JP2000260477A - Non-aqueous secondary battery - Google Patents

Abstract

(57) [Problem] To provide a flat non-aqueous secondary battery that can be easily connected to the outside and reduce the thickness of the battery. SOLUTION: In a flat non-aqueous secondary battery having an energy capacity of 30 Wh or more and a volume energy density of 180 Wh / l or more, the thickness of the battery is made less than 12 mm, and a positive electrode terminal 3 and a negative electrode terminal 4 outside the battery. To
Female screw portions 31 and 41 for connecting the positive terminal 3 and the negative terminal 4 to a crimp terminal connected to an external load are provided and screwed together, and the positive terminal 3 and the negative terminal 4 are connected to the positive tab 32.
And the negative electrode tab 42 by caulking.
2 and the negative electrode tab 42 are connected to the positive electrode current collector 106 a and the negative electrode current collector 106 b by bolts 33 and 43 and nuts 34 and 44.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous secondary battery and a method for manufacturing the same, and more particularly, to a non-aqueous secondary battery for a power storage system and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of effective use of energy for resource saving and global environmental problems, a home-use decentralized power storage system for late-night power storage and power storage for photovoltaic power generation has been developed. Power storage systems are attracting attention. For example, JP-A-6-86463 discloses that
As a system capable of supplying energy to an energy consumer under optimum conditions, a total system combining electricity supplied from a power plant, gas cogeneration, a fuel cell, a storage battery, and the like has been proposed. A secondary battery used in such a power storage system has an energy capacity of 10
Unlike small secondary batteries for portable devices of Wh or less, large batteries having large capacities are required. For this reason, in the above-described power storage system, a plurality of secondary batteries are stacked in series, and usually used as a battery pack having a voltage of, for example, 50 to 400 V. In most cases, a lead battery is used.

On the other hand, in the field of small rechargeable batteries for portable equipment, nickel-metal hydride batteries and lithium rechargeable batteries have been developed as new types of batteries in order to meet the needs of small size and high capacity, and volume energy of 180 Wh / l or more has been developed. Batteries having a density are commercially available. In particular, lithium-ion batteries
It has the potential of a volume energy density exceeding 350 Wh / l, and its reliability, such as safety and cycle characteristics, is superior to a lithium secondary battery using lithium metal as a negative electrode. Prolonged.

[0004] In response to this, in the field of large-sized batteries for power storage systems, lithium-ion batteries have been targeted as candidates for high-energy density batteries, and lithium battery power storage technology research associations (LIBES) and others have been vigorously developing them. Have been.

The energy capacity of these large lithium ion batteries is about 100 Wh to 400 Wh, and the volume energy density is 200 to 300 Wh / l, which is at the level of a small secondary battery for portable equipment. Its shape is
Diameter 50mm-70mm, length 250mm-450mm
And a rectangular prism having a thickness of 35 mm to 50 mm or an oblong prism or the like are typical.

[0006] As for the thin lithium secondary battery, for example, a film battery (for example, Japanese Patent Application Laid-Open Nos. Hei 5-159575 and Hei 7-15975) in which a thin film having a thickness of 1 mm or less in which metal and plastic are laminated is accommodated in a thin exterior. -5
No. 7788), a small rectangular battery having a thickness of about 2 mm to 15 mm (JP-A-8-195204, JP-A-8-195204).
138727, JP-A-9-213286, etc.) are known. The purpose of these lithium secondary batteries is to respond to the miniaturization and thinning of portable devices. For example, an area of about JIS A4 size with a thickness of several mm that can be stored on the bottom surface of a portable personal computer. Japanese Patent Application Laid-Open No. 5-28310 discloses a thin battery.
No. 5), since the energy capacity is 10 Wh or less, the capacity is too small for a secondary battery for a power storage system.

[0007]

When the above-mentioned large batteries are used in a power storage system, generally, 4 to 10 large batteries (cells) are connected in series to form a 15 to 50 V battery module. Modules are connected in series and in parallel, and are often used as a power storage system having a predetermined voltage and capacity. Generally, each battery is connected by tightening with a nut using a crimp terminal or the like. In this case, a male screw portion is formed on one side (contact portion with the load side outside the battery) of the external terminals (positive terminal and negative terminal) of the battery, and on the other side (contact portion on the electrode side inside the battery container). In many cases, a male screw portion is formed. As in the past, when the battery thickness is large, the double external thread structure as described above is practical, but in the case of a thin flat battery, it is difficult to connect by this method. Hereinafter, the reason will be described.

In a conventional large battery, as shown in FIG.
The external terminals are generally fixed using screws both outside and inside the battery. In FIG. 7A, the internal resistance is reduced by tightening the crimp terminal 32 with the external terminal 31 with the nut 33. The load side or the batteries were connected to each other with a small size and high strength. In FIG. 7B, the external terminal 31 is formed by forming a female screw at a connection portion outside the battery, and connecting the crimp terminal 32 with a bolt 34. The reason that such a general connection method can be performed relatively freely is that a conventional large battery has a thickness and a length allowed for an external terminal is 20 mm or more. On the other hand, in the case of a flat battery, it is difficult to take out a large-diameter external terminal through which a large current can flow from the side surface of the battery case, and it is necessary to take out the external terminal from the front and back surfaces that are the main surfaces of the battery case. In this case, the allowable length of the external terminal varies depending on the thickness of the battery, but is at most about 10 mm, and is often shorter than that. In addition, when the length protruding outside the battery is increased, when the batteries are arranged side by side to form a module, the gap becomes large, and the battery module becomes large. Accordingly, there has been a long-felt need for a new connection structure that can keep the length of the external terminal within a few millimeters and that can be connected with sufficient strength without generating an unnecessary gap with the outside.

