JP2021150111A - Electrode active material layer for nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery - Google Patents

Abstract

To provide: an electrode active material layer for a nonaqueous electrolyte secondary battery, by which a nonaqueous electrolyte secondary battery allowing both of a high capacity and quick charging to be achieved can be obtained; an electrode for a nonaqueous electrolyte secondary battery; and a nonaqueous electrolyte secondary battery which allows both of a high capacity and quick charging to be achieved.SOLUTION: An electrode active material layer for a nonaqueous electrolyte secondary battery, herein disclosed comprises: over 5.0 mass% to 99.0 mass% of metal active material particles containing 30.0-80.0 mass% of Cu and capable of occluding and/or releasing metal ions; and a binding agent. In the electrode active material layer, the requirements given by the following expressions(1)-(3): 1.00≤T≤6.00 (1); 1.00≤d≤3.50 (2); and 0.010≤R≤100.000 (3), provided that an electrode gas-permeation speed (μm/s) is substituted for T of the expression (1), an electrode density (g/cm3) is substituted for d of the expression (2), and a volume resistivity (Ωcm) is substituted for R of the expression (3).SELECTED DRAWING: Figure 1

Description

The present invention relates to an electrode active material layer for a non-aqueous electrolyte secondary battery, an electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.

In recent years, home video cameras, notebook computers, small electronic devices such as smartphones, and the like have become widespread, and increasing the capacity of batteries has become a technical issue.

As hybrid vehicles, plug-in hybrid vehicles, and electric vehicles become more widespread, making batteries compact is also a technical issue.

Currently, a graphite-based electrode active material is used for the negative electrode of a non-aqueous electrolyte secondary battery represented by a lithium ion battery. However, the graphite-based electrode active material has the above-mentioned technical problems.

Therefore, attention is being paid to alloy-based electrode active material materials having a higher capacity than graphite-based electrode active material materials. As the alloy-based electrode active material material, a silicon (Si) -based electrode active material material and a tin (Sn) -based electrode active material material are known. In order to put a lithium ion battery having a higher capacity and more compact into practical use, various studies have been made on the alloy-based electrode active material.

For example, the negative electrode active material described in International Publication No. 2014/156963 (Patent Document 1) is a silicon-copper alloy negative electrode active material containing a trace amount of oxygen represented by the following general formula (I). It is described in Patent Document 1 that an alloy-based negative electrode active material capable of occluding and releasing lithium having a high capacity and excellent cycle characteristics and charge storage characteristics can be obtained.
_{Si p Cu q M r O s} (I)
(However, p + q + r + s = 100, s = 0.01 to 5, q = 5 to 50, r = 0 to 10, M is Be, B, Al, P, Zn, Ga, Ge, In, Sn, Sb, Represents at least one or more elements selected from Y, Zr, Nb, Mo, and W.)

On the other hand, in addition to the above-mentioned high capacity and compactness, the non-aqueous electrolyte secondary battery is also required to have quick chargeability. For example, Japanese Patent Application Laid-Open No. 2017-183236 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2018-147672 (Patent Document 3) propose a negative electrode having improved quick chargeability.

The negative electrode described in Patent Document 2 is a negative electrode for a lithium ion secondary battery provided with a negative electrode active material layer formed by mixing a negative electrode active material made of a carbon material and a binder on a current collector, and is a negative electrode active material. The material layer has a void ratio of 50% or less, an air permeability measured by a Garley type densometer of 0.80 to 1.40 μm / sec, and a negative electrode volume of the negative electrode for the lithium ion secondary battery. The energy density [E (mAh / cm ³ )] satisfies the following equation 1 in relation to the air permeability. As a result, it is described in Patent Document 2 that a lithium ion secondary battery having a high energy density, safety, and excellent input / output characteristics can be obtained.
[Formula 1]
0.95 <E / (-145X + 545)
[However, X indicates the air permeability (μm / sec) of the negative electrode active material layer measured by the Garley type densometer. ]

The negative electrode described in Patent Document 3 has a negative electrode current collector and a negative electrode active material layer provided on the negative electrode current collector, and the negative electrode active material layer contains a carbon material and is a mercury press-fitting method. In the Log differential pore volume distribution graph obtained by, the product A × B of the peak pore diameter A (unit: μm) and the Log differential pore volume B (unit: cm ^{3 / g) at the peak pore diameter A is} , 0.2 or more and 1.0 or less. It is described in Patent Document 3 that a negative electrode having good quick charging characteristics can be obtained as a result.

International Publication No. 2014/156963 Japanese Unexamined Patent Publication No. 2017-183236 JP-A-2018-147672 International Publication No. 2014/034104 International Publication No. 2015/129264 International Publication No. 2015/129265 International Publication No. 2015/129266 International Publication No. 2015/129267 International Publication No. 2015/12927 International Publication No. 2017/200046 International Publication No. 2019/017349

However, even with the above-mentioned techniques, it may be difficult to obtain a non-aqueous electrolyte secondary battery having both high capacity and quick chargeability.

An object of the present disclosure is an electrode active material layer for a non-aqueous electrolyte secondary battery, which can obtain a non-aqueous electrolyte secondary battery having both high capacity and quick chargeability, and a non-aqueous electrolyte secondary battery having both high capacity and quick chargeability. It is an object of the present invention to provide an electrode for a non-aqueous electrolyte secondary battery from which a water electrolyte secondary battery can be obtained, and a non-aqueous electrolyte secondary battery having both high capacity and quick chargeability.

The electrode active material layer of the present disclosure is an electrode active material layer for a non-aqueous electrolyte secondary battery.
The amount of metal active material particles containing 30.0 to 80.0% by mass of Cu and occluding and / or releasing metal ions is more than 5.0% by mass to 99.0% by mass.
Contains a binder and
Equations (1) to (3) are satisfied.
1.00 ≤ T ≤ 6.00 (1)
1.00 ≤ d ≤ 3.50 (2)
0.010 ≤ R ≤ 100.000 (3)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1), the electrode density (g / cm ³ ) is substituted for d in the equation (2), and R in the equation (3). The volume resistivity (Ω · cm) is substituted for.

The electrodes of the present disclosure are electrodes for a non-aqueous electrolyte secondary battery.
The electrode active material layer of the present disclosure and
It is equipped with a current collector made of metal foil.

The non-aqueous electrolyte secondary battery of the present disclosure comprises the electrodes of the present disclosure.

The non-aqueous electrolyte secondary battery provided with the electrode active material layer of the present disclosure can achieve both high capacity and quick chargeability.

FIG. 1 is a schematic cross-sectional view of the electrode active material layer of the present embodiment. FIG. 2 is a schematic view of a cross section of the electrode in this embodiment. FIG. 3 is a schematic view of an example of the metal active material particle manufacturing apparatus of the present embodiment.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. The same or corresponding parts in the drawings are designated by the same reference numerals, and the description thereof will not be repeated.

The present inventors have investigated and investigated an electrode active material layer capable of achieving both high capacity and quick chargeability of a non-aqueous electrolyte secondary battery. As a result, the present inventors obtained the following findings.

Graphite-based active materials and alloy-based active materials are known as electrode active materials. In order to increase the capacity of the non-aqueous electrolyte secondary battery, it is effective to increase the discharge capacity per volume of the electrode. In order to increase the discharge capacity per volume of the electrode, it is effective to use an electrode active material having a high discharge capacity per volume for the electrode active material layer. The alloy-based active material has a higher discharge capacity per volume than the graphite-based active material. Therefore, it is effective to use an alloy-based active material for the electrode active material layer.

The metal active material particles containing 30.0 to 80.0% by mass of Cu are alloy-based active materials. The metal active material particles containing 30.0 to 80.0% by mass of Cu have a particularly high discharge capacity per volume. Therefore, it is effective to use metal active material particles containing 30.0 to 80.0% by mass of Cu as the electrode active material.

On the other hand, the present inventors investigated and investigated a method for improving the quick chargeability of the non-aqueous electrolyte secondary battery using the above-mentioned metal active material particles, and obtained the following findings.

Formulas (4) and (5) are chemical reaction formulas that outline the charge / discharge reaction of the non-aqueous electrolyte secondary battery.
A + xM ^{n +} + xne ⁻ → M _x A (4)
M _x A → A + xM ^{n +} + xne ⁻ (5)
In formulas (4) and (5), "A" represents an electrode active material, "M ^{n +} " represents an n-valent metal ion, and "e ⁻ " represents an electron. n is a natural number. A predetermined ratio (x) of metal ions (M ^{n +} ) is stored in the electrode active material (A) by chemically reacting with xn electrons (e ⁻ _{) that are chemically equivalent (M x} A). ). In the case of a lithium ion battery, M ^{n + in} the formulas (4) and (5) is Li ⁺ .

^{The present inventors considered that the moving speed of the M n +} and e ⁻ of the formulas (4) and (5) in the electrode active material layer affects the rapid chargeability of the non-aqueous electrolyte secondary battery. Therefore, the present inventors have investigated a method for increasing the moving speed of ^{Mn +} and e ⁻ of the formulas (4) and (5). As a result, the following findings were obtained.

