The present application claims priority to Japanese Patent Application No. 2021-26205 filed on Feb. 22, 2021, the entire contents whereof are incorporated in the present specification by reference.
The present disclosure relates to a secondary battery and to a method for producing a secondary battery.
A secondary battery such as a lithium ion secondary battery ordinarily has: an electrode body provided with a pair of electrode plates (positive electrode plate and negative electrode plate), a battery case in which the electrode body is accommodated, and electrode terminals (positive electrode terminal and negative electrode terminal) exposed to the outside of the battery case. Each electrode plate that makes up the electrode body has, for instance, an electrode core body (positive electrode core body and negative electrode core body) which is a foil-like metal member, and an electrode active material layer (Positive electrode active material layer and negative electrode active material layer) formed on the surface of the electrode core body.
Examples of such an electrode body of a secondary battery include a wound electrode body in which a positive electrode plate and a negative electrode plate are wound across a separator. A porous band-shaped film or the like having a base material layer made of a resin material such as polyethylene (PE) can be ordinarily used as a separator in such a wound electrode body. A separator having a heat-resistant layer formed on the surface of the base material layer may be used herein, from the viewpoint of improving the safety of the secondary battery. For instance WO 2012/124093 discloses a separator having a porous resin layer (base material layer) and a porous heat-resistant layer laid up on at least one face of the resin layer. The heat-resistant layer contains a filler and a binder made of an inorganic material. A separator having this type of heat-resistant layer suppresses heat shrinkage at the time of rises in temperature, and accordingly allows preventing the occurrence of internal short circuits, and improving the safety of the secondary battery.
Both ends in a direction (winding axis direction) along the winding axis of a wound electrode body having the above configuration are formed respectively with electrode tab groups being a stack of a plurality of electrode tabs with exposed electrode cores. Such electrode tab groups are connected to conductive members such as electrode collectors. These collector members are connected to respective electrode terminals, to enable, as a result, conduction between the wound electrode body inside the battery case and the electrode terminals outside the battery case.
Examples of the shape of the above wound electrode body include a flat shape. Such a flat-shaped wound electrode body is produced through press molding of the cylindrical wound electrode body (cylindrical body) that has been produced through winding of a positive electrode plate and a negative electrode plate across a separator. In such a wound electrode body there are formed a pair of curved portions the outer surface of which is curved, and a flat portion the outer surface of which, connecting the pair of curved portions, is flat. In the flat portion of such a flat-shaped wound electrode body the distance between the positive electrode plate and the negative electrode plate (inter-electrode distance) is small, and thus movement of charge carriers across the electrodes is promoted as a result.
In recent years in the field of secondary batteries, a structure, has been proposed in which a wound electrode body is accommodated inside a battery case, with an electrode tab groups in a bent state. As a result, space can be saved for the electrode tab groups, and the width of the wound electrode body can be increased up to a position in the vicinity of the inner wall of the battery case. In consequence, the volume of the wound electrode body with respect to the internal volume of the battery case increases, which can significantly contribute to improve battery performance. In secondary batteries having such a configuration, local increases in inter-electrode distance may however occur, in that stress at the time of bending of the electrode tab groups acts on the flat portion close to the electrode tab groups. For instance, in cases of local increases in inter-electrode distance, unevenness in charging and discharge reactions and charge carrier precipitation may occur.
It is an object of the present disclosure, arrived at in order to solve the above problems, to provide a secondary battery in which a battery case accommodates a wound electrode body having electrode tab groups in a bent state, and in which local increases in inter-electrode distance in a flat portion in the vicinity of the electrode tab groups is suppressed.
To attain the above object, the art disclosed herein provides a secondaty battery having the following configuration.
The secondary battery disclosed herein has a flat-shaped wound electrode body in which a positive electrode plate and a negative electrode plate are wound across a separator, and a battery case that accommodates the wound electrode body. The flat-shaped wound electrode body has a pair of curved portions, the outer surfaces of which are curved, and a flat portion, the outer surface of which is flat, and which connects the pair of curved portions; the positive electrode plate has a band-shaped positive electrode core body and a positive electrode active material layer formed on at least one surface of the positive electrode core body; and the negative electrode plate has a band-shaped negative electrode core body, and a negative electrode active material layer formed on at least one surface of the negative electrode core body. A positive electrode tab group, which is a stack of positive electrode tabs of the exposed positive electrode core body, is formed at one end portion of the wound electrode body in a winding axis direction, and a negative electrode tab group, which is a stack of negative electrode tabs of the exposed negative electrode core body is formed at another end portion of the wound electrode body in the winding axis direction. The positive electrode tab group is bent in a state of being joined to a positive electrode collector which is a plate-shaped conductive member, and the negative electrode tab group is bent in a state of being joined to a negative electrode collector which is a plate-shaped conductive member. The separator of the secondary battery disclosed herein has a band-shaped base material layer, and a surface layer formed on at least one surface of the base material layer, and containing inorganic particles and a binder; such that at least one of the positive electrode plate and the negative electrode plate in the flat portion is bonded to the surface layer of the separator.