SUMMARY OF THE INVENTION An object of the present invention is to provide a flat non-aqueous secondary battery which can be easily connected to the outside and can reduce the thickness of the battery.

[0010]

According to the present invention, there is provided a non-aqueous secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte containing a lithium salt.
The non-aqueous secondary battery has a flat shape with a thickness of less than 12 mm, an energy capacity of 30 Wh or more, and a volume energy density of 180 Wh / l or more. Is provided with a concave portion for connecting the positive electrode terminal and / or the negative electrode terminal to an external connection member, and the inside of the battery of the positive electrode terminal and / or the negative electrode terminal is provided with a positive electrode current collector and / or
Or directly joined to a negative electrode current collector of the negative electrode, or a relay member electrically connected to the positive electrode current collector and / or a relay member electrically connected to the negative electrode current collector. And a non-aqueous secondary battery.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A non-aqueous secondary battery according to one embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a flat rectangle (note type) according to an embodiment of the present invention.
FIG. 2 is a plan view and a side view of the non-aqueous secondary battery for a power storage system of FIG. 1, and FIG. 2 is a side view showing a configuration of an electrode laminate housed inside the battery shown in FIG.

As shown in FIGS. 1 and 2, a non-aqueous secondary battery according to the present embodiment includes a battery container including an upper lid 1 and a bottom container 2 and a plurality of positive electrodes housed in the battery container. 1
01a, negative electrodes 101b and 101c, and separator 10
4 of the present invention. In the case of the flat nonaqueous secondary battery as in the present embodiment, the positive electrode 101a and the negative electrode 101b (or the negative electrode 10 arranged on both outer sides of the laminate)
1c) is, for example, as shown in FIG.
4, the layers are alternately arranged and laminated.
The arrangement is not particularly limited, and the number of layers and the like can be variously changed according to the required capacity and the like. The shape of the non-aqueous secondary battery shown in FIGS.
mm × 210 mm × 6 mm in thickness.
In the case of a lithium secondary battery using LiMn ₂ O ₄ and a carbon material for the negative electrodes 101b and 101c, for example, it can be used for a power storage system.

Next, a positive electrode 101a, a negative electrode 101b, 10
1c, a positioning hole serving as an opening used for positioning the separator 104 during lamination will be described. The positioning hole is provided in any one of the positive electrode 101a, the negative electrodes 101b and 101c, and the separator 104, and has a sheet-like positive electrode 101a, negative electrodes 101b and 101c as shown in FIG.
In the case where the separator 104 and the separator 104 are stacked, it is more preferable that the separator 104 is provided on the positive electrode 101a and the negative electrodes 101b and 101c, and an example thereof will be specifically described below. Note that the present invention is not limited to the stacking jigs and positioning holes described below. The opening used for positioning is not particularly limited to a hole, and may be a notch, a recess, or the like as long as positioning is possible.

FIG. 3 shows a positive electrode 101a, a negative electrode 101b, and a negative electrode 101b.
It is explanatory drawing of an example of the lamination method of 01c separator 104. As shown in FIG. 3, each of two positive electrode positioning holes 10 is provided.
The negative electrode 7a and the negative electrode positioning hole 107b are provided in the positive electrode current collector 106a and the negative electrode current collector 106b, respectively, at positions that can be positioned outside the separator 104, which is the maximum size.

The laminating jig includes a base 81, four positive guide pins 82 fixed at predetermined positions on the base 81, four negative guide pins 83, and four L-shaped fixing portions 84. Is provided. First, the largest separator 104 is positioned so that its four corners are along the inside of the four L-shaped fixing portions 84. Next, the negative electrode guide pin 83 is inserted into the negative electrode positioning hole 107b, and the next largest negative electrode 101b (or 101c) is positioned. Next, the separator 104
Are positioned so that the four corners are along the inside of the four L-shaped fixing portions 84. Finally, the positive electrode guide pin 82 is inserted into the positive electrode positioning hole 107a to position the positive electrode 101a. Hereinafter, the positive electrode 101a and the negative electrode 101b (or 1
01c) and the number of separators 104, the above operation is repeated, whereby the positive electrode 101a, the negative electrode 101b,
The layers 101c and the separator 104 can be laminated in a state where they are aligned with high precision. Note that it is preferable that the guide pins be easily removed after the lamination is completed, because the positional displacement at the time of removing the electrode laminate is reduced.

