Electrode active material layer for non-aqueous electrolyte secondary battery, electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery

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

Technical Field

[0001] 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.

Background Art

[0002] In recent years, the spread of small electronic devices such as home video cameras, notebook personal computers, and smartphones has advanced, and increasing the battery capacity has become a technical issue.

[0003] In order for hybrid vehicles, plug-in hybrid vehicles, and electric vehicles to further spread, miniaturizing the battery has also become a technical issue.

[0004] Currently, graphite-based electrode active material materials are used for the negative electrodes of non-aqueous electrolyte secondary batteries typified by lithium ion batteries. However, graphite-based electrode active material materials have the above-described technical issues.

[0005] Therefore, alloy-based electrode active material materials having a higher capacity than graphite-based electrode active material materials have attracted attention. As alloy-based electrode active material materials, silicon (Si)-based electrode active material materials and tin (Sn)-based electrode active material materials are known. Various studies have been made on the above alloy-based electrode active material materials for the practical application of a lithium ion battery having a higher capacity and being more compact.

[0006] 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). Patent Document 1 describes that an alloy-based negative electrode active material capable of occluding and releasing lithium, which has 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, and M represents at least one element selected from Be, B, Al, P, Zn, Ga, Ge, In, Sn, Sb, Y, Zr, Nb, Mo, and W.)

[0007] On the other hand, for non-aqueous electrolyte secondary batteries, in addition to the above-mentioned high capacity and compactness, rapid chargeability is also required. For example, JP-A-2017-183236 (Patent Document 2) and JP-A-2018-147672 (Patent Document 3) propose negative electrodes with improved rapid chargeability.

[0008] 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. The negative electrode active material layer has a porosity of 50% or less and an air permeability measured by a Gurley densitometer of 0.80 to 1.40 μm / sec. The negative electrode volume energy density [E (mAh / cm 3 )] of the negative electrode for the lithium-ion secondary battery satisfies the following Mathematical Formula 1 in relation to the air permeability. According to this, it is described in Patent Document 2 that a lithium-ion secondary battery having a high energy density, excellent safety, and input / output characteristics can be obtained. [Mathematical Formula 1] 0.95 < E / (-145X + 545) (However, X represents the air permeability (μm / sec) of the negative electrode active material layer measured by a Gurley densitometer.)

[0009] 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. The negative electrode active material layer contains a carbon material, and in a Log differential pore volume distribution graph obtained by mercury intrusion porosimetry, 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. According to this, it is described in Patent Document 3 that a negative electrode with good rapid charge characteristics can be obtained.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Summary of the Invention

Problems to be Solved by the Invention

[0011] However, even with the above-described technology, it has been difficult to obtain a non-aqueous electrolyte secondary battery that achieves both high capacity and rapid chargeability in some cases.

[0012] An object of the present disclosure is to provide 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, from which a non-aqueous electrolyte secondary battery that achieves both high capacity and rapid chargeability can be obtained.

Means for Solving the Problems

[0013] The electrode active material layer of the present disclosure is an electrode active material layer for a non-aqueous electrolyte secondary battery, contains 30.0 to 80.0% by mass of Cu, and 5.0% by mass or more to 99.0% by mass of metal active material particles that occlude and / or release metal ions, and a binder, and satisfies 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 formula (1), the electrode density (g / cm 3 ) is substituted for d in formula (2), and the volume resistivity (Ω·cm) is substituted for R in formula (3).

[0014] The electrode of the present disclosure is an electrode for a non-aqueous electrolyte secondary battery, the electrode active material layer of the present disclosure, and a current collector made of a metal foil.

[0015] The non-aqueous electrolyte secondary battery of the present disclosure includes the electrode of the present disclosure.

Advantages of the Invention

[0016] A non-aqueous electrolyte secondary battery including the electrode active material layer of the present disclosure can achieve both high capacity and rapid chargeability.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0018] 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 denoted by the same reference numerals, and the description thereof will not be repeated.

[0019] The inventors of the present invention conducted investigations and studies on an electrode active material layer capable of achieving both high capacity and rapid chargeability of a non-aqueous electrolyte secondary battery. As a result, the inventors obtained the following findings.

[0020] As electrode active materials, carbonaceous active materials and alloy-based active materials are known. In order to increase the capacity of a non-aqueous electrolyte secondary battery, it is effective to increase the discharge capacity per unit volume of the electrode. In order to increase the discharge capacity per unit volume of the electrode, it is effective to use an electrode active material having a high discharge capacity per unit volume in the electrode active material layer. The alloy-based active material has a higher discharge capacity per unit volume than the carbonaceous active material. Therefore, it is effective to use the alloy-based active material in the electrode active material layer.

[0021] Metal active material particles containing 30.0 to 80.0% by mass of Cu are alloy-based active materials. Metal active material particles containing 30.0 to 80.0% by mass of Cu have a particularly high discharge capacity per unit 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.

[0022] On the other hand, the inventors of the present invention conducted investigations and studies on a method for enhancing the rapid chargeability of a non-aqueous electrolyte secondary battery using the above metal active material particles, and obtained the following findings.

[0023] Equations (4) and (5) are chemical reaction equations showing the outline of the charge and discharge reactions of a non-aqueous electrolyte secondary battery. A + xM n+ + xne - → M x A(4) M x A → A + xM n+ + xne - (5) In Equations (4) and (5), "A" represents the electrode active material, and "M" n+" represents an n-valent metal ion, and "e - " represents an electron. n is a natural number. A metal ion (M n+ ) at a predetermined ratio (x) undergoes a chemical reaction with xn electrons (e - ) that are chemically equivalent, and is stored in the electrode active material (A) as (M x A). In the case of a lithium-ion battery, M n+ in formulas (4) and (5) is Li + .

[0024] The inventors considered that the migration speeds of M n+ and e - in the electrode active material layer affect the rapid chargeability of the non-aqueous electrolyte secondary battery. Therefore, the inventors examined a method for increasing the migration speeds of M n+ and e - . As a result, the following findings were obtained.

[0025] M n+ in formulas (4) and (5) is a metal ion contained in the electrolyte of the non-aqueous electrolyte secondary battery. To increase the migration speed of M n+ in the electrode active material layer, it is effective to provide appropriately connected voids in the electrode active material layer. If appropriately connected voids exist in the electrode active material layer, the electrolyte fills the voids, and M n+ can move rapidly through the connected electrolyte.

[0026] On the other hand, to increase the migration 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 appropriately connected contact points. If the metal active material particles have appropriately connected contact points, e - can move rapidly through the contact points between the metal active material particles.

[0027] However, the migration speed of M n+ in formulas (4) and (5) is inversely proportional to the migration speed of e - . That is, when the migration speed of M n+ is large, the migration speed of e - is small. Conversely, when M n+When the moving speed of e is small, - the moving speed of - is large. This is for the following reason. When there are many voids in the electrode active material layer and the voids are connected to each other, much of the electrolyte is connected within the electrode active material layer. Therefore, n+ the moving speed of n+ becomes large. When there are many voids in the electrode active material layer and they are connected, the contact points between the electrode active materials, that is, the conductive points, decrease. As a result, - the moving speed of e becomes small. On the contrary, if the electrode active material exists at a high density, the connected voids in the electrode active material layer decrease, so the electrolyte exists separately in the electrode active material layer. Therefore, n+ the moving speed of n+ becomes small. If the electrode active material exists at a high density, the contact points between the electrode active materials, that is, the conductive points, increase. Therefore, - the moving speed of e becomes large.

