JP2010097730A - Nonaqueous electrolyte secondary battery, battery pack equipped with the same, and vehicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium-ion secondary battery enabled to detect bubbles existing between electrodes in high accuracy by X-ray irradiation, as well as a battery pack equipped with the same and a vehicle. <P>SOLUTION: Of the nonaqueous electrolyte secondary battery including a laminated structure 120 having a unit battery layer 340 with a cathode active material 211 formed on the surface of a collector 210, 220, an electrolyte layer 230, and an anode active material layer 221 formed on the surface of a collector laminated in that order, the laminated structure includes a first unit battery layer having a cutoff part, and a second unit battery layer without any cutoff part at a position conforming to the cutoff part of the first unit battery layer at lamination. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte secondary battery, and an assembled battery and a vehicle having the same, and more specifically, a non-aqueous electrolyte secondary battery capable of detecting air bubbles inside the battery by X-ray irradiation, and The present invention relates to an assembled battery and a vehicle having the same.

  In recent years, in order to cope with air pollution and global warming, reduction of the amount of carbon dioxide has been strongly desired. In the automobile industry, there is a great expectation for reducing carbon dioxide emissions by introducing electric vehicles (EV) and hybrid electric vehicles (HEV), and the development of secondary batteries for motor drive that holds the key to commercialization of these is thriving. Has been done.

  As secondary batteries for driving motors, non-aqueous electrolyte batteries (also called non-aqueous solvent-type secondary batteries), among them, lithium ion secondary batteries having the highest theoretical energy among all the batteries attracted attention. Currently, development is progressing rapidly.

  Such a lithium ion secondary battery generally includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of the negative electrode current collector using a binder. Have a power generation element (laminated structure) connected via an electrolyte layer. In addition, electrode terminals (a positive terminal and a negative terminal) are electrically connected to the power generation element for the purpose of extracting electric power to the outside. Generally, the power generation element is housed in a metal or laminate sheet so that the electrode terminals are led out to the outside.

  As described above, it is difficult to inspect the inside of the battery in which the power generation element has a structure covered with metal or laminate.

It is well known to use X-ray imaging to inspect the internal shape of a battery (for example, a wound shape) (Patent Document 1).
JP 2004-171960 A

  However, foreign substances inside the battery could not be detected unless the material has a high X-ray absorption rate such as metal. In addition, for bubbles existing between electrodes, even if X-rays are used, it is difficult to obtain a clear transmission image due to the high X-ray absorption rate of the current collector foil, and there is a large overlap in information contained in the transmission X-rays. Detection is more difficult because necessary information is buried.

  The present invention has been made to solve such a problem, and an object of the present invention is to detect air bubbles and foreign matter having a low X-ray absorption rate present between electrodes inside a battery with high accuracy.

  In order to solve the above-described problems, a nonaqueous electrolyte secondary battery according to the present invention includes a positive electrode active material layer and a negative electrode active material layer that face each other with an electrolyte layer interposed therebetween, and a positive electrode active material layer and a negative electrode active material layer. A non-aqueous electrolyte secondary battery including a stacked structure in which a plurality of single battery layers each including a current collector are stacked, wherein the stacked structure is notched at a position that is the same position when stacked It has the single cell layer which does not have, and the single cell layer which has a notch part, It is characterized by the above-mentioned.

  According to the nonaqueous electrolyte secondary battery according to the present invention, X-rays are efficiently irradiated locally on a portion where the number of stacked layers of the laminated structure is small, thereby avoiding overlapping of information included in transmitted X-rays. In addition, it is possible to detect air bubbles and foreign matter having a low X-ray absorption rate present between the electrodes inside the battery with high accuracy.

  Hereinafter, the nonaqueous electrolyte secondary battery according to the present invention will be described in detail by dividing it into first and second embodiments.

  Before describing these embodiments, a lithium ion secondary battery that is a non-aqueous electrolyte secondary battery will be briefly described in order to facilitate understanding of the present invention.

  FIG. 1 is an external view of a lithium ion secondary battery. FIG. 2 is a cross-sectional view of the lithium ion secondary battery shown in FIG.