The results of various studies by the inventors have revealed that when using a separator with a heat-resistant layer in order to improve safety, local increases in inter-electrode distance are prone to occur at the flat portion in the vicinity of the electrode tab groups. The present inventors addressed this finding as follows. As a result of press molding, an ordinary separator undergoes pressure-deformation along the irregularities of the surface of an electrode plate (positive electrode plate and negative electrode plate), whereupon separator fits the electrode plate. The inter-electrode distance between positive electrode plate and the negative electrode plate is readily maintained thus through such bonding between the separator and the electrode plate. On the other hand, a separator having a heat-resistant layer exhibits comparatively high strength, and is not prone to deform so as to fit the electrode plate. That is, the function of maintaining the inter-electrode distance, elicited by ordinary separators, is lost in a separator with a heat-resistant layer. The secondary battery disclosed herein was arrived at on the basis of such findings. Specifically, the separator of the secondary battery having the above configuration has a surface layer containing inorganic particles and a binder, in order to prevent internal short-circuits caused by heat shrinkage. Unlike in the case of a conventional heat-resistant layer, however, the surface layer in the art disclosed herein has enough adhesiveness so as to be fitted/bonded to the electrode plates, by press molding. As a result, the function of maintaining the inter-electrode distance derived from bonding of the separator and the electrode plates can be elicited properly, and accordingly it becomes possible to curtail local increases in inter-electrode distance at the flat portion in the vicinity of the electrode tab groups, without detracting from improvements in safety, even when a structure is resorted to in which the wound electrode body is accommodated, in a state here the electrode tab groups are bent, inside a battery case. As a result it is possible to obtain a secondary battery of stable quality in the vicinity of a joint portion between the electrode collector and the electrode tab groups.
In a preferred implementation of the secondary battery disclosed herein, the content of the inorganic particles relative to the total mass of the surface layer is from 70 mass % to 80 mass %. The effect of maintaining the inter-electrode distance derived from bonding of the electrode plates and the surface layer is brought out increasingly readily as the content of the inorganic particles in the surface layer is made smaller. When on the other hand the content of the inorganic particles in the surface layer is reduced excessively, the surface layer may become tacky, and the wound electrode body may be difficult to produce. Heat shrinkage of the separator can be suitably prevented through addition of a given or greater amount of inorganic particles to the surface layer. From these viewpoints, the content of the inorganic particles in the surface layer lies preferably in the range from 70 mass % to 80 mass %.
In a preferred implementation of the secondary battery disclosed herein, the surface layer contains at least one type from among alumina particles and boehmite particles, as the inorganic particles. Heat shrinkage of the separator can be prevented as a result.
In a preferred implementation of the secondary battery disclosed herein, the surface layer contains polyvinylidene fluoride as a binder. The effect of maintaining the inter-electrode distance derived from bonding of the electrode plates and the surface layer can be brought out yet more readily as a result.
In a preferred implementation of the secondary battery disclosed herein, the surface layer has a mesh-like structure containing a plurality of voids. High flexibility is elicited as a result in the surface layer, which can therefore contribute to uniformize the thickness of the flat portion of the wound electrode body and to suppress variability in inter-electrode distance.
In an implementation where a surface layer is formed having the above mesh-like structure, preferably the porosity of the surface layer of the separator disposed in a region not opposing the positive electrode plate or the negative electrode plate is 50% or higher. As a result it becomes possible to impart suitable flexibility to the surface Iayer, and to yet more suitably suppress variability in inter-electrode distance. In the present specification, the “porosity of the surface layer of the separator disposed in a region not opposing the positive electrode plate or the negative electrode plate” signifies the porosity of the surface layer of the separator before press molding.
In a preferred implementation of the secondary battery disclosed herein, the wound electrode body is provided in plurality and accommodated inside the battery case. In such a secondary battery, local increases in inter-electrode distance may occur in the vicinity of the electrode tab groups of a plurality of wound electrode bodies. In the art disclosed herein, by contrast, local increases in inter-electrode distance can be suppressed in each of the plurality of wound electrode bodies, and accordingly the art disclosed herein can be suitably adopted in secondary batteries that are provided with a plurality of wound electrode bodies.
In the above implementation where there is provided a plurality of wound electrode bodies, preferably the separator is disposed at the outermost periphery of the wound electrode bodies, and adjacent wound electrode bodies are bonded to each other via the surface layer of the separator. As a result, the movement of the wound electrode bodies in the interior of the battery case is restricted, which in turn allows preventing damage to the wound electrode bodies caused by an external impact or vibration.
In a preferred implementation of the secondary battery disclosed herein, the separator is disposed at the outermost periphery of the wound electrode body; a termination portion of the separator is affixed to the outermost surface of the wound electrode body by a winding stop tape; and the winding stop tape is disposed on a straight line that joins the positive electrode tab group and the negative electrode tab group. Unwinding of the wound electrode body can be prevented as a result, and hence it becomes possible to more suitably curtail increases in inter-electrode distance in a region in the vicinity of the electrode tab groups, and to stably join the electrode tab groups and the electrode collectors (positive electrode collector and negative electrode collector).