[0028] From the above, the consideration of increasing the moving speed of n+ and the consideration of increasing the moving speed of e n+ are contradictory considerations, and it is difficult to achieve both a large moving speed of n+ and a large moving speed of e - . However, the inventors of the present invention used the above metal active material particles as the electrode active material, and further increased the moving speed of n+ and n+ further increased the moving speed of e - . Then, it was considered that the high capacity and rapid chargeability of the non-aqueous electrolyte secondary battery could be achieved simultaneously. Therefore, the inventors of the present invention conducted various studies on an electrode active material layer having a structure capable of increasing the moving speed of n+ and further increasing the moving speed of e n+ , that is, an electrode active material layer having a structure with moderately connected voids and moderately sized contact points between the metal active material particles. However, the internal structure of the electrode active material layer is too minute, and it was difficult to directly identify the internal structure of the electrode active material layer. - Therefore, the inventors of the present invention conducted various studies on indicators indicating the connected voids in the electrode active material layer and the contact points between the metal active material particles. As a result, the following findings were obtained. n+ -

[0029] Therefore, the inventors of the present invention conducted various studies on indicators indicating the connected voids in the electrode active material layer and the contact points between the metal active material particles. As a result, the following findings were obtained.

[0030] The connected voids in the electrode active material layer can be expressed as the air permeability rate of the electrode active material layer. In the present disclosure, the air permeability rate (μm / s) refers to the moving distance (μm) of air per second when air is permeated in the thickness direction of the electrode active material layer with an area of 28.3 mm 2 (6 mmφ) of the electrode active material layer. That is, the air permeability rate indicates the connection of voids in the thickness direction of the electrode active material layer. When the air permeability rate 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 an electrolyte, and M n+ can move through the connected electrolyte. Thereby, the moving speed of M n+ in formulas (4) and (5) increases. That is, the moving speed of M n+ in the electrode active material layer can be expressed as the air permeability rate of the electrode active material layer.

[0031] More specifically, if the air permeability rate of the electrode active material layer satisfies formula (1), the moving speed of M n+ in the electrode active material layer is high, and the movement of e - is not inhibited. 1.00 ≦ T ≦ 6.00 (1) Here, the air permeability rate (μm / s) is substituted into T in formula (1).

[0032] 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 electrically connected so that e - can move smoothly through the electrode active material layer. In this case, the moving speed of e - in formulas (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.

[0033] More specifically, if the volume resistivity of the electrode active material layer satisfies formula (3), the moving speed of e - in the electrode active material layer is high, and Mn+ does not inhibit the movement of. 0.010 ≦ R ≦ 100.000 (3) Here, the volume resistivity (Ω·cm) is substituted for R in formula (3).

[0034] The volume resistivity is a numerical value inherent to the substance. However, the volume resistivity of the electrode active material alone does not necessarily match the volume resistivity of the electrode active material layer formed using the electrode active material. The electrode active material layer is a layer formed by binding particulate electrode active materials with a binder. There may be a binder 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. When a binder or an oxide film exists at the boundary between the electrode active material particles, the movement speed of e - may decrease. In this case, the volume resistivity of the electrode active material layer becomes higher than the volume resistivity of the electrode active material alone.

[0035] Furthermore, when using the above metal active material particles, it is necessary that the electrode density of the electrode active material layer satisfies formula (2). If the electrode active material layer satisfies 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 formula (2).

[0036] Summarizing the above, the inventors of the present invention have found that, when using metal active material particles with a high discharge capacity per unit volume, if the electrode air permeability, density, and volume resistivity of the electrode active material layer are within an appropriate range, the discharge capacity per unit volume of the electrode active material layer increases, and further, M n+ and e -Since the moving speeds of both increase, it was considered that the high capacity and rapid chargeability of the non-aqueous electrolyte secondary battery could be further enhanced. That is, the electrode active material layer for the non-aqueous electrolyte secondary battery of the present disclosure was completed based on findings completely different from previous knowledge. Specifically, when metal active material particles containing 30.0 to 80.0% by mass of Cu are used as the active material, if the electrode active material layer satisfies formulas (1) to (3), both the high capacity and excellent rapid chargeability of the non-aqueous electrolyte secondary battery can be achieved. 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 formula (1), the electrode density (g / cm 3 ) is substituted for d in formula (2), and the volume resistivity (Ω·cm) is substituted for R in formula (3).

[0037] Based on the above findings, the configuration of the electrode active material layer of the present embodiment is as follows.

[0038] The electrode active material layer of [1] is an electrode active material layer for a non-aqueous electrolyte secondary battery, containing 30.0 to 80.0% by mass of Cu and 5.0% by mass or more to 99.0% by mass of metal active material particles that occlude and / or release metal ions, and a binder, satisfying 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 formula (1), the electrode density (g / cm 3 ) is substituted for d in formula (2), and the volume resistivity (Ω·cm) is substituted for R in formula (3).

[0039] The electrode active material layer of [2] is the electrode active material layer described in [1], wherein the metal active material particles further contain Sn.

[0040] The electrode active material layer of [3] is the electrode active material layer described in [2], wherein the metal active material particles further contain one or two selected from the group consisting of Si and Ti.

[0041] The electrode active material layer of [4] is the electrode active material layer described in [2] or [3], wherein the metal active material particles further contain one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B, and C.

[0042] The electrode active material layer of [5] is the electrode active material layer described in any one of [1] to [4], and further contains graphite.

[0043] The electrode of the present embodiment is an electrode for a non-aqueous electrolyte secondary battery, and includes the electrode active material layer described in any one of [1] to [5], and a current collector made of a metal foil.

[0044] The non-aqueous electrolyte secondary battery of the present embodiment includes the electrode of the present embodiment.

[0045] Hereinafter, the electrode active material layer, the electrode, and the non-aqueous electrolyte secondary battery of the present embodiment will be described in detail. "%" regarding an element means "mass%" unless otherwise specified.

[0046] [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. Referring 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.

[0047] The electrode active material layer 1 contains metal active material particles 2 in an amount exceeding 5.0% by mass and up 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 many. 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 permeability rate T (μm / s) of the electrode active material layer 1 becomes less than 1.00. For this reason, the rapid chargeability of the non-aqueous electrolyte secondary battery deteriorates. 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 deteriorates, and the cycle characteristics of the non-aqueous electrolyte secondary battery deteriorate. If the content of the metal active material particles 2 exceeds 99.0% by mass, furthermore, the electrode adhesion of the metal active material particles 2 deteriorates and the electrode may not be manufacturable. Therefore, the content of the metal active material particles 2 is more than 5.0% by mass and up 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, still more preferably 93.0% by mass.

[0048] The electrode active material layer 1 satisfies 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 rate (μm / s) is substituted for T in formula (1), the electrode density (g / cm 3 ) is substituted for d in formula (2), and the volume resistivity (Ω·cm) is substituted for R in formula (3).

[0049] [Electrode air permeability rate of the electrode active material layer] The electrode active material layer 1 satisfies formula (1). 1.00 ≦ T ≦ 6.00 (1) Here, the electrode air permeability rate (μm / s) is substituted for T in formula (1).

