The present invention relates to an electrode plate and a secondary battery using the same.
For power sources for driving an electric vehicle (EV), a hybrid electric vehicle (HEV, PHEV), and the like, secondary batteries such as an alkali secondary battery and a non-aqueous electrolyte secondary battery have been used.
In each of the secondary batteries, a bottomed cylindrical exterior member having an opening and a sealing plate that seals the opening constitute a battery case. An electrode assembly composed of a positive electrode plate, a negative electrode plate, and a separator, together with an electrolyte, is housed in the battery case. A positive electrode terminal and a negative electrode terminal are attached to the sealing plate. The positive electrode terminal is electrically connected to the positive electrode plate via a positive electrode current collector, and the negative electrode terminal is electrically connected to the negative electrode plate via a negative electrode current collector.
As the secondary battery, a secondary battery comprising a flat-shaped wound electrode assembly obtained by winding a strip-shaped positive electrode plate having a plurality of positive electrode tabs and a strip-shaped negative electrode plate having a plurality of negative electrode tabs with a strip-shaped separator therebetween has been proposed (Patent Literature 1, described below).
A technique for cutting a positive electrode plate or a negative electrode plate using a continuous oscillation laser to form a curved portion having a larger thickness than a thickness of a core body (current collector foil) constituting the positive electrode plate or the negative electrode plate in a cut end portion of the core body has been proposed (Patent Literature 2, described below).
It is an advantage of the present invention to provide a highly reliable electrode plate and a secondary battery using the same.
An electrode plate according to an aspect of the present invention is
an electrode plate having a core body and an active material layer formed on the core body, in which
the core body has a thick-walled part having a larger thickness than a thickness in a central region of the core body in an end portion of the core body,
the thick-walled part includes a protrusion protruding in a thickness direction of the core body from one surface of the core body, and
the core body is composed of an aluminum alloy containing 0.5 to 2.0% by mass of Mn.
When an electrode original plate is cut by irradiation of an energy beam such as a laser, the core body is melted and solidified by irradiation of the energy beam. Accordingly, the melted core body is solidified with it being rounded due to surface tension. Thus, a thick-walled part having a larger thickness than that in a central portion of the core body occurs in an end portion of the core body in a cut end portion. The thick-walled part may be detached from the core body, which may cause a positive electrode plate and a negative electrode plate to be short-circuited. When the thick-walled part is large, the thick-walled part damages a separator, which may cause the positive electrode plate and the negative electrode plate to be short-circuited.
A configuration of the electrode plate according to an aspect of the present invention enables the thickness of the thick-walled part to be made relatively small even if the electrode original plate is cut by irradiation of an energy beam such as a laser. Therefore, it is possible to prevent the protrusion formed in the end portion of the core body from dropping out of the core body and to prevent the protrusion formed in the end portion of the core body from damaging the separator.
The core body is preferably composed of an aluminum alloy containing 1.0 to 1.5% by mass of Mn.
The core body is preferably composed of an aluminum alloy containing 0.05 to 0.2% by mass of Cu.
The aluminum alloy preferably contains 0.6% or less by mass of Si, 0.7% or less by mass of Fe, and 0.1% or less by mass of Zn.
The thick-walled part preferably includes a melted and solidified part formed by melting and solidifying the core body.
The electrode plate preferably has a first end side on which a plurality of electrode tabs are formed, and
the end portion is preferably the first end side.
A secondary battery according to an aspect of the present invention comprises the electrode plate, and another electrode plate having a different polarity from that of the electrode plate.
According to the present invention, there can be provided a highly reliable electrode plate and a secondary battery using the same.
A configuration of a rectangular secondary battery 20 as a secondary battery according to an embodiment will be described below. The present invention is not limited to the following embodiment.
As illustrated in
A positive electrode tab group 40A composed of a plurality of positive electrode tabs 40 and a negative electrode tab group 50A composed of a plurality of negative electrode tabs 50 are provided in an end portion on the sealing plate 2 side of the wound electrode assembly 3. The positive electrode tab group 40A is electrically connected to a positive electrode terminal 7 via a second positive electrode current collector 6b and a first positive electrode current collector 6a. The negative electrode tab group 50A is electrically connected to a negative electrode terminal 9 via a second negative electrode current collector 8b and a first negative electrode current collector 8a. The first positive electrode current collector 6a and the second positive electrode current collector 6b constitute a positive electrode current collector 6. The positive electrode current collector 6 may be one component. The first negative electrode current collector 8a and the second negative electrode current collector 8b constitute a negative electrode current collector 8. The negative electrode current collector 8 may be one component.