^{M n +} of the formulas (4) and (5) is a metal ion contained in the electrolyte of the non-aqueous electrolyte secondary battery. In ^{order to increase the moving speed of Mn + in} the electrode active material layer, it is effective to provide an appropriately connected void in the electrode active material layer. If there are appropriately connected voids in the electrode active material layer, the voids are filled with the electrolyte, and ^{Mn +} can move rapidly in the connected electrolytes.

On the other hand, ^{in order to increase the moving speed of e − in} the electrode active material, it is sufficient that the metal active material particles contained in the electrode active material layer have an appropriate contact point with each other. If the metal active material particles have appropriate contact points, e ⁻ can move quickly through the contact points between the metal active material particles.

However, the moving speed ^{of M n + in} the formulas (4) and (5) is inversely proportional to the moving speed of ^{e −.} That is, when the moving speed of ^{M n +} is high, the moving speed of ^{e − is low.} On the contrary, when the moving speed of ^{M n +} is small, the moving speed of ^{e − is high.} This is for the following reasons. When there are many voids in the electrode active material layer and the voids are connected to each other, most of the electrolytes are connected in the electrode active material layer. Therefore, the moving speed of ^{M n + increases.} If there are many voids in the electrode active material layer and they are connected to each other, the number of contacts between the electrode active materials, that is, points of conduction is reduced. As a result, the moving speed of ^{e − becomes small.} On the contrary, if the electrode active material is present at a high density, the number of connected voids in the electrode active material layer is reduced, so that the electrolyte is divided and exists in the electrode active material layer. Therefore, the moving speed of ^{M n + becomes small.} If the electrode active material is present at a high density, there are many points of contact between the electrode active materials, that is, points of conduction. Therefore, the moving speed of ^{e − increases.}

From the above, the ^{study of increasing the moving speed of M n +} and the study of increasing the moving speed of e ⁻ are contradictory studies, and it is difficult to achieve both a large moving speed of ^{M n + and} a large moving speed of e ^−. However, if the above-mentioned metal active material particles are used as an electrode active material, the moving speed of ^{Mn + is increased, and the moving speed of e −} is further increased, the present inventors make a non-aqueous electrolyte secondary battery. We thought that it would be possible to achieve both high capacity and quick chargeability. Therefore, the present inventors have an electrode active material layer having a structure capable of increasing the moving speed of ^{M n +} and further increasing the moving speed of e ^{−, that is, appropriately connected voids and metal active material particles.} Various studies were conducted on the electrode active material layer having a structure having appropriate contacts. However, the internal structure of the electrode active material layer is so small that it is difficult to directly identify the internal structure of the electrode active material layer.

Therefore, the present inventors have conducted various studies on the connected voids in the electrode active material layer and the indexes indicating the contact points between the metal active material particles. As a result, the following findings were obtained.

The connected voids in the electrode active material layer can be expressed as the electrode air permeation rate of the electrode active material layer. In the present disclosure, the electrode air permeability (μm / s) ^{means that air is blown into the electrode active material layer having an area of 28.3 mm 2} (6 mmφ) in the thickness direction of the electrode active material layer by using a Garley type densometer. It refers to the moving distance (μm) of air per second when permeated. That is, the electrode air permeation rate indicates the connection of voids in the thickness direction of the electrode active material layer. When the electrode air permeability is high, it indicates that more voids are connected in the thickness direction of the electrode active material layer. In this case, the connected voids are filled with the electrolyte, and ^{Mn +} can move in the connected electrolyte. As a result, the moving speed of ^{Mn + in} the equations (4) and (5) increases. That is, ^{the moving speed of Mn + in} the electrode active material layer can be expressed as the electrode air permeation speed of the electrode active material layer.

More specifically, if the electrode air permeability of the electrode active material layer satisfies the equation (1), the movement speed of ^{Mn + in the electrode active material layer is high and the movement of e −} is not hindered.
1.00 ≤ T ≤ 6.00 (1)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1).

On the other hand, the contact points between the metal active material particles can be expressed as the volume resistivity of the electrode active material layer. When the volume resistivity of the electrode active material layer is low, it indicates that the electrode active materials are conducting each other so ^{that e − can move quickly in the electrode active material layer.} In this case, the moving speed ^{of e −} of the equations (4) and (5) increases. That is, ^{the moving speed of e − in} the electrode active material layer can be expressed as the volume resistivity of the electrode active material layer.

More specifically, if the volume resistivity of the electrode active material layer satisfies the equation (3), the moving speed ^{of e − in the electrode active material layer is high and the movement of M n +} is not hindered.
0.010 ≤ R ≤ 100.000 (3)
Here, the volume resistivity (Ω · cm) is substituted for R in the equation (3).

Volume resistivity is a numerical value peculiar to a substance. However, the volume resistivity of the electrode active material alone and the volume resistivity of the electrode active material layer formed by using the electrode active material do not always match. The electrode active material layer is a layer formed by binding particulate electrode active materials with a binder. A binder may be present at the contact points between the particles of the electrode active material. Further, the electrode active material layer of the present disclosure contains metal active material particles. An oxide film may be formed around the metal active material particles. If a binder or an oxide film is present at the boundary between the electrode active material particles, the moving speed of ^{e − may be reduced.} In this case, the volume resistivity of the electrode active material layer is higher than the volume resistivity of the electrode active material alone.

Further, it is necessary that the electrode density of the electrode active material layer satisfies the formula (2) after using the metal active material particles. If the electrode active material layer satisfies the formula (2), ^{the movement of e −} and M ^{n + in} the electrode active material layer is not inhibited.
1.00 ≤ d ≤ 3.50 (2)
Here, the electrode density (g / cm ³ ) is substituted for d in the equation (2).

Summarizing the above, the present inventors used metal active material particles having a high discharge capacity per volume, and the electrode air permeation rate, density, and volume resistance of the electrode active material layer were within an appropriate range. If there is, the discharge capacity per volume of the electrode active material layer is increased, ^{and the moving speed of both Mn +} and e ⁻ is increased, so that the high capacity and quick chargeability of the non-aqueous electrolyte secondary battery can be further enhanced. I thought I could do it. That is, the electrode active material layer for the non-aqueous electrolyte secondary battery of the present disclosure has been completed based on a knowledge completely different from the previous knowledge. Specifically, if the metal active material particles containing 30.0 to 80.0% by mass of Cu are used as the active material and the electrode active material layer satisfies the formulas (1) to (3), It is possible to achieve both the high capacity of a non-aqueous electrolyte secondary battery and excellent quick chargeability.
1.00 ≤ T ≤ 6.00 (1)
1.00 ≤ d ≤ 3.50 (2)
0.010 ≤ R ≤ 100.000 (3)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1), the electrode density (g / cm ³ ) is substituted for d in the equation (2), and R in the equation (3). The volume resistivity (Ω · cm) is substituted for.

The structure of the electrode active material layer of the present embodiment completed based on the above findings is as follows.

The electrode active material layer of [1] is
An electrode active material layer for non-aqueous electrolyte secondary batteries.
The amount of metal active material particles containing 30.0 to 80.0% by mass of Cu and occluding and / or releasing metal ions is more than 5.0% by mass to 99.0% by mass.
Contains a binder and
Equations (1) to (3) are satisfied.
1.00 ≤ T ≤ 6.00 (1)
1.00 ≤ d ≤ 3.50 (2)
0.010 ≤ R ≤ 100.000 (3)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1), the electrode density (g / cm ³ ) is substituted for d in the equation (2), and R in the equation (3). The volume resistivity (Ω · cm) is substituted for.

The electrode active material layer of [2] is
The electrode active material layer according to [1].
The metal active material particles further contain Sn.

The electrode active material layer of [3] is
The electrode active material layer according to [2].
The metal active material particles are further
Contains one or two selected from the group consisting of Si and Ti.

The electrode active material layer of [4] is
The electrode active material layer according to [2] or [3].
The metal active material particles are further
It contains one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B and C.

The electrode active material layer of [5] is
The electrode active material layer according to any one of [1] to [4], and further.
Contains graphite.

The electrode of this embodiment is an electrode for a non-aqueous electrolyte secondary battery.
The electrode active material layer according to any one of [1] to [5] and
It is equipped with a current collector made of metal foil.

The non-aqueous electrolyte secondary battery of the present embodiment includes the electrodes of the present embodiment.

Hereinafter, the electrode active material layer, the electrode, and the non-aqueous electrolyte secondary battery of the present embodiment will be described in detail. "%" For an element means "mass%" unless otherwise specified.

[Electrode active material layer]
The electrode active material layer of the present embodiment is an electrode active material layer for a non-aqueous electrolyte secondary battery. FIG. 1 is a schematic cross-sectional view of the electrode active material layer of the present embodiment. With reference to FIG. 1, the electrode active material layer 1 contains metal active material particles 2 and a binder. Although not shown, the binder is scattered on the surface of the metal active material particles 2 and binds the metal active material particles 2 to each other.