[0050] If the air permeability rate (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 M in the battery reactions of formulas (4) and (5) n+ is blocked, and the movement speed of M n+ decreases. Therefore, the DC resistance of the electrode active material layer 1 increases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases. On the other hand, if the air permeability rate (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 many. In this case, since the contact points between the electrode active materials are few, the electron conduction path in the electrode active material layer 1 decreases. Therefore, the DC resistance of the electrode active material layer 1 increases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases. Therefore, the air permeability rate (μm / s) is 1.00 or more and 6.00 or less.

[0051] The lower limit of the air permeability rate (μm / s) is preferably 1.20 μm / s, more preferably 1.50 μm / s. The upper limit of the air permeability rate (μm / s) is preferably 5.00 μm / s, more preferably 4.00 μm / s.

[0052] [Measurement method of air permeability rate] The air permeability rate 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. Also, when peeling by 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. For the obtained electrode active material layer 1, using a Gurley densitometer, the time for air to pass through the electrode active material layer 1 is measured. The area of the electrode active material layer 1 is 28.3 mm 2 (6 mm φ), the amount of air is 25 mL, and the air passage direction is the thickness direction of the electrode active material layer 1. Substitute the measured air passage time (s) and the thickness (μm) of the electrode active material layer 1 into the following formula to obtain the air permeability rate T (μm / s). Air permeability rate T (μm / s) = Thickness of electrode active material layer 1 (μm) / Air passage time (s)

[0053] [Electrode density of the electrode active material layer] The electrode active material layer 1 satisfies formula (2). 1.00 ≦ d ≦ 3.50 (2) Here, the electrode density (g / cm 3 ) is substituted into d in formula (2).

[0054] If the electrode density (g / cm 3 ) of the electrode active material layer 1 is less than 1.00, excessive voids will occur in the electrode active material layer 1. In this case, the electrode air permeability and 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. If 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 will be blocked. In this case, the movement path of M in the battery reaction of formula (4) n+ is blocked, and the movement speed of M n+ decreases. Therefore, the DC resistance of the electrode active material layer 1 increases, and the rapid 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.

[0055] The lower limit of the electrode density (g / cm 3 ) is preferably 1.50 (g / cm 3 ), and more preferably 2.00 (g / cm 3 ). The upper limit of the electrode density (g / cm 3 ) is preferably 3.20 (g / cm 3 ), and more preferably 3.00 (g / cm 3 ).

[0056] [Volume resistivity of the electrode active material layer] The electrode active material layer 1 satisfies formula (3). 0.010 ≦ R ≦ 100.000 (3) Here, the volume resistivity (Ω·cm) is substituted into R in formula (3).

[0057] If 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 M in the battery reaction of formula (4) n+ is blocked, and the movement speed of M n+ decreases. Therefore, the DC resistance of the electrode active material layer 1 increases, and the rapid 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 increases, and the rapid 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.

[0058] 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). 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).

[0059] [Measurement method of volume resistivity] The volume resistivity of the electrode active material layer 1 is measured using an electrode resistance measurement system (manufactured by Hioki E.E. Corporation, product name: RM2610). In advance, the volume resistivity and thickness of the current collector, and the thickness of the electrode active material layer 1 are input into the electrode resistance measurement system. The measurement probe is brought into contact with the electrode active material layer 1, and then a constant current is applied from the surface of the electrode active material layer 1 to calculate the volume resistivity of the electrode active material layer 1. The volume resistivity of the current collector is measured using the 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 the 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, range: AUTO RANGE.

[0060] An electrode active material layer 1 containing metal active material particles 2 containing 30.0 to 80.0% by mass of Cu and satisfying formulas (1) to (3) can be obtained, and only by this can a non-aqueous electrolyte secondary battery in which high capacity and rapid chargeability are compatible be obtained.

[0061] [Metal 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 ions are, for example, one selected from the group consisting of lithium ions, magnesium ions, aluminum ions, and sodium ions. The metal ions may be lithium ions.

[0062] [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 unit 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 increases. 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.

[0063] In the case of the metal active material particles 2, the element(s) contained in addition to Cu may be one or more selected from the group consisting of a metal element, a metalloid element, oxygen, and carbon. That is, the chemical composition of the metal active material particles 2 may be a chemical composition consisting of 30.0 to 80.0 mass% of Cu, one or more selected from the group consisting of a metal element, a metalloid element, oxygen, and carbon, and impurities.

[0064] The metal element is, for example, one or more selected from the group consisting of tin (Sn), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), and 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 may be a chemical composition consisting of 30.0 to 80.0 mass% of Cu, and one or more selected from the group consisting of Sn, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Al, Si, B, O, and C, and impurities.

[0065] The chemical composition of the metal active material particles 2 may be a chemical composition consisting of 30.0 to 80.0 mass% of Cu, Sn, and impurities. The chemical composition of the metal active material particles 2 may be a chemical composition consisting of 30.0 to 80.0 mass% of Cu, Sn, and one or two selected from the group consisting of Si and Ti, and impurities. The chemical composition of the metal active material particles 2 may be a chemical composition consisting of 30.0 to 80.0 mass% of Cu, Sn, and one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B, 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 mass% of Cu, Sn, and one or two selected from the group consisting of Si and Ti, and one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B, and C, and impurities. The content of each element may be as follows.

[0066] Sn: 10.0 to 65.0 mass% Tin (Sn) increases the discharge capacity per unit volume of the electrode active material layer 1. If the Sn content is 10.0 mass% or more, this effect can be obtained more effectively. If the Sn content is 65.0 mass% or less, this effect can be obtained more effectively. Therefore, the Sn content may be 10.0 to 65.0 mass%. The lower limit of the Sn content is more preferably 15.0 mass%, and even more preferably 30.0 mass%. The upper limit of the Sn content is more preferably 60.0 mass%, and even more preferably 55.0 mass%.

[0067] Si: 1.0 to 20.0 mass% Silicon (Si) increases the discharge capacity per unit volume of the electrode active material layer 1. If the Si content is 1.0 mass% or more, this effect can be obtained more effectively. If the Si content is 20.0 mass% or less, this effect can be obtained more effectively. Therefore, the Si content may be 1.0 to 20.0 mass%. The lower limit of the Si content is more preferably 2.0 mass%, and even more preferably 3.0 mass%. The upper limit of the Si content is more preferably 15.0 mass%, and even more preferably 10.0 mass%.

[0068] Ti: 0.1 to 10.0 mass% Titanium (Ti) suppresses the excessive oxidation of Cu and Sn. Thereby, Ti reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Ti content is 0.1 mass% or more, this effect can be obtained more effectively. If the Ti content is 10.0 mass% or less, this effect can be obtained more effectively. Therefore, the Ti content may be 0.1 to 10.0 mass%. The lower limit of the Ti content is more preferably 0.5 mass%, and even more preferably 1.0 mass%. The upper limit of the Ti content is more preferably 5.0 mass%, and even more preferably 2.0 mass%.

[0069] V: 0.5 to 5.0 mass% Vanadium (V) suppresses the excessive oxidation of Cu and Sn. Thereby, V reduces the electrode resistance of the electrode provided with the electrode active material layer 1. If the V content is 0.5 mass% or more, this effect can be obtained more effectively. If the V content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the V content may be 0.5 to 5.0 mass%. The lower limit of the V content is more preferably 1.0 mass%. The upper limit of the V content is more preferably 2.0 mass%.