The first positive electrode current collector 6a, the second positive electrode current collector 6b, and the positive electrode terminal 7 are each preferably made of metal and more preferably made of aluminum or an aluminum alloy. An outer-side insulating member 10 made of resin is arranged between the positive electrode terminal 7 and the sealing plate 2. An inner-side insulating member 11 made of resin is arranged between the first positive electrode current collector 6a and the second positive electrode current collector 6b and the sealing plate 2.
The first negative electrode current collector 8a, the second negative electrode current collector 8b, and the negative electrode terminal 9 are each preferably made of metal and more preferably made of copper or a copper alloy. The negative electrode terminal 9 preferably has a portion made of aluminum or an aluminum alloy and a portion made of copper or a copper alloy. In this case, the portion made of copper or a copper alloy is preferably connected to the first negative electrode current collector 8a, and the portion made of aluminum or an aluminum alloy preferably protrudes more outwardly than the sealing plate 2. An outer-side insulating member 12 made of resin is arranged between the negative electrode terminal 9 and the sealing plate 2. An inner-side insulating member 13 made of resin is arranged between the first negative electrode current collector 8a and the second negative electrode current collector 8b and the sealing plate 2.
An electrode assembly holder 14 composed of a resin sheet made of resin is arranged between the wound electrode assembly 3 and the rectangular exterior member 1. The electrode assembly holder 14 is preferably shaped by bending an insulating sheet made of resin in a bag shape or a box shape. The sealing plate 2 is provided with an electrolyte injection hole 15, and the electrolyte injection hole 15 is sealed with a sealing member 16. The sealing plate 2 is provided with a gas discharge valve 17 that is broken when pressure in the battery case 100 reaches a predetermined value or more and discharges gas in the battery case 100 out of the battery case 100.
Then, details of a method of manufacturing the rectangular secondary battery 20 and each of components in the rectangular secondary battery 20 will be described.
[Positive Electrode Plate]
First, a method of manufacturing a positive electrode plate will be described.
[Production of Positive Electrode Active Material Layer Slurry]
A lithium-nickel-cobalt-manganese composite oxide as a positive electrode active material, polyvinylidene fluoride (PVdF) as a binder, a carbon material as a conductive agent, and N-methyl-2-pyrrolidone (NMP) as a dispersion medium are kneaded such that a mass ratio of the lithium-nickel-cobalt-manganese composite oxide, the PVdF, and the carbon material is 97.5:1:1.5, to produce a positive electrode active material layer slurry.
[Production of Positive Electrode Protective Layer Slurry]
Alumina powder, a carbon material as a conductive agent, polyvinylidene fluoride (PVdF) as a binder, and N-methyl-2-pyrrolidone (NMP) as a dispersion medium are kneaded such that a mass ratio of the alumina powder, the carbon material, and the PVdF is 83:3:14, to produce a protective layer slurry.
[Formation of Positive Electrode Active Material Layer and Positive Electrode Protective Layer]
The positive electrode active material layer slurry and the positive electrode protective layer slurry produced in the above-described method are each applied to both surfaces of an aluminum foil having a thickness of 15 μm as a positive electrode core body with a die coater. At this time, the positive electrode active material layer slurry is applied to a center in a width direction of the positive electrode core body. The positive electrode protective layer slurry is applied to both ends in a width direction of a region to which the positive electrode active material layer slurry is applied.
The positive electrode core body to which the positive electrode active material layer slurry and the positive electrode protective layer slurry are applied is dried, to remove the NMP included in each of the positive electrode active material layer slurry and the positive electrode protective layer slurry. As a result, a positive electrode active material layer and a protective layer are formed. Then, the positive electrode active material layer is compressed by being passed between paired press rollers, to obtain a positive electrode original plate 400.
When the positive electrode original plate 400 is cut using a laser, an output of the laser is preferably 100 W to 1500 W, more preferably 550 W to 1000 W, and still more preferably 600 W to 1000 W. A scanning speed of the laser is preferably 100 mm/s to 5000 mm/s. However, the present invention is not limited to this. A continuous oscillation (CW) laser may be used, or a pulse laser may be used.
