SECONDARY BATTERY AND ELECTRODE PRODUCTION METHOD
Secondary battery includes a battery assembly configured by alternately stacking positive electrodes 1 and negative electrodes 6 via separators 20, in which the positive electrode and the negative electrode respectively include collectors 3 and 8, and active materials 2 and 7 applied on the collectors. On each surface of the collector, a coated portion coated with the active material and an uncoated portion not coated with any active material are provided. In one or both of the positive electrode and the negative electrode, boundary portion 4a between the coated portion and the uncoated portion on the front surface of the collector, is positioned planarly away from boundary portion 4b between the coated portion and the uncoated portion on the rear surface of the collector.
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This application is a Divisional of U.S. patent application Ser. No. 14/895,667, filed on Dec. 3, 2015, which is a National Stage of International Application No. PCT/JP2013/083136, filed on Dec. 10, 2013, which claims priority from Japanese Patent Application No. 2013-131006 filed Jun. 21, 2013, the contents of all of which are incorporated herein by reference in their entirety.
TECHNICAL FIELDThe present invention relates to a secondary battery configured by alternately stacking positive electrodes and negative electrodes via separators, and an electrode production method.
BACKGROUND ARTThe secondary battery is widely used not only as a power source for a portable device such as a mobile phone, a digital camera, or a laptop computer but also as a power source for a vehicle or a household, and a lightweight lithium-ion secondary battery having a high energy density among others is now an energy storage device indispensable to our life style.
The secondary batteries can be largely classified as a wound type and a laminated type. The battery assembly of the wound type secondary battery has a structure in which a long positive electrode sheet and a long negative electrode sheet are wound a plurality of times with a separator interposed between positive electrode sheet and negative electrode sheet which are stacked. The battery assembly of the laminated type secondary battery has a structure in which positive electrode sheets and negative electrode sheets are alternately stacked together repeatedly with a separator interposed between each positive and negative electrode sheet. The positive electrode sheet and the negative electrode sheet include coated portions in which active material (including combined agent that include binder, conductive material or the like) are applied to collectors, and uncoated portions in which any active material are applied to collectors so that the uncoated portions can connect to an electrode terminal.
In both the wound type secondary battery and the laminated type secondary battery, the battery assembly is sealed in an exterior container so that one end of a positive electrode terminal can be electrically connected to the uncoated portion of the positive electrode sheet, the other end can be drawn out of the exterior container (exterior case), one end of a negative electrode terminal can be electrically connected to the uncoated portion of the negative electrode sheet, and the other end can be drawn out of the exterior container. An electrolytic solution is sealed together with the battery assembly in the exterior container. The trend is for an increase in secondary battery capacity year by year which may lead to higher heat generation that results in greater safety issues of short-circuiting. Thus, battery safety measures are becoming more important.
As an example of the safety measures, in order to prevent short-circuiting between the positive electrode and the negative electrode, there is known a technology for forming an insulating member in a boundary portion between the coated portion and the uncoated portion (Patent Document 1).
RELATED ART DOCUMENT LIST Patent DocumentPatent Document 1: JP2012-164470A
SUMMARY OF INVENTION Problems to be Solved by the InventionAccording to the technology disclosed in Patent Document 1, as illustrated in
Further, in order to stabilize electric characteristics or reliability, a tape or the like is used to adhere the battery assembly so that uniform pressure can be applied. However, when an insulating member similar to that described in Patent Document 1 is used for the laminated type secondary battery, the battery assembly cannot be uniformly pressed due to a difference in thickness between a part where insulating member 40 is present and a part where insulating member 40 is not present. As a result, the electric characteristics may vary or battery cycle characteristics may be reduced which lowers battery performance.
It is therefore an object of the present invention to provide a high-quality secondary battery having high reliability and high electric characteristics, and an electrode production method, which can solve the aforementioned problems, prevent short-circuiting between a positive electrode and a negative electrode by an insulating member, and suppress an increase in battery volume or deformation of the battery assembly.
Means to Solve the ProblemThe present invention provides a secondary battery including a battery assembly configured by alternately stacking positive electrodes and negative electrodes via separators, in which the positive electrode and the negative electrode respectively include collectors and active materials applied on the collectors. On each surface of the collector, a coated portion coated with the active material and an uncoated portion not coated with any active material are provided. In one or both of the positive electrode and the negative electrode, a boundary portion between the coated portion and the uncoated portion on the front surface of the collector, is positioned planarly away from a boundary portion between the coated portion and the uncoated portion on the rear surface of the collector.
