Positive electrode plate and non-aqueous electrolyte secondary battery

Abstract

To provide a positive electrode plate having a positive electrode current collector, a first active material layer containing agglomerated particles, and a second active material layer containing single particles in this order, and having reduced input / output resistance of a single particle nonaqueous electrolyte secondary battery.SOLUTION: In a positive electrode plate, a first active material layer has a concave structure with a plurality of recesses formed on a second active material layer side, and the second active material layer has a convex structure with a plurality of protrusions formed on the first active material layer side, and in a cross section in a thickness direction passing through the plurality of recesses and protrusions of a positive electrode active material layer, a shape of an interface where the first active material layer and the second active material layer are in contact is an uneven shape formed by the plurality of recesses and the plurality of protrusions combined with each other, and a mass ratio of the second active material layer to the first active material layer in the positive electrode active material layer is 1 / 9 or more and 3 / 7 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a positive electrode plate, and further to a non-aqueous electrolyte secondary battery including the positive electrode plate. [Background technology]

[0002] Japanese Patent Application Laid-Open No. 2022-63677 (Patent Document 1) discloses a positive electrode including a first layer containing single particles and a second layer containing secondary particles formed by aggregation of primary particles, the second layer containing a positive electrode active material disposed between the first layer and a positive electrode substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-63677 Summary of the Invention [Problem to be solved by the invention]

[0004] In the positive electrode plate described in JP 2022-63677 A, only the same type of active material is present in the longitudinal direction (direction parallel to the plane) of the positive electrode active material layer, so the resistance of the first layer, where single particles with higher resistance than agglomerated particles contact each other, tends to be difficult to sufficiently reduce. As a result, the input / output resistance of non-aqueous electrolyte secondary batteries may not be sufficiently reduced, and further reduction of input / output resistance is required.

[0005] An object of the present disclosure is to provide a positive electrode plate having a positive electrode current collector, a first active material layer containing agglomerated particles, and a second active material layer containing single particles, in this order, which has reduced input / output resistance for a single-particle non-aqueous electrolyte secondary battery. [Means for solving the problem]

[0006] [1] A positive electrode plate including a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer includes a first active material layer and a second active material layer, the first active material layer is disposed on the positive electrode current collector side, the second active material layer is disposed in contact with the first active material layer on a side of the first active material layer opposite the positive electrode current collector, the first active material layer contains secondary particles formed by aggregation of primary particles, the second active material layer includes a single particle, the first active material layer has a recessed structure in which a plurality of recesses are formed on the second active material layer side, the second active material layer has a convex structure in which a plurality of protrusions are formed on the first active material layer side, in a cross section of the positive electrode active material layer in a thickness direction passing through the plurality of recesses and the plurality of protrusions, the shape of an interface where the first active material layer and the second active material layer contact each other is an uneven shape formed by the plurality of recesses and the plurality of protrusions being combined with each other, A positive electrode plate, wherein the mass ratio of the second active material layer to the first active material layer in the positive electrode active material layer is 1 / 9 or more and 3 / 7 or less. [2] When the depth of the depression is C and the thickness of the second active material layer present in the portion of the first active material layer where no depression is formed is D, the ratio of C to D (C / D) satisfies the following formula (1): (1) C / D≦3.0 The positive electrode plate according to [1], which satisfies the above. [3] When the thickness of the positive electrode active material layer is T, the depth of the recess is C, and the thickness of the second active material layer present in the portion of the first active material layer that is not the recess is D, the ratio of the sum of C and D to T [(C+D) / T] satisfies the following formula (2): (2) (C+D) / T<0.5 The positive electrode plate according to [1] or [2], which satisfies the above. [4] When the width of the protrusion is A and the interval between the protrusions is B, the ratio of B to A (B / A) satisfies the following formula (3): (3) 2≦B / A The positive electrode plate according to any one of [1] to [3], which satisfies the above. [5] When the width of the protrusion is A and the average particle diameter of the single particle is R2, the ratio of A to R2 (A / R2) satisfies the following formula (4): (4) A / R2≦6.0 The positive electrode plate according to any one of [1] to [4], which satisfies the above. [6] A non-aqueous electrolyte secondary battery comprising the positive electrode plate according to any one of [1] to [5]. [Effects of the Invention]