[0070] Cr: 0.5 to 5.0 mass% Chromium (Cr) suppresses the excessive oxidation of Cu and Sn. Thereby, Cr reduces the electrode resistance of the electrode provided with the electrode active material layer 1. If the Cr content is 0.5 mass% or more, this effect can be obtained more effectively. If the Cr content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Cr content may be 0.5 to 5.0 mass%. The lower limit of the Cr content is more preferably 1.0 mass%. The upper limit of the Cr content is more preferably 2.0 mass%.

[0071] Mn: 0.5 to 5.0 mass% Manganese (Mn) suppresses the excessive oxidation of Cu and Sn. Thereby, Mn reduces the electrode resistance of the electrode provided with the electrode active material layer 1. If the Mn content is 0.5 mass% or more, this effect can be obtained more effectively. If the Mn content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Mn content may be 0.5 to 5.0 mass%. The lower limit of the Mn content is more preferably 1.0 mass%. The upper limit of the Mn content is more preferably 2.0 mass%.

[0072] Fe: 0.5 to 5.0 mass% Iron (Fe) suppresses excessive oxidation of Cu and Sn. Thereby, Fe reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Fe content is 0.5 mass% or more, this effect can be obtained more effectively. If the Fe content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Fe content may be 0.5 to 5.0 mass%. The lower limit of the Fe content is more preferably 1.0 mass%. The upper limit of the Fe content is more preferably 2.0 mass%.

[0073] Co: 0.5 to 5.0 mass% Cobalt (Co) suppresses excessive oxidation of Cu and Sn. Thereby, Co reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Co content is 0.5 mass% or more, this effect can be obtained more effectively. If the Co content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Co content may be 0.5 to 5.0 mass%. The lower limit of the Co content is more preferably 1.0 mass%. The upper limit of the Co content is more preferably 2.0 mass%.

[0074] Ni: 0.5 to 5.0 mass% Nickel (Ni) suppresses excessive oxidation of Cu and Sn. Thereby, Ni reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Ni content is 0.5 mass% or more, this effect can be obtained more effectively. If the Ni content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Ni content may be 0.5 to 5.0 mass%. The lower limit of the Ni content is more preferably 1.0 mass%. The upper limit of the Ni content is more preferably 2.0 mass%.

[0075] Zn: 0.5 to 5.0 mass% Zinc (Zn) suppresses excessive oxidation of Cu and Sn. Thereby, Zn reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Zn content is 0.5 mass% or more, this effect can be obtained more effectively. If the Zn content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Zn content may be 0.5 to 5.0 mass%. The lower limit of the Zn content is more preferably 1.0 mass%. The upper limit of the Zn content is more preferably 2.0 mass%.

[0076] Al: 0.5 - 5.0 mass% Aluminum (Al) suppresses excessive oxidation of Cu and Sn. Thereby, Al reduces the electrode resistance of the electrode including the electrode active material layer 1. If the Al content is 0.5 mass% or more, this effect can be obtained more effectively. If the Al content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the Al content may be 0.5 to 5.0 mass%. The lower limit of the Al content is more preferably 1.0 mass%. The upper limit of the Al content is more preferably 2.0 mass%.

[0077] B: 0.5 - 5.0 mass% Boron (B) suppresses excessive oxidation of Cu and Sn. Thereby, B reduces the electrode resistance of the electrode including the electrode active material layer 1. If the B content is 0.5 mass% or more, this effect can be obtained more effectively. If the B content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the B content may be 0.5 to 5.0 mass%. The lower limit of the B content is more preferably 1.0 mass%. The upper limit of the B content is more preferably 2.0 mass%.

[0078] C: 0.5 - 5.0 mass% Carbon (C) reduces the volume expansion rate during the occlusion of metal ions in the metal active material. If the C content is 0.5 mass% or more, this effect can be obtained more effectively. If the C content is 5.0 mass% or less, this effect can be obtained more effectively. Therefore, the C content may be 0.5 to 5.0 mass%. The lower limit of the C content is more preferably 1.0 mass%. The upper limit of the C content is more preferably 2.0 mass%.

[0079] The metal active material particles 2 may further contain a Group 2 element and / or a rare earth element (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).

[0080] The metal active material particles 2 include one or more selected from the group consisting of a metal, a metalloid, an alloy, an intermetallic compound, and a metal oxide. Preferably, the metal active material particles 2 consist of one or more selected from the group consisting of a metal, a metalloid, an alloy, an intermetallic compound, and a metal oxide and impurities. The metal active material particles 2 may further contain other substances. The other substance is, for example, a carbonaceous material.

[0081] Metal active material particles 2 having the chemical composition as described above are disclosed, for example, in International Publication No. 2014 / 034104 (Patent Document 4), International Publication No. 2015 / 129264 (Patent Document 5), International Publication No. 2015 / 129265 (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).

[0082] [Median diameter of metal active material particles] The median diameter (d50) of the metal active material particles 2 is not particularly limited. If the median diameter (d50) of the metal active material particles 2 is 0.5 μm or more, it is possible to suppress the specific surface area of the metal active material particles 2 from becoming too large. Therefore, the irreversible capacity can be effectively suppressed, and further, the discharge capacity per unit volume is further improved. If 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, and even 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, and even more preferably 20.0 μm.

[0083] [Method for Measuring Median Diameter of Metal Active Material Particles] The median diameter (d50) of the metal active material particles 2 is determined by the following method. In accordance with JIS Z 8825 (2013), using a laser diffraction / scattering particle size distribution analyzer, the median diameter (d50) of the metal active material particles 2 is measured by the laser diffraction scattering method. The dispersion medium in the measurement is water with 0.1 mass% of a surfactant containing alkyl glyoxide added thereto. The dispersion method is ultrasonic treatment for 5 minutes. The particle size (volume average particle size by the laser diffraction scattering method) at which the cumulative volume with respect to the volume of all the metal active material particles 2 becomes 50% is defined as the average particle size (median diameter (d50)) of the metal active material particles 2.

[0084] [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 the binder is not particularly limited. The binder is, for example, one or more selected from the group consisting of a water-insoluble resin which is insoluble in the solvent used for the non-aqueous electrolyte of the battery, a water-soluble resin, and styrene-butadiene rubber (SBR). The water-insoluble resin which is insoluble in the solvent used for the non-aqueous electrolyte of the battery is, for example, one or more selected from the group consisting of polyimide (PI), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and polytetrafluoroethylene (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 may be one or more selected from the group consisting of polyimide (PI), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), and polyvinyl alcohol (PVA).

[0085] 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 peel off from the current collector during electrode manufacturing.

[0086] The content of the binder in the electrode active material layer 1 is not particularly limited. However, if 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 increased. Also, the battery characteristics, particularly the cycle characteristics, are stably increased. On the other hand, if 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 is more stably decreased. Therefore, the rapid chargeability of the non-aqueous electrolyte secondary battery is more stably increased. Accordingly, the content of the binder in the electrode active material layer 1 may be 0.5 to 10% by mass.

[0087] [Other components of the electrode active material layer] In addition to the above-described metal active material particles 2 and the binder, the electrode active material layer 1 may contain other electrode active materials such as graphite and conductive aids such as carbon black. 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 including the electrode active material layer 1 decreases. In this case, the rapid chargeability of the nonaqueous electrolyte secondary battery including the electrode active material layer 1 is further enhanced.

