collector coating layers on both sides were formed so that the coating amount and thickness were equal to each other.

As positive electrode active material particles, active material granules in which a large number of core parts (lithium iron phosphate) are integrated via an active material coating part (carbon), or a core part (lithium iron phosphate) and an active material coating A single coated particle (non-granulated body) consisting of 50% (carbon) was used.
Active material granules (1): average particle diameter 7.8 μm, carbon content 2.5% by mass.
Active material granules (2): average particle diameter 10.3 μm, carbon content 2.5% by mass.
Active material granules (3): average particle diameter 14.9 μm, carbon content 2.5% by mass.
Active material granules (4): average particle diameter 3.0 μm, carbon content 2.5% by mass.
Coated particles (1): average particle diameter 1.1 μm, carbon content 1.5% by mass, coverage rate 90% or more.
When active material granules (1) to (4) were observed using a scanning electron microscope (SEM) with a mapping function and a transmission electron microscope (TEM), it was found that many cores were composed of lithium iron phosphate. The particles were approximately spherical particles (granules) containing 1,000 particles. Carbon existed between adjacent core parts, and the outer surface of the granule was coated with a thin film of carbon. The coverage of the core was 90% or more, and the coverage of the outer surface was 90% or more.

Carbon black (CB) was used as a conductive aid. CB has impurities below the quantitative limit and can be considered to have a carbon content of 100% by mass.
Polyvinylidene fluoride (PVDF), which is a resin component, was used as a binder.
Polyvinylpyrrolidone (PVP), which is a resin component, was used as a dispersant.
N-methylpyrrolidone (NMP) was used as a solvent.
As the positive electrode current collector, the aluminum foil having the current collector coating layer obtained in Production Example 2 or the aluminum foil (15 μm thick) without the current collector coating layer was used.

<Examples 1 to 9>
Examples 1 to 4 are examples, and Examples 5 to 9 are comparative examples.
A positive electrode active material layer was formed by the following method.
Positive electrode active material particles, a conductive aid, a binder, a dispersant, and a solvent (NMP) having the composition shown in Table 1 were mixed in a mixer to obtain a composition for manufacturing a positive electrode. The amount of solvent used was the amount necessary for coating the composition for producing a positive electrode. Note that the formulations shown in the table are the proportions when the total of raw materials other than the solvent is 100% by mass.
The obtained composition for producing a positive electrode was applied onto both surfaces of a positive electrode current collector, and after preliminary drying, vacuum drying was performed in a 120° C. environment to form a positive electrode active material layer. The coating amount of the positive electrode manufacturing composition was set to be 20 mg/cm ² in total on both sides. The positive electrode active material layers on both sides were formed so that the coating amount and thickness were equal to each other. The obtained laminate was pressed under pressure to obtain a positive electrode sheet. The load of the pressure press was 10 kN.
The obtained positive electrode sheet was punched out to form a positive electrode.

Regarding the obtained positive electrode sheet, the particle size distribution of the positive electrode active material layer, the content of the resin component relative to the total mass of the positive electrode active material layer, the content of conductive carbon, and the volume density of the positive electrode active material layer were determined. The results are shown in Table 2.
Specifically, the particle size distribution of the positive electrode active material layer, and the thickness and volume density of the positive electrode active material layer were measured using the above method. Based on the measurement results of particle size distribution, values for each item shown in Table 2 were determined. As an example, the particle size distributions of the positive electrode active material layers of Examples 3 and 8 are shown in FIG.
In the particle size distribution curves of Examples 1 to 9, the number of peaks was 2, and the peak with a larger particle size had a higher frequency. In other words, the particle diameter at the peak where the particle diameter is large was the mode diameter.
The content of conductive carbon relative to the total mass of the positive electrode active material layer was calculated based on the carbon content and amount of the positive electrode active material particles and the carbon content and amount of the conductive additive. It is also possible to confirm using the method described in the above <<Method for Measuring Conductive Carbon Content>>.
Based on the blending amounts of the binder and dispersant, the total content of the binder and dispersant with respect to the total mass of the positive electrode active material layer was calculated, and was taken as the content of the resin component. It is also possible to confirm using the method described in the above <<Method for Measuring Content of Resin Component>>.