  As shown in FIG. 1, the lithium ion secondary battery 100 has, for example, a rectangular flat shape, and a positive electrode tab 110 </ b> A and a negative electrode tab 110 </ b> B for taking out electric power from both sides thereof are drawn out. The power generation element (laminated structure) 120 is wrapped by an exterior material (for example, a laminate film) 130 of the lithium ion secondary battery 100, and the periphery thereof is heat-sealed, and the positive electrode tab 110A and the negative electrode tab 110B are drawn out. Sealed in state.

  As shown in FIG. 2, the power generation element 120 includes a positive electrode made of a positive electrode current collector 210 and a positive electrode active material layer 211 formed on both surfaces of the positive electrode current collector 210, a negative electrode current collector 220, and a negative electrode current collector 220. A negative electrode made of a negative electrode active material layer 221 formed on both sides of the negative electrode active material layer 221. The power generation element 120 is formed by laminating a plurality of positive electrodes and negative electrodes with an electrolyte layer 230 interposed therebetween. The positive electrode current collector 210 is connected to a positive electrode tab for taking out electricity. The negative electrode current collector 220 is connected to a negative electrode tab for taking out electricity.

  Hereinafter, the current collector, the active material layer, and the electrolyte layer constituting the power generation element will be described.

[Current collector]
The current collectors 210 and 220 are made of a conductive material such as an aluminum foil, a copper foil, or a stainless steel (SUS) foil. The general thickness of the current collector is 1 to 30 μm. However, a current collector having a thickness outside this range may be used. The positive electrode current collector 210 is preferably an aluminum foil, and the negative electrode current collector 220 is preferably a copper foil.

[Active material layer]
The active material layer contains an active material, and further contains other additives as necessary.

The positive electrode active material layer 211 includes a positive electrode active material. Examples of the positive electrode active material include lithium-transition metal oxides such as LiMn ₂ O ₄ and LiNiO ₂ , lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds. In some cases, two or more positive electrode active materials may be used in combination. Of course, positive electrode active materials other than those described above may be used.

  The negative electrode active material layer 221 includes a negative electrode active material. Examples of the negative electrode active material include carbon materials such as graphite, soft carbon, and hard carbon, lithium-transition metal compounds as described above, metal materials, and lithium-metal alloy materials. In some cases, two or more negative electrode active materials may be used in combination. Of course, negative electrode active materials other than those described above may be used.

  The average particle diameter of each active material contained in each active material layer 211, 221 is not particularly limited, but is usually about 0.1 to 100 μm, preferably 1 to 20 μm. However, a form outside this range may be adopted.

  Examples of the additive that can be included in the positive electrode active material layer 211 and the negative electrode active material layer 221 include a binder, a conductive additive, and an electrolyte salt (lithium salt).

  Examples of the binder include polyvinylidene fluoride (PVdF) and a synthetic rubber binder.

  The conductive additive refers to an additive that is added to improve the conductivity of the positive electrode active material layer 211 or the negative electrode active material layer 221. Examples of the conductive aid include carbon materials such as graphite and vapor grown carbon fiber.

Examples of the electrolyte salt (lithium salt) include Li (C ₂ F ₅ SO ₂ ) ₂ N), LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , and LiCF ₃ SO ₃ .

[Electrolyte layer]
The electrolyte layer 230 includes a separator and an electrolyte injected into the separator.

  The separator has a function of separating the positive and negative active material layers and preventing a short circuit therebetween. A separator consists of a microporous film comprised from polyolefin, such as polyethylene and a polypropylene, for example. Depending on the case, you may form a separator with the nonwoven fabric and particle | grains which are comprised from the same material.

  There is no restriction | limiting in particular about the thickness of a separator, In consideration of desired battery performance etc., it can set suitably. Specifically, the thickness of the separator is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. On the other hand, the lower limit of the thickness of the separator is not particularly limited, but from the viewpoint of effectively preventing a short circuit between the positive and negative active material layers, the thickness of the separator is preferably 0.1 μm or more, more preferably. It is 0.5 μm or more, more preferably 1 μm or more. However, in some cases, a separator having a thickness outside these ranges may be used.

  Furthermore, the separator also has a function of holding the electrolyte. Examples of the electrolyte retained in the separator include a liquid electrolyte and a gel electrolyte.

The liquid electrolyte has a form in which a lithium salt as a supporting salt is dissolved in a non-aqueous solvent (organic solvent) as a plasticizer. As the non-aqueous solvent and the lithium salt, for example, carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), and compounds that can be added to the active material layer of the electrode such as LiBF ₄ can be similarly used. .