The electrode active material layer 1 contains the metal active material particles 2 in an amount of more than 5.0% by mass to 99.0% by mass. If the content of the metal active material particles 2 is 5.0% by mass or less, the components other than the metal active material particles 2 contained in the electrode active material layer 1 become too large. In this case, the components other than the metal active material particles 2 are deformed during the production of the electrode active material layer 1 to fill the voids, and the electrode air permeation velocity T (μm / s) of the electrode active material layer 1 becomes less than 1.00. .. Therefore, the quick chargeability of the non-aqueous electrolyte secondary battery is lowered. On the other hand, if the content of the metal active material particles 2 exceeds 99.0% by mass, the electrode adhesion of the metal active material particles 2 is lowered, and the cycle characteristics of the non-aqueous electrolyte secondary battery are lowered. If the content of the metal active material particles 2 exceeds 99.0% by mass, the electrode adhesion of the metal active material particles 2 may further deteriorate and the electrode may not be manufactured. Therefore, the content of the metal active material particles 2 is more than 5.0% by mass to 99.0% by mass. The lower limit of the content of the metal active material particles 2 is preferably 10.0% by mass, more preferably 30.0% by mass. The upper limit of the content of the metal active material particles 2 is preferably 97.0% by mass, more preferably 95.0% by mass, and further preferably 93.0% by mass.

The electrode active material layer 1 satisfies the formulas (1) to (3).
1.00 ≤ T ≤ 6.00 (1)
1.00 ≤ d ≤ 3.50 (2)
0.010 ≤ R ≤ 100.000 (3)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1), the electrode density (g / cm ³ ) is substituted for d in the equation (2), and R in the equation (3). The volume resistivity (Ω · cm) is substituted for.

[Electrode permeation rate of electrode active material layer]
The electrode active material layer 1 satisfies the formula (1).
1.00 ≤ T ≤ 6.00 (1)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1).

When the electrode air permeation velocity (μm / s) of the electrode active material layer 1 is less than 1.00, it indicates that the air permeation path of the electrode active material layer 1 is blocked. In this case, the movement path of ^{Mn +} in the battery reaction of the formulas (4) and (5) is blocked, and the movement speed of ^{Mn + decreases.} Therefore, the DC resistance of the electrode active material layer 1 becomes high, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. On the other hand, if the electrode air permeation velocity (μm / s) of the electrode active material layer 1 exceeds 6.00, the air permeation path of the electrode active material layer 1 becomes too large. In this case, since there are few contacts between the electrode active materials, the number of electron conduction paths in the electrode active material layer 1 is reduced. Therefore, the DC resistance of the electrode active material layer 1 becomes high, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. Therefore, the electrode air permeability (μm / s) is 1.00 or more and 6.00 or less.

The lower limit of the electrode air permeability (μm / s) is preferably 1.20 μm / s, more preferably 1.50 μm / s. The upper limit of the electrode air permeability (μm / s) is preferably 5.00 μm / s, more preferably 4.00 μm / s.

[Measurement method of electrode air permeability]
The electrode air permeability of the electrode active material layer 1 is measured by the following method. The electrode active material layer 1 is separated from the electrode. Specifically, the electrode active material layer 1 is separated from the electrode by etching the current collector or by peeling the electrode active material layer 1 from the current collector using tweezers or the like. When peeling with tweezers or the like is difficult, the current collector may be removed by a known processing method using a focused ion beam such as a Ga ion beam. With respect to the obtained electrode active material layer 1, the time for air to pass through the electrode active material layer 1 is measured using a Garley type densometer. The area of the electrode active material layer 1 is 28.3 mm ² (6 mmφ), the amount of air is 25 mL, and the air passing direction is the thickness direction of the electrode active material layer 1. By substituting the measured air passage time (s) and the thickness (μm) of the electrode active material layer 1 into the following equation, the electrode air permeation velocity T (μm / s) is obtained.
Electrode air permeation velocity T (μm / s) = Thickness of electrode active material layer 1 (μm) / Air passage time (s)

[Electrode density of electrode active material layer]
The electrode active material layer 1 satisfies the formula (2).
1.00 ≤ d ≤ 3.50 (2)
Here, the electrode density (g / cm ³ ) is substituted for d in the equation (2).

If the electrode density (g / cm ³ ) of the electrode active material layer 1 is less than 1.00, excessive voids are generated in the electrode active material layer 1. In this case, the electrode air permeation rate and the volume resistivity of the electrode active material layer 1 become too high, and the rapid chargeability of the non-aqueous electrolyte secondary battery using the electrode active material layer 1 decreases. When the electrode density (g / cm ³ ) of the electrode active material layer 1 exceeds 3.50, the air permeation path of the electrode active material layer 1 is blocked. In this case, the movement path of ^{Mn +} in the battery reaction of the formula (4) is blocked, and the movement speed of ^{Mn + decreases.} Therefore, the DC resistance of the electrode active material layer 1 becomes high, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. Therefore, the electrode density (g / cm ³ ) is 1.00 or more and 3.50 or less.

The lower limit of the electrode density (g / cm ³ ) is preferably 1.50 (g / cm ³ ), more preferably 2.00 (g / cm ³ ). The upper limit of the electrode density (g / cm ³ ) is preferably 3.20 (g / cm ³ ), more preferably 3.00 (g / cm ³ ).

[Volume resistivity of electrode active material layer]
The electrode active material layer 1 satisfies the formula (3).
0.010 ≤ R ≤ 100.000 (3)
Here, the volume resistivity (Ω · cm) is substituted for R in the equation (3).

When the volume resistivity (Ω · cm) of the electrode active material layer 1 is less than 0.010, it indicates that there are many contacts between the electrode active materials in the electrode active material layer 1. However, it indicates that the air permeation path in the electrode active material layer 1 is blocked. In this case, the movement path of ^{Mn +} in the battery reaction of the formula (4) is blocked, and the movement speed of ^{Mn + decreases.} Therefore, the DC resistance of the electrode active material layer 1 becomes high, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. On the other hand, if the volume resistivity (Ω · cm) of the electrode active material layer 1 exceeds 100.000, there are too few electron conduction paths in the electrode active material layer 1. Therefore, the DC resistance of the electrode active material layer 1 becomes high, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. Therefore, the volume resistivity (Ω · cm) is 0.010 or more and 100.000 or less.

The lower limit of the volume resistivity (Ω · cm) is preferably 0.100 (Ω · cm), more preferably 1.000 (Ω · cm). The upper limit of the volume resistivity (Ω · cm) is preferably 90.000 (Ω · cm), more preferably 80.000 (Ω · cm). When the electrode active material layer 1 contains graphite, the upper limit of the volume resistivity (Ω · cm) may be 50.000 (Ω · cm) or 30.000 (Ω · cm). May be good. When the electrode active material layer 1 does not contain graphite, the lower limit of the volume resistivity (Ω · cm) may be 20.000 (Ω · cm) or 50.000 (Ω · cm). May be good.

[Measurement method of volume resistivity]
The volume resistivity of the electrode active material layer 1 is measured using an electrode resistance measuring system (manufactured by Hioki Electric Co., Ltd., product name: RM2610). The volume resistivity and thickness of the current collector and the thickness of the electrode active material layer 1 are input to the electrode resistance measurement system in advance. The volume resistivity of the electrode active material layer 1 is calculated by bringing the measurement probe into contact with the electrode active material layer 1 and then applying a constant current from the surface of the electrode active material layer 1. The volume resistivity of the current collector is measured using a well-known four-probe method. The thickness of the current collector is measured using a micrometer. The thickness of the electrode active material layer 1 is obtained as a difference between the electrode thickness and the thickness of the current collector. The measurement conditions of the electrode resistance measuring instrument are: measurement speed: MEDIUM and range: AUTO range.

Only when the metal active material particles 2 containing 30.0 to 80.0% by mass Cu are contained and the formulas (1) to (3) are satisfied, high capacity and quick chargeability are achieved at the same time. The electrode active material layer 1 from which the water electrolyte secondary battery can be obtained can be obtained.

[Metallic active material particles]
The metal active material particles 2 contain 30.0 to 80.0% by mass of Cu and occlude and / or release metal ions. Here, the metal ion is, for example, one selected from the group consisting of lithium ion, magnesium ion, aluminum ion and sodium ion. The metal ion may be a lithium ion.

[Chemical composition of metal active material particles]
The metal active material particles 2 contain 30.0 to 80.0% by mass of Cu. Copper (Cu) has a high discharge capacity per volume and reduces the electrode resistance of the electrode provided with the electrode active material layer 1. If the Cu content is less than 30.0% by mass, the electrode resistance becomes high. On the other hand, if the Cu content exceeds 80.0% by mass, the discharge capacity cannot be increased. Therefore, the Cu content is 30.0 to 80.0% by mass. The lower limit of the Cu content is preferably 35.0% by mass, more preferably 40.0% by mass. The upper limit of the Cu content is preferably 75.0% by mass, more preferably 70.0% by mass.

In the metal active material particles 2, the element contained in addition to Cu may be one kind or two or more kinds selected from the group consisting of metal elements, metalloid elements, oxygen and carbon. That is, the chemical composition of the metal active material particles 2 is selected from one or more selected from the group consisting of 30.0 to 80.0% by mass of Cu, metal elements, metalloid elements, oxygen and carbon, and impurities. The chemical composition may be.

Metallic elements include, for example, tin (Sn), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co) and nickel (Ni), zinc (Zn) and One or more selected from the group consisting of aluminum (Al). The metalloid element is, for example, one or two selected from the group consisting of silicon (Si) and boron (B). That is, the chemical composition of the metal active material particles 2 is 30.0 to 80.0% by mass of Cu, and Sn, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, It may be a chemical composition consisting of one or more selected from the group consisting of O and C and impurities.