A non-aqueous electrolyte secondary battery having the configuration shown in FIG. 2 was manufactured by the following method.
LiPF ₆ was dissolved as an electrolyte at 1 mol/liter in a solvent containing ethylene carbonate (EC) and diethyl carbonate (DEC) mixed at a volume ratio of EC:DEC of 3:7. An aqueous electrolyte was prepared.
The positive electrode obtained in this example and the negative electrode obtained in Production Example 1 were alternately laminated with separators interposed therebetween to produce an electrode laminate in which the outermost layer was the negative electrode. A polyolefin film (thickness: 15 μm) was used as a separator.
In the step of producing the electrode laminate, first, the separator 2 and the positive electrode 1 were laminated, and then the negative electrode 3 was laminated on the separator 2.
Terminal tabs are electrically connected to each of the positive electrode current collector exposed portion 13 and the negative electrode current collector exposed portion 33 of the electrode laminate, and the electrodes are laminated with an aluminum laminate film so that the terminal tabs protrude to the outside. The body was sandwiched and the three sides were laminated and sealed.
Subsequently, a non-aqueous electrolyte was injected from one side left unsealed, and vacuum-sealed to produce a non-aqueous electrolyte secondary battery (laminate cell).
The gravimetric energy density was measured using the method described above. In addition, large current characteristics were evaluated using the method described above. The results are shown in Table 2.

As shown in the results in Table 2, the positive electrode active material layer has a current collector coating layer, contains a resin component of 0.8 to 3.0% by mass, and the mode diameter of the particles present in the positive electrode active material layer is Examples 1 to 4, in which the diameter is 50.0 to 100.0 μm and the frequency in the mode diameter is 5 to 15%, have a high gravimetric energy density and are excellent in large current characteristics.

On the other hand, in Example 5, which had a current collector coating layer but had a high resin component content and a mode diameter exceeding 100.0 μm, the weight energy density decreased.
On the other hand, in Example 6, which had a current collector coating layer but had a small content of the resin component, the frequency in the mode diameter was less than 5%, and the large current characteristics were deteriorated.
In Example 7, in which no current collector coating layer was provided, the large current characteristics were significantly inferior. It is thought that the conductive path between the current collector and the positive electrode active material was insufficient.
Example 8, in which the mode diameter of particles present in the positive electrode active material layer was smaller than 50.0 μm, had poor large current characteristics. Because the particle size of the active material granules is small, the conductivity inside the active material granules is good, but the number of points connecting the active material granules increases relatively, making the conductive path uneven. Conceivable.
Example 9 is an example in which a large amount of conductive additive was added and the amount of binder added was also increased to bind the conductive additive, resulting in a decrease in the weight energy density. Furthermore, despite the high content of conductive carbon, the large current characteristics were somewhat inferior. It is thought that the conductive path became non-uniform due to the large amount of conductive aid.

1 Positive electrode 2 Separator 3 Negative electrode 5 Exterior body 10 Secondary battery 11 Current collector (positive electrode current collector)
12 Positive electrode active material layer 13 Positive electrode current collector exposed portion 14 Positive electrode current collector main body 15 Current collector coating layer

Claims (10)

comprising a current collector and a positive electrode active material layer present on the current collector,
A current collector coating layer is present on at least a part of the surface of the current collector on the positive electrode active material layer side,
The current collector coating layer includes a conductive material,
The positive electrode active material layer includes positive electrode active material particles and a resin component,
The content of the resin component is 0.8 to 3.0% by mass with respect to the total mass of the positive electrode active material layer,
In the volume-based particle size distribution curve of the particles present in the positive electrode active material layer, the most frequent particle size is 50.0 to 100.0 μm, and the frequency of the particles in the most frequent particle size is 5 to 15%. Positive electrode for water electrolyte secondary batteries. According to claim 1, in the particle size distribution curve with frequency as the vertical axis, there are a plurality of maximum points, and the particle size at the maximum point having the largest particle size among the plurality of maximum points is the most frequent particle size. Positive electrode for non-aqueous electrolyte secondary batteries. The positive electrode for a nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein in the particle size distribution curve, the distribution width obtained by subtracting the 10% diameter from the 90% diameter is 80.0 to 200.0 μm. The positive electrode for a nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein the positive electrode active material layer has a volume density of 2.00 to 2.40 g/cm ³ . The positive electrode active material particles are represented by the general formula LiFe _x M _(1-x) PO ₄ (wherein 0≦x≦1, M is Co, Ni, Mn, Al, Ti, or Zr). The positive electrode for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, comprising a compound. Claims 1 to 3, wherein the positive electrode active material layer contains conductive carbon, and the content of the conductive carbon is 0.5% by mass or more and less than 3.0% by mass with respect to the total mass of the positive electrode active material layer. 5. The positive electrode for a non-aqueous electrolyte secondary battery according to any one of 5. The positive electrode for a nonaqueous electrolyte secondary battery according to any one of claims 1 to 6, wherein the positive electrode active material layer contains a binder, and the binder contains the resin component. The positive electrode for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 7, wherein the positive electrode active material layer does not contain a conductive additive. A non-aqueous electrolyte battery comprising: a positive electrode for a non-aqueous electrolyte secondary battery, a negative electrode according to any one of claims 1 to 8, and a non-aqueous electrolyte present between the positive electrode for a non-aqueous electrolyte secondary battery and the negative electrode Water electrolyte secondary battery. A battery module or a battery system comprising a plurality of non-aqueous electrolyte secondary batteries according to claim 9.

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