Here, the shape of the positioning opening is not particularly limited, and in the case of a hole, it may be circular, oval,
Examples include an L-shape, a crescent, a triangle, a square, a rectangle, a polygon, and the like. In the case of a notch or a recess, a U-shape, a wedge, and the like. The number of positioning openings provided in one electrode is not particularly limited, and may be at least one. However, in order to further prevent displacement in the vertical and horizontal directions, as shown in FIG. One or more may be provided. Further, the number of openings for positioning provided in one electrode is not particularly limited, and may be provided at at least one position as shown in FIG. 3 to further prevent displacement in the vertical and horizontal directions. for,
It may be provided at two places, such as diagonally or opposing positions of the electrodes, or may be provided at more places. In the case where positioning holes are provided at a plurality of locations and electrical connection to the outside is made using one positioning hole as described later, it is also possible to cut other portions after the completion of lamination. Also,
The position at which the positioning opening provided in one electrode is provided is not particularly limited either. The position may be provided at one end as shown in FIG. 3 or may be provided at the middle of one side. Good.

The external terminals, that is, the positive electrode terminal 3 and / or the negative electrode terminal 4 shown in FIG. It can also be used as a hole for connection with the positive electrode 101a and / or the negative electrodes 101b and 101c. Alternatively, an electrical connection may be made between the external terminal and the electrode via the relay member, and a bolt may be passed through a hole on one end side of the relay member and the positioning hole and fastened with a nut.

As described above, when making electrical connection to the outside by using the positioning holes, the positioning holes are preferably not circular. This reason will be described with reference to FIGS. FIG. 4A is a diagram illustrating a state in which electrodes and the like are stacked using a stacking jig provided with the guide pins 83 (the guide pins 82 are not shown), and FIG.
FIG. 6 is a diagram showing a state in which the negative electrode current collecting pieces 106b of the negative electrodes 101b and 101c are fastened by bolts 91 and nuts 92 after positioning. In the figure, for simplicity of explanation,
The number of layers is reduced.

As shown in FIG. 4 (a), after positioning using a laminating jig, as shown in FIG. 4 (b), when connection is attempted using bolts 91 and nuts 92,
The distance from the end of each of the negative electrodes 101b and 101c to the position fixed by the bolt 91 and the nut 92 differs for each negative electrode. The outer negative electrode is farther, and the intermediate negative electrode is closest. Therefore, when a circular positioning hole is used, the negative electrode current collector piece 106b of the intermediate negative electrode is loosened, and the current collector piece is damaged, such as being broken, and fixing with the bolts and nuts is complicated. This is the same in the case of the positive electrode. Therefore, in order to avoid such inconvenience, it is preferable that at least one of the positioning holes has a non-circular shape, for example, an elliptical shape obtained by extending a circular shape in one direction so as to absorb the difference in the distance. .

Although the case where the sheet-like electrodes and the like are stacked has been described above, for example, when one of the electrodes is folded and the separator and the other electrode are interposed therebetween, the same positioning holes as described above are used. Can be used. Further, for example, it is also possible to position the separator and the negative electrode bonded together by the L-shaped fixing portion 84 in FIG. 3, provide the above-described positioning holes only in the positive electrode, and perform positioning using a guide pin or the like. is there.

An external connection for connecting the positive terminal 3 and / or the negative terminal 4 to the outside of the battery, for example, an external load, is provided on the outside of the battery of the positive terminal 3 and / or the negative terminal 4 serving as an external terminal. A concave portion for connecting members, for example, a female screw portion or a concave portion for fitting is provided, and an external connection member is connected to the concave portion for electrical connection. The connection is
For the reasons described below, it is preferable to use fitting or screwing. For example, bolts, screws,
Electrical connection can be obtained by screwing, press-fitting, wedging, or the like using a rivet or the like. The inside of the battery of the positive electrode terminal 3 and / or the negative electrode terminal 4 is connected to the positive electrode current collector 10.
5a and / or a negative electrode current collector 105b or a relay member electrically connected to the positive electrode current collector 105a and / or a direct connection to a relay member electrically connected to the negative electrode current collector 105b for electrical connection Has been taken. The joining is preferably performed by crimping or welding by caulking for the reasons described below.

FIG. 5 is an explanatory view showing an example of a connection structure between the positive electrode terminal 3 and the negative electrode terminal 4 and the positive electrode current collector 105a and the negative electrode current collector 105b. Female screw portions 31 and 41 are formed in the head portions of the positive electrode terminal 3 and the negative electrode terminal 4 as concave portions for fastening crimp terminals, which are external connection members connected to an external load, with bolts. In addition, the depth necessary for connection is ensured by engraving the inside of the battery of the negative electrode terminal 4. On the other hand, the connection between the positive terminal 3 and the negative terminal 4 inside the battery is performed by caulking the lower part of the positive terminal 3 with the positive tab 32 serving as a relay member insulated from the upper lid 1 of the battery container, thereby forming a negative electrode serving as a relay member. The tab 42 is caulked with the lower part of the negative electrode terminal 4 while being insulated from the upper lid 1 of the battery container. Further, the positive electrode current collector 106a of the positive electrode current collector 105a and the positive electrode tab 32 are connected using bolts 33 and nuts 34, and the negative electrode current collector 106b of the negative electrode current collector 105b and the negative electrode tab 42 are connected to each other by bolts. A connection is made by using a nut 43 and an electrical connection.