[0007] The present disclosure provides a positive electrode plate having, in this order, a positive electrode current collector, a first active material layer containing agglomerated particles, and a second active material layer containing single particles, and which reduces the input / output resistance of a non-aqueous electrolyte secondary battery. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view of a positive electrode plate of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Positive electrode> The positive electrode plate of the present disclosure includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector. The positive electrode active material layer includes a first active material layer and a second active material layer. The first active material layer is disposed on the positive electrode current collector side. The second active material layer is disposed in contact with the first active material layer on the side of the first active material layer opposite the positive electrode current collector. The first active material layer includes secondary particles formed by aggregation of primary particles. The second active material layer includes single particles. The first active material layer has a concave structure with multiple depressions formed on the second active material layer side. The second active material layer has a convex structure with multiple protrusions formed on the first active material layer side. In a cross section in the thickness direction passing through the multiple depressions and multiple protrusions of the positive electrode active material layer, the shape of the interface where the first active material layer and the second active material layer contact each other (hereinafter also referred to as the interface shape) is an uneven shape formed by combining the multiple depressions and multiple protrusions. The mass ratio of the first active material layer to the second active material layer is 9:1 to 7:3.

[0010] The positive electrode plate of the present disclosure has a concave structure in which multiple recesses are formed on the first active material layer facing the second active material layer, and a convex structure in which multiple protrusions are formed on the second active material layer facing the first active material layer, so that the interface shape is uneven. This results in a structure in which high-resistance individual particles arranged on the protrusions are surrounded by low-resistance agglomerated particles arranged in the recesses. As a result, the relatively high-resistance individual particles can come into contact with the relatively low-resistance agglomerated particles, which tends to reduce the resistance of the second active material layer containing the individual particles. Even when the interface shape is uneven, the cycle life of the battery is not reduced.

[0011] 1 is a schematic cross-sectional view of a positive electrode plate. The positive electrode plate 10 includes a positive electrode current collector 11 and a positive electrode active material layer 12. The positive electrode plate 10 may be a strip-shaped sheet having a longitudinal direction and a lateral direction, and may be a sheet having a rectangular shape when viewed in the thickness direction (hereinafter also referred to as a plan view) (for example, a rectangular sheet having a longitudinal direction and a lateral direction). The positive electrode active material layer 12 includes a first active material layer 13 and a second active material layer 15.

[0012] The positive electrode current collector 11 is a conductive sheet. The positive electrode current collector 11 may have a thickness of, for example, 10 μm to 30 μm. The positive electrode current collector 11 may include, for example, an Al foil.

[0013] The thickness T of the positive electrode active material layer 12 can be, for example, 10 μm to 200 μm. The thickness T of the positive electrode active material layer 12 can be, for example, 50 μm to 150 μm. The thickness T of the positive electrode active material layer 12 can be, for example, 50 μm to 100 μm.

[0014] The first active material layer 13 is disposed closer to the positive electrode current collector 11 than the second active material layer 15. The first active material layer 13 is a lower layer than the second active material layer 15. The first active material layer 13 is disposed between the second active material layer 15 and the positive electrode current collector 11. The first active material layer 13 may, for example, be in contact with the positive electrode current collector 11. The first active material layer 13 may, for example, be formed on the surface of the positive electrode current collector 11. The first active material layer 13 contains a first particle group as a main positive electrode active material. The first particle group may have a mass fraction of, for example, 95% to 100%, or a mass fraction of 99% to 100%, or a mass fraction of 100%, relative to the entire positive electrode active material contained in the first active material layer 13.

[0015] The first particle group includes a plurality of agglomerated particles 14. The agglomerated particles 14 are a positive electrode active material. The first particle group may, for example, consist essentially of agglomerated particles 14. The second positive electrode active material particles may, for example, consist of agglomerated particles 14. The agglomerated particles 14 may have any shape. The agglomerated particles 14 may be, for example, spherical, cylindrical, or lumpy. The average particle diameter R1 of the plurality of agglomerated particles 14 may be, for example, 7 μm to 20 μm, or 8 μm to 16 μm. The average particle diameter R1 may be larger than the average particle diameter R2. The average particle diameters R1 and R2 are the particle diameter D50 at which the cumulative frequency of the smaller particle diameters in the volume-based particle size distribution is 50%. The average particle diameters R1 and R2 can be measured according to the measurement method described in the Examples section below.

[0016] Agglomerated particle 14 is formed by agglomerating 50 or more primary particles. Each primary particle contained in agglomerated particle 14 tends to have a low diffusion resistance of Li ions.