Three end sides other than a first end side 4A on which the positive electrode tabs 40 are formed (end sides extending in a longitudinal direction of the positive electrode plate 4 and on the opposite side to the first end side 4A and two end sides extending in a transverse direction of the positive electrode plate 4) in the positive electrode plate 4 are preferably cut in a method other than irradiation of an energy beam, for example, a metal mold or a cutter (cutting blade). The positive electrode plate 4 can be adapted such that a thick-walled part 4x is not formed in end portions of the positive electrode core body 4a respectively positioned on the three end sides other than the first end side 4A on which the positive electrode tabs 40 are formed.
To obtain a higher output secondary battery, in the wound electrode assembly 3, the positive electrode tabs 40 are preferably provided for each layer of the positive electrode plate 4. That is, the number of positive electrode plate 4 to be laminated and the number of positive electrode tabs 40 to be laminated are preferably the same or substantially the same. Therefore, as illustrated in
An end portion of the positive electrode core body 4a on the first end side 4A of the positive electrode plate 4 has the thick-walled part 4x. A thickness T2 of the thick-walled part 4x is larger than a thickness T1 in a central portion of the positive electrode core body 4a. T2/T1 is preferably 2.0 or less, and is more preferably 1.5 or less.
The positive electrode plate 4 can be adapted such that the thick-walled part 4x is not formed in the end portions of the positive electrode core body 4a respectively positioned on the three end sides other than the first end side 4A on which the positive electrode tabs 40 are formed (the end side extending in the longitudinal direction of the positive electrode plate 4 and on the opposite side to the first end side 4A and the two end sides extending in the transverse direction of the positive electrode plate 4).
The thick-walled part 4x includes the first protrusion 4y and the second protrusion 4z. The second protrusion 4z is not an essential component. The second protrusion 4z need not be formed. The protrusion height of the first protrusion 4y and the protrusion height of the second protrusion 4z may differ from each other.
[Negative Electrode Plate]
Then, a method of manufacturing a negative electrode plate will be described.
[Production of Negative Electrode Active Material Layer Slurry]
Graphite as a negative electrode active material, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) as a binder, and water as a dispersion medium are kneaded such that a mass ratio of the graphite, the SBR, and the CMC is 98:1:1, to produce a negative electrode active material layer slurry.
[Formation of Negative Electrode Active Material Layer]
The negative electrode active material layer slurry produced in the above-described method is applied to both surfaces of a copper foil having a thickness of 8 μm as a negative electrode core body with a die coater.
The negative electrode core body to which the negative electrode active material layer slurry is applied is dried, to remove the water included in the negative electrode active material layer slurry. As a result, the negative electrode active material layer is formed. Then, the negative electrode active material layer is compressed by being passed between paired press rollers, to obtain a negative electrode original plate 500.
[Production of Wound Electrode Assembly]
The positive electrode plate 4 and the negative electrode plate 5 produced in the above-described methods are each wound with a strip-shaped separator 70 made of polyolefin therebetween, to manufacture the flat-shaped wound electrode assembly 3. As described above, one end of the final positive electrode original plate 402 and one end of the final negative electrode original plate 502 are fed to a winding device, and the final positive electrode original plate 402 and the final negative electrode original plate 502 are preferably respectively cut at predetermined positions while or after the winding.
In the wound electrode assembly 3, when the number of positive electrode plates 4 to be laminated is set to N1 (layers), the number of positive electrode tabs 40 to be laminated is preferably 0.8×N1 or more and more preferably 0.9×N1 or more.
In the wound electrode assembly 3, when the number of negative electrode plates 5 to be laminated is set to N2 (layers), the number of negative electrode tabs 50 to be laminated is preferably 0.8×N2 or more and more preferably 0.9×N2 or more.
[Connection Between Current Collector and Tab]
As illustrated in
A thin-walled part 6c is formed in the second positive electrode current collector 6b, and a current collector opening 6d is formed in the thin-walled part 6c. In the thin-walled part 6c, the second positive electrode current collector 6b is bonded to the first positive electrode current collector 6a. In the second positive electrode current collector 6b, a current collector through hole 6e is formed at a position opposing the electrolyte injection hole 15 in the sealing plate 2. A thin-walled part 8c is formed in the second negative electrode current collector 8b, and a current collector opening 8d is formed in the thin-walled part 8c. In the thin-walled part 8c, the second negative electrode current collector 8b is bonded to the first negative electrode current collector 8a.