[0088] [Thickness of the electrode active material layer] The thickness of the electrode active material layer 1 is not particularly limited. However, if the thickness of the electrode active material layer 1 is 15 μm or more, appearance defects due to coating unevenness caused by variations in the particle size of the electrode active material and the formation of secondary aggregates are suppressed. On the other hand, if the thickness of the electrode active material layer 1 is 75 μm or less, the path along which M n+ moves does not become too long. Therefore, M n+ easily moves, and the DC resistance of the electrode active material layer 1 increases more stably. As a result, the rapid chargeability of the nonaqueous electrolyte secondary battery increases more stably. 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, and even more preferably 30 μm. The upper limit of the thickness of the electrode active material layer 1 is more preferably 70 μm, and even more preferably 55 μm.

[0089] 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.

[0090] [Electrode] Figure 2 is a schematic cross-sectional view of the electrode in the present embodiment. Referring to Figure 2, the electrode 4 of the present embodiment is an electrode 4 for a non-aqueous electrolyte secondary battery, and includes the above-described 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 is in the form of a thin film or a plate 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, nickel-plated copper, and stainless steel. In the case of the electrode 4 for a lithium-ion secondary battery, preferably, the current collector 5 is made of Cu. This is because Cu is less likely to form an alloy with lithium and has excellent formability. The thickness of the current collector 5 is, for example, 10 to 20 μm.

[0091] [Non-aqueous electrolyte secondary battery] The non-aqueous electrolyte secondary battery of the present embodiment includes the above-described electrode 4. The non-aqueous electrolyte secondary battery includes the above-described 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 it may be cylindrical, rectangular, coin-shaped, or sheet-shaped. The non-aqueous electrolyte secondary battery may be selected from the group consisting of a lithium-ion battery, a sodium-ion battery, a magnesium-ion battery, an aluminum-ion battery, an all-solid-state battery, and a lithium-sulfur battery.

[0092] When the electrode 4 is used as a negative electrode, the positive electrode only needs to 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. The Li-containing transition metal compound is, for example, LiM 1 -xM’ x O 2 , and / or, LiM 2 yM’O 4That is, in the formula, 0 ≦ x, y ≦ 1, and M and M' are each one or more selected from the group consisting of barium (Ba), cobalt (Co), nickel (Ni), manganese (Mn), chromium (Cr), titanium (Ti), vanadium (V), iron (Fe), zinc (Zn), aluminum (Al), indium (In), tin (Sn), scandium (Sc), and yttrium (Y).

[0093] The non-aqueous electrolyte secondary battery of this embodiment may include, as the positive electrode having the above configuration, other well-known positive electrodes such as transition metal chalcogenides, vanadium oxides and their lithium (Li) compounds, niobium oxides and their lithium compounds, conjugated polymers using organic conductive substances, Chevrel phase compounds, activated carbon, and activated carbon fibers.

[0094] When the electrolyte is an electrolytic solution, the electrolytic solution may be a non-aqueous electrolytic solution in which a lithium salt as a supporting electrolyte is dissolved in an organic solvent. The lithium salt is, 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 SO 3 , Li(CF 3 SO 2 )2N, LiC 4 F 9 SO 3 , Li(CF 2 SO 2 ) 2, LiCl, LiBr, LiI, etc. may also be used. These may be used alone or in combination. The organic solvent may be a carbonate such as propylene carbonate, ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, or diethyl carbonate. However, various other organic solvents such as carboxylic acid esters and ethers 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 battery, etc.

[0095] The separator is installed between the positive electrode and the negative electrode. The separator serves as an insulator. The separator also greatly contributes to the retention of the electrolyte. A well-known configuration of the separator suffices. The separator is, for example, a polyolefin-based material such as polypropylene, polyethylene, or a mixture of both, or a porous body such as a glass filter.

[0096] [Method for manufacturing electrode active material layer and electrode] An example of the method for manufacturing the electrode active material layer 1 and the electrode 4 of the present embodiment will be described. The manufacturing method described hereinafter 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 other manufacturing methods other than the manufacturing method described hereinafter. However, the manufacturing method described hereinafter is a preferred example of the method for manufacturing the electrode active material layer 1 and the electrode 4 of the present embodiment.

[0097] The method for manufacturing 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. Each step will be described below.

[0098] [Metal active material particle preparation step] In the metal active material particle preparation step, metal active material particles 2 are prepared. The metal active material particles 2 may be those supplied by a third party or may be manufactured. When manufacturing, the metal active material particles 2 are manufactured, for example, by rapidly cooling a molten metal. Methods for rapidly cooling a molten metal include, for example, a roll cooling method, a gas atomization method, a rotary liquid spinning method, a melt spinning method, and the like.

[0099] Preferably, the metal active material particles 2 are manufactured by the following method. A molten metal having the components of the above-described metal active material particles 2 is manufactured. The molten metal is manufactured by melting raw materials by a well-known melting method such as arc melting or resistance heating melting.

[0100] Using the obtained molten metal, a thin strip of the metal active material is manufactured. Methods for manufacturing the thin strip include, for example, an ingot casting method, a strip casting method, and a melt spinning method.

[0101] In consideration of production efficiency, for example, the metal thin strip 600 may be manufactured using the manufacturing apparatus 100 shown in FIG. 3. FIG. 3 is a schematic diagram of an example of the manufacturing apparatus 100 for the metal active material particles 2 of the present embodiment. Referring to FIG. 3, the manufacturing apparatus 100 includes a cooling roll 200, a tundish 300, and a blade member 400.

[0102] The cooling roll 200 has an outer peripheral surface and cools and solidifies the molten metal 500 on the outer peripheral surface while rotating. The cooling roll 200 rotates around the central axis of the cooling roll 200 by a drive source. RD shown in FIG. 3 is the rotation direction of the cooling roll 200. When manufacturing the metal thin strip 600, the cooling roll 200 rotates in a fixed direction RD. Thereby, in FIG. 3, the molten metal 500 in contact with the cooling roll 200 partially solidifies 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 onto the outer peripheral surface of the cooling roll 200.

[0103] The blade member 400 is disposed with a gap provided between it and the outer peripheral surface of the cooling roll 200 downstream in the rotational direction of the cooling roll 200 from the tundish 300. The blade member 400 is a member separate from the tundish 300, and is disposed downstream in the rotational direction RD of the cooling roll 200, away from the tundish 300. By the blade member 400, the thickness of the molten metal 500 on the outer peripheral surface of the cooling roll 200 is regulated to the thickness of the gap between the outer peripheral surface of the cooling roll 200 and the blade member 400, to produce 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. Thereby, the molten metal 500 is rapidly cooled, and the metal strip 600 is produced.

[0104] A mechanical alloying treatment (MA treatment) may be performed on the produced metal strip 600 to produce the metal active material particles 2. The mechanical alloying apparatus is, for example, a high-speed planetary mill. An example of the high-speed planetary mill is the product name High-Zee BX manufactured by Kurimoto Iron Works, Ltd. Also, there is no particular limitation as long as it is a manufacturing method corresponding to the MA treatment. For example, a conventionally known pulverizing apparatus such as a Turbra shaker mixer (T2F type manufactured by Shinmaru Enterprises Co., Ltd.) or a small vibration rod mill (1045 type manufactured by Yoshida Seisakusho Co., Ltd.) may be used to produce the metal active material particles 2.

[0105] [Electrode active material layer manufacturing process] In the electrode active material layer manufacturing process, the electrode active material layer 1 is formed using the metal active material particles 2 and a binder. First, the prepared metal active material particles 2 and the binder are kneaded to produce an electrode mixture slurry. To the electrode mixture slurry, a conductive auxiliary agent, a solvent, etc. are added as necessary. 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 roll pressing.