The chemical composition of the metal active material particles 2 may be a chemical composition consisting of 30.0 to 80.0% by mass of Cu, Sn and impurities. The chemical composition of the metal active material particles 2 is one or two selected from the group consisting of 30.0 to 80.0% by mass of Cu, Sn, and Si and Ti, and an impurity. May be good. The chemical composition of the metal active material particles 2 is selected from the group consisting of 30.0 to 80.0% by mass of Cu, Sn, and V, Cr, Mn, Fe, Co, Ni, Zn, Al, B and C. It may be a chemical composition composed of one kind or two or more kinds and impurities. The chemical composition of the metal active material particles 2 is one or two selected from the group consisting of 30.0 to 80.0% by mass of Cu, Sn, and Si and Ti, and V, Cr, Mn, It may be a chemical composition composed of one or more selected from the group consisting of Fe, Co, Ni, Zn, Al, B and C and impurities. The content of each element may be as follows.

Sn: 10.0 to 65.0% by mass
Tin (Sn) increases the discharge capacity per volume of the electrode active material layer 1. When the Sn content is 10.0% by mass or more, this effect can be obtained more effectively. When the Sn content is 65.0% by mass or less, this effect can be obtained more effectively. Therefore, the Sn content may be 10.0 to 65.0% by mass. The lower limit of the Sn content is more preferably 15.0% by mass, still more preferably 30.0% by mass. The upper limit of the Sn content is more preferably 60.0% by mass, still more preferably 55.0% by mass.

Si: 1.0 to 20.0% by mass
Silicon (Si) increases the discharge capacity per volume of the electrode active material layer 1. When the Si content is 1.0% by mass or more, this effect can be obtained more effectively. When the Si content is 20.0% by mass or less, this effect can be obtained more effectively. Therefore, the Si content may be 1.0 to 20.0% by mass. The lower limit of the Si content is more preferably 2.0% by mass, still more preferably 3.0% by mass. The upper limit of the Si content is more preferably 15.0% by mass, still more preferably 10.0% by mass.

Ti: 0.1 to 10.0% by mass
Titanium (Ti) suppresses excessive oxidation of Cu and Sn. As a result, Ti lowers the electrode resistance of the electrode including the electrode active material layer 1. When the Ti content is 0.1% by mass or more, this effect can be obtained more effectively. When the Ti content is 10.0% by mass or less, this effect can be obtained more effectively. Therefore, the Ti content may be 0.1 to 10.0% by mass. The lower limit of the Ti content is more preferably 0.5% by mass, still more preferably 1.0% by mass. The upper limit of the Ti content is more preferably 5.0% by mass, still more preferably 2.0% by mass.

V: 0.5 to 5.0% by mass
Vanadium (V) suppresses excessive oxidation of Cu and Sn. As a result, V lowers the electrode resistance of the electrode including the electrode active material layer 1. When the V content is 0.5% by mass or more, this effect can be obtained more effectively. When the V content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the V content may be 0.5 to 5.0% by mass. The lower limit of the V content is more preferably 1.0% by mass. The upper limit of the V content is more preferably 2.0% by mass.

Cr: 0.5 to 5.0% by mass
Chromium (Cr) suppresses excessive oxidation of Cu and Sn. As a result, Cr reduces the electrode resistance of the electrode including the electrode active material layer 1. When the Cr content is 0.5% by mass or more, this effect can be obtained more effectively. When the Cr content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Cr content may be 0.5 to 5.0% by mass. The lower limit of the Cr content is more preferably 1.0% by mass. The upper limit of the Cr content is more preferably 2.0% by mass.

Mn: 0.5 to 5.0% by mass
Manganese (Mn) suppresses excessive oxidation of Cu and Sn. As a result, Mn reduces the electrode resistance of the electrode including the electrode active material layer 1. When the Mn content is 0.5% by mass or more, this effect can be obtained more effectively. When the Mn content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Mn content may be 0.5 to 5.0% by mass. The lower limit of the Mn content is more preferably 1.0% by mass. The upper limit of the Mn content is more preferably 2.0% by mass.

Fe: 0.5 to 5.0% by mass
Iron (Fe) suppresses excessive oxidation of Cu and Sn. As a result, Fe lowers the electrode resistance of the electrode including the electrode active material layer 1. When the Fe content is 0.5% by mass or more, this effect can be obtained more effectively. When the Fe content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Fe content may be 0.5 to 5.0% by mass. The lower limit of the Fe content is more preferably 1.0% by mass. The upper limit of the Fe content is more preferably 2.0% by mass.

Co: 0.5 to 5.0% by mass
Cobalt (Co) suppresses excessive oxidation of Cu and Sn. As a result, Co reduces the electrode resistance of the electrode including the electrode active material layer 1. When the Co content is 0.5% by mass or more, this effect can be obtained more effectively. When the Co content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Co content may be 0.5 to 5.0% by mass. The lower limit of the Co content is more preferably 1.0% by mass. The upper limit of the Co content is more preferably 2.0% by mass.

Ni: 0.5 to 5.0% by mass
Nickel (Ni) suppresses excessive oxidation of Cu and Sn. As a result, Ni lowers the electrode resistance of the electrode including the electrode active material layer 1. When the Ni content is 0.5% by mass or more, this effect can be obtained more effectively. When the Ni content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Ni content may be 0.5 to 5.0% by mass. The lower limit of the Ni content is more preferably 1.0% by mass. The upper limit of the Ni content is more preferably 2.0% by mass.

Zn: 0.5 to 5.0% by mass
Zinc (Zn) suppresses excessive oxidation of Cu and Sn. As a result, Zn lowers the electrode resistance of the electrode including the electrode active material layer 1. When the Zn content is 0.5% by mass or more, this effect can be obtained more effectively. When the Zn content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Zn content may be 0.5 to 5.0% by mass. The lower limit of the Zn content is more preferably 1.0% by mass. The upper limit of the Zn content is more preferably 2.0% by mass.

Al: 0.5 to 5.0% by mass
Aluminum (Al) suppresses excessive oxidation of Cu and Sn. As a result, Al reduces the electrode resistance of the electrode including the electrode active material layer 1. When the Al content is 0.5% by mass or more, this effect can be obtained more effectively. When the Al content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the Al content may be 0.5 to 5.0% by mass. The lower limit of the Al content is more preferably 1.0% by mass. The upper limit of the Al content is more preferably 2.0% by mass.

B: 0.5 to 5.0% by mass
Boron (B) suppresses excessive oxidation of Cu and Sn. As a result, B reduces the electrode resistance of the electrode including the electrode active material layer 1. When the B content is 0.5% by mass or more, this effect can be obtained more effectively. When the B content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the B content may be 0.5 to 5.0% by mass. The lower limit of the B content is more preferably 1.0% by mass. The upper limit of the B content is more preferably 2.0% by mass.

C: 0.5 to 5.0% by mass
Carbon (C) reduces the coefficient of thermal expansion of the metal active material during metal ion occlusion. When the C content is 0.5% by mass or more, this effect can be obtained more effectively. When the C content is 5.0% by mass or less, this effect can be obtained more effectively. Therefore, the C content may be 0.5 to 5.0% by mass. The lower limit of the C content is more preferably 1.0% by mass. The upper limit of the C content is more preferably 2.0% by mass.

The metal active material particles 2 may further contain Group 2 elements and / or rare earth elements (REM). The Group 2 element is, for example, one or two selected from the group consisting of magnesium (Mg) and calcium (Ca). The rare earth element (REM) is, for example, one or more selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr) and neodymium (Nd).

The metal active material particles 2 include one or more selected from the group consisting of metals, metalloids, alloys, intermetallic compounds and metal oxides. Preferably, the metal active material particles 2 consist of one or more selected from the group consisting of metals, metalloids, alloys, intermetallic compounds and metal oxides and impurities. The metal active material particles 2 may further contain other substances. Other substances are, for example, carbonaceous materials.

The metal active material particles 2 having the above-mentioned chemical composition are, for example, International Publication No. 2014/034104 (Patent Document 4), International Publication No. 2015/129264 (Patent Document 5), International Publication No. 2015/129265 (Patent Document 4). Patent Document 6), International Publication No. 2015/129266 (Patent Document 7), International Publication No. 2015/129267 (Patent Document 8), International Publication No. 2015/129270 (Patent Document 9), International Publication No. 2017/200046 (Patent Document 10) and International Publication No. 2019/017349 (Patent Document 11).

[Median diameter of metal active material particles]
The median diameter (d50) of the metal active material particles 2 is not particularly limited. When the median diameter (d50) of the metal active material particles 2 is 0.5 μm or more, it is possible to prevent the specific surface area of the metal active material particles 2 from becoming too large. Therefore, the irreversible capacity can be effectively suppressed, and the discharge capacity per volume is further improved. When the median diameter (d50) of the metal active material particles 2 is 50.0 μm or less, it is easy to manufacture a flat and thin electrode. Therefore, the median diameter (d50) of the metal active material particles 2 may be 0.5 to 50.0 μm. The lower limit of the median diameter (d50) of the metal active material particles 2 is more preferably 1.0 μm, still more preferably 1.5 μm. The upper limit of the median diameter (d50) of the metal active material particles 2 is more preferably 40.0 μm, still more preferably 20.0 μm.