[0017] The number of primary particles contained in aggregated particles 14 is measured in an SEM image of aggregated particles 14. The magnification of the SEM image may be, for example, 10,000 to 30,000 times. Aggregated particles 14 may be formed by aggregating, for example, 100 or more primary particles. There is no upper limit to the number of primary particles in aggregated particles 14. Aggregated particles 14 may be formed by aggregating, for example, 10,000 or fewer primary particles. Aggregated particles 14 may be formed by aggregating, for example, 1,000 or fewer primary particles. The primary particles may have any shape. The primary particles may be, for example, spherical, columnar, or lumpy.

[0018] Primary particles refer to particles in which grain boundaries cannot be visually identified in an SEM image of the particles. Primary particles have a first maximum diameter. The first maximum diameter refers to the distance between the two most distant points on the outline of a primary particle. Primary particles may have a first maximum diameter of, for example, less than 0.5 μm. Primary particles may have a first maximum diameter of, for example, 0.05 μm to 0.2 μm. When 10 or more primary particles randomly sampled from an SEM image of a single agglomerate particle have a first maximum diameter of 0.05 μm to 0.2 μm, all of the primary particles contained in the agglomerate can be considered to have a first maximum diameter of 0.05 μm to 0.2 μm. Primary particles may have a first maximum diameter of, for example, 0.1 μm to 0.2 μm. The average first maximum diameter may be, for example, 0.1 μm to 0.2 μm. The average value is the arithmetic mean of 100 or more primary particles. The 100 or more primary particles are randomly sampled.

[0019] The second active material layer 15 is disposed in contact with the first active material layer 13 on the side of the first active material layer 13 opposite to the positive electrode current collector 11. The second active material layer 15 is an upper layer compared to the first active material layer 13. The second active material layer 15 may, for example, form the surface of the positive electrode active material layer 12. The second active material layer 15 contains a second particle group as a main positive electrode active material. The mass fraction of the second particle group relative to the entire positive electrode active material contained in the second active material layer 15 may be, for example, 95% to 100%, or 99% to 100%, or may even be 100%.

[0020] The second particle group includes a plurality of single particles 16. The single particles 16 are a positive electrode active material. The second particle group may, for example, consist essentially of single particles 16. The second positive electrode active material particles may, for example, consist of single particles 16. The single particles 16 may have any shape. The single particles 16 may, for example, be spherical, columnar, or lumpy. The single particles 16 may have an average particle diameter R2 of, for example, 1 μm to 6 μm.

[0021] The single particles 16 are particles that have grown relatively large. The single particles 16 are particles in which grain boundaries cannot be seen in the SEM image of the particles. Because there are fewer grain boundaries, the single particles tend to be less susceptible to cracking than agglomerated particles. The single particles 16 may be contained in the second particle group in the form of a single particle, or may be contained in the form of an agglomeration of 2 to 10 single particles.

[0022] Aggregate particles 14 and single particles 16 can each independently have any crystal structure. Single particles 16 and aggregate particles 14 can each independently have, for example, a layered structure, a spinel structure, an olivine structure, or the like.

[0023] Aggregate particles 14 and single particles 16 may each independently have any composition. Single particles 16 may, for example, have the same composition as aggregate particles 14. Aggregate particles 14 may, for example, have a different composition from single particles 16. Aggregate particles 14 and single particles 16 may each independently contain at least one selected from the group consisting of LiNiO2, Li(NiCoMn)O2, and Li(NiCoAl)O2. Here, for example, a notation such as "(NiCoMn)" in a composition formula such as "Li(NiCoMn)O2" indicates that the sum of the composition ratios in parentheses is 1.

[0024] Aggregate particles 14 and individual particles 16 may each independently comprise, for example, a layered metal oxide. The layered metal oxide may be, for example, a metal oxide represented by the formula (1): Li(Li a Ni x Mn y M z)O2(1) In formula (1), -0.1≦a≦0.1, 0.7≦x≦1.0, 0≦y≦0.3, 0≦z≦0.3, and a+x+y+z=1 are satisfied. M represents at least one element selected from the group consisting of Co, Al, Zr, B, Mg, Fe, Cu, Zn, Sn, Na, K, Ba, Sr, Ca, W, Mo, Nb, Ti, Si, V, Cr, and Ge.

[0025] The aggregated particles 14 and the single particles 16 are each independently made of, for example, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi 0.7 Co 0.2 Mn 0.1 O2, LiNi 0.7 Co 0.1 Mn 0.2 O2, LiNi 0.6 Co 0.3 Mn 0.1 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, and LiNi 0.6 Co 0.1 Mn 0.3 O2.

[0026] The aggregated particles 14 and the single particles 16 are each independently made of, for example, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi 0.7 Co 0.2 Mn 0.1 O2, and LiNi 0.6 Co 0.2 Mn 0.2 O2.

