Nonaqueous electrolyte secondary battery

A nonaqueous electrolyte secondary battery which includes a metal foil collector of one of a positive electrode plate and a negative electrode plate which is exposed at at least part of the outermost circumferential surface of the electrode group in a rolling direction, and the collector is in contact with the inner surface of a case main body. When a region of the inner surface of the case main body from the opening-portion-side edge to the position in contact with the bottom-portion-side edge of the gasket is denoted as a first region S1 and a region of the inner surface of the case main body opposing the outermost circumferential surface of the electrode group is denoted as a second region S2, the arithmetic mean roughness Ra1 of the first region S1 and the arithmetic mean roughness Ra2 of the second region S2 satisfy Ra1<Ra2.

TECHNICAL FIELD

The present invention relates to a nonaqueous electrolyte secondary battery.

BACKGROUND ART

In the related art, a known secondary battery includes a power generation element in which a positive electrode plate and a negative electrode plate are rolled with a separator interposed therebetween (electrode group) and a metal case (case main body) storing the power generation element, wherein the metal case is hermetically sealed by a sealing plate (sealing body) with a gasket interposed therebetween, and includes a configuration in which unevenness of the inner surface of the sealing portion of the metal case is reduced and the number of peaks is reduced (refer to PTL 1). It is disclosed that, according to the configuration, a high-viscosity sealing agent being made to readily fill the space causing the unevenness enables a battery having excellent resistance to leakage of an electrolytic solution to be obtained.

In addition, in a known configuration, a battery can constituting an alkaline manganese battery or the like is in the shape of a tube that has a bottom and that has a side-wall main portion and a swaged portion into which a gasket is inserted and which is located at a position nearer than the side-wall main portion to an opening, wherein the swaged portion is smoother than the side-wall main portion (refer to PTL 2). It is disclosed that, according to the configuration, the contact area between the battery can and the positive electrode mixture being increased enables the contact resistance to be reduced and enables leakage of a liquid to be suppressed from occurring.

Further, in a known secondary battery, a metal foil negative electrode collector is exposed at the outermost circumferential surface of an electrode group, and the negative electrode collector is in contact with the inner surface of the battery case so that the heat dissipation effect can be improved (refer to PTL 3).

CITATION LIST

Patent Literature

SUMMARY OF INVENTION

Technical Problem

In recent years, uses for secondary batteries have expanded to, for example, drive power supplies for electric cars and storage battery devices for utilizing natural energy, and secondary batteries are required for realizing higher capacity and higher output characteristics and for realizing high reliability of sealing portions. However, there is a possibility of the reliability of the sealed portion deteriorating. For example, an electrolytic solution remaining on a grooved portion formed in the vicinity of an opening portion so as to protrude toward the inside of the case main body may seep to the outside when the opening portion of the case main body is sealed during assembly of the battery, or an electrolytic solution interposed between a gasket and the case main body after assembly may cause rust formation.

Meanwhile, regarding the secondary battery in which a metal foil negative electrode collector is exposed at the outermost circumferential surface of an electrode group and the negative electrode collector is in contact with the inner surface of the battery case, as in the configuration described in PTL 3, if a contact state is poor, since the battery resistance is increased, the output of the secondary battery may be hindered from increasing.

It is an object of the present invention to realize higher output and high reliability of a sealed portion in a nonaqueous electrolyte secondary battery in which a metal foil negative electrode collector is exposed at the outermost circumferential surface of an electrode group and the negative electrode collector is in contact with the inner surface of the battery case.

Solution to Problem

A nonaqueous electrolyte secondary battery according to the present disclosure includes a tubular case main body having an opening portion and a bottom portion, a sealing body fixed to the opening portion of the case main body by swaging with a gasket interposed therebetween, and a roll-type electrode group which is stored in the case main body and in which a positive electrode plate and a negative electrode plate are rolled with a separator interposed therebetween, wherein a metal foil collector of one electrode plate of the positive electrode plate and the negative electrode plate is exposed at at least part of the outermost circumferential surface of the electrode group in the rolling direction, the collector being in contact with the inner surface of the case main body, and when a region of the inner surface of the case main body from the opening-portion-side edge to the position in contact with the bottom-portion-side edge of the gasket is denoted as a first region and a region of the inner surface of the case main body opposing the outermost circumferential surface of the electrode group is denoted as a second region, the arithmetic mean roughness Ra1of the first region and the arithmetic mean roughness Ra2of the second region satisfy Ra1<Ra2.