In a preferred implementation of the secondary battery disclosed herein, the separator is disposed at the outermost periphery of the wound electrode body, and a termination portion of the separator is affixed to the outermost surface of the wound electrode body by a winding stop tape; and a proportion of the thickness of the surface layer of the separator interposed between the positive electrode plate and the negative electrode plate, relative to the thickness of the surface layer of separator disposed in a region not opposing the positive electrode plate or the negative electrode plate, is 0.9 or lower. As a result it becomes possible to prevent the formation of level differences derived from the thickness of the winding stop tape, and to prevent drops in battery performance derived from variability in surface pressure exerted on the flat portion.
In a preferred implementation of the secondary battery disclosed herein, one end portion of the positive electrode plate in a longitudinal direction is disposed, as a positive electrode start portion, inside the flat portion of the wound electrode body, and another end portion is disposed, as a positive electrode termination portion, outside the flat portion of the wound electrode body; and one end portion of the negative electrode plate in the longitudinal direction is disposed, as a negative electrode start portion, inside the flat portion of the wound electrode body, and another end portion is disposed, as a negative electrode termination portion, outside the flat portion of the wound electrode body. In such a configuration the start portions of the electrode plates of the positive electrode and the negative electrode are disposed inside the flat portion of the flat-shaped wound electrode bodies, while the termination portions are disposed outside the flat portion.
In the above-described implementation where the positive electrode start portion and the positive electrode termination portion are disposed at the flat portion, preferably the adhesive strength between the positive electrode start portion and the surface layer is larger than the adhesive strength between the positive electrode termination portion and the surface layer. Thus the effect of maintaining the inter-electrode distance can be elicited yet more suitably by relatively increasing the adhesive strength in the interior of wound electrode body.
In the above-described implementation where the positive electrode start portion and the negative electrode termination portion are disposed at the flat portion, preferably the adhesive strength between the positive electrode termination portion and the surface layer is larger than the adhesive strength between the negative electrode termination portion and the surface layer. Permeability of the electrolyte solution into the wound electrode body can be increased as a result.
In an implementation where the positive electrode start portion and the negative electrode termination portion are disposed inside the flat portion, a plurality of the wound electrode bodies are accommodated inside the battery case, the separator is disposed at the outermost periphery of the wound electrode bodies, and in a case where adjacent wound electrode bodies are bonded to each other via the surface layer of the separator, preferably the adhesive strength between the adjacent wound electrode bodies is larger than the adhesive strength between the positive electrode termination portion and the surface layer. As a result, the movement of the wound electrode bodies inside the battery case can be restricted more reliably, and damage to the wound electrode bodies can be prevented yet more properly.
In another aspect, the art disclosed herein provides a method for producing a secondary battery. This production method includes producing a cylindrical body by winding of a positive electrode plate and a negative electrode plate across a separator; producing a flat-shaped wound electrode body by pressing the cylindrical body; and accommodating the wound electrode body in the interior of a battery case. The wound electrode body in the production method disclosed herein is any one of the wound electrode bodies of the implementations described above. Such a production method allows producing a secondary battery in which there are suppressed local increases in inter-electrode distance at a flat portion in the vicinity of electrode tab groups.
FIG.1 is a perspective-view diagram illustrating schematically a secondary battery according to an embodiment;
Embodiments of the art disclosed herein will be explained next with reference to accompanying drawings. Any features other than the matter specifically set forth in the present specification and that may be necessary for carrying out the present specification (for instance the general configuration and production process of a battery) can be regarded as instances of design matter, for a person skilled in the art, based on known art in the relevant technical field. The art disclosed herein can be implemented on the basis of the disclosure of the present specification and common technical knowledge in the relevant technical field. In the present specification, the notation “A to B” for a range signifies a value “equal to or larger than A and equal to or smaller than B”, and is meant to encompass also the meaning of being “preferably larger than A” and “preferably smaller than B”.
In the present specification, the term “secondary battery” denotes a power storage device in general that is capable of being charged and discharged repeatedly as a result of movement of charge carriers across a pair of electrodes (positive electrode and negative electrode) via an electrolyte. Such a secondary battery encompasses not only so-called storage batteries such as lithium ion secondary batteries nickel-metal hydride batteries and nickel cadmium batteries, but also for instance capacitors such as electrical double layer capacitors. An embodiment targeting a lithium ion secondary battery, from among these secondary batteries, will be explained below.
The reference symbol X in the figures of the present specification denotes a “width direction”, the reference symbol Y denotes a “depth direction”, and the reference symbol Z denotes a “height direction”. Further, the reference symbol F in the depth direction X denotes “front” and Rr denotes “rear”. The reference symbol L in the width direction Y denotes “left” and R denotes “right”. The reference symbol U in the height direction Z denotes “up”, and D denotes “down”. These directions are defined however for convenience of explanation, and are not intended to limit the manner in thich the secondary battery disclosed herein is disposed during use.
Embodiments of the secondary battery disclosed herein will be explained next with reference to
As illustrated in
(1) Battery Case
The battery case 50 is a housing that accommodates the wound electrode bodies 40. Although not illustrated in the figures, also a nonaqueous electrolyte solution is accommodated inside the battery case 50. As illustrated in
As illustrated in
(2) Electrolyte Solution
As described above, also an electrolyte solution (not shown) is accommodated, besides the wound electrode bodies 40, inside the battery case 50. Electrolyte solutions used in conventionally known secondary batteries can be used, without particular limitations, as the electrolyte solution. For instance a nonaqueous electrolyte solution in which a supporting salt is dissolved in a nonaqueous solvent can be used as the electrolyte solution. Examples of the nonaqueous solvent include carbonate solvents such as ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate. Examples of the supporting salt include fluorine-containing lithium salts such as LiPF6.