For example, in the external terminal outside the battery, M
In the case of forming the female screw of No. 3, in order to form a male screw on the inner part of the battery of the external terminal to have sufficient strength,
For example, it is necessary to form external threads M6 to M8, and the diameter of the external terminal is as large as 12 mm. In addition, M6
When the M8 to M8 male screws are fastened using a nut, the nut becomes thicker and the external terminals become larger. However,
In the above connection structure, the connection inside the battery can obtain sufficient strength by caulking or welding, and it is not necessary to form an external thread on the inside portion of the battery, so that the connection portion can be made small and thin. .

It is also conceivable to use welding to connect the external terminals outside the battery, but unlike the inside of the battery, a sufficient strength is required for the connection outside the battery. In addition, since the material of the external terminal is selected from materials having high electrical conductivity such as copper and aluminum, welding is difficult, and even in the case of welding, sufficient strength is obtained in connection between batteries or a load. Because it cannot be obtained,
Poor reliability for use outside the battery. In addition, it is conceivable to provide a convex portion on the external terminal and connect the external terminal to the outside of the battery and caulk the convex portion. However, since the length of the portion protruding to the outside of the battery is limited, sufficient strength is obtained. I can't. However, in the above connection structure, the connection outside the battery is
Since the concave portion provided in the external terminal is used, the above problem does not occur.

The connection structure inside the above-mentioned battery is not particularly limited to this example, and the electrode current collector can be directly caulked or welded to the external terminal. It is also possible to caulk or weld.

With the above connection structure, the positive electrode current collector 105a of each positive electrode 101a is electrically connected to the positive electrode terminal 3, and similarly, the negative electrode current collector 1 of each of the negative electrodes 101b and 101c.
05b is electrically connected to the negative electrode terminal 4. The positive electrode terminal 3 and the negative electrode terminal 4 are attached in a state of being insulated from the battery container, that is, the upper lid 1.

The upper lid 1 and the bottom container 2 are welded by melting the upper lid at the point A shown in the enlarged view of FIG. An electrolyte injection port 5 is opened in the upper lid 1.
After electrolyte injection, for temporary sealing, for example, aluminum-
Once sealed using a sealing film 6 made of a modified polypropylene laminate film,
After being charged several times, it is removed, and the battery container is finally sealed in a state where the pressure in the battery container is lower than the atmospheric pressure. In this case, the sealing film 6 can also have a safety valve for releasing when the internal pressure inside the battery rises. The pressure in the battery container after the final sealing step by the sealing film 6 is lower than the atmospheric pressure, preferably 650 Torr or less, more preferably 550 Torr or less. This pressure is determined in consideration of the separator used, the type of electrolyte, the material and thickness of the battery container, the shape of the battery, and the like. If the internal pressure is equal to or higher than the atmospheric pressure, the battery becomes larger than the designed thickness, or the thickness of the battery varies widely, which causes the internal resistance and capacity of the battery to vary, which is not preferable.

The positive electrode active material used for the positive electrode 101a is not particularly limited as long as it is a lithium-based positive electrode material. A lithium composite cobalt oxide, a lithium composite nickel oxide, a lithium composite manganese oxide, or a mixture thereof is used. Further, a system in which one or more different metal elements are added to these composite oxides can be used, and a high-voltage, high-capacity battery can be obtained, which is preferable. When importance is placed on safety, a manganese oxide having a high thermal decomposition temperature is preferable. Examples of the manganese oxide include a lithium composite manganese oxide represented by LiMn ₂ O ₄ , a system in which one or more different metal elements are added to these composite oxides, and an excess of lithium, oxygen, etc. in excess of the stoichiometric ratio. LiMn
₂ O ₄ .

The negative electrode active material used for the negative electrodes 101b and 101c is not particularly limited as long as it is a lithium-based negative electrode material. A material capable of doping and undoping lithium can be used for safety and cycle life. This is preferable because the reliability of the device is improved. As a material capable of doping and undoping lithium, a graphite-based material, a carbon-based material, a tin oxide-based material, which is used as a negative electrode material of a known lithium ion battery,
Examples thereof include metal oxides such as silicon oxides, and conductive polymers typified by polyacene-based organic semiconductors. In particular, from the viewpoint of safety, a polyacene-based substance that generates a small amount of heat at about 150 ° C. or a material containing the same is desirable.

The structure of the separator 104 is not particularly limited, but a single-layer or multi-layer separator can be used, and it is preferable to use at least one non-woven fabric. In this case, the cycle characteristics are improved. . Also, the material of the separator 104 is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyamide, kraft paper, and glass. However, polyethylene and polypropylene are preferable from the viewpoints of cost, water content, and the like. . When polyethylene or polypropylene is used as the separator 104, the basis weight of the separator is preferably 5 g / m ² or more and 30 g or more.
/ M ² or less, more preferably 5 g / m ² or more and 20 g
/ M ² or less, more preferably 8 g / m ² or more and 20
g / m ² or less. The basis weight of the separator is 30 g / m ²
If it exceeds, the separator becomes too thick or the porosity decreases and the internal resistance of the battery increases, and if it is less than 5 g / m ² , it is not preferable because practical strength cannot be obtained.