Effects of InventionAccording to the present invention, since an increase in the volume of the battery assembly or deformation of the battery assembly caused by the insulating member can be suppressed, a high-quality secondary battery having a high energy density can be provided.
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Hereinafter, the exemplary embodiments of the present invention will be described with reference to the drawings.
Positive electrode 1 includes positive electrode collector 3 and positive electrode active material 2 applied on positive electrode collector 3. Coated portions coated with positive electrode active materials 2 and uncoated portions not coated with positive electrode active material 2 are arranged side by side in a longitudinal direction, on the front surface and the rear surface of positive electrode collector 3. Similarly, negative electrode 6 includes negative electrode collector 8 and negative electrode active material 7 applied on negative electrode collector 8. Coated portions and uncoated portions are arranged side by side in the longitudinal direction, on the front surface and the rear surface of negative electrode collector 8.
The uncoated portion of each of positive electrode 1 and negative electrode 6 is used as a tab for connection to an electrode terminal (positive electrode terminal 11 or negative electrode terminal 16). Positive electrode tabs of positive electrodes 1 are collected on positive electrode terminal 11, and connected to each other together with positive electrode terminal 11 by ultrasonic welding or the like. Negative electrode tabs of negative electrodes 6 are collected on negative electrode terminal 16, and connected to each other together with negative electrode terminal 16 by ultrasonic welding or the like. Then, the other end of positive electrode terminal 11 and the other end of negative electrode terminal 16 are drawn out of the exterior container.
As illustrated in
The outer dimensions of the coated portion (negative electrode active material 7) of negative electrode 6 are larger than those of the coated portion (positive electrode active material 2) of positive electrode 1 and smaller or equal to those of separator 20.
In the battery illustrated in
For the negative electrode active material, a carbon material such as graphite, amorphous carbon, diamond carbon, fullerene, carbon nanotube, or carbon nanohorn, a lithium metal material, an alloy material such as silicon or tin, or an oxide material such as Nb2O5 or TiO2,or a compound of these materials can be used.
Binders, conductive auxiliary agents, or the like can be added to positive electrode active material 2 and negative electrode active material 7 when appropriate. For the conductive auxiliary agent, one material in a group including carbon black, a carbon fiber, and graphite, or combination of two or more materials in the group can be used. For the binder, polyvinylidene fluoride, polytetrafluoroethylene, carboxymethylcellulose, modified acrylonitrile rubber particles, or the like can be used.
For positive electrode collector 3, aluminum, stainless steel, nickel, titanium, or an alloy of these can be used, and the aluminum is particularly preferable. For negative electrode collector 8, copper, stainless steel, nickel, titanium, or an alloy of these can be used. For the electrolytic solution, one of organic solvents including annular carbonate such as ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, or the like, chain carbonate such as ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), or the like, fatty carboxylic acid ester, γ-lactone such as γ-butyrolactone, chain ester, and annular ester, or composite including two or more of the organic solvents can be used. Further, lithium salt can be dissolved in these organic solvents.
Separator 20 mainly includes a resin porous membrane, resin woven cloth, resin unwoven cloth, or the like, and, for the resin component of them, for example, a polyolefin rein such as polypropylene or polyethylene, a polyester resin, an acrylic resin, a styrene resin, or a nylon resin can be used. The polyolefin microporous membrane is particularly preferable because of its high ion permeability and because the membrane properties enable physically isolating the positive electrode and the negative electrode from each other. In addition, when necessary, a layer including inorganic particles may be formed in separator 20. For the inorganic particles, an insulating oxide, an insulating nitride, an insulating sulfide, or an insulating carbide can be used, and particularly TiO2 or Al2O3 is preferably included.
For the exterior container, a case including flexible film 30, a can case, or the like can be used, and flexible film 30 is preferably used from the standpoint of achieving a light weight battery. For flexible film 30, a film having resin layers formed in the front surface and the rear surface of a metal layer serving as a base can be used. For the metal layer, a layer having barrier characteristics to prevent the leakage of the electrolytic solution, the incursion of moisture, or the like can be selected, and therefore aluminum and stainless steel can be used. A thermal adhesive resin layer such as modified polyolefin is provided on at least one surface of the metal layer. The exterior container is formed by setting the thermal adhesive resin layers of flexible film 30 opposite each other and heat-sealing the surroundings of a part to receive an electrode laminated body. A resin layer such as a nylon film or a polyester film can be provided on the surface of the exterior body opposite the surface on which the thermal adhesive resin layer is formed.