(3) Electrode Terminals
A positive electrode terminal 60 is attached to one end (left side in
(4) Electrode Collector
In the secondary battery 100 according to the present embodiment, a plurality (three) of wound electrode bodies 40 are accommodated in the battery case 50, as illustrated in
Specifically, each positive electrode tab group 42 of the plurality of wound electrode bodies 40 is connected to the positive electrode terminal 60 via the positive electrode collector 70. The positive electrode collector 70 is accommodated inside the battery case 50. The positive electrode collector 70 has, as illustrated in
Meanwhile, each negative electrode tab group 44 of the plurality of wound electrode bodies 40 is connected to the negative electrode terminal 65 via the negative electrode collector 75. The connection structure on the negative electrode side is substantially identical to the connection structure on the positive electrode side described above. Specifically, the negative electrode collector 75 has a negative electrode first collector 76 which is a plate-shaped conductive member extending in the width direction Y along the inner surface of the sealing plate 54, and a plurality of negative electrode second collectors 77 which are plate-shaped conductive member extending in the height direction Z (see
(5) Insulating Member
In the secondary battery 100 various insulating members are further attached in order to prevent conduction between the wound electrode bodies 40 and the battery case 50. Specifically, a respective external insulating member 92 is interposed between the positive electrode external conductive member 62 (negative electrode external conductive member 67) and the outer surface of the sealing plate 54 (see
(6) Wound Electrode Bodies
As illustrated in
As described above, the wound electrode bodies 40 in the present embodiment are accommodated inside the battery case 50 in a state where the positive electrode tab group 42 and the negative electrode tab group 44 are bent. As a result, the width of the wound electrode bodies 40 can be increased up to a position in the vicinity of the inner wall of the battery case 50, which in turn can contribute to significantly improve battery performance. However, stress at the time of bending of the positive electrode tab group 42 (negative electrode tab group 44) acts on the flat portion 40f positioned in the vicinity of the positive electrode tab group 42 (negative electrode tab group 44), and as a result local increases in inter-electrode distance may occur. The secondary battery 100 according to the present embodiment, by contrast, has a configuration that allows properly suppressing increases in inter-electrode distance also in a case where the positive electrode tab group 42 (negative electrode tab group 44) of the wound electrode bodies 40 is bent. The concrete configuration of the wound electrode bodies 40 of the present embodiment will be explained next.
(a) Positive Electrode Plate
As illustrated in
Conventionally known materials that can be used in secondary batteries in general (for instance in lithium ion secondary batteries) can be utilized, without particular limitations, in the members that make up the positive electrode plate 10. For instance a metallic material having a predetermined conductivity can be preferably used in the positive electrode core body 12. Preferably, such a positive electrode core body 12 is for instance made up of aluminum or an aluminum alloy.
The positive electrode active material layer 14 is a layer containing a positive electrode active material. The positive electrode active material is a particulate material capable of reversibly storing and releasing charge carriers. A lithium-transition metal-based complex oxide is preferable as the positive electrode active material, from the viewpoint of stably producing a high-performance positive electrode plate 10. Particularly preferred among lithium-transition metal-based complex oxides is a lithium-transition metal-based complex oxide that contains at least one selected from the group consisting of nickel (Ni), cobalt (Co) and manganese (Mn) as the transition metal. Concrete examples include lithium-nickel-cobalt-manganese-based complex oxides (NCMs), lithium-nickel-based complex oxides, lithium-cobalt-based complex oxides, lithium-manganese-based complex oxides, lithium-nickel-manganese-based complex oxides, lithium-nickel-cobalt-aluminum-based complex oxides (NCAs), and lithium-iron-nickel-manganese-based-based complex oxides. Preferable examples of lithium-transition metal-based complex oxides not containing Ni, Co or Mn include lithium iron phosphate-based complex oxides (LFPs). The term. “lithium-nickel-cobalt-manganese complex oxide” in the present specification encompasses oxides that contain an additional element, besides a main constituent element (Li, Ni, Co, Mn and O). Examples of such additional elements include transition metal elements and main-group metal elements such as Mg, Ca, Al, Ti, V, Cr, Si, Y, Zr, Nb, Mo, Hf, Ta, W, Na, Fe, Zn or Sn. The additional element may be a metalloid element such as B, C, Si or P, or a non-metal element such as S, F, Cl, Br or I. Although a detailed explanation will be omitted, the same applies to other lithium transition metal-based complex oxides notated as “-based complex oxides”. Further, the positive electrode active material layer 14 may contain additives other than the positive electrode active material. Examples of such additives include conductive materials and binders, Concrete examples of conductive materials include carbon materials such as acetylene black (AB). Concrete examples of binders include resin binders such as polyvinylidene fluoride (PVdF). The content of the positive electrode active material relative to 100 mass % as the total solids of the positive electrode active material layer 14 is about 80 mass % or higher, and is typically 90 mass % or higher.