[0027] Both the agglomerated particles 14 and the single particles 16 are made of, for example, LiNi 0.8 Co 0.1 Mn 0.1 It may also contain O2.

[0028] The first active material layer 13 and the second active material layer 15 may each further contain additional components in addition to the positive electrode active material. The first active material layer 13 and the second active material layer 15 may each independently contain, for example, a conductive material and a binder. The conductive material may contain any component. The conductive material may contain, for example, at least one selected from the group consisting of carbon black, graphite, vapor-grown carbon fiber (VGCF), carbon nanotubes (CNT), and graphene flakes. The conductive material may be blended in an amount of, for example, 0.1 to 10 parts by mass per 100 parts by mass of the positive electrode active material. The binder may contain any component. The binder may include, for example, at least one selected from the group consisting of polyvinylidene fluoride (PVdF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), polytetrafluoroethylene (PTFE), and polyacrylic acid (PAA). The amount of the binder may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the positive electrode active material.

[0029] In the positive electrode active material layer 12, the mass ratio of the second active material layer 15 to the first active material layer 13 (mass of the first active material layer / mass of the second active material layer) is preferably 1 / 9 or more and 3 / 7 or less, more preferably 1 / 9 or more and less than 3 / 7, and even more preferably 1 / 9 or more and 2 / 8 or less, from the viewpoint of input / output resistance.

[0030] First active material layer 13 has a recessed structure in which a plurality of recesses are formed on the side facing second active material layer 15. The recesses are shown in Fig. 1 as regions F where aggregated particles 14 are not present.

[0031] The second active material layer 15 has a convex structure with a plurality of protrusions formed on the side of the first active material layer 13. The protrusions are shown as regions in region F in FIG.

[0032] The recesses of the first active material layer 13 and the protrusions of the second active material layer 15 are combined to form an uneven interface. In the recesses of the first active material layer 13, the relatively high-resistance single particles 16 present in the protrusions of the second active material layer 15 are surrounded by the relatively low-resistance aggregate particles 14, improving conduction and tending to reduce input / output resistance. When the positive electrode plate 10 is a strip-shaped sheet or a rectangular sheet, the positive electrode active material layer may have an uneven interface in a direction parallel to the longitudinal direction, or in a direction parallel to the lateral direction, or in either direction.

[0033] The cross-sectional shape of the depressions and protrusions (for example, the shape of region F) may be, for example, rectangular, semicircular, semi-elliptical, triangular, trapezoidal, etc. The uneven shape of the interface is formed by the combination of depressions and protrusions arranged at regular intervals.

[0034] In a plan view of the positive electrode plate 10, the depressions and protrusions may be regularly arranged, such as in a pattern (striped) in which one or more linear depressions and protrusions are arranged in a direction parallel to the longitudinal or lateral direction, a pattern (lattice) in which one or more linear depressions and protrusions are arranged crossing each other in the longitudinal and lateral directions, or a pattern (dotted) in which point-like depressions and protrusions are regularly arranged. The type of pattern of the depressions and protrusions may correspond to the type of pattern of a concave-convex mold used to form the first active material layer, which will be described later.

[0035] When the recesses and protrusions are arranged in a striped pattern in a plan view of the positive electrode plate 10, they may be arranged in a direction parallel to either the longitudinal direction or the lateral direction of the positive electrode plate 10. When the recesses and protrusions are arranged in a striped pattern in a plan view of the positive electrode plate 10, the interface shape in the direction perpendicular to the stripes may be uneven.

[0036] When the recesses and protrusions are arranged in a grid pattern in a plan view of the positive electrode plate 10, the interface shape of the straight lines connecting the centers of adjacent grids can be uneven.

[0037] When the depressions and protrusions are arranged in a dot pattern in a plan view of the positive electrode plate 10, the interface shape of the straight line connecting the centers of adjacent dots can be uneven. When the depressions and protrusions are arranged in a dot pattern in a plan view of the positive electrode plate 10, the shape of the dots may be, for example, rectangular (square, oblong, rhombus, etc.), circular, elliptical, etc. When the depressions and protrusions are arranged in a dot pattern in a plan view of the positive electrode plate 10, the three-dimensional shape of the protrusions and depressions may be, for example, a rectangular parallelepiped, cube, cylinder, cone, truncated cone, square pyramid, truncated square pyramid, etc.