A terminal made of aluminum or an aluminum alloy can be used for positive electrode terminal 11, and a terminal made of copper, a copper alloy, or such a material plated with nickel can be used for negative electrode terminal 16. The other ends of respective terminals 11 and 16 are drawn out of the exterior container. At the positions of respective terminals 11 and 16 that corresponds to the heat-sealed portion of the outer periphery of the exterior container, thermal adhesive resins can be provided in advance.
For insulating member 40 formed to cover boundary portion 4 between the coated portion and the uncoated portion of positive electrode active material 2, polyimide, a glass fiber, polyester, polypropylene, or a material including them can be used. Insulating member 40 can be formed by applying heat to a tape-shaped resin member to be fused to boundary portion 4 or applying and then drying a gel resin on boundary portion 4.
As illustrated in
Because of the possibility that sufficient insulation may not be secured when the thickness of insulating member 40 is small, the thickness is preferably equal to or more than 10 μm. When the thickness of insulating member 40 is too large, preventing an increase in the thickness of the electrode laminated body of the present invention cannot be achieved, and thus insulating member 40 may be preferably thinner than the thickness of the layer of positive electrode active material 2. Preferably, the thickness of insulating member 40 is equal to or less than 90% of the thickness of the layer of positive electrode active material 2, and more preferably equal to or less than 60% of the thickness of the layer of positive electrode active material 2.
As illustrated in
Then, in order to obtain positive electrode 1 used for each laminated type battery, positive electrode collector 3 is cut to be divided along cut line 90 indicated by a broken line illustrated in
Though not illustrated, in order to manufacture a plurality of negative electrodes (negative electrode sheets) 6 as in the case of positive electrodes 1, negative electrode active material 7 is applied to both surfaces of large negative electrode collector 8. Then, to obtain negative electrode 6 used for each laminated type batteries, negative electrode collector 8 is cut to be divided, and negative electrode 6 having a desired size is obtained.
Positive electrode 1 illustrated in
In secondary battery 100, insulating member 40 that is formed on the one side [rear surface (lower surface in
The end of the coated portion (positive electrode active material 2) in boundary portion 4 with the uncoated portion may be slightly inclined as illustrated in
As illustrated in
Modified examples of the exemplary embodiment are illustrated in
The distance or the thickness of each member according to the present invention means, unless otherwise specified, an average value among measurement results in three or more points in the case of measurement carried out at any place.
EXAMPLE Example 1<Positive Electrode>
The mixed active material of LiMn2O4 and LiNi0.8Co0.1Al0.1O2 was used as a positive electrode active material, carbon black was used as a conductive agent, and PVdF was used as a binder, and a slurry having the combined agents thereof dispersed in an organic solvent was prepared. This slurry was continuously applied on one surface of positive electrode collector 3 mainly including aluminum with a thickness of 20 μm and then was dried to form positive electrode active material 2 with a thickness of 80 μm as illustrated in
A method for coating the collector with the active material will be described. As a device for applying the active material, a device for implementing various coating methods such as a doctor blade, a die coater, a gravure coater, a transfer method, and a deposition method can be used. According to the present invention, in order to control the position of the end of coated portion of the active material, the use of the die coater is particularly preferable. The coating methods of the active material by the die coater are largely classified into two types, namely, a continuous coating method for continuously forming the active material along the longitudinal direction of the long collector, and an intermittent coating method for alternately and repeatedly forming the coated portions and the uncoated portions of the active material along the longitudinal direction of the collector.
In addition, by using a die coater schematically illustrated in
After the application of positive electrode material 2 on positive electrode collector 3 in the above-mentioned manner, as illustrated in
<Negative Electrode>
Graphite having an amorphous covered surface was used as negative electrode active material 7, PVdF was used as binder, and a slurry having the combined agents thereof dispersed in an organic solvent was prepared. This slurry was continuously applied on copper foil with a thickness of 15 μm that was negative electrode collector 8 and then was dried, and a negative electrode roll including the coated portion and the uncoated portion of negative electrode active material 7 was manufactured, as in the case of the positive electrode. The thickness of negative electrode active material 7 was 55 μm on one side. In this example, insulating material 40 was not provided on negative electrode 6.
<Manufacturing of Laminated Type Secondary Battery>
Obtained positive electrodes 1 and negative electrodes 6 were alternately stacked via separators 20 including polypropylene having a thickness of 25 μm, and negative electrode terminal 16 and positive electrode terminal 11 were attached thereto, and received in an exterior container including flexible film 30 to obtain a laminated type secondary battery having a thickness of 8 mm.