[0106] 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 metal active material particles 2, a binder, and, if necessary, a conductive aid, a solvent, etc. is kneaded at a peripheral speed of 15 to 35 m / s for 30 to 60 seconds to produce an electrode mixture slurry. In the present embodiment, the peripheral speed refers to the speed of the tip of the rotating blade of the kneader used when producing the electrode mixture slurry.

[0107] When the electrode mixture slurry does not contain graphite, if the peripheral speed is less than 15 m / s, among the metal active material particles 2, the metal active material particles 2 with a large particle size preferentially settle, and locally excessive voids are generated between the current collector 5 and the electrode active material layer 1. In this case, the volume resistivity of the electrode active material layer 1 increases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases. When the electrode mixture slurry contains graphite, if the peripheral speed is less than 15 m / s, the metal active material particles 2 and the graphite are separated, and the metal active material particles 2 form secondary aggregates. The secondary aggregates of the metal active material particles 2 block the voids in the electrode active material layer 1. In this case, the electrode air permeability of the electrode active material layer 1 decreases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases. Or, the density of the electrode active material layer 1 becomes inappropriate. On the other hand, if the peripheral speed exceeds 35 m / s, the temperature of the electrode mixture slurry rises and gels during kneading, so that the metal active material particles 2 form secondary aggregates. In this case, the electrode air permeability of the electrode active material layer 1 decreases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases.

[0108] In the production of the above 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 permeability of the electrode active material layer 1 decreases, and further, 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 and gels during kneading, so that the metal active material particles 2 form secondary aggregates. In this case, the electrode air permeability of the electrode active material layer 1 decreases, and the rapid chargeability of the non-aqueous electrolyte secondary battery decreases.

[0109] The electrode mixture slurry produced under the above conditions is applied onto the current collector 5 and dried. The application of the electrode mixture slurry may be performed by a conventionally known method. For example, a tabletop coater (Control Coater, model 7017, manufactured by Imoto Seisakusho Co., Ltd.), a continuous coater (die coater, or a continuous coater 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 onto the current collector 5. By adjusting the gap of the coater part, the thickness of the electrode mixture slurry before drying can be appropriately changed. When polyimide is used as the binder, a vacuum drying treatment may be applied at 200°C after the electrode mixture slurry is dried.

[0110] The dried electrode mixture slurry and the current collector 5 are roll-pressed. The roll pressing may be performed by a conventionally known method. For example, a roll press device (No. R080802, manufactured by Yoshida Kinen Co., Ltd.) is used for roll pressing. By adjusting the gap (thickness) of the roll, an electrode 4 having an electrode active material layer 1 with a predetermined thickness can be manufactured.

[0111] 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.

[0112] [Method for manufacturing a non-aqueous electrolyte secondary battery] The non-aqueous electrolyte secondary battery having the above electrode 4 is manufactured by a well-known method. A laminate in which the above electrode 4 (negative electrode or positive electrode) and a separator are laminated is manufactured. The laminate is housed in a case to manufacture the battery.

Example

[0113] The effect of the electrode active material layer of the present embodiment will be further specifically described by way of examples. The conditions in the following examples are one example of the conditions adopted to confirm 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 example of conditions. The present invention can adopt various conditions without departing from the gist of the present invention and as long as the object of the present invention is achieved.

[0114] Metal active material particles having the chemical composition shown in Table 1 were prepared as follows.

[0115] [Table 1]

[0116] A molten metal was prepared so that the metal active material particles had the chemical composition of each alloy number shown in Table 1. The temperature of the molten metal was maintained at 1400 °C. Then, the molten metal at 1400 °C was rapidly cooled by the strip casting method to cast a metal strip with 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 rotational speed of the cooling roll 200 was 300 m / min in terms of the peripheral speed of the roll surface. In an argon atmosphere, the above-mentioned molten metal 500 was supplied to the rotating cooling roll 200 through a horizontal tundish 300 (made of alumina). The molten metal 500 was placed on the surface of the rotating cooling roll 200 and sandwiched between the cooling roll 200 and the blade member 400, whereby the molten metal 500 was rapidly solidified. 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.

[0117] The obtained metal strip 600 was further subjected to a pulverization treatment to produce metal active material particles having a plurality of convex portions. For the pulverization treatment, a high-speed planetary mill (manufactured by Kurimoto Iron Works Co., Ltd., trade name: High Gee BX) was used. In order to control the particle size of the metal active material particles, the pulverization time was adjusted as follows. The rotational speed was 500 rpm. After pulverization, stainless steel sieves were used to remove coarse powder having a particle size exceeding the following particle size.

[0118] Specifically, in Test Nos. 1 to 8, 11 to 15, 17, and 19, the pulverization time was set to 5 hours. Further, a sieve with an aperture of 45 μm was used. As a result, the median diameter d50 of the metal active material particles in Test Nos. 1 to 8, 11 to 15, 17, and 19 was 2.0 μm. In Test Nos. 9, 10, and 18, the pulverization time was set to 1 hour. Further, a sieve with an aperture of 75 μm was used. As a result, the median diameter d50 of the metal active material particles in Test Nos. 9, 10, and 18 was 10.0 μm. In the column of "alloy particle size (μm)" in Table 2, the median diameter d50 (μm) of the metal active material particles for each test number is shown.

[0119] Note that the average particle size of the active material particles for each test number was measured by the following method. For the measurement of the average particle size, the laser diffraction scattering method conforming to JIS Z 8825 (2013) was adopted. The dispersion medium in the measurement was water with 0.1 mass% of a surfactant containing alkyl glycoxide added thereto. The dispersion method was set to 5 minutes by ultrasonic waves. The particle size (volume average particle size by the laser diffraction scattering method) at which the cumulative volume with respect to the volume of all the metal active material particles reached 50% was defined as the average particle size (median diameter (d50)) of the metal active material particles.

[0120] [Manufacture of Electrode Binder Slurry] For each test number, an electrode binder slurry was manufactured under the conditions shown in Table 2.

[0121] [Table 2]

[0122] Mixture for aqueous slurry: Test Nos. 2 to 8, 11, 13, and 15 to 19 A mixture was manufactured by mixing metal active material particles, graphite particles, acetylene black (AB) as a conductive aid, styrene-butadiene rubber (SBR) (doubly diluted solution) as a binder, and carboxymethyl cellulose (CMC) as a thickener at the mixing ratios shown below.

[0123] As the graphite particles, SG-BH (average particle size: 20 μm) manufactured by Ito Graphite Industry Co., Ltd. was used. As the acetylene black, HS-100 manufactured by Denka Co., Ltd. was used. As the styrene-butadiene rubber, TRD2001 manufactured by JSR Corporation was used. As the carboxymethyl cellulose, the product with product number 2200 manufactured by Daicel Finechem 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

[0124] Mixture for organic solvent-based slurry: Test numbers 1, 9, 10, 12, and 14 A mixture was produced by mixing metal active material particles, graphite particles, carbon black as a conductive aid, and polyimide and polyvinylidene fluoride (PVDF) as binders at the mixing ratios shown below.

[0125] As the graphite particles, SG-BH (average particle size: 20 μm) manufactured by Ito Graphite Industry Co., Ltd. was used. As the carbon black, SuperC65 manufactured by Imerys Graphite&Carbon was used. As the polyimide, DREAM BOND manufactured by IST Corporation was used. As the polyvinylidene fluoride, KF Polymer W♯9100 manufactured by Kureha Corporation was used.