  The gel electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer made of an ion conductive polymer. Similarly, a polymer that can be added to the active material layer of the electrode, such as polyethylene oxide (PEO) or polypropylene oxide (PPO), can be used as the ion conductive polymer used as the matrix polymer.

  In addition, the matrix polymer of gel electrolyte can express the outstanding mechanical strength by forming a crosslinked structure. In order to form a crosslinked structure, an appropriate polymerization initiator is used, and thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam is applied to a matrix polymer (for example, PEO or PPO) according to the action factor of the polymerization initiator. A polymerization process such as polymerization may be performed.

  Hereinafter, a lithium ion secondary battery according to an embodiment of the present invention will be described.

[First Embodiment]
FIG. 3 is a diagram showing a part of a cross-sectional view of the lithium ion secondary battery according to the first embodiment of the present invention.

  As shown in FIG. 3, in the lithium ion secondary battery according to this embodiment, a notch structure portion 350 is formed by laminating a cell layer (first cell layer) 340 having a notch 351. Has been. The notch 351 formed in the unit cell layer 340 is formed so that the notch structure portion 350 is formed when the unit cell layer 340 is laminated. That is, the notch 351 is formed so that the notch 351 is located at the same location when the unit cell layers 340 are stacked.

  The laminated structure (power generation element) 120 constitutes the notched structure portion 350 by overlapping the notched portions 351 except for at least one unit cell layer 340. That is, the notch structure portion 350 of the stacked structure 120 is adjacent to the single battery layer (second single battery layer) 340 that does not penetrate the stacked structure 120 and does not form the notch 351 in the stacking direction of the single battery layers. To do.

  As will be described later, a portion of the unit cell layer 340 adjacent to the notch structure portion 350 in the stacking direction of the unit cell layer (a portion indicated by a dotted frame in FIG. 3, hereinafter referred to as a portion to be inspected 360) is X-rayed. It becomes a part to be inspected for bubbles between the electrodes. That is, in the inspected portion 360, the number of single cell layers 340 locally decreases in the laminated structure 120, so that information included in transmitted X-rays can be obtained by inspecting the inspected portion 360 by X-ray irradiation. Can be detected, and bubbles and foreign matter inside the electrode can be detected with high accuracy.

  The notch structure portion 350 may be formed at a plurality of locations of the laminated structure 120. Further, the portion where the portion to be inspected 360 is formed is not limited to the uppermost layer or the lowermost layer of the laminated structure 120 and may be the center of the laminated structure 120.

  As is well known, a unit cell made up of the unit cell layer 340 is the smallest unit that functions as a power generation element, and has a positive electrode active material layer 211, a negative electrode active material layer 221, and a positive electrode active material layer 211 that face each other via an electrolyte layer 230. And current collectors 210 and 220 provided on the upper and negative electrode active material layers 221, respectively.

  The notch 351 is formed by notching a part of all the layers constituting the single battery layer 340. That is, the notch 351 is formed by removing a part of the electrolyte layer 230, the positive electrode active material layer 211, the negative electrode active material layer 221, and the current collectors 210 and 220 constituting the single battery layer 340. Therefore, the notch structure 350 in which the notch 351 overlaps also includes all of the electrolyte layer 230, the positive electrode active material layer 211, the negative electrode active material layer 221, and the current collectors 210 and 220 in the laminated structure 120. It becomes a part that does not.

  The lithium ion secondary battery according to this embodiment shown in FIG. 3 has a stacked structure 120 in which planar cell layers are stacked while maintaining a planar shape. However, for example, even in the case of a lithium ion secondary battery having a structure in which a single battery layer is wound, the single battery layer is broadly stacked by winding the single battery layer to form a stacked structure. . That is, the present invention also includes a lithium ion secondary battery having such a structure.

  The lithium ion secondary battery according to the present embodiment shown in FIG. 3 is a non-bipolar secondary battery, but may be a bipolar secondary battery.

  It is desirable to fill the notch structure with a resin material. FIG. 4 is a view showing a part of a cross-sectional view of the lithium ion secondary battery according to the present embodiment, in which the notched structure portion 350 is filled with the resin material 400.