[Attachment of Each Component to Sealing Plate]
The outer-side insulating member 10 is arranged on the outer surface side of the battery around a positive electrode terminal insertion hole 2a of the sealing plate 2. The inner-side insulating member 11 and the first positive electrode current collector 6a are arranged on the inner surface side of the battery around the positive electrode terminal insertion hole 2a of the sealing plate 2. The positive electrode terminal 7 is inserted into a through hole of the outer-side insulating member 10, the positive electrode terminal insertion hole 2a of the sealing plate 2, a through hole of the inner-side insulating member 11, and a through hole of the first positive electrode current collector 6a from the outer side of the battery, to caulk a distal end of the positive electrode terminal 7 onto the first positive electrode current collector 6a. As a result, the positive electrode terminal 7 and the first positive electrode current collector 6a are fixed to the sealing plate 2. A portion caulked in the positive electrode terminal 7 and the first positive electrode current collector 6a are preferably welded to each other.
The outer-side insulating member 12 is arranged on the outer surface side of the battery around a negative electrode terminal insertion hole 2b of the sealing plate 2. The inner-side insulating member 13 and the first negative electrode current collector 8a are arranged on the inner surface side of the battery around the negative electrode terminal insertion hole 2b of the sealing plate 2. The negative electrode terminal 9 is inserted into a through hole of the outer-side insulating member 12, the negative electrode terminal insertion hole 2b of the sealing plate 2, a through hole of the inner-side insulating member 13, and a through hole of the first negative electrode current collector 8a from the outer side of the battery, to caulk a distal end of the negative electrode terminal 9 onto the first negative electrode current collector 8a. As a result, the negative electrode terminal 9 and the first negative electrode current collector 8a are fixed to the sealing plate 2. A portion caulked in the negative electrode terminal 9 and the first negative electrode current collector 8a are preferably welded to each other.
A portion, opposing the electrolyte injection hole 15 provided in the sealing plate 2, in the inner-side insulating member 11 is provided with an injection opening 11a. An edge portion of the injection opening 11a is provided with a cylindrical part 11b.
[Connection Between First Current Collector and Second Current Collector]
The second positive electrode current collector 6b to which the positive electrode tab groups 40A are connected is arranged on the inner-side insulating member 11 such that its part overlaps the first positive electrode current collector 6a. The thin-walled part 6c is irradiated with a laser, to bond the second positive electrode current collector 6b and the first positive electrode current collector 6a to each other. As a result, a bonding part 62 is formed. The second negative electrode current collector 8b to which the negative electrode tab groups 50A are connected is arranged on the inner-side insulating member 13 such that its part overlaps the first negative electrode current collector 8a. The thin-walled part 8c is irradiated with a laser, to bond the second negative electrode current collector 8b and the first negative electrode current collector 8a to each other. As a result, a bonding part 63 is formed.
[Production of Secondary Battery]
The two positive electrode tab groups 40A and the two negative electrode tab groups 50A are curved such that an upper surface of one of the wound electrode assemblies 3 and an upper surface of the other wound electrode assembly 3 in
The one positive electrode tab group 40A and the other positive electrode tab group 40A enter a state where they are respectively curved in different directions. The one negative electrode tab group 50A and the other negative electrode tab group 50A enter a state where they are respectively curved in different directions.
The two wound electrode assemblies 3 wrapped by the electrode assembly holder 14 are inserted into the rectangular exterior member 1. The sealing plate 2 and the rectangular exterior member 1 are welded to each other, and the opening of the rectangular exterior member 1 is sealed with the sealing plate 2. An electrolyte is injected into the rectangular exterior member 1 via the electrolyte injection hole 15 provided in the sealing plate 2. Then, the electrolyte injection hole 15 is sealed with the sealing member 16 such as a blind rivet. As a result, the rectangular secondary battery 20 is completed.
Positive electrode plates respectively associated with samples 1 to 4 were produced in the following method.
[Sample 1]
A positive electrode original plate 400 was produced in the above-described method using an aluminum alloy foil having a thickness of 15 μm composed of an aluminum 1085 material (A1085) in the Japanese Industrial Standards JIS as a positive electrode core body 4a.
The positive electrode original plate 400 associated with a sample 1 was cut using a continuous oscillation laser, to produce a positive electrode original plate 401 after tab formation. Conditions of the laser were an output of 600 W and a scanning speed of 4000 mm/s.
Then, the positive electrode original plate 401 after tab formation was cut to a predetermined size using a cutter, to obtain a positive electrode plate in the sample 1.
[Sample 2]
A positive electrode original plate 400 was produced in the above-described method using an aluminum alloy foil having a thickness of 15 μm composed of an aluminum 3003 material (A3003) in the Japanese Industrial Standards JIS as a positive electrode core body 4a.