Advantageous Effects of Invention

According to the nonaqueous electrolyte secondary battery of the present disclosure, in the configuration in which the metal foil collector of the electrode plate as the outermost circumferential surface of the electrode group is in contact with the case main body, since the contact area between the collector and the second region of the case main body increases and the contact resistance can be reduced, higher output can be realized. Further, since the wettability of the first region of the case main body deteriorates and the electrolytic solution is readily repelled, the electrolytic solution is suppressed from seeping. Therefore, according to the nonaqueous electrolyte secondary battery of the present disclosure, higher output and, in addition, high reliability of the sealing portion can be realized.

DESCRIPTION OF EMBODIMENTS

The embodiment according to the present invention will be described below in detail with reference to the attached drawings. In the following explanations, specific shapes, materials, numerical values, directions, and the like are exemplifications for the sake of facilitating understanding of the present invention and can be appropriately changed in accordance with the specifications of nonaqueous electrolyte secondary batteries. In this regard, the word “substantially” below is used to denote the case of completely the same and, in addition, the case assumed to be essentially the same. Further, in the case in which a plurality of embodiments and examples are included below, it is essentially intended that features of these be used in appropriate combinations.

FIG.1is a sectional view of a nonaqueous electrolyte secondary battery10according to an embodiment.FIG.2is a sectional view of a roll outer portion (outer-circumferential-surface-side portion) of an electrode group in the direction perpendicular to the axis direction in the embodiment.FIG.3is a sectional view of a case main body15before an electrode group14is inserted. That is,FIG.3is a sectional view of the case main body15before a shoulder portion20and a grooved portion21inFIG.1are formed. As illustrated inFIG.1toFIG.3, the nonaqueous electrolyte secondary battery10includes a roll-type electrode group14, a nonaqueous electrolyte (not shown in the drawing) serving as an electrolytic solution, the case main body15, and a sealing body16. The electrode group14includes a positive electrode plate11, a negative electrode plate12, and a separator13, and the positive electrode plate11and the negative electrode plate12are spirally rolled with the separator13interposed therebetween. One direction of the rolling axis direction of the electrode group14may be referred to as “upward”, and the other direction of the rolling axis direction may be referred to as “downward”. The nonaqueous electrolyte contains a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.

Referring toFIG.2, the positive electrode plate11has a band-like positive electrode collector31and a positive electrode lead19connected to the positive electrode collector31(FIG.1). The positive electrode lead19is a conductive member for electrically connecting the positive electrode collector31to a positive electrode terminal and extends from the upper end of the positive electrode collector31in the electrode group14in one direction of the rolling axis direction α (upward). The positive electrode lead19is disposed at, for example, a substantially center portion of the electrode group14in the radial direction β. The positive electrode lead19is a band-like conductive member. There is no particular limitation regarding the constituent material of the positive electrode lead. Preferably, the positive electrode lead19is composed of a metal containing aluminum as a primary component. Further, in the positive electrode plate11, positive electrode active material layers32and33are disposed on the roll inner surface (inner surface in the radial direction) and on the roll outer surface (outer surface in the radial direction), respectively, of the positive electrode collector. InFIG.2, the positive electrode active material layers32and33are indicated by thin dotted portions.

Referring toFIG.2, the negative electrode plate12includes a band-like metal foil negative electrode collector35and negative electrode active material layers36and37disposed on the roll inner surface (inner surface in the radial direction) and on the roll outer surface (outer surface in the radial direction), respectively, of the negative electrode collector35. InFIG.2, the negative electrode active material layers36and37are indicated by diagonally shaded portions. Regarding the negative electrode plate12as the outermost circumferential surface of the electrode group14, the negative electrode collector35is in contact with the inner surface of the tubular portion of the case main body15serving as a negative electrode terminal, described later, so as to be electrically connected to the case main body15. For this purpose, the negative electrode collector35is exposed at the outermost circumferential surface of the electrode group14in the circumferential direction, and the negative electrode collector35is in contact with the case main body15. Consequently, the current collecting performance between the negative electrode plate12and the case main body15can be ensured.