[Measurement method of median diameter of metal active material particles]
The median diameter (d50) of the metal active material particles 2 is determined by the following method. According to JIS Z 8825 (2013), the median diameter (d50) of the metal active material particles 2 is measured by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution meter. The dispersion medium in the measurement is water to which 0.1% by mass of a surfactant containing alkyl glycolide is added. The dispersion method is ultrasonic waves for 5 minutes. The particle size when the cumulative volume with respect to the volume of all the metal active material particles 2 becomes 50% (volume average particle size by the laser diffraction scattering method) is the average particle size of the metal active material particles 2 (median diameter (d50)). And.

[Binder]
The electrode active material layer 1 contains a binder. The binder is scattered on the surface of the metal active material particles 2 and binds the metal active material particles 2 to each other. The type of binder is not particularly limited. The binder is, for example, one selected from the group consisting of a water-insoluble resin that is insoluble in the solvent used for the non-aqueous electrolyte of the battery, a water-soluble resin, and styrene-butadiene rubber (SBR). There are two or more types. The solvent-insoluble resins used for the non-aqueous electrolyte of the battery are, for example, polyimide (PI), polyvinylidene fluoride (PVDF), polymethylmethacrylate (PMMA), and polytetrafluoroethylene. One or more selected from the group consisting of (PTFE). The water-soluble resin is, for example, one or more selected from the group consisting of carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA). Two or more of these binders may be mixed and used. That is, the binder is a group consisting of polyimide (PI), polyvinylidene fluoride (PVDF), polymethylmethacrylate (PMMA), and polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA). It may be one kind or two or more kinds selected from.

Preferably, the binder is one or more selected from the group consisting of carboxymethyl cellulose (CMC), polyimide (PI) and polyvinylidene fluoride (PVDF). Since these binders have excellent electrode adhesion, the electrode active material layer 1 is less likely to be peeled off from the current collector during electrode production.

The content of the binder in the electrode active material layer 1 is not particularly limited. However, when the content of the binder in the electrode active material layer 1 is 0.5% by mass or more, the adhesion of the electrode active material layer 1 to the current collector is stably enhanced. In addition, battery characteristics, especially cycle characteristics, are stably enhanced. On the other hand, when the content of the binder in the electrode active material layer 1 is 10% by mass or less, the volume resistivity of the electrode active material layer 1 decreases more stably. Therefore, the quick chargeability of the non-aqueous electrolyte secondary battery is more stably enhanced. Therefore, the content of the binder in the electrode active material layer 1 may be 0.5 to 10% by mass.

[Other components of the electrode active material layer]
The electrode active material layer 1 may contain other electrode active materials such as graphite and a conductive auxiliary agent such as carbon black in addition to the metal active material particles 2 and the binder described above. When the electrode active material layer 1 contains graphite in addition to the metal active material particles 2, the volume resistivity of the electrode active material layer 1 decreases. Therefore, the electrode resistance of the electrode provided with the electrode active material layer 1 decreases. In this case, the quick chargeability of the non-aqueous electrolyte secondary battery including the electrode active material layer 1 is further enhanced.

[Thickness of electrode active material layer]
The thickness of the electrode active material layer 1 is not particularly limited. However, when the thickness of the electrode active material layer 1 is 15 μm or more, the appearance defect due to the uneven coating due to the variation in the particle size of the electrode active material and the formation of secondary agglomerates can be suppressed. On the other hand, when the thickness of the electrode active material layer 1 is 75 μm or less, ^{the path through which M n +} moves in the thickness direction of the electrode active material layer 1 does not become too long. Therefore, M ^{n +} becomes easy to move, and the DC resistance of the electrode active material layer 1 increases more stably. As a result, the quick chargeability of the non-aqueous electrolyte secondary battery is more stably enhanced. Therefore, the thickness of the electrode active material layer 1 may be 15 to 75 μm. The lower limit of the thickness of the electrode active material layer 1 is more preferably 20 μm, still more preferably 30 μm. The upper limit of the thickness of the electrode active material layer 1 is more preferably 70 μm, still more preferably 55 μm.

In the present embodiment, the electrode active material layer 1 may be a positive electrode active material layer or a negative electrode active material layer.

[electrode]
FIG. 2 is a schematic view of a cross section of the electrode in this embodiment. With reference to FIG. 2, the electrode 4 of the present embodiment is an electrode 4 for a non-aqueous electrolyte secondary battery, and includes the above-mentioned electrode active material layer 1 and a current collector 5 made of a metal foil. In the present embodiment, the electrode 4 may be a positive electrode or a negative electrode. The electrode active material layer 1 is formed on the surface of the current collector 5. The current collector 5 has a thin film shape or a plate shape and supports the electrode active material layer 1. The current collector 5 is made of a metal foil. The current collector 5 is made of a well-known material such as Cu, Ni, Ni-plated copper and stainless steel. In the case of the electrode 4 for a lithium ion secondary battery, the current collector 5 is preferably made of Cu. This is because Cu is difficult to form an alloy with lithium and has excellent moldability. The thickness of the current collector 5 is, for example, 10 to 20 μm.

[Non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery of the present embodiment includes the above-mentioned electrode 4. The non-aqueous electrolyte secondary battery includes the above-mentioned electrode 4, a positive electrode or a negative electrode, a separator, and an electrolyte. The shape of the non-aqueous electrolyte secondary battery is not particularly limited, and may be cylindrical, square, coin-shaped, or sheet-shaped. The non-aqueous electrolyte secondary battery may be selected from the group consisting of lithium ion batteries, sodium ion batteries, magnesium ion batteries, aluminum ion batteries, all-solid-state batteries, and lithium-sulfur batteries.

When the electrode 4 is used as the negative electrode, the positive electrode need only have a well-known configuration. Preferably, the positive electrode contains a transition metal compound containing a metal ion as an active material. More preferably, the positive electrode contains a lithium (Li) -containing transition metal compound as an active material. Li-containing transition metal compound, for _{example, LiM 1 -xM 'x O 2} , and / or a _LiM 2 _{yM'O 4.} Here, in the formula, 0 ≦ x and y ≦ 1, and M and M ′ are barium (Ba), cobalt (Co), nickel (Ni), manganese (Mn), chromium (Cr), and titanium, respectively. 1 selected from the group consisting of Ti), vanadium (V), iron (Fe), zinc (Zn), aluminum (Al), indium (In), tin (Sn), scandium (Sc) and yttrium (Y) 1 Species or two or more species.

The non-aqueous electrolyte secondary battery of the present embodiment uses a transition metal chalcogenide, vanadium oxide and its lithium (Li) compound, niobium oxide and its lithium compound, and an organic conductive substance as a positive electrode having the above configuration. Other well-known positive electrodes such as conjugated polymers, sheprell phase compounds, activated charcoal, and activated carbon fibers may be provided.

When the electrolyte is an electrolytic solution, the electrolytic solution may be a non-aqueous electrolyte solution in which a lithium salt as a supporting electrolyte is dissolved in an organic solvent. Lithium salts include, for example, lithium perchlorate (LiClO ₄ ), lithium borofluoride (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ) _{, LiAsF 6} , LiB (C ₆ H ₅ ), LiCF ₃ SO ₃ , LiCH ₃ It _{may be SO 3} , Li (CF ₃ SO ₂ ) 2N, LiC ₄ F ₉ SO ₃ , Li (CF ₂ SO ₂ ) ₂ , LiCl, LiBr, LiI or the like. These may be used alone or in combination. The organic solvent may be carbonic acid esters such as propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate and diethyl carbonate. However, various other organic solvents such as carboxylic acid ester and ether can also be used. These organic solvents may be used alone or in combination. When the electrolyte is a solid electrolyte, the non-aqueous electrolyte secondary battery is, for example, a polymer battery, an all-solid-state battery, or the like.

The separator is installed between the positive electrode and the negative electrode. The separator acts as an insulator. The separator also contributes significantly to the retention of the electrolyte. A well-known configuration is sufficient for the separator. The separator is, for example, a polyolefin-based material such as polypropylene, polyethylene, or a mixture thereof, or a porous body such as a glass filter.

[Method for manufacturing electrode active material layer and electrode]
An example of the manufacturing method of the electrode active material layer 1 and the electrode 4 of the present embodiment will be described. The manufacturing method described below is an example for manufacturing the electrode active material layer 1 and the electrode 4 of the present embodiment. Therefore, the electrode active material layer 1 and the electrode 4 having the above-described configuration may be manufactured by a manufacturing method other than the manufacturing methods described below. However, the manufacturing method described below is a preferable example of the manufacturing method of the electrode active material layer 1 and the electrode 4 of the present embodiment.

The method for producing the electrode active material layer 1 and the electrode 4 of the present embodiment includes a metal active material particle preparation step and an electrode active material layer manufacturing step. Hereinafter, each step will be described.

[Metallic active material particle preparation process]
In the metal active material particle preparation step, the metal active material particles 2 are prepared. The metal active material particles 2 may be supplied from a third party or may be manufactured. In the case of production, the metal active material particles 2 are produced by, for example, quenching the molten metal. Examples of the method for rapidly cooling the molten metal include a roll cooling method, a gas atomizing method, a spinning method in a rotating liquid, and a melt spinning method.