The positive electrode original plate 400 associated with the sample 1 was cut using a continuous oscillation laser, to produce a positive electrode original plate 401 after tab formation. Conditions of the laser were an output of 600 W and a scanning speed of 4000 mm/s.
Then, the positive electrode original plate 401 after tab formation was cut to a predetermined size using a cutter, to obtain a positive electrode plate in a sample 2.
[Sample 3]
A positive electrode original plate 400 was produced in the above-described method using an aluminum alloy foil having a thickness of 15 μm composed of an aluminum 1085 material (A1085) in the Japanese Industrial Standards JIS as a positive electrode core body 4a.
The positive electrode original plate 400 associated with the sample 1 was cut using a continuous oscillation laser, to produce a positive electrode original plate 401 after tab formation. Conditions of the laser were an output of 900 W and a scanning speed of 4000 mm/s.
Then, the positive electrode original plate 401 after tab formation was cut to a predetermined size using a cutter, to obtain a positive electrode plate in a sample 3.
[Sample 4]
A positive electrode original plate 400 was produced in the above-described method using an aluminum alloy foil having a thickness of 15 μm composed of an aluminum 3003 material (A3003) in the Japanese Industrial Standards JIS as a positive electrode core body 4a.
The positive electrode original plate 400 associated with the sample 1 was cut using a continuous oscillation laser, to produce a positive electrode original plate 401 after tab formation. Conditions of the laser were an output of 900 W and a scanning speed of 4000 mm/s.
Then, the positive electrode original plate 401 after tab formation was cut to a predetermined size using a cutter, to obtain a positive electrode plate in a sample 4.
For the respective positive electrode plates 4 in the samples 1 to 4, a cross section of a portion where the positive electrode tabs 40 are not formed on the first end side 4A was observed, to measure a thickness T2 (μm) of a thick-walled part 4x. T2/T1 obtained when the thickness of a central portion of the positive electrode core body 4a (a portion having positive electrode active material layers 4b formed on both its surfaces in the positive electrode core body 4a) is set to T1 (μm) is illustrated in Table 1.
Table 1 indicates that the thickness of the thick-walled part 4x formed in an end portion of the positive electrode core body 4a can be reduced by using an aluminum alloy foil containing 0.5 to 2.0% by mass of Mn as the positive electrode core body 4a. The reason is considered that the thick-walled part 4x can be prevented from increasing because the positive electrode core body 4a is not easily melted at the time of laser cutting and the melted positive electrode core body 4a is not easily rounded by using the aluminum alloy foil containing 0.5 to 2.0% by mass of Mn as the positive electrode core body 4a.
An aluminum alloy used as a core body preferably contains 0.05 to 0.2% by mass of Cu. The aluminum alloy used as a core body preferably contains 0.6% or less by mass of Si, 0.7% or less by mass of Fe, and 0.1% or less by mass of Zn.
<Others>
Although an example in which the aluminum alloy is used as the positive electrode core body is illustrated in the above-described embodiment, a negative electrode core body may be made of aluminum alloy.
Although an example in which the positive electrode plate is provided with the positive electrode protective layer is illustrated in the above-described embodiment, the positive electrode protective layer is not an essential component. The positive electrode protective layer need not be provided. The positive electrode protective layer can be a resin layer. Alternatively, the positive electrode protective layer can also be a layer including ceramic particles and a binder. The positive electrode protective layer may include a carbon material. The positive electrode protective layer is preferably a layer having lower electric conductivity than that of the positive electrode active material layer.
Although an example in which the two wound electrode assemblies are arranged in the battery case has been illustrated in the above-described embodiment, the number of wound electrode assemblies may be one, or may be three or more. An electrode assembly may be a laminated-type electrode assembly including a plurality of positive electrode plates and a plurality of negative electrode plates.
Although an example in which each of the positive electrode current collector and the negative electrode current collector is composed of two components has been illustrated in the above-described embodiment, each of the positive electrode current collector and the negative electrode current collector may be composed of one component. If each of the positive electrode current collector and the negative electrode current collector is composed of one component, the positive electrode current collector and the negative electrode current collector are preferably respectively connected to the positive electrode terminal and the negative electrode terminal attached to the sealing plate after the positive electrode tab group and the negative electrode tab group are respectively connected to the positive electrode current collector and the negative electrode current collector.
Known materials can be respectively used for a positive electrode plate, a negative electrode plate, a separator, an electrolyte, and the like.
Number | Date | Country | Kind |
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2018-244061 | Dec 2018 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2019/049494 | 12/17/2019 | WO | 00 |