The protective layer 16 is a layer configured to have a lower electrical conductivity than that of the positive electrode active material layer 14. By providing the protective layer 16 in a region adjacent to an edge of the positive electrode plate 10 it becomes possible to prevent internal short circuits caused by direct contact between the positive electrode core body 12 and the negative electrode active material layer 24 when the separator 30 is damaged. Preferably, for instance a layer containing insulating ceramic particles is formed as the protective layer 16. Examples of such ceramic particles include inorganic oxides such as alumina (Al2O3), magnesia (MgO), silica (SiO2) and titania (TiO2); nitrides such as aluminum nitride and silicon nitride; metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; clay minerals such as mica, talc, boehmite, zeolite, apatite and kaolin; and glass fibers. Alumina, boehmite, aluminum hydroxide, silica and titania are preferred among the foregoing, in terms of insulation properties and heat resistance. The protective layer 16 may contain a binder for fixing the ceramic particles on the surface of the positive electrode core body 12. Examples of such a binder include resin binders such as polyvinylidene fluoride (PVdF). The protective layer is not an essential constituent element of the positive electrode plate. That is, a positive electrode plate having no protective layer formed thereon can also be used in the secondary battery disclosed herein.
The thickness t2 of the positive electrode plate 10 (see
Further, the surface roughness of the positive electrode plate 10 (typically, the surface roughness of the positive electrode active material layer 14) is preferably 0.01 μm or larger, more preferably 0.02 μm or larger. Although details will be described later on, in the present embodiment the separator 30 and the positive electrode plate 10 are fitted to each other by causing the surface layer 34 of the separator 30 to deform conforming to the relief of the surface of the positive electrode plate 10; as a result, the separator 30 and the positive electrode plate 10 are bonded to each other, and a function of maintaining the inter-electrode distance is brought out. From the viewpoint of suitably bonding the separator 30 and the positive electrode plate 10 to each other, preferably the positive electrode plate 10 has a certain or higher surface roughness. The upper limit of the surface roughness of the positive electrode plate 10 is not particularly limited, and may be 3 μm or smaller. The term “surface roughness” in the present specification denotes arithmetic mean roughness Ra.
Preferably, the positive electrode active material layer 14 includes large positive electrode active material particles having a peak particle size in the range from 10 μm to 20 μm and small positive electrode active material particles having a peak particle size in the range from 2 μm to 6 μm, in a particle size distribution analyzed by laser diffraction/scattering. By mixing thus two types of positive electrode active material particles having different particle sizes, fine irregularities become formed on the surface of the positive electrode active material layer 14, and as a result the positive electrode plate 10 and the separator 30 can be bonded to each other more suitably. The large particles and small particles described above may be of a lithium-transition metal-based complex oxide of the same type, or of lithium-transition metal-based complex oxides of different types.
Attempts have been made in recent years to form a positive electrode active material layer having a packing density of 2 g/cc or higher, from the viewpoint of increasing battery capacity. However, this type of high-density positive electrode active material layers exhibits a large reaction force against press molding, and accordingly such an active material layer may constitute a factor that promotes the above-described increases in inter-electrode distance caused by springback. By contrast, the art disclosed herein allows suitably suppressing springback of the wound electrode bodies, even upon formation of a high-density positive electrode active material layer of 2 g/cc or higher (suitably 2.5 g/cc or higher). In other words, the art disclosed herein allows easily using a high-density positive electrode active material layer that was difficult to use in conventional art, and can thus contribute to enhancing battery capacity. The packing density of the positive electrode active material layer 14 is preferably 4 g/cc or lower, from the viewpoint of properly preventing springback.
(b) Negative Electrode Plate
As illustrated in
Conventionally known materials that can be used in secondary batteries in general (for instance in lithium ion secondary batteries) can be utilized herein, without particular limitations, in the members that make up the negative electrode plate 20. For instance a metallic material having a predetermined conductivity can be preferably used in the negative electrode core body 22. Preferably, such a negative electrode core body 22 is for instance made up of copper or a copper alloy.
The negative electrode active material layer 24 is a layer containing a negative electrode active material. The negative electrode active material is not particularly limited, so long as charge carriers can be reversibly stored and released, in a relationship with the positive electrode active material described above, and thus materials that can be utilized in conventional secondary batteries in general can be used herein without particular limitations. Examples of such negative electrode active materials include carbon materials and silicon-based materials, For instance graphite, hard carbon, soft carbon, amorphous carbon and the like can be used as the carbon material, Amorphous carbon-coated graphite in which the surface of graphite is coated with amorphous carbon can also be used herein. Examples of silicon-based materials include silicon and silicon oxide (silica). The silicon-based material may contain a metal element (for instance an alkaline-earth metal), or an oxide thereof. The negative electrode active material layer 24 may contain additives besides the negative electrode active material. Examples of such additives include a binder and a thickener. Concrete examples of the binder include rubber-based binders such as styrene butadiene rubber (SBR). Concrete examples of the thickener include carboxymethyl cellulose (CMC). The content of the negative electrode active material relative to 100 mass % as the total solids of the negative electrode active material layer 24 is about 30 mass % or higher, and is typically 50 mass % or higher. The negative electrode active material may take up 80 mass % or higher, or 90 mass % or higher, of the negative electrode active material layer 24. A width dimension w2 of the negative electrode active material layer 24 is preferably from 200 mm to 450 mm, more preferably from 250 mm to 350 mm, and even more preferably from 270 mm to 320 mm.