As described above, the electrode group14has a rolled structure in which the positive electrode plate11and the negative electrode plate12are spirally rolled with the separator13interposed therebetween. Each of the positive electrode plate11, the negative electrode plate12, and the separator13is formed into a band-like shape and is spirally rolled around a roll core so as to take on a state of being alternately stacked in the radial direction β of the electrode group14. The roll core is removed so as to form a space28in the electrode group14, and the center axis in the longitudinal direction of the space28is a rolling axis29. Regarding the electrode group14, the longitudinal direction of each electrode plate is the rolling direction γ (FIG.2), and the width direction of each electrode plate is the rolling axis direction α (FIG.1). The rolling-end edge E of the electrode group14(FIG.2) is fixed to the outermost circumferential surface of the electrode group14by attaching a rolling-stop tape (not illustrated in the drawing). InFIG.2, the separator13is omitted from the drawing.

The case main body15and the sealing body16constitute a metal battery case for storing the electrode group14and the nonaqueous electrolyte. Insulating plates17and18are disposed on the top and bottom, respectively, of the electrode group14. The positive electrode lead19extends toward the sealing body16through a through hole of the upper insulating plate17and is welded to the lower surface of a filter22serving as the bottom plate of the sealing body16. In the nonaqueous electrolyte secondary battery10, a cap26that is the top plate of the sealing body16electrically connected to the filter22serves as a positive electrode terminal.

The case main body15is a metal container having the shape of a tube with an opening portion15aand a bottom portion15b, for example, having the shape of a circular cylinder with a bottom. The sealing body16is fixed to the opening portion15aof the case main body15by swaging with a gasket27interposed therebetween so as to ensure sealing performance inside of the battery case. The case main body15has a shoulder portion20, which is formed by swaging all around the opening end portion toward the inner circumference, and a grooved portion21. The grooved portion21is formed by, for example, pressing the side surface portion from the outside and is a portion for supporting the sealing body16. Preferably, the grooved portion21is formed into an annular shape in the circumferential direction of the case main body15, and the upper surface thereof supports the sealing body16. The sealing body16seals the opening portion of the case main body15. The surface roughness of the inner surface of the case main body15is specified. This will be described later in detail.

The sealing body16includes the filter22, a lower valve body23, an insulating member24, an upper valve body25, and the cap26which are stacked successively from the electrode group14. Each member constituting the sealing body16has, for example, a disc shape or a ring shape, and the members excluding the insulating member24are electrically connected to each other. The center portion of the lower valve body23and the center portion of the upper valve body25are connected to each other, and the insulating member24is interposed between the peripheral edge portions of the lower valve body23and the upper valve body25. When the internal pressure of the battery is increased due to abnormal heat generation, for example, the lower valve body23ruptures, and the upper valve body25thereby bulges toward the cap26so as to be separated from the lower valve body23. As a result, electrical connectivity between the lower valve body23and the upper valve body25is broken. When the internal pressure is further increased, the upper valve body25ruptures, and gas is discharged through an opening portion26aof the cap26.

The positive electrode plate11and the negative electrode plate12constituting the electrode group14will be described below in detail. The positive electrode plate11includes the positive electrode collector31and the positive electrode active material layers32and33disposed on the positive electrode collector31. In the present embodiment, the positive electrode active material layers32and33are disposed on the respective surfaces of the positive electrode collector31. Regarding the positive electrode collector31, for example, metal foil of aluminum or the like or a film provided with the metal as a surface layer is used. A favorable positive electrode collector31is metal foil containing aluminum or an aluminum alloy as a primary component. The thickness of the positive electrode collector31is, for example, 10 μm to 30 μm.

Preferably, the positive electrode active material layers32and33contain a positive electrode active material, a conductive agent, and a binder. The positive electrode plate11is produced by coating both surfaces of the positive electrode collector31with a positive electrode mixture slurry containing the positive electrode active material, the conductive agent, the binder, and a solvent such as N-methyl-2-pyrrolidone (NMP) and performing drying and rolling.