[0038] In a cross section of the positive electrode active material layer in the thickness direction, when the depth of the depression (the dimension in the thickness direction of the positive electrode active material layer 12) is C and the thickness of the second active material layer present in a portion where no depression is formed in the first active material layer (the dimension in the thickness direction of the positive electrode active material layer 12) is D, for example, the ratio of C to D (C / D) (hereinafter also referred to as the first ratio) is calculated by the following formula (1): (1) C / D≦3.0 can be satisfied. From the viewpoint of input / output resistance, the upper limit of the first ratio is preferably 2 or less, and the lower limit of the first ratio may be, for example, 0.3 or more or 0.5 or more. When the first ratio is in the above range, the distance (C+D) from the liquid surface of the single particles 16 present in region F falls within an appropriate range, which tends to make it easier to reduce the resistance of second active material layer 15 and easier to reduce input / output resistance.

[0039] In a cross section of the positive electrode active material layer in the thickness direction, when the thickness of the positive electrode active material layer is T, the depth of the depression (the dimension in the thickness direction of the positive electrode active material layer 12) is C, and the thickness of the second active material layer present in a portion of the first active material layer that is not a depression (the dimension in the thickness direction of the positive electrode active material layer 12) is D (hereinafter also referred to as dimension D), for example, the ratio of the sum of C and D to T [(C+D) / T] (hereinafter also referred to as second ratio) is calculated by the following formula (2): (2) (C+D) / T<0.5 can be satisfied. From the viewpoint of input / output resistance, the upper limit of the second ratio is preferably 0.4 or less. The lower limit of the second ratio may be, for example, 0.1 or more. When the second ratio is in the above range, the distance from the liquid surface of the second active material layer 15 falls within an appropriate range, which tends to make it easier to reduce the input / output resistance.

[0040] In a cross section of the positive electrode active material layer in the thickness direction, when the width of the protrusions [the dimension in the planar direction of the positive electrode active material layer 12 (the direction perpendicular to the thickness direction)] is A and the spacing between the protrusions [the dimension in the planar direction of the positive electrode active material layer 12 (the direction perpendicular to the thickness direction)] is B, for example, the ratio of B to A (B / A) (hereinafter also referred to as a third ratio) is expressed by the following formula (3): (3) 2≦B / A The upper limit of the third ratio is preferably 16 or less, more preferably 5 or less, from the viewpoint of input / output resistance. When the second ratio is within the above range, an appropriate amount of aggregated particles 14 is easily arranged in the spaces between the protrusions, thereby ensuring sufficient conductivity with single particles 16 present in region F, and as a result, input / output resistance tends to be easily reduced.

[0041] In a cross section of the positive electrode active material layer in the thickness direction, when the width of the protrusion is A and the average particle diameter of the single particle is R2, the ratio of A to R2 (A / R2) (hereinafter also referred to as the fourth ratio) is expressed by the following formula (4): (4) A / R2≦6.0 The lower limit of the fourth ratio is preferably 2.0 or more from the viewpoint of input / output resistance. When the fourth ratio is within the above range, the protrusions are easily filled with an appropriate amount of single particles 16, which tends to make the single particles 16 present inside the protrusions more conductive and to reduce the input / output resistance.

[0042] The thickness T of the positive electrode active material layer 12, the depth C of the depressions, the thickness D of the second active material layer present in the portion of the first active material layer that is not a depression, the width A of the protrusions, and the spacing B between the protrusions are measured according to the method described in the Examples section below.

[0043] In order to satisfy the first to fourth ratios, for example, the rolling conditions and basis weight of first active material layer 13 and second active material layer 15 can be adjusted, and the types of aggregated particles 14 and single particles 16 can be selected.

[0044] The positive electrode plate 10 can be fabricated, for example, by the following procedure. First, a positive electrode mixture slurry (hereinafter also referred to as the first slurry) for forming a first active material layer is applied to a positive electrode current collector and dried. Next, a predetermined uneven mold is prepared, and the mold is sandwiched between the press rolls of a roll press and rolled to form a recessed structure with multiple recesses on the surface of the first active material layer. Thereafter, a positive electrode mixture slurry (hereinafter also referred to as the second slurry) for forming a second active material layer is applied to the first active material layer at a predetermined mass ratio, and the second slurry fills the recesses formed in the first active material layer. After drying, the first active material layer and the second active material layer formed on the upper surface of the positive electrode current collector are rolled to a predetermined thickness, whereby the protrusions of the second active material layer fit into the recesses formed in the first active material layer, forming a positive electrode active material layer with an uneven interface, thereby producing the positive electrode plate 10. In addition to the positive electrode active material, the positive electrode mixture slurry may contain, for example, a conductive material, a binder, a solvent, etc. The pattern of the concave-convex mold may be, for example, striped, lattice, dotted, or the like.