Preferably, the metal active material particles 2 are produced by the following method. A molten metal having the above-mentioned components of the metal active material particles 2 is produced. The molten metal is produced by melting the raw materials by a well-known melting method such as arc melting or resistance heating melting.

The obtained molten metal is used to produce a strip of metal active material. The method for producing the strip is, for example, an ingot casting method, a strip casting method, and a melt spin method.

In consideration of production efficiency, for example, the metal strip 600 may be manufactured by using the manufacturing apparatus 100 shown in FIG. FIG. 3 is a schematic view of an example of the manufacturing apparatus 100 for the metal active material particles 2 of the present embodiment. With reference to FIG. 3, the manufacturing apparatus 100 includes a cooling roll 200, a tundish 300, and a blade member 400.

The cooling roll 200 has an outer peripheral surface, and while rotating, the molten metal 500 on the outer peripheral surface is cooled and solidified. The cooling roll 200 is rotated around the central axis of the cooling roll 200 by the drive source. The RD shown in FIG. 3 is the rotation direction of the cooling roll 200. When manufacturing the metal strip 600, the cooling roll 200 rotates in a certain direction RD. As a result, in FIG. 3, the molten metal 500 in contact with the cooling roll 200 is partially solidified on the outer peripheral surface of the cooling roll 200 and moves as the cooling roll 200 rotates. The tundish 300 can store the molten metal 500, and supplies the molten metal 500 on the outer peripheral surface of the cooling roll 200.

The blade member 400 is arranged downstream of the tundish 300 in the rotation direction of the cooling roll 200 with a gap between the blade member 400 and the outer peripheral surface of the cooling roll 200. The blade member 400 is a separate member from the tundish 300, and is arranged downstream of the rotation direction RD of the cooling roll 200, away from the tundish 300. The blade member 400 regulates the thickness of the molten metal 500 on the outer peripheral surface of the cooling roll 200 to the thickness of the gap between the outer peripheral surface of the cooling roll 200 and the blade member 400 to manufacture the metal strip 600. .. The thickness of the molten metal 500 is limited to the thickness of the gap between the blade member 400 and the cooling roll 200, and the molten metal 500 is cooled by the cooling roll 200 and the blade member 400. As a result, the molten metal 500 is rapidly cooled, and the metal strip 600 is manufactured.

The metal active material particles 2 may be produced by performing a mechanical alloying treatment (MA treatment) on the produced metal strip 600. The mechanical alloying device is, for example, a high-speed planetary mill. An example of a high-speed planetary mill is the trade name Heidi BX manufactured by Kurimoto, Ltd. Further, as long as it is a manufacturing method equivalent to MA processing, there are no particular restrictions, for example, a particle shaker mixer (T2F type manufactured by Simmal Enterprises Co., Ltd.), a small vibration rod mill (1045 type manufactured by Yoshida Seisakusho Co., Ltd.), etc. The metal active material particles 2 may be produced by using a conventionally known pulverizer.

[Electrode active material layer manufacturing process]
In the electrode active material layer manufacturing process, the electrode active material layer 1 is formed by using the metal active material particles 2 and the binder. First, the prepared metal active material particles 2 and the binder are kneaded to produce an electrode mixture slurry. If necessary, a conductive auxiliary agent, a solvent, or the like is added to the electrode mixture slurry. Next, the electrode mixture slurry is applied onto the current collector 5 and dried. Further, the thickness of the electrode active material layer 1 is adjusted by a roll press.

In order for the electrode active material layer 1 to satisfy the above formulas (1) to (3), for example, the electrode active material layer 1 is manufactured under the following conditions. A mixture of the metal active material particles 2, a binder, and a conductive additive, a solvent, etc., if necessary, is kneaded at a peripheral speed of 15 to 35 m / s for 30 to 60 seconds to prepare an electrode mixture. Produce a slurry. In the present embodiment, the peripheral speed refers to the speed at the tip of the rotary blade of the kneader used when producing the electrode mixture slurry.

When the electrode mixture slurry does not contain graphite and the peripheral speed is less than 15 m / s, the metal active material particles 2 having a large particle size preferentially settle among the metal active material particles 2, and the current collector 5 Excessive voids are locally generated between the electrode active material layer 1 and the electrode active material layer 1. In this case, the volume resistivity of the electrode active material layer 1 increases, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. When the electrode mixture slurry contains graphite and the peripheral speed is less than 15 m / s, the metal active material particles 2 and graphite are separated, and the metal active material particles 2 form secondary aggregates. The secondary aggregate of the metal active material particles 2 closes the voids in the electrode active material layer 1. In this case, the electrode air permeation rate of the electrode active material layer 1 decreases, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases. Alternatively, the density of the electrode active material layer 1 becomes inappropriate. On the other hand, when the peripheral speed exceeds 35 m / s, the temperature of the electrode mixture slurry rises during kneading and gels, so that the metal active material particles 2 form secondary aggregates. In this case, the electrode air permeation rate of the electrode active material layer 1 decreases, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases.

In the production of the electrode mixture slurry, the kneading time is 30 to 60 seconds. If the kneading time is less than 30 seconds, the metal active material particles 2 settle and form secondary aggregates. In this case, the electrode air permeation rate of the electrode active material layer 1 decreases, the volume resistivity of the electrode active material layer 1 increases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases. If the kneading time exceeds 60 seconds, the temperature of the electrode mixture slurry rises during kneading and gels, so that the metal active material particles 2 form secondary aggregates. In this case, the electrode air permeation rate of the electrode active material layer 1 decreases, and the quick chargeability of the non-aqueous electrolyte secondary battery decreases.

The electrode mixture slurry produced under the above conditions is applied onto the current collector 5 and dried. The electrode mixture slurry may be applied by a conventionally known method. For example, a desktop coating machine (control coater (7017 type manufactured by Imoto Seisakusho Co., Ltd.)), a continuous coating machine (die coater or a continuous coating machine having a shutter type blade coater (TM-MC type manufactured by Hirano Texseed Co., Ltd.)). Can be used to apply and dry the electrode mixture slurry on the current collector 5. By adjusting the gap in the coater portion, the thickness of the electrode mixture slurry before drying can be appropriately changed. When polyimide is used, vacuum drying treatment may be added at 200 ° C. after drying the electrode mixture slurry.

The dried electrode mixture slurry and the current collector 5 are roll-pressed. The roll press may be performed by a conventionally known method. For example, a roll press device (No. R080802 manufactured by Yoshida Memorial Co., Ltd.) is used for roll pressing. By adjusting the roll gap (thickness), the electrode 4 having the electrode active material layer 1 having a predetermined thickness can be manufactured.

Through the above steps, the electrode active material layer 1 of the present embodiment and the electrode 4 of the present embodiment can be manufactured.

[Manufacturing method of non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery having the above-mentioned electrode 4 is manufactured by a well-known method. A laminate in which the above-mentioned electrode 4 (negative electrode or positive electrode) and a separator are laminated is manufactured. The laminate is placed in a case to manufacture the battery.

The effect of the electrode active material layer of the present embodiment will be described more specifically by way of examples. The conditions in the following examples are one condition example adopted for confirming the feasibility and effect of the electrode active material layer of the present embodiment. Therefore, the electrode active material layer of the present embodiment is not limited to this one condition example. The present invention may adopt various conditions as long as the gist of the present invention is not deviated and the object of the present invention is achieved.

The metal active material particles having the chemical compositions shown in Table 1 were prepared as follows.

The molten metal was prepared so that the metal active material particles had the chemical composition of each alloy number shown in Table 1. The molten metal temperature was maintained at 1400 ° C. Then, the molten metal at 1400 ° C. was rapidly cooled by a strip casting method to cast a metal strip having a thickness of 75 μm. In strip casting, the manufacturing apparatus 100 shown in FIG. 3 was used. Specifically, a water-cooled copper cooling roll 200 was used. The rotation speed of the cooling roll 200 was set to 300 m / min at the peripheral speed of the roll surface. The above-mentioned molten metal 500 was supplied to the rotating cooling roll 200 via the horizontal tundish 300 (made of alumina) in an argon atmosphere. The molten metal 500 was rapidly cooled and solidified by placing the molten metal 500 on the surface of the rotating cooling roll 200 and sandwiching the molten metal 500 between the cooling roll 200 and the blade member 400. The width of the gap between the blade member 400 and the cooling roll 200 was 80 μm. The blade member 400 was made of alumina.

The obtained metal strip 600 was further subjected to a pulverization treatment to produce metal active material particles having a plurality of convex portions. A high-speed planetary mill (manufactured by Kurimoto, Ltd., trade name HIZY BX) was used for the crushing treatment. In order to control the particle size of the metal active material particles, the grinding time was adjusted as follows. The rotation speed was 500 rpm. After pulverization, a stainless steel sieve was used to remove coarse coarse powder having a particle size exceeding the following particle size.