A thickness t3 of the negative electrode plate 20 (see
Similarly to the surface roughness of the positive electrode plate 10, the surface roughness of the negative electrode plate 20 (typically the surface roughness of the negative electrode active material layer 24) is preferably regulated from the viewpoint of suitably eliciting bonding between the separator 30 and the negative electrode plate 20. For instance the surface roughness of the negative electrode plate 20 is preferably 0.05 μm or larger, more preferably 0.1 μm or larger. As a result the separator 30 and the negative electrode plate 20 are properly bonded to each other, and the effect of maintaining the inter-electrode distance elicited by the art disclosed herein can be brought out yet more suitably. The upper limit of the surface roughness of the negative electrode plate 20 is not particularly restricted, and may be 5 μm or smaller.
(c) Separator
As illustrated in
As illustrated in
Firstly a material used in separators of conventionally known secondary batteries can be used, without particular limitations, in the base material layer 32. For instance the base material layer 32 is preferably a porous sheet-shaped member containing a polyolefin resin or the like. As a result, the flexibility of the separators 30 can be sufficiently ensured, and the wound electrode bodies 40 can be easily produced (wound and press molded). Polyethylene (PE), polypropylene (PP) or a mixture thereof can be used as the polyolefin resin. The porosity of the base material layer 32 is preferably from 20% to 70%, more preferably from 30% to 60%, and yet more preferably from 40% to 50%. Charge carriers can be allowed to properly move as a result between the positive electrode plate 10 and the negative electrode plate 20. Unless otherwise noted, the term “porosity” in the present specification denotes porosity before press molding. The “porosity before press molding” can be obtained by performing a measurement on the separators disposed in regions not facing the positive electrode plate or the negative electrode plate. Examples of the “region not facing the positive electrode plate or the negative electrode plate” include a “region 30a in which only the separator 30 extends”, formed on both side edges of the wound electrode body 40 in
As illustrated in
A conventionally known resin material having a certain viscosity can be used, without particular limitations, as the hinder of the surface layer 34. For instance the binder of the surface layer 34 is preferably a resin material such as an acrylic resin, a polyolefin resin, a cellulosic resin or a fluororesin. A resin containing a polymer of an acrylic acid ester as a main component can be used as the acrylic resin. For instance polyethylene (PE) or polypropylene (PP) can be used as the polyolefin resin. For instance carboxymethyl cellulose (CMC) can be used as the cellulosic resin. For instance polyvinylidene fluoride (PVdF) can be used as the fluororesin. The surface layer 34 may contain two or more of these binder resins. Among the foregoing binder resins, PVdF can more suitably elicit adhesiveness to the electrode plates. The surface layer 34 preferably contains a binder of the same type as that of the binder of the electrode active material layer of the opposing electrode plate. As an example, in a case where the positive electrode active material layer 14 contains PVdF, it is preferable to use PVdF as the binder of the surface layer 34 that opposes the positive electrode active material layer 14. This allows further increasing the adhesive strength between the surface layer 34 and the positive electrode plate 10.
Preferably, the content of the inorganic particles is adjusted so that the surface layer 34 exhibits a predetermined adhesiveness towards the positive electrode plate 10 (or the negative electrode plate 20). For instance the content of the inorganic particles in the surface layer 34 is preferably lower than 90 mass %, and is more preferably 85 mass % or lower, and particularly preferably 80 mass % or lower. When the content of inorganic particles in the surface layer 34 is thus kept at or below a given value, the surface layer 34 deforms readily at the time of press molding, and accordingly the effect of maintaining the inter-electrode distance elicited through fitting (bonding) of the positive electrode plate 10 (or negative electrode plate 20) and the surface layer 34 can be properly brought out as a result. When conversely the content of the inorganic particles in the surface layer 34 is reduced too much, the content of the resin material such as a binder becomes relatively large, and the surface layer 34 before press molding may develop tackiness as a result. In such a case it may be difficult to wind the positive electrode plate 10 and the negative electrode plate 20 across the separators 30. From this viewpoint, the content of the inorganic particles in the surface layer 34 is preferably 60 mass or higher, more preferably 65 mass % or higher, and particularly preferably 70 mass % or higher. By forming the surface layer 34 containing thus no less than a certain amount of inorganic particles it becomes possible to suitably prevent internal short circuits derived from heat shrinkage of the separators 30. The term “content of inorganic particles” in the present specification denotes the mass ratio of inorganic particles relative to the total mass of the surface layer.