[0126] 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

[0127] Using a kneader, distilled water was added to the above mixture for the aqueous slurry, and N-methyl-2-pyrrolidone (NMP) was added to the above mixture for the organic solvent slurry, followed by kneading to produce a negative electrode mixture slurry. 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 swirling high-speed mixer manufactured by Primix Corporation (product name: Filmix 40-40 type) was used. Note that only for Test No. 15, a planetary mixer manufactured by Primix Corporation (product name: T.K. Hibismix) was used. The speed (peripheral speed) of the tip of the rotating blade of the kneader and the kneading time were as shown in Table 2.

[0128] [Manufacture of Electrode] The manufactured negative electrode mixture slurry was applied to one side of an electrolytic copper foil with a thickness of 21 μm using an applicator (75 μm) and dried at 100°C for 20 minutes. The dried copper foil had a coating film of the electrode active material layer on its surface. The mixtures for the organic solvent slurries of Test Nos. 1, 9, 10, 12, and 14 contained a polyimide binder. Therefore, in Test Nos. 1, 9, 10, 12, and 14, after drying the negative electrode mixture slurry, heat treatment was further performed at 200°C for 2 hours under reduced pressure drying conditions. The heat-treated copper foil had a coating film of the electrode active material layer on its surface. Punching was performed on the copper foil on which the electrode active material layer was formed to produce a disk-shaped copper foil with a diameter of 13 mm. The punched copper foil was pressed by a roll press to have the electrode density shown in Table 2 to manufacture a plate-shaped electrode. The thickness of the obtained electrode active material layer was 50 μm.

[0129] The density of the electrode active material layer was calculated using the following formula. Density of electrode active material layer = (Weight of electrode active material layer) (g) / (Electrode plate area × Thickness of electrode active material layer) (cm 3 ) Note that the weight (g) of the electrode active material layer was obtained by subtracting the weight of the metal foil from the weight of the electrode plate. The area of the electrode plate was the diameter of the punching tool. 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.

[0130] [Electrode Permeability Measurement Test] The air permeability of the electrode active material layer for each test number was measured using a Gurley densometer (manufactured by Toyo Seiki Seisaku-sho, Ltd.). The copper foil was removed from the electrode by etching or peeling it off with tweezers to obtain the electrode active material layer (self-supporting film). The air permeability of the obtained electrode active material layer was determined. Specifically, using the above-mentioned Gurley densometer, with the inner cylinder weight (pressure) of 567 ± 0.5 g, the permeation area of 28.3 mm 2 (diameter 6 mm), and the permeated air volume of 25 mL, the time for air to pass through the electrode active material layer in the thickness direction of the electrode active material layer was measured. During the measurement, the electrode active material layer was sandwiched between two porous Ni (200 μm mesh) and then measured. From the obtained air passage time, the air permeability of the electrode was calculated as follows. The air permeability of the electrode active material layer for each test number is shown in Table 2. Air permeability (μm / s) = Thickness of the electrode active material layer (μm) / Air passage time (s)

[0131] [Volume Resistivity Measurement Test] The volume resistivity of the electrode active material layer for each test number was measured using an electrode resistance measurement system (manufactured by Hioki E.E. Corporation, product name: RM2610). In advance, the volume resistivity, thickness of the current collector, and thickness of the electrode active material layer 1 were input into the electrode resistance measurement system. The measurement probe was brought into contact with the electrode active material layer 1, and then a constant current was applied from the surface of the electrode active material layer 1 to calculate the volume resistivity of the electrode active material layer 1. The volume resistivity of the current collector was measured using the 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 set as measurement speed: MEDIUM, range: AUTO RANGE. The volume resistivity of the electrode active material layer for each test number is shown in Table 2.

[0132] [Evaluation Test] [Measurement Test of Discharge Capacity per Unit Volume of Electrode] For each electrode of each test number, the discharge capacity per unit volume was measured as an index for evaluating the volume energy density.

[0133] [Fabrication of Coin Cell (for Measuring Discharge Capacity per Unit Volume)] Using the electrodes, counter electrodes, electrolytes, and separators for each test number, coin-type non-aqueous test cells were manufactured. The electrodes for each test number were used as the negative electrodes. Li metal foil was used as the counter electrode. As the electrolyte, a non-aqueous solution was used. The non-aqueous solution was prepared by dissolving LiPF 6 such that the concentration became 1 M in a mixed solvent of ethylene carbonate (EC):ethyl methyl carbonate (EMC) = 1:3 (volume ratio). A polyolefin separator (φ19 mm) was used as the separator. On both sides of the separator, the lithium metal foils of the negative electrode and the counter electrode were placed in a stainless steel coin cell filled with the electrolyte. In the evaluation with respect to the counter electrode Li, originally, the doping of Li into the graphite negative electrode is treated as discharge. However, in this example, in order to evaluate the negative electrode material, the "charge capacity" without special mention below means the capacity on the doping side, and the "discharge capacity" means the capacity on the de-doping side.

[0134] [Measurement of Discharge Capacity per Unit Volume] Using a charge-discharge device manufactured by Electro Field Co., Ltd., the discharge capacity per unit volume was determined as follows. The temperature during measurement was measured at room temperature (23 °C). The coin-type non-aqueous test cell was charged at a constant current with a current value of 0.1 C until the potential difference with respect to the counter electrode reached 0.005 V. Then, while maintaining 0.005 V, charging was continued at a constant voltage with respect to the counter electrode until it reached 0.05 C, and the charge capacity was measured. Next, discharge was performed at a current value of 0.1 C until the potential difference reached 1.5 V, and the discharge capacity was measured. The discharge capacity per unit volume [mAh / cm 3 was calculated as (initial charge capacity [mAh / g]) × (electrode density [g / cm 3 ).

[0135] [DC Resistance Measurement Test of Electrodes] For the electrodes of each test number, the DC resistance was measured as an index for evaluating the rapid chargeability. In this measurement test, the electrodes of each test number were used as the negative electrodes.

[0136] [Fabrication of Positive Electrode] As the positive electrode active material, NMC111 of the lithium composite oxide system of Co-Ni-Mn (manufactured by Nippon Chemical Industry Co., Ltd., composition: LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 ) was used. The positive electrode was manufactured as follows. 3 parts by mass of KS6 powder (manufactured by Imerys Graphite&Carbon) and 1 part by mass of Super C65 powder (manufactured by Imerys Graphite&Carbon) were mixed with 92 parts by mass of the positive electrode active material (powder) to prepare a mixture. Further, 4 parts by mass of PVDF dispersion was added to the mixture and then stirred to prepare a positive electrode binder slurry.

[0137] The positive electrode binder slurry was applied onto one side of a 20-μm-thick aluminum foil using an applicator (gap thickness: 150 μm) and dried to form a coating film. The coating amount of the positive electrode active material on the aluminum foil was 10 mg / cm 2 . This coating film was punched out using a punch with a diameter of 13 mm to obtain pellets. The pellets were pressed using a press molding machine to manufacture the positive electrode. The electrode density was adjusted to be 2.8 g / cm 3 . Note that the gap thickness of the applicator may be varied for the purpose of controlling the coating amount on the aluminum foil.

[0138] [Fabrication of Laminate Cell] The same negative electrode used in the initial charge-discharge efficiency evaluation was used as the negative electrode. The electrodes were cut out so that the negative electrode was 2.5 cm × 2.5 cm and the positive electrode was 2.3 cm × 2.3 cm, and two separators (Celgard 2100) were sandwiched between the negative electrode and the positive electrode. An aluminum wire (0.25 mmφ) was installed between the two separators.