Examples of the positive electrode active material include lithium transition metal oxides containing transition metal elements such as Co, Mn, and Ni. There is no particular limitation regarding the lithium transition metal oxides, and complex oxides denoted by a general formula Li1+xMO2(in the formula, −0.2<x≤0.2 and M contains at least one of Ni, Co, Mn, and Al) are preferable.

Examples of the conductive agent include carbon materials such as carbon black (CB), acetylene black (AB), Ketjenblack, and graphite. Examples of the binder include fluororesins such as polytetrafluoroethylenes (PTFE) and polyvinylidene fluorides (PVdF), polyacrylonitriles (PAN), polyimides (PI), acrylic resins, and polyolefin-based resins. Meanwhile, these resins may be used in combination with carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO), or the like. These may be used alone, or at least two types may be used in combination.

A plain portion (not illustrated in the drawing) at which the surface of the metal constituting the positive electrode collector31is exposed is disposed in the positive electrode plate11. The plain portion is a portion to be connected to the positive electrode lead19and is a portion in which the surface of the positive electrode collector31is not covered by the positive electrode active material layer. The positive electrode lead19is connected to the plain portion by, for example, ultrasonic welding.

The negative electrode plate12includes the negative electrode collector35and the negative electrode active material layers36and37disposed on the negative electrode collector35. In the present embodiment, the negative electrode active material layers36and37are disposed on the respective surfaces of the negative electrode collector35. Further, in the negative electrode plate12, a rolling-start-side plain region (not illustrated in the drawing), a double-sided active material region12a, a single-sided active material region12b, and a rolling-end-side plain region12care arranged successively from where rolling starts toward where rolling ends. In the double-sided active material region12a, the negative electrode active material layers36and37are disposed on the respective surfaces of the negative electrode collector35. In the single-sided active material region12b, the negative electrode active material layer36is disposed on the roll inner surface only of the negative electrode collector35. In the plain region, both surfaces of the negative electrode collector35are exposed without being covered with the negative electrode active material layer. The single-sided active material region12bextends about one revolution from the rolling-end edge of the double-sided active material region12ato the rolling-end edge of the single-sided active material region12b, and the plain region12cfurther extends from the rolling-end edge of the single-sided active material region12b. Consequently, the negative electrode collector35in part of the single-sided active material region12band in the plain region12cis exposed at the outermost circumferential surface of the electrode group14in the circumferential direction. The negative electrode collector35is composed of, for example, metal foil of copper or the like. The thickness of the negative electrode collector35is, for example, 5 μm to 30 μm. InFIG.2, the plain region12cof the negative electrode plate12is indicated as being at a distance from the roll outer surface of the single-sided active material region12binside the plain region12c. However, actually, the roll inner surface of the plain region12cis in contact with the roll outer surface of the single-sided active material region12b.

Preferably, the negative electrode active material layers36and37contain a negative electrode active material and a binder. The negative electrode plate12is produced by, for example, coating both surfaces of the negative electrode collector35with a negative electrode mixture slurry containing the negative electrode active material, the binder, water, and the like and performing drying and rolling.

There is no particular limitation regarding the negative electrode active material provided that lithium ions can be reversibly occluded and released, and, for example, carbon materials such as natural graphite and artificial graphite, metals such as Si and Sn which are alloyed with lithium, and alloys, complex oxides, and the like containing these materials can be used. In particular, using a negative electrode active material that expands to a great extent during charging enables the contact resistance between the negative electrode collector35and the case main body15to be reduced. Consequently, it is preferable that the negative electrode active material contain a silicon material such as Si, a Si alloy, or a Si oxide. Regarding the binder contained in the negative electrode active material layers36and37, for example, the same resins as in the case of the positive electrode plate11are used. In the case in which the negative electrode mixture slurry is prepared from an aqueous solvent, styrene-butadiene rubber (SBR), CMC or a salt thereof, polyacrylic acid or a salt thereof, polyvinyl alcohol, and the like can be used. These may be used alone, or at least two types may be used in combination.