[0045] <Nonaqueous electrolyte secondary battery> The battery of the present disclosure (hereinafter also referred to as the present battery) has a positive electrode plate and includes the above-described positive electrode plate, which tends to make it easier to reduce output resistance.

[0046] The battery typically includes an electrode assembly including a positive electrode and a nonaqueous electrolyte. The battery may have a battery case that houses the electrode assembly and the nonaqueous electrolyte. The battery case may include an exterior body having an opening and a sealing plate that seals the opening. The exterior body and the sealing plate may be formed using a metal such as Al, an Al alloy, iron, or an iron alloy, for example, an Al laminate film. A resin sheet serving as an electrode holder may be disposed between the electrode assembly and the exterior body.

[0047] The electrode assembly may include the above-mentioned positive electrode plate, negative electrode plate, and separator. In the electrode assembly, the active material layer of the positive electrode plate and the negative electrode active material layer of the negative electrode plate face each other via the separator. The electrode assembly may be a laminated type in which the positive electrode plate, negative electrode plate, and separator are stacked, or a wound type in which a laminate in which the positive electrode plate, negative electrode plate, and separator are stacked is wound.

[0048] A negative electrode plate typically includes a negative electrode current collector and a negative electrode active material layer formed on one or both sides of the negative electrode current collector. The negative electrode current collector is a metal foil made of a copper material such as copper or a copper alloy. The negative electrode active material layer contains a negative electrode active material and may further contain a conductive material, a binder, and the like.

[0049] Examples of the negative electrode active material include known materials, such as carbon-based active material particles such as graphite, and metal-based active material particles containing an element selected from the group consisting of Si, Sn, Sb, Bi, Ti, and Ge. Examples of the conductive material include those described above. Examples of the binder include cellulose-based resins such as CMC, methyl cellulose (MC), and hydroxypropyl cellulose; polyacrylic acid; and styrene-butadiene rubber (SBR). CMC can also be used as a thickener.

[0050] The separator may have a substrate with a single-layer or multi-layer structure and a functional layer on at least one side of the substrate. The substrate may be a film made of a resin such as a polyolefin (e.g., polyethylene or polypropylene), polyester, cellulose, or polyamide, or a porous sheet such as a nonwoven fabric. The functional layer may be, for example, an adhesive layer and / or a heat-resistant layer. The adhesive layer may be formed, for example, with an adhesive. The heat-resistant layer may contain, for example, a filler and a binder.

[0051] The non-aqueous electrolyte preferably contains an electrolyte in a non-aqueous solvent such as an organic solvent. Examples of the electrolyte include one or more of LiPF6, LiBF4, LiClO4, LiFSO3, and LiBOB. Examples of the non-aqueous solvent include one or more of ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate (PC), butylene carbonate (BC), and diethyl carbonate (DEC). The non-aqueous electrolyte may further contain additives such as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and fluoroethylene carbonate.

[0052] The present invention will be described in more detail below with reference to examples. [Example]

[0053] [Evaluation of input / output resistance] (Fabrication of non-aqueous electrolyte secondary battery) The positive electrode plate and graphite negative electrode prepared in the examples and comparative examples were cut to the specified dimensions. A separator consisting of two layers of polyethylene / heat-resistant layer was interposed between them, and they were laminated so that the heat-resistant layer and the positive electrode active material layer were in contact and the aluminum foil of the positive electrode current collector was exposed to produce an electrode assembly. The aluminum foil of the positive electrode current collector was welded to an aluminum plate for external current collection, and the graphite negative electrode was welded to a copper plate for external current collection. The assembly was then inserted into an outer shell of an aluminum laminate film and welded. An electrolyte solution of 1.15 mol / L LiPF6, EC+EMC+DMC (3:3:4 volume ratio) was poured into the laminate film, and the laminate film was sealed and left to stand for 12 hours to produce a nonaqueous electrolyte secondary battery.

[0054] (Measurement of input and output resistance) A nonaqueous electrolyte secondary battery (counter electrode: graphite) was charged at 0.5C to a state of charge (SOC) of 50% in a -10°C environment. After a 15-minute rest period, the battery was discharged at 0.1C for 10 seconds. The voltage and discharge current were recorded 0.1 and 10 seconds after the start of discharge, and then the battery was charged at 0.1C for 10 seconds. The voltage and charge current were recorded 0.1 and 10 seconds after the start of charge. The same procedure was repeated at current rates of 0.33C, 0.5C, 1C, and 1.5C. The discharge (charge) resistance between 0.1 and 10 seconds after the start of discharge (charge) was calculated from the relationship between the voltage and current 0.1 and 10 seconds after the start of discharge (charge).