Example 2By using a combined agent including LiMn2O4 as an active material, carbon black as a conductive agent, and PVdF as a binder, positive electrode active material 2 having a thickness of 35 μm was formed on the front and rear sides of positive electrode collector 3, respectively. Negative electrode active material 7 having a thickness of 35 μm made of non-graphitizable carbon was formed on the front and rear sides of negative electrode collector 8, respectively. Other conditions such as the forming positions of active materials 2 and 7 and insulating member 40 were similar to those of the Example 1, and a laminated type battery having a thickness of 3 mm was obtained.
Example 3End 40b of insulating member 40 on positive electrode active material 2 of positive electrode collector 3 was shifted by 0.3 mm from end 4a of positive electrode active material 2 located on the surface of an opposite side via positive electrode collector 3, and other conditions were set similar to those of the Example 1 to obtain a laminated type battery. The thickness of the obtained laminated type battery was 8.1 mm.
Example 4Boundary portion 4b between the coated portion and the uncoated portion of positive electrode active material 2 on the other surface of positive electrode collector 3 was shifted inside by 1 mm from boundary portion 4a of the one surface, and other conditions were set similar to those of the Example 3 to obtain a laminated type battery. The thickness of the obtained laminated type battery was 8.1 mm.
Example 5During the formation of positive electrode 1 and negative electrode 6, positive electrode active material 2 and negative electrode active material 7 were intermittently applied to positive electrode collector 3 and negative electrode collector 8. Other conditions were set similar to those of the Example 1 to obtain a laminated type battery. The thickness of the obtained laminated type battery was 8 mm.
Comparative Example 1Ends 4a and 4b of the coated portion of positive electrode active material 2 and ends 40a and 40b of insulating member 40 were arranged between the front surface and the rear surface of positive electrode collector 3 without being shifted from each other. Other conditions were similar to those of the Example 1 to obtain a laminated type battery. The thickness of this laminated type battery was 8.5 mm.
Comparative Example 2Ends 4a and 4b of the coated portion of positive electrode active material 2 and ends 40a and 40b of insulating member 40 were arranged between the front surface and the rear surface of positive electrode collector 3 without being shifted from each other. Other conditions were similar to those of the Example 2 to obtain a laminated type battery. The thickness of this laminated type battery was 3.4 mm.
<Evaluation>
We obtained ten laminated type batteries for each example in the aforementioned manner, and then we evaluated their discharge capacities and the cycle characteristics. We confirmed that the laminated type batteries according to the Examples 1 to 5 exhibited very stable discharge capacities and cycle characteristics while the batteries according to the Comparative Examples 1 and 2 exhibited unstable discharge capacities and cycle characteristics compared with the batteries according to the Examples 1 to 5.
In addition, when the active material was continuously applied during the manufacturing of positive electrode 1 and negative electrode 6, it was confirmed that we were able to prevent the distortion of an electrode roll similar to that illustrated in
The present invention is useful for producing the electrode of the lithium-ion secondary battery and producing the lithium-ion secondary battery that uses the electrode. However, the present invention can be advantageously applied to a secondary battery other than a lithium-ion secondary battery.
This application claims priority from Japanese Patent Application No. 2013-131006 filed on Jun. 21, 2013, which is hereby incorporated by reference herein in its entirety.
REFERENCE NUMERALS
- 1 Positive electrode
- 2 Positive electrode active material
- 3 Positive electrode collector
- 4, 4a, 4b Boundary portion
- 6 Negative electrode
- 7 Negative electrode active material
- 8 Negative electrode collector
- 11 Positive electrode terminal
- 16 Negative electrode terminal
- 20 Separator
- 40 Insulating member
Claims
1. A production method of electrode for a secondary battery in which the electrodes are stacked with a separator interposed the electrodes, comprising:
- providing a coated portion coated with the active material and an uncoated portion not coated with the active material along a longitudinal direction so that the coated portion and the uncoated portion are adjacent to each other, by continuously applying an active material on a collector;
- arranging a boundary portion between the coated portion and the uncoated portion on front or rear surface of the collector at a position not facing a boundary portion between the coated portion and the uncoated portion on the other front or rear surface; and
- providing an insulating member which covers the boundary portion between the coated portion and the uncoated portion.
2. The production method of the electrodes according to claim 1, further comprising arranging a double-side coated portion in which the active material is applied on both sides of the collector, a one-side coated portion in which the active material is applied on front or rear surface of the collector and in which the active material is not applied on the other front or rear surface, and a double-side uncoated portion in which the active material is not applied on the both sides of the collector, side by side in the longitudinal direction of the electrodes.
Type: Application
Filed: Jun 21, 2017
Publication Date: Oct 5, 2017
Applicant: NEC ENERGY DEVICES, LTD. (Sagamihara-shi)
Inventor: Kazuya MIMURA (Kanagawa)
Application Number: 15/629,296