As the electrolyte of the non-aqueous secondary battery of the present embodiment, a known non-aqueous electrolyte containing a lithium salt can be used, which is appropriately determined according to the conditions of use such as a positive electrode material, a negative electrode material, and a charging voltage. , More specifically LiPF ₆ ,
LiBF ₄ , a lithium salt such as LiClO ₄ , propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, γ-butyrolactone, methyl acetate, methyl formate, or a mixed solvent of two or more of these Examples thereof include those dissolved in an organic solvent. Further, the concentration of the electrolytic solution is not particularly limited, but is generally practically 0.5 mol / l to 2 mol / l. Naturally, the electrolytic solution has a water content of 100 ppm or less. Preferably, it is used. In addition, the non-aqueous electrolyte used in this specification means a concept including a non-aqueous electrolyte and an organic electrolyte, and also a concept including a gel or solid electrolyte.

The non-aqueous secondary battery configured as described above can be used for home power storage systems (nighttime power storage, cogeneration, solar power generation, etc.), power storage systems for electric vehicles, etc. It can have capacity and high energy density. In this case, the energy capacity is preferably 30 Wh or more, more preferably 50 Wh or more, and the energy density is preferably 180 Wh /
1 or more, more preferably 200 Wh / l. When the energy capacity is less than 30 Wh or when the volume energy density is less than 180 Wh / l, the capacity is small for use in a power storage system, and it is necessary to increase the number of series-parallel batteries in order to obtain a sufficient system capacity. In addition, it is not preferable for a power storage system because a compact design is difficult.

In general, a large lithium secondary battery (energy capacity of 30 Wh or more) for a power storage system can obtain a high energy density, but the battery design is an extension of a small battery for a portable device. Alternatively, the battery has a cylindrical shape, a square shape, or the like having a thickness three times or more that of a small battery for a portable device. In this case, heat easily accumulates inside the battery due to Joule heat generated by the internal resistance of the battery during charge / discharge or internal heat generated by the battery due to a change in entropy of the active material due to the entrance and exit of lithium ions. For this reason, the difference between the temperature inside the battery and the temperature near the battery surface is large, and the internal resistance differs accordingly. As a result, the charge amount and the voltage are likely to vary. Also, since a plurality of batteries of this type are used as assembled batteries, the heat storage easiness varies depending on the installation position of the batteries in the system, causing variations among the batteries, and accurate control of the entire assembled battery. It becomes difficult. In addition, the battery temperature rises due to insufficient heat dissipation during high-rate charge / discharge, etc., and the battery is placed in an unfavorable state. Problems such as induction of reliability and, in particular, safety remain.

The flat non-aqueous secondary battery of the present embodiment has a large heat radiation area and is advantageous for heat radiation, so that the above-mentioned problems can be solved. That is, the non-aqueous secondary battery of the present embodiment has a flat shape,
Its thickness is preferably less than 12 mm, more preferably less than 10 mm, even more preferably less than 8 mm. The lower limit of the thickness is practically 2 mm or more in consideration of the filling rate of the electrode and the battery size (the smaller the thickness, the larger the area for obtaining the same capacity). Battery thickness is 12
mm or more, it becomes difficult to sufficiently radiate the heat generated inside the battery to the outside, or the temperature difference between the inside of the battery and the vicinity of the battery surface increases, resulting in a difference in internal resistance.
Variations in the amount of charge and voltage in the battery increase. Although the specific thickness is appropriately determined according to the battery capacity and the energy density, it is preferable to design the thickness so as to obtain the expected heat radiation characteristics.

The shape of the non-aqueous secondary battery of the present embodiment is, for example, that the flat front and back surfaces are square, circular,
Various shapes such as an oval shape can be used. In the case of a square shape, the shape is generally a rectangle, but it can also be a polygon such as a triangle or a hexagon. Further, it may be a cylindrical shape such as a thin-walled cylinder. In the case of a cylindrical shape, the thickness of the cylinder is the thickness referred to here. Further, from the viewpoint of ease of production, the flat front and back surfaces of the battery are preferably rectangular, and a notebook-type shape as shown in FIG. 1 is preferable.

The materials used for the upper lid 1 and the bottom container 2 which are to be battery containers are appropriately selected depending on the use and shape of the battery.
There is no particular limitation, and iron, stainless steel, aluminum and the like are common and practical. Also, the thickness of the battery container is appropriately determined depending on the use and shape of the battery or the material of the battery case, and is not particularly limited. Preferably, the thickness of a portion of 80% or more of the battery surface area (the thickness of the portion having the largest area constituting the battery container) is 0.2 mm or more. If the thickness is less than 0.2 mm, the strength required for manufacturing the battery cannot be obtained, which is not desirable. From this viewpoint, the thickness is more preferably 0.3 mm or more. Further, it is desirable that the thickness of the portion is 1 mm or less. When the thickness exceeds 1 mm, the force for pressing down the electrode surface increases, but it is not desirable because the internal volume of the battery is reduced and a sufficient capacity cannot be obtained, or the weight increases, which is not desirable. Preferably 0.
7 mm or less.