[0055] [Measurement of average particle size R1 and R2] A measurement sample was prepared by dispersing a desired positive electrode active material in approximately 1 g of water. The measurement sample was introduced into a particle size distribution analyzer (Microtrack-Bell Corporation, laser diffraction particle size distribution analyzer "MT3000II") to obtain a volumetric particle size distribution. The particle diameter D50 was determined as the particle diameter at which the cumulative frequency of the smallest particle diameters in the volumetric particle size distribution reached 50%. The particle diameter D50 of agglomerated particles was determined as the average particle diameter R1, and the particle diameter D50 of single particles was determined as the average particle diameter R2.

[0056] [Measurement of thickness T of the positive electrode active material layer, width A and spacing B of the protrusions, depth C and dimension D of the recesses] The cross section of the positive electrode active material layer in the thickness direction was observed using a scanning electron microscope (SEM) to obtain cross-sectional SEM images. The thickness T of the positive electrode active material layer, the width A of the protrusions, the spacing B between the protrusions, the depth C of the depressions, and the dimension D were measured from 10 cross-sectional SEM images of the cross section at randomly selected positions on the positive electrode active material layer, and the average values ​​were calculated. The thickness T, the width A of the protrusions, the depth C of the depressions, and the dimension D were measured by selecting the position where the value was largest in the cross-sectional SEM image. The spacing B between the protrusions was measured by selecting the position where the value was smallest in the cross-sectional SEM image.

[0057] Example 1 A first slurry was prepared by mixing 100 parts by mass of the first active material [agglomerated particles, D50(R1): 10.2 μm], 1.5 parts by mass of a conductive material (graphite), 1 part by mass of a binder (PVdF powder), and an appropriate amount of a dispersion medium (N-methyl-2-pyrrolidone). A second slurry was prepared by mixing 100 parts by mass of the second active material [single particles, D50(R2): 3.9 μm], 1.5 parts by mass of a conductive material (graphite), 1 part by mass of a binder (PVdF powder), and an appropriate amount of a dispersion medium (N-methyl-2-pyrrolidone). The compositions of both the first and second active materials were LiNi 0.8 Co 0.1 Mn 0.1 It was O2.

[0058] The first active material layer was fabricated by applying the first slurry to the surface of a rectangular positive electrode current collector (Al foil) in a planar view and drying it. A predetermined concave-convex mold was prepared, and the mold was sandwiched between the press rolls of a roll press and rolled to form a recessed structure on the surface of the first active material layer, with multiple striped recesses parallel to the longitudinal direction. The concave-convex mold had a pattern in which striped recesses with a rectangular cross-section were arranged, with the protrusion width A of 10 μm (approximately 2.5 times R2), the protrusion spacing B of 20 μm, and the recess depth C of 0.075 times the total thickness T of the positive electrode active material layer. The second active material layer was then fabricated by applying the second slurry to the surface of the first active material layer and drying it. The basis weight of the second active material layer was adjusted to 1 / 9 of the basis weight of the first active material layer. A positive electrode plate was manufactured by rolling the first and second active material layers formed on the substrate surface to a predetermined thickness. The rolling conditions for the first and second active material layers were adjusted so that the first ratio (C / D) was 1.0, the second ratio [(C+D) / T] was 0.15, the third ratio (B / A) was 2, and the fourth ratio (A / R2) was 2.5. The second active material layer had a convex structure with multiple protrusions formed on the first active material layer side. In the cross section of the positive electrode active material layer in the short direction, the interface shape was an uneven shape where the protrusions of the first active material layer and the recesses of the second active material layer were combined. The results are shown in Table 1.

[0059] <Examples 2 to 7> Positive electrode plates were fabricated in the same manner as in Example 1, except that the rolling conditions for the first and second active material layers were adjusted to achieve the first to fourth ratios shown in Table 1. In Examples 2 to 7, the interface shape was an uneven shape in which protrusions in the first active material layer and depressions in the second active material layer were combined. The results are shown in Table 1.

[0060] <Comparative Example 1> A positive electrode plate was produced in the same manner as in Example 1, except that no recessed structure was formed in the first active material layer and no protruding structure was formed in the second active material layer. The results are shown in Table 1.

[0061] [Table 1]

[0062] Example 8 A positive electrode plate was fabricated in the same manner as in Example 1, except that the mass ratio of the second active material layer to the first active material layer was set to the mass ratio shown in Table 2, and the rolling conditions for the first active material layer and the second active material layer were adjusted to achieve the first to fourth ratios shown in Table 2. The interface shape was an uneven shape in which protrusions in the first active material layer and depressions in the second active material layer were combined. The results are shown in Table 2.