Specifically, in test numbers 1 to 8, 11 to 15, 17 and 19, the crushing time was set to 5 hours. Further, a sieve having an opening of 45 μm was used. As a result, the median diameter d50 of the metal active material particles of test numbers 1 to 8, 11 to 15, 17 and 19 was 2.0 μm. In test numbers 9, 10 and 18, the crushing time was set to 1 hour. Further, a sieve having a mesh opening of 75 μm was used. As a result, the median diameter d50 of the metal active material particles of test numbers 9, 10 and 18 was 10.0 μm. The median diameter d50 (μm) of the metal active material particles of each test number is shown in the “Alloy particle size (μm)” column of Table 2.

The average particle size of the active material particles of each test number was measured by the following method. A laser diffraction / scattering method based on JIS Z 8825 (2013) was adopted for the measurement of the average particle size. The dispersion medium in the measurement was water to which 0.1% by mass of a surfactant containing alkyl glycolide was added. The dispersion method was ultrasonic waves for 5 minutes. The particle size (volume average particle size by laser diffraction scattering method) when the cumulative volume with respect to the volume of all metal active material particles becomes 50% was defined as the average particle size (median diameter (d50)) of the metal active material particles. ..

[Manufacturing of electrode mixture slurry]
For each test number, an electrode mixture slurry was produced under the conditions shown in Table 2.

Mixtures for aqueous slurries: test numbers 2-8, 11, 13 and 15-19
Metal active material particles, graphite particles, acetylene black (AB) as a conductive auxiliary agent, styrene butadiene rubber (SBR) (2-fold diluted solution) as a binder, and carboxymethyl cellulose (CMC) as a thickener. ) And were mixed at the mixing ratio shown below to produce a mixture.

As the graphite particles, SG-BH (average particle size 20 μm) manufactured by Ito Graphite Industry Co., Ltd. was used. HS-100 manufactured by Denka Corporation was used as acetylene black. TRD2001 manufactured by JSR Corporation was used as the styrene-butadiene rubber. As carboxymethyl cellulose, product number 2200 manufactured by Daicel FineChem Co., Ltd. was used. The mixing ratio (solid content ratio) was as follows. Active material (metal active material particles and graphite): Acetylene black: Styrene butadiene rubber: Carboxymethyl cellulose = 97: 1: 1: 1

Mixtures for organic solvent-based slurries: test numbers 1, 9, 10, 12 and 14
A mixture of metal active material particles, graphite particles, carbon black as a conductive auxiliary agent, polyimide as a binder, and polyvinylidene fluoride (PVDF) at the mixing ratio shown below was produced.

As the graphite particles, SG-BH (average particle size 20 μm) manufactured by Ito Graphite Industry Co., Ltd. was used. As carbon black, Super C65 manufactured by Imerys Graphite & Carbon was used. As the polyimide, DREAM BOND manufactured by IST Co., Ltd. was used. As the polyvinylidene fluoride, KF polymer W # 9100 manufactured by Kureha Corporation was used.

In test numbers 1, 9, 10 and 14, the mixing ratio (solid content ratio) was as follows.
Active Material (Metal Active Material Particles and Graphite): Carbon Black: Polyimide: Polyvinylidene Fluoride = 92: 1: 5: 2
In test number 12, the mixing ratio (solid content ratio) was as follows.
Active Material (Metal Active Material Particles and Graphite): Carbon Black: Polyimide: Polyvinylidene Fluoride = 99.5: 0: 0.5: 0

Using a kneader, distilled water is added to the mixture for the aqueous slurry, and N-methyl-2-pyrrolidone (NMP) is added to the mixture for the organic solvent slurry, and the mixture is kneaded to produce a negative mixture slurry. bottom. The amount of distilled water or NMP added to each mixture was adjusted so that the viscosity of the slurry was 2000 to 4000 mPa · s. As the kneader, a thin film swirl type high-speed mixer (product name: Philmix 40-40 type) manufactured by Primix Corporation was used. A planetary mixer (product name: TK Hibismix) manufactured by Primix Corporation was used only for test number 15. Table 2 shows the speed (peripheral speed) of the tip of the rotary blade of the kneader and the kneading time.

[Manufacturing of electrodes]
The produced electrode mixture slurry was applied to one side of a 21 μm-thick electrolytic copper foil using an applicator (75 μm), and dried at 100 ° C. for 20 minutes. The dried copper foil had a coating film of an electrode active material layer on the surface. Mixtures for organic solvent-based slurries of test numbers 1, 9, 10, 12 and 14 contain a polyimide binder. Therefore, in Test Nos. 1, 9, 10, 12 and 14, the electrode mixture slurry was dried and then heat-treated at 200 ° C. for 2 hours under reduced pressure drying conditions. The copper foil after the heat treatment had a coating film of an electrode active material layer on the surface. The copper foil on which the electrode active material layer was formed was punched to produce a disk-shaped copper foil having a diameter of 13 mm. The punched copper foil was pressed with a roll press so as to have the electrode densities shown in Table 2 to produce a plate-shaped electrode. The thickness of the obtained electrode active material layer was 50 μm.

The density of the electrode active material layer was calculated using the following formula.
Density of electrode active material layer = (electrode active material layer weight) (g) / (electrode plate area x electrode active material layer thickness) (cm ³ )
The weight of the electrode active material layer (g) was obtained by subtracting the weight of the metal foil from the weight of the electrode plate. The area of the electrode plate is the diameter of the punch. The thickness (cm) of the electrode active material layer was obtained by subtracting the thickness of the metal foil from the thickness of the electrode plate measured using a micrometer.

[Electrode air permeability measurement test]
The electrode air permeation rate of the electrode active material layer of each test number was measured using a Garley type densometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The copper foil was removed from the electrode by etching or peeling with tweezers to obtain an electrode active material layer (self-supporting film). The electrode air permeation rate of the obtained electrode active material layer was determined. Specifically, using the Garley type densometer, the inner cylinder weight (pressure) is 567 ± 0.5 g, the permeation area is 28.3 mm ² (diameter 6 mm), and the permeation air volume is 25 mL, in the thickness direction of the electrode active material layer. In addition, the time for air to pass through the electrode active material layer was measured. At the time of measurement, the electrode active material layer was sandwiched between two porous Ni (200 μm mesh) before the measurement. From the passing time of the obtained air, the electrode air permeability was calculated as follows. Table 2 shows the electrode air permeation rate of the electrode active material layer of each test number.
Electrode air permeation rate (μm / s) = thickness of electrode active material layer (μm) / air passage time (s)

[Volume resistivity measurement test]
The volume resistivity of the electrode active material layer of each test number was measured using an electrode resistance measuring system (manufactured by Hioki Electric Co., Ltd., product name: RM2610). In advance, the volume resistivity and thickness of the current collector and the thickness of the electrode active material layer 1 were input to the electrode resistance measurement system. The volume resistivity of the electrode active material layer 1 was calculated by bringing the measurement probe into contact with the electrode active material layer 1 and then applying a constant current from the surface of the electrode active material layer 1. The volume resistivity of the current collector was measured using a well-known four-probe method. The thickness of the current collector was measured using a micrometer. The thickness of the electrode active material layer 1 was obtained as the difference between the electrode thickness and the thickness of the current collector. The measurement conditions of the electrode resistance measuring instrument were: measurement speed: MEDIUM and range: AUTO range. Table 2 shows the volume resistivity of the electrode active material layer of each test number.

[Evaluation test]
[Discharge capacity measurement test per electrode volume]
For the electrodes of each test number, the discharge capacity per volume was measured as an index for evaluating the volumetric energy density.

[Making coin cells (for measuring discharge capacity per volume)]
A coin-shaped non-aqueous test cell was manufactured using the electrodes, counter electrodes, electrolyte and separator of each test number. The electrodes of each test number were used as negative electrodes. Li metal foil was used as the counter electrode. A non-aqueous solution was used as the electrolytic solution. The non-aqueous solution was _{prepared by dissolving LiPF 6} as a supporting electrolyte in a mixed solvent of ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 1: 3 (volume ratio) so as to have a concentration of 1 M. A polyolefin separator (φ19 mm) was used as the separator. Lithium metal foils of the negative electrode and the counter electrode were placed on both sides of the separator in a stainless steel coin cell containing an electrolytic solution. In the evaluation with the counter electrode Li, the doping of Li to the graphite negative electrode is originally treated as a discharge. However, in this embodiment, since the negative electrode material is evaluated, the “charge capacity” and the “discharge capacity”, which are not specified below, mean the capacity on the doping side and the “discharge capacity” means the capacity on the dedoping side.

[Measurement of discharge capacity per volume]
Using a charging / discharging device manufactured by Electrofield Co., Ltd., the discharge capacity per volume was determined as follows. The temperature at the time of measurement was measured at room temperature (23 ° C.). The coin-type non-aqueous test cell was constantly charged with a current value of 0.1 C until the potential difference was 0.005 V with respect to the counter electrode. Then, while maintaining 0.005 V, charging was continued with respect to the counter electrode at a constant voltage until the voltage reached 0.05 C, and the charge capacity was measured. Next, with a current value of 0.1 C, discharge was performed until the potential difference became 1.5 V, and the discharge capacity was measured. The discharge capacity [mAh / cm ³ ] per volume was calculated as (initial charge capacity [mAh / g]) × (electrode density [g / cm ^3]).

[DC resistance measurement test of electrodes]
For the electrodes of each test number, the DC resistance was measured as an index for evaluating the quick chargeability. In this measurement test, the electrodes of each test number were used as the negative electrode.