The surface layer 34 preferably has a mesh-like structure that includes a plurality of voids. Such a surface layer 34 has inorganic particles dispersed in the interior of the binder resin having been cured to a mesh shape. The surface layer 34 having this mesh-like structure has high flexibility, and accordingly deforms so as to be crushed during press molding. Variability in the thickness t1 of the wound electrode bodies 40 can therefore be absorbed by the separators 30, and thus precipitation of charge carriers due to variability in inter-electrode distance can be suppressed as a result. The porosity of the surface layer 34 having a mesh-like structure is preferably 50% or higher, more preferably 60% or higher, and particularly preferably 70% or higher. As a result, suitable flexibility can be imparted to the surface layer 34, and variability in the thickness t1 of the wound electrode bodies 40 can be suppressed. In terms of strength of the separator 30, on the other hand, the porosity of the surface layer 34 is preferably 90% or lower, more preferably 80% or lower.
Preferably, the surface layer 34 having the mesh-like structure is formed so that the packing density on the electrode plate side (outward of the separator 30) is higher than the packing density on the base material layer 32 side (inward of the separator 30). As a result, the surface layer 34 on the base material layer 32 side is pressure-deformed preferentially at the time of press molding, thanks to which the voids in the surface layer 34 on the electrode plate side can be prevented from collapsing. It becomes accordingly possible to suppress drops in the permeability of the electrolyte solution into the vicinity of the electrode plates, and to contribute for instance to prevent dry-out.
The thickness t4 of the separator 30 (see
The structure of the secondary battery 100 according to the present embodiment has been described above. The effect of maintaining the inter-electrode distance elicited by the art disclosed herein will be specifically explained next while describing a procedure for producing the secondary battery 100. The method for producing the secondary battery 100 according to the present embodiment includes (1) a winding step, (2) a press molding step, and (3) an accommodation step.
(1) Winding Step
In the present step there is firstly produced a stack resulting from laying up a separator 30, a negative electrode plate 20, a separator 30 and a positive electrode plate 10, in this order (see
(2) Press Molding Step
In the present step a flat-shaped wound electrode body 40 (see
In the present embodiment a surface layer 34 of each separator 30 is bonded to the positive electrode plate 10 (negative electrode plate 20) at the time of press molding. Specifically, the wound body is squashed at the time of press molding, and accordingly significant pressure acts upon the sheet-shaped members (positive electrode plate 10, negative electrode plate 20 and separators 30) positioned at the flat portion 40f. In the present embodiment, for instance the content of inorganic particles in the surface layer 34 and the press molding pressure are regulated, so that the surface layer 34 deforms as a result in accordance with the irregularities on the surface of the positive electrode active material layer 14 (or the negative electrode active material layer 24). As a result, the separator 30 and the positive electrode plate 10 (negative electrode plate 20) become fixed to each other and bonded to each other at the interface between the separator 30 and the positive electrode plate 10 (or the negative electrode plate 20) at the flat portion 40f of the wound electrode body 40. The inter-electrode distance between the positive electrode plate 10 and the negative electrode plate 20 is held by the separators 30.
The adhesive strength of the electrode plate (typically the positive electrode plate 10) and the surface layer 34 disposed at the flat portion 40f of the wound electrode body 40 prior to accommodation in the battery case 50 is preferably 0.5 N/m or larger, more preferably 0.75 N/m in or larger, and yet more preferably 1.0 N/m or larger. Preferably, the content of the inorganic particles in the surface layer 34 and the press molding pressure are regulated so that a suitable adhesive strength is ensured between the surface layer 34 and each electrode plate. As a result, this allows suppressing more suitably local increases in inter-electrode distance derived from bending of the electrode tab group, and/or increases in inter-electrode distance caused by springbuck. The term “adhesive strength” in the present specification denotes 90° peel strength according to JIS Z0237.
As illustrated in
In a case where the winding stop tape 38 is affixed to the termination portion 30e of the separator 30, preferably the flexibility of the surface layer 34 and the press molding pressure are regulated so that the proportion of the thickness of the surface layer 34 before press molding relative to the thickness of the surface layer 34 after press molding is 0.9 or lower (more preferably 0.8 or lower, yet more preferably 0.7 or lower, and particularly preferably 0.6 or lower). In consequence it becomes possible to absorb the thickness of the winding stop tape 38 through pressure deformation of the surface layer 34, and to prevent the occurrence of large level differences at the flat portion 40f. As a result this allows suppressing deterioration of battery performance due to variability in surface pressure on the flat portion 40f. This effect can be elicited particularly suitably in the secondary battery 100 having a plurality of wound electrode bodies 40, such as that of the present embodiment. Similarly to the “porosity of the surface layer before press molding” described above, the “thickness of the surface layer before press molding” can be detected by performing a measurement in a region at which the negative electrode plate and the positive electrode plate do not face each other (for instance the region denoted by the reference symbol 30a in FIG. 7). On the other hand, the “thickness of the surface layer after press molding” can be measured on the basis of the thickness of the surface layer 34 of the separator 30 that is interposed (for instance in the vicinity of the central portion of the flat portion 40f) between the positive electrode plate 10 and the negative electrode plate 20.
In the wound electrode body 40 after press molding, as illustrated in
In the wound electrode body 40 having the structure illustrated in
In the wound electrode body 40 illustrated in
Substantial pressure does not act on the curved portions 40r of the wound electrode body 40 during press molding. As a result, the surface layer 34 of the separators 30 positioned in the curved portions 40r tends to be larger than the surface layer 34 of the separators 30 positioned at the flat portion 40f. Specifically, the thickness of the surface layer 34 in the curved portions 40r can be 1.5 times to 3 times the thickness of the surface layer 34 at the flat portion 40f. More specifically, the thickness of the surface layer 34 in the curved portions 40r tends to be thicker by about 1μm than the thickness of the surface layer 34 at the flat portion 40f.