As described above, the thickness of the non-aqueous secondary battery is set to 1
By designing it to be less than 2 mm, for example,
When the battery has a large capacity of 0 Wh or more and a high energy density of 180 Wh / l, the battery temperature rise is small even during high-rate charging and discharging, and excellent heat radiation characteristics can be obtained. Therefore, heat storage of the battery due to internal heat generation is reduced, and as a result, thermal runaway of the battery can be suppressed, and a non-aqueous secondary battery excellent in reliability and safety can be provided.

Next, the final sealing step of the method for manufacturing the non-aqueous secondary battery having the above-described structure will be described in detail. In the nonaqueous secondary battery of the present embodiment, the positive electrode 101a, the internal pressure of the completed battery is less than the atmospheric pressure,
After the negative electrodes 101b and 101c, the separator 104, and the non-aqueous electrolyte are accommodated in the battery container and charged at least once, the final sealing step of the battery container is performed in a state in which the pressure in the battery container is lower than the atmospheric pressure.

The above-mentioned final sealing step is preferably performed after at least one charging operation. The above charging operation employs various conditions according to the type of the positive electrode material, the negative electrode material, the separator, the electrolytic solution, etc. used in the battery, the water content and impurities of these materials, the voltage at which the battery is used, and the like. Can be. For example, up to 4-8 battery operating voltage
The final sealing step may be performed after charging at a rate of about an hour rate, applying a constant voltage as needed, and discharging at a rate of about an 8 hour rate. Alternatively, it is possible to perform various charging operations such as sealing after performing only the charging operation less than or equal to the capacity of the battery, or sealing after repeating charging and discharging two or more times. Maintaining the internal pressure of the battery below atmospheric pressure.

In particular, when a liquid electrolyte using graphite for the negative electrode and a lithium composite oxide for the positive electrode is used, gas is generated inside by decomposition of the electrolyte at the beginning of the first charging.
For example, even if the final sealing step is performed at a pressure lower than the atmospheric pressure without performing the charging operation, the inside of the battery is pressurized (atmospheric pressure or more) by the first charging operation thereafter, and the thickness of the battery increases. The internal resistance and capacity of the battery may fluctuate, and stable cycle characteristics may not be obtained. However,
This problem can be solved by performing the final sealing step at a pressure lower than the atmospheric pressure after performing the charging operation to generate gas as in the present embodiment. In this case, when performing the first charging operation, the inside of the battery may be made to be lower than the atmospheric pressure, but the pressure inside the battery at this time is not particularly limited.

The method for reducing the inside of the battery to a pressure lower than the atmospheric pressure is not particularly limited. Specifically, the method can be performed as follows.

First, as shown in FIG.
The negative electrodes 101b and 101c and the separator 104 are laminated, the obtained electrode laminate and the like are accommodated in the upper lid 1 and the bottom container 2, and the outer peripheral portions of the upper lid 1 and the bottom container 2 are welded. next,
An electrolyte is injected into the battery container from the injection port 5. Next, for the temporary sealing, the injection port 5 is temporarily closed by using a heat-sealing type sealing film 6 having a low moisture permeability represented by the above-mentioned aluminum-modified polypropylene laminated film and aluminum-modified polyethylene laminated film. And
Then, after charging at least once as described above, the sealing film 6 is removed. The method of the temporary sealing is not particularly limited to the above example, and the opening may be temporarily sealed using a screw or the like, or in a state where moisture is removed, for example, air is shut off. In an environment or a dry atmosphere having a dew point of −40 ° C. or less, the above charging operation may be performed without sealing.

Next, as a final sealing step, the sealing film 6 is heat-sealed. The method used in the final sealing step is not particularly limited to the above example, and the inside of the battery is brought to a predetermined pressure (less than atmospheric pressure) by welding a metal plate or foil, or attaching a cock to the battery container. After reducing the pressure, the cock may be closed.

The pressure in the final sealing step is lower than atmospheric pressure, preferably 650 Torr or less, more preferably 550 Torr or less. This pressure is determined according to the internal pressure required for the finally completed battery. The peripheral length of the opening provided in the battery container for performing the final sealing step is 1/1 / the outer peripheral length of the battery.
It is preferably at most 10 and more preferably at most 1/20. If the perimeter of the opening exceeds 1/10 of the perimeter, the fusion area increases as described above, and a large heat fusion device is required, and the reliability of the fusion portion is lacking. Problems arise. Further, the portion where the opening is provided is preferably on the front and back surfaces except for the outer peripheral portion of 5 mm of the battery. If the opening is provided within 5 mm of the outer peripheral portion of the battery, sufficient strength cannot be obtained, and poor sealing such as leakage of the electrolyte is likely to occur.