[0063] <Comparative Example 2> A positive electrode plate was produced in the same manner as in Example 1, except that the mass ratio of the second active material layer to the first active material layer was set to the mass ratio shown in Table 2, that no recessed structure was formed in the first active material layer, and that no protruding structure was formed in the second active material layer. The results are shown in Table 2.

[0064] [Table 2]

[0065] <Comparative Example 3> A positive electrode plate was fabricated in the same manner as in Example 1, except that the mass ratio of the second active material layer to the first active material layer was set to the mass ratio shown in Table 3, and the rolling conditions for the first active material layer and the second active material layer were adjusted to achieve the first to fourth ratios shown in Table 3. The interface shape was an uneven shape in which protrusions in the first active material layer and depressions in the second active material layer were combined. The results are shown in Table 3.

[0066] <Comparative Example 4> A positive electrode plate was produced in the same manner as in Example 1, except that the mass ratio of the second active material layer to the first active material layer was set to the mass ratio shown in Table 3, that no recessed structure was formed in the first active material layer, and that no protruding structure was formed in the second active material layer. The results are shown in Table 3.

[0067] [Table 3]

[0068] Examples 1 to 7, in which the interface of the positive electrode active material layer had an uneven shape, exhibited reduced input / output resistance compared to Comparative Example 1, in which the interface of the positive electrode active material layer did not have an uneven shape. Furthermore, Example 8, in which the interface of the positive electrode active material layer had an uneven shape, exhibited reduced input / output resistance compared to Comparative Example 2, in which the interface of the positive electrode active material layer did not have an uneven shape. On the other hand, Comparative Example 3, in which the interface of the positive electrode active material layer had an uneven shape, did not exhibit a reduction in input / output resistance compared to Comparative Example 4, in which the interface of the positive electrode active material layer did not have an uneven shape, because the mass ratio of the second active material layer was high and the distance from the liquid surface of the second active material layer increased, resulting in a greater impact of deterioration in diffusion resistance. [Explanation of symbols]

[0069] 10 positive electrode plate, 11 positive electrode current collector, 12 positive electrode active material layer, 13 first active material layer, 14 agglomerated particles, 15 second active material layer, 16 single particles.

Claims

1. A positive electrode plate including a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer includes a first active material layer and a second active material layer, the first active material layer is disposed on the positive electrode current collector side, the second active material layer is disposed in contact with the first active material layer on a side of the first active material layer opposite to the positive electrode current collector, the first active material layer contains secondary particles formed by aggregation of primary particles, the second active material layer includes a single particle, the first active material layer has a recessed structure in which a plurality of recesses are formed on the second active material layer side, the second active material layer has a convex structure in which a plurality of protrusions are formed on the first active material layer side, in a cross section of the positive electrode active material layer in a thickness direction passing through the plurality of recesses and the plurality of protrusions, the shape of an interface where the first active material layer and the second active material layer contact each other is an uneven shape formed by the plurality of recesses and the plurality of protrusions combined with each other, a mass ratio of the second active material layer to the first active material layer in the positive electrode active material layer is 1 / 9 or more and 3 / 7 or less.

2. When the depth of the recess is C and the thickness of the second active material layer present in the portion of the first active material layer where the recess is not formed is D, the ratio of C to D (C / D) is expressed by the following formula (1): (1) C / D≦3.0 The positive electrode plate according to claim 1 , which satisfies the above.

3. When the thickness of the positive electrode active material layer is T, the depth of the recess is C, and the thickness of the second active material layer present in the portion of the first active material layer that is not the recess is D, the ratio [(C+D) / T] of the sum of C and D to T is expressed by the following formula (2): (2) (C+D) / T<0.5 The positive electrode plate according to claim 1 or 2, which satisfies the above.

4. When the width of the protrusion is A and the interval between the protrusions is B, the ratio of B to A (B / A) is expressed by the following formula (3): (3) 2≦B / A The positive electrode plate according to claim 1 or 2, which satisfies the above.

5. The width of the protrusion is A, and the average particle diameter of the single particle is R ２ When this is done, R ２ The ratio of A to ２ ) is expressed by the following formula (4): (4) A / R ２ ≦6.0 The positive electrode plate according to claim 1 or 2, which satisfies the above.

6. A non-aqueous electrolyte secondary battery comprising the positive electrode plate according to claim 1 or 2.

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