Regarding the separator13(FIG.1), a porous sheet having ion permeability and insulation performance is used. Specific examples of the porous sheet include microporous thin films, woven fabrics, and nonwoven fabrics. Olefin resins such as polyethylenes and polypropylenes are favorable as the material for forming the separator13. The thickness of the separator13is, for example, 10 μm to 50 μm. The thickness of the separator13tends to be reduced in accordance with increased capacity and increased output of the battery. The separator13has a melting temperature of, for example, about 130° C. to 180° C.

Meanwhile, a rolling-stop tape (not illustrated in the drawing) is attached to the outermost circumferential surface of the electrode group14at which the negative electrode collector35of the negative electrode plate12is exposed so as to fix the rolling-end edge E of the negative electrode plate12(FIG.2) that is the rolling-end edge of the electrode group14.

The surface roughness of the inner surface of the case main body15is specified as described below.FIG.3is a sectional view of the case main body15before the shoulder20and the grooved portion21are formed. At least part of the inner surface of the case main body15in the longitudinal direction (corresponding to the rolling axis direction α inFIG.1) is allocated to the first region S1and the second region S2. The first region S1is a region of the inner surface of the case main body15from an opening-portion-side edge15cto the position in contact with the bottom-portion-side edge27aof the gasket27(FIG.1). InFIG.3, the position at which the inner surface of the case main body15is in contact with the bottom-portion-side edge27aof the gasket27is indicated by L1, and the first region S1is indicated by arrow A1.

The second region S2is a region of the inner surface of the case main body15opposing the outermost circumferential surface of the negative electrode collector35that is the outermost circumferential surface of the electrode group14in the radial direction. InFIG.3, the portions corresponding to both ends of the second region S2in the length direction (corresponding to the rolling axis direction a inFIG.1) are indicated by L2and L3, and the second region S2is indicated by arrow A2. At this time, the arithmetic mean roughness Ra1of the first region S1and the arithmetic mean roughness Ra2of the second region S2are specified to satisfy Ra1<Ra2.

For example, on a basis of the arithmetic mean roughness specified in JIS B 0601-2001, the arithmetic mean roughness Ra1of the first region S1is less than 0.4 μm, and the arithmetic mean roughness Ra2of the second region S2is 0.4 μm or more and 3 μm or less.

According to the nonaqueous electrolyte secondary battery10above, the arithmetic mean roughness Ra1and the arithmetic mean roughness Ra2of the first region S1and the second region S2, respectively, of the inner surface of the case main body15are specified to satisfy Ra1<Ra2. Consequently, in the configuration in which the metal foil negative electrode collector35of the negative electrode plate12as the outermost circumferential surface of the electrode group14is in contact with the case main body15, the electrical contact resistance between the negative electrode collector35and the second region S2of the case main body15can be reduced. In general, to reduce electrical contact resistance with respect to surface-to-surface contact between two metal materials, it is considered that the surface roughness of the metal material has to be reduced so as to increase the contact area. However, the inventors of the present disclosure found that the metal foil negative electrode collector35as described in the embodiment has flexibility and is deformed along the uneven shape of the inner surface of the case main body15. Therefore, setting the arithmetic mean roughness Ra2of the second region S2to be greater than Ra1enables the contact area between the negative electrode collector35and the second region S2of the case main body15to be increased. As a result, since the electrical contact resistance between the negative electrode collector35and the second region S2of the case main body15can be reduced, higher output of the nonaqueous electrolyte secondary battery10can be realized.

Further, since the arithmetic mean roughness Ra1of the first region S1of the case main body15is reduced, the wettability of the first region S1deteriorates, and the electrolytic solution is readily repelled. Consequently, the electrolytic solution attached to the surface of the case main body15readily flows down toward the bottom portion15balong the surface of the case main body15, and, in addition, the electrolytic solution can be suppressed from creeping up toward the opening. Therefore, the electrolytic solution is suppressed from seeping. As a result, high reliability can be realized with respect to the sealing portion that is formed based on contact between the first region S1and the gasket27.