[0045]

The present invention will be described more specifically below with reference to examples of the present invention. (Example 1) (1) 100 parts by weight of LiCo ₂ O ₄ , 8 parts by weight of acetylene black, polyvinylidene fluoride (PVDF) 3
The mixture was mixed with 100 parts by weight of N-methylpyrrolidone (NMP) to obtain a positive electrode mixture slurry. The slurry was applied to both sides of a 20 μm-thick aluminum foil serving as a current collector, dried, and then pressed to obtain a positive electrode. FIG. 6A is an explanatory diagram of the positive electrode. In this embodiment, the coating area (W1 × W2) of the positive electrode 101a is 262.5 × 192 mm ² , and the positive electrode 101a is coated on both surfaces of the 20 μm current collector 105a with a thickness of 103 μm. As a result, the electrode thickness t is 226 μm.
m. On the short side of the electrode, a positive electrode current collector 106a to which no electrode is applied is provided.
2 mm long holes are drilled.

(2) Graphitized mesocarbon microbeads (MCMB, manufactured by Osaka Gas Chemical Co., Ltd., product number 6-28) 10
0 parts by weight and 10 parts by weight of PVDF were mixed with 90 parts by weight of NMP to obtain a negative electrode mixture slurry. The slurry was applied on both sides of a 14 μm-thick copper foil serving as a current collector, dried, and then pressed to obtain a negative electrode. FIG. 6B is an explanatory diagram of the negative electrode. The negative electrode 101b is larger than the positive electrode by 2.25 mm on both sides in the long side direction and 1.5 mm on both sides in the short side direction. The coating area (W1 × W2) of the negative electrode 101b is 267 × 19
5 mm ² , and 1 mm on both sides of an 18 μm current collector 105b.
It is applied with a thickness of 08 μm. As a result, the electrode thickness t is 234 μm. Further, a negative electrode current collector 106b to which no electrode is applied is provided on the short side of the electrode, and two long holes of 5 mm × 3 mm are formed. Further, a single-sided electrode having a thickness of 126 μm was prepared in the same manner except that the coating was performed on one side only. The single-sided electrode is disposed outside in the electrode laminate of item (3) (101c in FIG. 2).

(3) FIG. 6C is an explanatory view of the separator. The area (W1 × W2) of the separator 104 is 2
It is 71 × 197 mm ^2, which is larger by 2 mm on both sides in the long side direction and 1 mm on both sides in the short side direction than the negative electrode 104b. FIG.
As shown in the above, eight positive electrodes and nine negative electrodes (two inside one side) obtained in the above item (1) were used as separators 104a (polypropylene nonwoven fabric: Nippon Kodoshi Paper Industries, MP1050, basis weight 10 g / m ² ) and separators 104b. (Polyethylene microporous membrane; Asahi Kasei Corporation HIPORE6022, basis weight 13.
3 g / m ² ) were alternately laminated via a separator 104 bonded thereto, and a separator 104 b was further arranged outside the outer negative electrode 101 c for insulation from a battery container, thereby producing an electrode laminate. The separator 104
Means that the separator 104b is on the positive electrode side,
It was arranged such that a was on the negative electrode side. At the time of the above lamination, the lamination jig shown in FIG. 3 was used, and the lamination time was 28 minutes on average for ten times.

(4) As shown in FIG.
Of the SUS304 thin plate was squeezed to a depth of 5 mm to prepare the bottom container 2, and the upper lid 1 was also formed of a 0.5 mm thick SUS304 thin plate. Next, as shown in FIG. 5, a positive electrode terminal 3 made of aluminum and a negative electrode terminal 4 made of copper (terminal maximum portion 6 mmφ, female screw portion M3 for external connection) were attached to the upper lid 1. The positive and negative terminals 3 and 4 were insulated from the upper lid 1 by a polypropylene gasket. The positive electrode terminal 3 is caulked with an aluminum positive electrode tab 32 serving as a relay member, and the negative electrode terminal 4 is provided with a copper negative electrode tab 4 serving as a relay member.
2 were caulked and electrically connected to each other, and if necessary, each part was insulated using a PET adhesive tape.

(5) An aluminum nut is passed through two positioning holes of each positive electrode current collector piece 106a and two holes of the positive electrode tab 32 of the electrode laminate prepared in the above item (3). 34, two positioning holes of each negative electrode current collector 106b and two of the negative electrode tabs 42.
Copper bolts 43 were passed through the holes and fastened by copper nuts 44, and each was electrically connected. The connected electrode laminate was fixed with an insulating tape, and the corner A of FIG. 1 was laser-welded over the entire circumference. After that, injection port 5 (6mmφ)
Then, a solution obtained by dissolving LiPF ₆ at a concentration of 1 mol / l into a solvent obtained by mixing ethylene carbonate: diethyl carbonate: methyl ethyl carbonate at a weight ratio of 6: 7: 7 was poured as an electrolytic solution. Next, under a reduced pressure of 300 Torr, the injection port 5 was temporarily closed using a temporary fixing bolt.