(3) Accommodation Step
In the present step the wound electrode body 40 molded in the press molding step is accommodated inside the battery case 50. Specifically, the positive electrode second collectors 72 are joined to the positive electrode tab group 42 of the wound electrode body 40 and the negative electrode second collectors 77 are joined to the negative electrode tab group 44, as illustrated in
In the connection between the sealing plate 54 and the wound electrode bodies 40 described above, stress at the time of bending of the electrode tab groups acts on the flat portion 40f in the vicinity of the electrode tab groups (positive electrode tab group 42 and negative electrode tab group 44). As a result, the inter-electrode distance increases at the flat portion 40f in the vicinity of the electrode tab groups, and hence charge carrier precipitation or the like may occur. In the present embodiment, however, the electrode plates and the separators 30 are bonded to each other, and accordingly it becomes possible to prevent increases in inter-electrode distance even under the action of stress at the time of bending of the electrode tab groups.
In the present step, next, the wound electrode bodies 40 attached to the sealing plate 54 are covered by the electrode body holder 98 (see
An embodiment of the art disclosed herein has been explained above. The above-described embodiment illustrates an example to which the art disclosed herein is applied, but is not meant to limit the art disclosed herein. Other embodiments of the art disclosed herein will be explained next.
(1) Surface on Which the Surface Layer is Formed
In the embodiments described above, the surface layer 34 is formed on both faces of the base material layer 32. However, the surface layer need not be formed on both faces of the base material layer, and it suffices that the surface layer be formed on at least one face of the surface of the base material layer. Preferably, the surface layer is formed on both faces of the base material layer, for instance in terms of adhesiveness between the separator and the electrode bodies, and in terms of suppression of heat shrinkage in the separator. As described above, the surface layer tends to exhibit better adhesiveness towards the positive electrode plate than to the negative electrode plate. Such being the case, the surface layer is preferably formed on the face in contact with the positive electrode plate, in a case where the surface layer is to be formed in just one surface of the base material layer.
(2) Number of Wound Electrode Bodies
In the secondary battery 100 according to the above-described embodiment three wound electrode bodies 40 are accommodated inside the battery case 50. However, the number of electrode bodies accommodated within one battery case is not particularly limited, and may be two or more (plurality of electrode bodies), or one. In a secondary battery 100 provided with a plurality of wound electrode bodies 40, such as that illustrated in
In the secondary battery 100 having a plurality of wound electrode bodies 40 it is preferable, as in the above-described embodiment, that each separator 30 having the surface layer 34 be disposed at the outermost periphery of the wound electrode bodies 40. In consequence, adjacent wound electrode bodies 40 are bonded to each other across respective separators 30 at the outermost periphery, and accordingly movement of the wound electrode bodies 40 in the interior of the battery case 50 can be therefore restricted. As a result it becomes possible to prevent damage to the wound electrode bodies 40 caused by an external impact or vibration (external force). In a case for instance where the wound electrode bodies 40 and the electrode collectors (positive electrode second collector 72 and negative electrode second collector 77) are connected via the electrode tab groups (positive electrode tab group 42 and negative electrode tab group 44), as illustrated in
In a case where the separator 30 is disposed at the outermost periphery of the wound electrode bodies 40, the wound electrode bodies 40 on both outer sides in the depth direction X and the electrode body holder 98 can be bonded to each other via the surface layer 34 of that separator 30. As a result it becomes possible to restrict more reliably the movement of the wound electrode bodies 40 within the battery case 50, and in consequence to prevent damage to the wound electrode bodies 40 yet more suitably.
(3) External Dimensions of the Wound Electrode Body
As described above, the art disclosed herein allows suppressing not only local increases in inter-electrode distance in the vicinity of the electrode tab groups, but also expansion (springback) of the flat portions of the wound electrode body. Such wound electrode body springback is particularly prone to occur in a wound electrode body having the external dimensions below. The art disclosed herein, however, allows suitably suppressing springback also when using a wound electrode body having the below-described external dimensions. That is, the art disclosed herein can be used particularly suitably in secondary batteries provided with a wound electrode body having the external dimensions below.
Firstly, a width dimension w1 (see
Secondly, the thickness dimension t1 (see
Thirdly, a height dimension h1 (see
In the secondary battery provided with a plurality of wound electrode bodies, the external dimensions described above may be shared by the wound electrode bodies, or may be dissimilar among these. It is not necessary that all the wound electrode bodies have the above-described external dimensions, and it suffices that at least one wound electrode body has these external dimensions. In a case however where all the wound electrode bodies have the above-described external dimensions, the springback suppression effect elicited by the art disclosed herein can be more suitably elicited, since springback readily occurs in each wound electrode body.
The present disclosure has been explained in detail above, but the explanation is merely illustrative in character. That is, the art disclosed herein encompasses various alterations and modifications of the concrete examples described above.
Number | Date | Country | Kind |
---|---|---|---|
2021-26205 | Feb 2021 | JP | national |