[Manufacturing of positive electrode]
As the positive electrode active material, Co—Ni—Mn lithium composite oxide-based NMC111 (manufactured by Nippon Chemical Industrial Co., Ltd., composition: LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ) was used. The positive electrode was manufactured as follows. A mixture was prepared by mixing 3 parts by mass of KS6 powder (manufactured by Imerys Graphite & Carbon) and 1 part by mass of Super C65 powder (manufactured by Imeryis Graphite & Carbon) with 92 parts by mass of the positive electrode active material (powder). Further, 4 parts by mass of the PVDF dispersion was added to the mixture and then stirred to prepare a positive electrode mixture slurry.

The positive electrode mixture slurry was applied on one side of a 20 μm thick aluminum foil using an applicator (gap thickness 150 μm) and dried to form a coating film. The amount of the positive electrode active material applied on the aluminum foil was 10 mg / cm ² . This coating film was punched out using a punch having a diameter of 13 mm to obtain pellets. A positive electrode was produced by pressurizing the pellets using a press molding machine. The electrode density was adjusted to ^{2.8 g / cm 3.} The gap thickness of the applicator may be varied for the purpose of controlling the coating amount on the aluminum foil.

[Preparation of laminated cell]
As the negative electrode, the same negative electrode used in the initial charge / discharge efficiency evaluation was used. The electrodes were cut out so that the negative electrode had a size of 2.5 cm × 2.5 cm and the positive electrode had a size of 2.3 cm × 2.3 cm, and two separators (cell guard 2100) were sandwiched between the negative electrode and the positive electrode. An aluminum wire (0.25 mmφ) was installed between the two separators.

[Laminate cell pretreatment (pretreatment before DC resistance calculation)]
As a pretreatment for calculating the reaction resistance, a charge / discharge test was carried out on the laminated cell at room temperature (23 ° C.) so that the charge rate (System Of Charge: SOC) was 50%. As the charging / discharging device, a charging / discharging device manufactured by Electrofield Co., Ltd. was used. The specific processing method is described below. After constant current charging at 0.1 C to 4.2 V, constant potential charging was performed at 4.2 V until the current value reached 0.05 C. Subsequently, a constant current was discharged to 3.0 V at 0.1 C. The above charging / discharging was repeated for 2 cycles. After that, it was charged with a constant current so that the SOC became 50%.

[Create reference pole]
For the pretreated laminated cell, the positive electrode and the reference electrode were connected by terminals, and Li was alloyed with the Al wire. Specifically, it was charged with a constant current charge of 0.03 mA so that the amount of electricity was 0.3 mAh to obtain a LiAl alloy wire.

[Measurement of DC resistance]
The DC resistance was calculated as a resistance component corresponding to the resistance of the negative electrode generated by pulse charging / discharging. The product name modulab manufactured by solartron analog was used for the pulse charge / discharge measurement. The structure of the electrochemical cell uses a 3-electrode laminated cell, the negative electrode is the electrode of each test number, and the counter electrode is the Co-Ni-Mn lithium composite oxide-based NMC111 (manufactured by Nippon Kagaku Kogyo Co., Ltd., composition: LiNi _{1 /). 3} Co _1/3 Mn _1/3 O ₂ ), measured using a LiAl wire for the reference electrode. A non-aqueous solution was used as the electrolytic solution. The non-aqueous solution was _{prepared by dissolving LiPF 6} as a supporting electrolyte in a mixed solvent of ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 1: 3 (volume ratio) so as to have a concentration of 1 M. As for the reaction resistance, the resistance of only the negative electrode was calculated by connecting the negative electrode and the reference electrode with a terminal and measuring the DC resistance. The measurement was carried out in a constant temperature bath, and the reaction temperature was set to −10 ° C. The laminated cell for which the pretreatment and the preparation of the reference electrode were completed was held in a constant temperature bath at a set temperature of −10 ° C. for 3 hours or more. Then, the DC resistance was measured using the product name modulab manufactured by solartron analog. At this time, the DC resistance between the negative electrode and the reference electrode was measured with the negative electrode as the working electrode. The measurement conditions were calculated by setting the current value to 10C, calculating the voltage ΔV of the difference between 0.1 seconds and 20 seconds later, and dividing by the added current value (10C). Table 2 shows the DC resistance of the electrodes of each test number.

[Evaluation results]
With reference to Tables 1 and 2, the electrode active material layers of test numbers 1 to 10 contain 30.0 to 80.0% by mass of Cu and are metal active material particles that occlude and / or release metal ions. Was contained in an amount of more than 5.0% by mass to 99.0% by mass and a binder. The electrode active material layers of test numbers 1 to 10 further satisfied the above formulas (1) to (3). As a result, the electrodes provided with the electrode active material layers of test numbers 1 to 10 had a discharge capacity of 650 mAh / cm ³ or more per volume. The electrodes provided with the electrode active material layers of test numbers 1 to 10 further had a DC resistance of 20 Ω or less. That is, the non-aqueous electrolyte secondary battery provided with the electrodes provided with the electrode active material layers of test numbers 1 to 10 was able to achieve both high capacity and quick chargeability.

The electrode active material layers of Test Nos. 2 to 4 and 8 contained graphite in addition to the metal active material particles. Therefore, the electrodes having the electrode active material layers of test numbers 2 to 4 and 8 are compared with the electrodes having the electrode active material layers of test numbers 1 and 9 using metal active material particles having the same chemical composition (alloy number 1). Then, the DC resistance was low.

On the other hand, the electrode active material layer of Test No. 11 contained too low a metal active material particle. Therefore, the discharge capacity per volume of the electrode provided with the electrode active material layer of Test No. 11 was 550 mAh / cm ^3, which was too low.

The electrode active material layer of Test No. 12 contained too high a metal active material particle. Therefore, the electrode adhesion of the metal active material particles is lowered, and an appropriate electrode active material layer cannot be produced. At test number 12, various tests could not be performed.

In the electrode active material layer of Test No. 13, the Cu content of the metal active material particles was as high as 85.0% by mass. Therefore, the discharge capacity per volume of the electrode provided with the electrode active material layer of Test No. 13 was 648 mAh / cm ^3, which was too low.

The electrode active material layer of test number 14 had a volume resistivity R of 120.000 Ω · cm, which was too high. Therefore, the DC resistance of the electrode provided with the electrode active material layer of Test No. 14 was as high as 24Ω.

The electrode active material layer of Test No. 15 had an electrode air permeability T of 0.05 μm / s, which was too low. Therefore, the DC resistance of the electrode provided with the electrode active material layer of Test No. 15 was as high as 26Ω.

The electrode active material layer of test number 16 did not contain metal active material particles. Therefore, the discharge capacity per volume of the electrode provided with the electrode active material layer of Test No. 14 was 540 mAh / cm ^3, which was too low.

The electrode active material layer of test number 17 had an electrode air permeability T of 0.10 μm / s, which was too low. Therefore, the DC resistance of the electrode provided with the electrode active material layer of Test No. 17 was as high as 25Ω.

In the electrode active material layer of test number 18, the electrode density d was ^{too low at 0.95 g / cm 3} , so the electrode air permeability T was too high at 6.50 μm / s, and the volume resistivity R was 156.000 Ω.・ It was too high at cm. Therefore, the DC resistance of the electrode provided with the electrode active material layer of Test No. 18 was as high as 28Ω.

The electrode active material layer of Test No. 19 had an electrode air permeability T of 0.85 μm / s, which was too low. Therefore, the DC resistance of the electrode provided with the electrode active material layer of Test No. 19 was as high as 22Ω.

The embodiments of the present disclosure have been described above. However, the embodiments described above are merely examples for carrying out the present disclosure. Therefore, the present disclosure is not limited to the above-described embodiment, and the above-described embodiment can be appropriately modified and implemented within a range that does not deviate from the gist thereof.

1 Electrode active material layer 2 Metal active material particles

Claims (7)

An electrode active material layer for non-aqueous electrolyte secondary batteries.
The amount of metal active material particles containing 30.0 to 80.0% by mass of Cu and occluding and / or releasing metal ions is more than 5.0% by mass to 99.0% by mass.
Contains a binder and
An electrode active material layer satisfying the formulas (1) to (3).
1.00 ≤ T ≤ 6.00 (1)
1.00 ≤ d ≤ 3.50 (2)
0.010 ≤ R ≤ 100.000 (3)
Here, the electrode air permeability (μm / s) is substituted for T in the equation (1), the electrode density (g / cm ³ ) is substituted for d in the equation (2), and R in the equation (3). The volume resistivity (Ω · cm) is substituted for. The electrode active material layer according to claim 1.
The metal active material particles further contain Sn, an electrode active material layer. The electrode active material layer according to claim 2.
The metal active material particles are further
An electrode active material layer containing one or two selected from the group consisting of Si and Ti. The electrode active material layer according to claim 2 or 3.
The metal active material particles are further
An electrode active material layer containing one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B and C. The electrode active material layer according to any one of claims 1 to 4, further comprising.
An electrode active material layer containing graphite. Electrodes for non-aqueous electrolyte secondary batteries
The electrode active material layer according to any one of claims 1 to 5,
An electrode with a current collector made of metal leaf. A non-aqueous electrolyte secondary battery comprising the electrode according to claim 6.

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