FIG.4is a sectional view of the lower half portion of a nonaqueous electrolyte secondary battery10ain another example of the embodiment. Regarding the nonaqueous electrolyte secondary battery10a, in the same manner as the configuration inFIG.1toFIG.4, a negative electrode collector exposed at the outermost circumferential surface of the electrode group14is in contact with the inner surface of a tubular portion of the case main body15. In addition to this, regarding the negative electrode collector, a negative electrode lead38is connected to a portion located at the inner circumferential portion of the electrode group14. Regarding the negative electrode lead38, a portion that extends downward from the negative electrode collector is electrically connected to a bottom portion15bof the case main body15. Consequently, the rolling-start-side edge of the negative electrode plate12is electrically connected to the bottom portion15bof the case main body15through the negative electrode lead38. The negative electrode lead38is a band-like conductive member. There is no particular limitation regarding the constituent material of the negative electrode lead38. Preferably, the negative electrode lead38is composed of a metal containing nickel or copper as a primary component or a metal containing both nickel and copper. According to the above-described configuration, further favorable current collecting performance of the negative electrode can be readily ensured. In the present example, the other components and the operations are the same as in the configurations illustrated inFIG.1toFIG.3.

EXAMPLES

Next, a nonaqueous electrolyte secondary battery in example 1 will be described.

[Production of Positive Electrode Plate]

A lithium-nickel-cobalt-aluminum complex oxide represented by LiNi0.88Co0.09Al0.03O2was used as a positive electrode active material. Thereafter, 100 parts by mass of LiNi0.88Co0.09Al0.03O2(positive electrode active material), 1.0 parts by mass of acetylene black, and 0.9 parts by mass of polyvinylidene fluoride (PVDF) (binder) were mixed in a solvent, N-methyl-2-pyrrolidone (NMP), so as to prepare a positive electrode mixture slurry. Subsequently, both surfaces of an elongated aluminum foil positive electrode collector were uniformly coated with the paste-like positive electrode mixture slurry, drying was performed in a dryer so as to remove NMP, and rolling by using a roll press machine was performed so as to obtain an elongated positive electrode plate having a predetermined thickness. Further, the positive electrode plate subjected to rolling was cut into a predetermined electrode size so as to produce a positive electrode plate11. In this regard, the crystal structure of LiNi0.88Co0.09Al0.03O2is a layered rock salt structure (hexagonal crystal, space group R3-m). In addition, a plain portion in which an active material was not disposed was formed in the center portion of the positive electrode plate11in the length direction, and an aluminum positive electrode lead was connected to the resulting plain portion by ultrasonic welding.

[Production of Negative Electrode Plate]

A mixture of 95 parts by mass of graphite powder and 5 parts by mass of silicon oxide was used as a negative electrode active material. Thereafter, 100 parts by mass of negative electrode active material, 1 part by mass of styrene-butadiene rubber (SBR) serving as a binder, and 1 part by mass of carboxymethyl cellulose (CMC) serving as a thickener were mixed. The resulting mixture was dispersed in water so as to prepare a negative electrode mixture slurry. Both surfaces of a copper foil negative electrode collector were coated with the resulting negative electrode mixture slurry, drying was performed by using a dryer, and rolling was performed by using a compression roller so as to produce an elongated negative electrode plate having a predetermined thickness. The elongated negative electrode plate was cut into a predetermined electrode size so as to produce a negative electrode plate12. In addition, a negative electrode lead composed of a nickel-copper-nickel clad material was connected, by ultrasonic welding, to a position in the plain portion of the negative electrode plate12that serves as the inner circumferential portion of the electrode group after rolling.

Ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed at a volume ratio of EC:DMC=1:3, 5 parts by mass of vinylene carbonate (VC) was added to 100 parts by mass of the resulting mixture, and 1.5 mol/L of LiPF6was dissolved so as to prepare a nonaqueous electrolytic solution serving as a nonaqueous electrolyte.

A roll-type electrode group14was produced by spirally rolling the resulting positive electrode plate11and negative electrode plate12with a polyolefin-based resin separator13interposed therebetween. At this time, a copper foil negative electrode collector35was exposed at the outermost circumference of the electrode group14. The outer diameter of the electrode group14was controlled so that the contact area of 290 mm2or more was ensured when the electrode group14was arranged in the case main body15and the negative electrode collector35was brought into contact with the inner surface of the tubular portion of the case main body15.