[0139] [Pretreatment of Laminate Cell (Pretreatment before Calculation of DC Resistance)] As a pretreatment for calculating the reaction resistance, a charge-discharge test was carried out at room temperature (23°C) so that the state of charge (SOC) of the laminate cell became 50%. The charge-discharge device used was a charge-discharge device manufactured by Electro Field Co., Ltd. The specific treatment method is described below. After constant current charging to 4.2V at 0.1C, constant potential charging was carried out at 4.2V until the current value became 0.05C. Subsequently, constant current discharge was carried out at 0.1C to 3.0V. The above charging / discharging was repeated for 2 cycles. After that, constant current charging was carried out so that the SOC became 50%.

[0140] [Creation of reference electrode] Regarding the pretreated laminate cell, the positive electrode and the reference electrode were connected with a terminal, and Li was alloyed with an Al wire. Specifically, charging was carried out at a constant current of 0.03 mA so that the amount of electricity became 0.3 mAh to obtain a LiAl alloy wire.

[0141] [Measurement of DC resistance] The DC resistance was calculated as a resistance component corresponding to the resistance of the negative electrode generated by pulse charge and discharge. For the pulse charge and discharge measurement, modulab, a product of solartron analytical, was used. The structure of the electrochemical cell used a three-electrode laminate cell, with the electrode of each test number at the negative electrode, NMC111 (manufactured by Nippon Chemical Industry Co., Ltd., composition: LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O 2 ) of a lithium composite oxide system of Co-Ni-Mn at the counter electrode, and a LiAl wire at the reference electrode for measurement. As the electrolyte solution, a non-aqueous solution was used. The non-aqueous solution used LiPF as a supporting electrolyte 6It was prepared by dissolving it in a mixed solvent of ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 1:3 (volume ratio) so that the concentration became 1 M. The reaction resistance was calculated by connecting the negative electrode and the reference electrode with a terminal and measuring the direct current resistance to obtain the resistance of only the negative electrode. The measurement was carried out in a thermostat, and the reaction temperature was measured at -10°C. The laminated cell after the pretreatment and the preparation of the reference electrode was held in the thermostat at a set temperature of -10°C for 3 hours or more. Then, the direct current resistance was measured using modulab, a product name manufactured by Solartron Analytical. At this time, the direct current 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 difference ΔV between 0.1 second later and 20 seconds later, and dividing by the applied current value (10C). The direct current resistance of the electrodes for each test number is shown in Table 2.

[0142] [Evaluation Results] Referring to Table 1 and Table 2, the electrode active material layers of Test Nos. 1 to 10 contained 30.0 to 80.0 mass% of Cu, more than 5.0 mass% to 99.0 mass% of metal active material particles that occlude and / or release metal ions, and a binder. The electrode active material layers of Test Nos. 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 Nos. 1 to 10 had a discharge capacity per volume of 650 mAh / cm 3 or more. The electrodes provided with the electrode active material layers of Test Nos. 1 to 10 further had a direct current 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 Nos. 1 to 10 could achieve both high capacity and rapid chargeability.

[0143] 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 provided with the electrode active material layers of Test Nos. 2 to 4 and 8 had a lower direct current resistance compared to the electrodes provided with the electrode active material layers of Test Nos. 1 and 9 that used metal active material particles with the same chemical composition (alloy number 1).

[0144] On the one hand, the electrode active material layer of Test No. 11 had too low a content of metal active material particles. Therefore, the discharge capacity per unit volume of the electrode having the electrode active material layer of Test No. 11 was as low as 550 mAh / cm 3 which was too low.

[0145] The electrode active material layer of Test No. 12 had too high a content of metal active material particles. As a result, the adhesion of the metal active material particles to the electrode decreased, and an appropriate electrode active material layer could not be manufactured. In Test No. 12, various tests could not be conducted.

[0146] The electrode active material layer of Test No. 13 had too high a Cu content of metal active material particles, which was 85.0 mass%. Therefore, the discharge capacity per unit volume of the electrode having the electrode active material layer of Test No. 13 was as low as 648 mAh / cm 3 which was too low.

[0147] The electrode active material layer of Test No. 14 had too high a volume resistivity R of 120,000 Ω·cm. Therefore, the DC resistance of the electrode having the electrode active material layer of Test No. 14 was as high as 24 Ω.

[0148] The electrode active material layer of Test No. 15 had too low an electrode gas permeability rate T of 0.05 μm / s. Therefore, the DC resistance of the electrode having the electrode active material layer of Test No. 15 was as high as 26 Ω.

[0149] The electrode active material layer of Test No. 16 did not contain metal active material particles. Therefore, the discharge capacity per unit volume of the electrode having the electrode active material layer of Test No. 14 was as low as 540 mAh / cm 3 which was too low.

[0150] The electrode active material layer of Test No. 17 had too low an electrode gas permeability rate T of 0.10 μm / s. Therefore, the DC resistance of the electrode having the electrode active material layer of Test No. 17 was as high as 25 Ω.

[0151] The electrode active material layer of Test No. 18 had an electrode density d of 0.95 g / cm 3Since it was too low, the electrode gas permeability rate T was too high at 6.50 μm / s, and furthermore, the volume resistivity R was too high at 156,000 Ω·cm. Therefore, the DC resistance of the electrode including the electrode active material layer of Test No. 18 was too high at 28 Ω.

[0152] The electrode active material layer of Test No. 19 had an electrode gas permeability rate T that was too low at 0.85 μm / s. Therefore, the DC resistance of the electrode including the electrode active material layer of Test No. 19 was too high at 22 Ω.

[0153] The embodiments of the present disclosure have been described above. However, the above-described embodiments are merely examples for implementing the present disclosure. Therefore, the present disclosure is not limited to the above-described embodiments, and the above-described embodiments can be appropriately modified and implemented without departing from the spirit thereof.

Explanation of Reference Numerals

[0154] 1 Electrode active material layer 2 Metal active material particles

Claims

1. An electrode active material layer for a non-aqueous electrolyte secondary battery, containing 30.0 to 80.0% by mass of Cu, 29.0% to 99.0% by mass of metal active material particles that occlude and / or release metal ions, and a binder, the electrode active material layer satisfying formulas (1) to (3). 1.50 ≦ T ≦ 6.00 (1) 1.00 ≦ d ≦ 3.50 (2) 0.010 ≦ R ≦ 100.000 (3) Here, the electrode permeability (μm / s) is substituted for T in the formula (1), and the electrode density (g / cm ３ ) is substituted for d in the formula (2), and the volume resistivity (Ω·cm) is substituted for R in the formula (3).

2. The electrode active material layer according to Claim 1, wherein the metal active material particles further contain Sn.

3. The electrode active material layer according to Claim 2, wherein the metal active material particles further contain one or two selected from the group consisting of Si and Ti.

4. The electrode active material layer according to Claim 2 or Claim 3, wherein the metal active material particles further contain one or more selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Zn, Al, B, and C.

5. The electrode active material layer according to any one of Claims 1 to 4, further containing graphite.

6. An electrode for a non-aqueous electrolyte secondary battery, comprising the electrode active material layer according to any one of Claims 1 to 5 and a current collector made of a metal foil.

7. A non-aqueous electrolyte secondary battery comprising the electrode according to Claim 6.

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