(6) This battery is charged to a current of 5 A up to 4.1 V, and thereafter, a constant current constant voltage charging of applying a constant voltage of 4.1 V is performed for 12 hours, and then a constant current of 5 A is applied to the battery.
After the battery was discharged to 5 V, the temporary fixing bolts of the battery were removed, and the sealing film 6 made of an aluminum foil-modified polypropylene laminated film having a thickness of 0.08 mm and punched into 12 mmφ under a reduced pressure of 300 Torr was heated to a temperature of 250 mm. By performing heat fusion under the conditions of 〜350 ° C., pressure 1-3 kg / cm ² and pressurization time 5-10 seconds, the injection port 5
Was finally sealed. Next, measurement tabs were attached to the positive electrode terminal 3 and the negative electrode terminal 4 of the obtained battery using M3 screws. At this time, the internal resistance of the battery is 4.6 mΩ,
It was stable even when the measurement tab was pulled strongly. When the battery was charged and discharged at a constant current and a constant voltage under the same conditions as described above, the discharge capacity was 27.2 Ah and the energy capacity was 100 Wh. When the battery was discharged at a constant current of 25 A, the discharge capacity was 24.0 Ah. The rise in battery temperature at the end of discharging was less than that in the case where a box-shaped (thickness of 12 mm or more) battery of the same capacity was assembled. (Comparative Example 1) A battery was assembled in the same manner as in Example 1 except that a positive terminal and a negative terminal (terminal maximum part: 6 mmφ) having no female screw part for external connection of M3 were used. Next, the measurement tab was attached to the positive electrode terminal and the negative electrode terminal using laser welding, and the internal resistance was measured in the same manner as in Example 1. The internal resistance of the battery was 5.4 mΩ. Pulled off easily.

[0051]

As is apparent from the above description, according to the present invention, in a flat battery, in particular, a flat battery having a large capacity and a high volume energy density, a novel positive electrode and a negative electrode terminal are employed. A flat nonaqueous secondary battery that can be easily attached to each other or to an external load, has sufficient strength, and can reduce the thickness of the battery can be provided.

[Brief description of the drawings]

FIG. 1 is a plan view and a side view of a non-aqueous secondary battery for a power storage system according to an embodiment of the present invention.

FIG. 2 is a side view showing a configuration of an electrode laminate housed inside the battery shown in FIG.

FIG. 3 is an explanatory diagram of an example of a method of laminating a positive electrode, a negative electrode, and a separator of the battery shown in FIG.

FIG. 4 is a diagram showing a state when electrodes and the like are stacked using a positioning jig and a state when the negative electrode current collector is fastened with bolts and nuts after positioning.

FIG. 5 is an explanatory diagram showing an example of a connection structure between a positive electrode terminal and a negative electrode terminal of the battery shown in FIG.

FIG. 6 is an explanatory diagram of a positive electrode, a negative electrode, and a separator used in an example of the nonaqueous secondary battery of the present invention.

FIG. 7 is an explanatory view showing a connection structure of external terminals of a conventional battery.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Top cover 2 Bottom container 3 Positive electrode terminal 4 Negative terminal 5 Injection port 6 Sealing film 31, 41 Female screw part 101a Positive electrode (both sides) 101b Negative electrode (both sides) 101c Negative electrode (one side) 104, 104a, 104b Separator 105a Positive electrode collector 105b Negative electrode current collector 106a Positive electrode current collector 106b Negative current collector 107a Positive electrode positioning hole 107b Negative electrode positioning hole

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Shizukuni Yada 4-1-2 Hirano-cho, Chuo-ku, Osaka-shi, Osaka Prefecture Inside Kansai New Technology Research Institute Co., Ltd. (72) Haruo Kikuta, Hirano-cho, Chuo-ku, Osaka-shi, Osaka 4-Chome 1-2 Term in Osaka Gas Co., Ltd. F-term (reference) 5E012 BA12 5H011 AA09 CC06 CC10 DD09 5H014 AA04 EE08 EE10 5H022 AA09 CC05 5H029 AJ14 AK02 AK03 AL07 AM03 AM05 AM07 BJ04 DJ02 DJ05 HJ04 HJ19

Claims (6)

[Claims] 1. A non-aqueous secondary battery including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte containing a lithium salt, wherein the non-aqueous secondary battery has a flat shape with a thickness of less than 12 mm. The energy capacity is 30 Wh or more and the volume energy density is 180 Wh / l or more, and the positive electrode terminal and / or the negative electrode terminal and the external connection member are connected to the positive electrode terminal and / or the negative electrode terminal outside the battery. A concave portion for the positive electrode terminal and / or the negative electrode terminal inside the battery is electrically connected to the positive electrode current collector of the positive electrode and / or the negative electrode current collector of the negative electrode or the positive electrode current collector. A non-aqueous secondary battery, which is directly joined to a connected relay member and / or a relay member electrically connected to the negative electrode current collector. 2. The non-aqueous secondary battery according to claim 1, wherein the joining of the positive electrode terminal and / or the negative electrode terminal to the inside of the battery is performed by crimping or welding by caulking. 3. The non-aqueous secondary battery according to claim 1, wherein the connection of the positive electrode terminal and / or the negative electrode terminal to the outside of the battery is performed by fitting or screwing. 4. The non-aqueous secondary battery according to claim 1, wherein the positive electrode includes a manganese oxide, and the negative electrode includes a material capable of doping and undoping lithium. Next battery. 5. The non-aqueous secondary battery according to claim 1, wherein the flat front and back surfaces are rectangular. 6. The non-aqueous secondary battery according to claim 1, wherein the thickness of the battery container of the non-aqueous secondary battery is 0.2 mm or more and 1 mm or less.