[Adjustment of Surface Roughness of Case Main Body]

The case main body15was produced by using a steel plate. The inner surface of the case main body15is a worked portion based on plastic deformation, and the surface roughness of the worked portion is in accordance with the surface roughness of the material. Therefore, the case main body15was produced by preparing a material having an arithmetic mean roughness based on JIS B 0601-2001 of 0.4 to 3 μm so as to reduce the contact resistance between the second region S2of the inner surface of the case main body15and the copper foil negative electrode collector as the outermost circumference of the electrode group14. Regarding the inner surface of the case main body15, the first region S1that had low surface roughness and that was upper than the grooved portion21was worked by using a drawing die having surface roughness of less than 0.4 μm during a plasticity step, and the surface roughness was adjusted by transferring the surface roughness of the die to the first region S1.

A disc-like insulating plate18was inserted inside the above-described case main body15, the electrode group14was inserted above the insulating plate18, and the negative electrode lead connected to the negative electrode plate12was connected to the inner surface of the bottom portion15bof the case main body15by welding. Subsequently, an insulating plate17was inserted above the electrode group14inside the case main body15. The grooved portion21having a cross section in the shape of the letter U was formed by plastic working all around the circumference of the case main body on the opening-portion-side above the insulating plate17. Thereafter, a predetermined amount of the prepared nonaqueous electrolytic solution was placed inside the case main body15in which the electrode group14was placed. The positive electrode lead connected to the positive electrode plate11was connected to the sealing body16by welding, the sealing body16was inserted inside the opening portion of the case main body15with the gasket27interposed therebetween, and the opening end portion of the case main body15was swaged so as to produce a hermetic nonaqueous electrolyte secondary battery10.

The inventors of the present disclosure performed a simulation of the surface roughness by using a can material test specimen imitating the case main body15and a metal foil test specimen imitating the negative electrode collector35. Each of the can material test specimen and the metal foil test specimen was in the shape of a sheet having a size of 19.5 mm×19.5 mm.

In a first simulation, a pressure imitating the inside of the battery was applied to the two test specimens stacked one another, and an electrical resistance value between the test specimens was measured by using a four-terminal method.FIG.5illustrates the relationship between the contact resistivity based on the electrical resistance value measured in the experiment and the surface roughness (arithmetic mean roughness Ra2) of the can material test specimen. The contact resistivity illustrated inFIG.5is indicated by a relative value where the contact resistivity was assumed to be 100 when the arithmetic mean roughness Ra2was 0.1 μm. According to the result illustrated inFIG.5, there was a tendency of the contact resistivity to reduce when the arithmetic mean roughness Ra2was 0.4 μm or more. Consequently, it is conjectured that a result having the same tendency will be obtained in the embodiment.

In a second simulation, two tabular can material test specimens were used. The arithmetic mean roughness Ra1of the surface of each of the two can material test specimens was 0.1 μm or 0.4 μm. Each of the two test specimens was stood perpendicularly to a horizontal plane, and the electrolytic solution was dripped along the surface by using a dropping pipette. After a lapse of 10 seconds, the amount of the electrolytic solution remaining at the dripping place was compared. As a result, regarding the test specimen having an arithmetic mean roughness Ra1of 0.1 μm, the electrolytic solution did not remain, but regarding the test specimen having an arithmetic mean roughness Ra1of 0.4 μm, the electrolytic solution remained. Consequently, it was ascertained that the amount of the electrolytic solution remaining on the surface of the case main body15can be decreased by reducing the surface roughness.

In this regard, in the above-described embodiment, the case in which the negative electrode collector35was exposed at the outermost circumferential surface of the electrode group14in the rolling direction and in which the negative electrode collector35was in contact with the inner surface of the case main body15was explained. Meanwhile, a configuration in which the negative electrode collector is exposed at only part of the outermost circumferential surface of the electrode group in the rolling direction and in which the negative electrode collector is in contact with the inner surface of the case main body15may be adopted. Alternatively, the positive electrode plate11may be arranged at the outermost circumference of the electrode group14so that the positive electrode collector is in contact with the inner surface of the case main body15.

REFERENCE SIGNS LIST