  As described above, the resin material 400 is filled in the notch structure portion 350 because the mechanical strength of the lithium ion secondary battery may be weakened by forming the notch structure portion 350 in the laminated structure. This is to prevent this and improve the reliability of the lithium ion secondary battery.

  The resin material 400 is preferably one or a mixture of two or more selected from polyethylenes, polypropylenes, polyvinylidene fluorides, and polyethylene oxides. Since the inside of the battery is exposed to an oxidizing atmosphere in the vicinity of the positive electrode and a reducing atmosphere in the vicinity of the negative electrode, the battery material is required not to affect the battery characteristics. This is because these materials rarely affect the battery characteristics even if they coexist with the electrode in the battery. Moreover, since these materials have a small X-ray absorption rate, the influence on the transmitted X-rays is small.

  3 and 4 show the lithium ion secondary battery in which the notch structure portion 350 also has a hole shape because the notch 351 of the cell layer 340 is a hole penetrating the cell layer 340. . Since bubbles remaining between the electrodes are assumed to come off from the end of the unit cell layer 340, it is considered that the probability that bubbles remain is higher as the position is closer to the center of the unit cell layer 340. Therefore, from the viewpoint of accurately detecting bubbles inside the battery, the notch 351 is formed near the center of the unit cell layer 340 (for example, the notch 351 is formed on the short side from the outer periphery of the unit cell layer. It is desirable to form it within 1/5 or more of the length. In this way, by forming the notch 351 of the unit cell layer 340 in a portion not including the outer periphery, that is, by forming the notch 351 in the shape of a hole penetrating the unit cell layer 340, Detection sensitivity is improved, and a highly reliable battery can be obtained.

  However, even if the cutout portion 351 of the single cell layer 340 is formed in a portion including the outer periphery, it is a matter of course that the effects of the present invention are exhibited. FIG. 5 is a diagram showing a part of a cross-sectional view of a lithium ion secondary battery having a laminated structure in which a notch portion of the single battery layer is formed in a portion including the outer periphery of the single battery layer. 6 is a diagram showing a part of a cross-sectional view of a lithium ion secondary battery in which a notch structure portion of the lithium ion secondary battery shown in FIG. 5 is filled with a resin material. The lithium ion secondary battery shown in FIG. 5 and FIG. 6 is the lithium ion shown in FIG. 3 and FIG. 4 except for the place where the notch portion of the single cell layer is formed (that is, the place where the notch structure portion is formed). Since it has the same configuration as that of the ion secondary battery, description thereof is omitted.

  FIG. 7 is an explanatory diagram for detecting bubbles existing inside the lithium ion secondary battery according to the present embodiment by X-ray irradiation.

  As shown in FIG. 7, the X-ray 701 generated by the X-ray source 700 is irradiated to the lithium ion secondary battery 100, and transmitted X-rays are detected by a detector 710.

  As described above, in the lithium ion secondary battery 100 according to the present embodiment, a notched structure portion is formed in a part of the laminated structure, and a portion to be inspected that is adjacent in the stacking direction of the notched structure portion and the single cell layer. Have Since the number of single cell layers locally decreases in the layered structure, the portion to be inspected avoids overlapping of information contained in transmitted X-rays by irradiating and inspecting the portion to be inspected. In addition, it is possible to detect bubbles and foreign matters inside the electrode with high accuracy.

  Therefore, it is desirable to irradiate the portion to be inspected with X-rays more directly. As shown in FIG. 7, by irradiating X-rays in parallel with the stacking direction of the stacked structure of the lithium ion secondary battery 100, X-rays can be directly irradiated by the portion to be inspected.

  In general, the current collectors 210 and 220 have a high X-ray absorption rate, so that it is necessary to increase the X-ray intensity to some extent in order to allow the X-rays to pass through the secondary battery as the object. However, when the intensity of X-rays is increased, it is almost impossible to detect a difficult observation such as a bubble. Since the portion to be inspected of the secondary battery according to the present embodiment has a small number of single battery layers, the X-ray intensity can be made relatively small. As a result, even bubbles that are difficult to observe can be detected.

  If X-rays having a high degree of parallelism are used, bubbles and foreign substances can be detected with higher sensitivity by using a refraction image of X-rays, but the type of X-rays is not limited.

  FIG. 8 is an external view of an embodiment of an assembled battery in which a plurality of lithium ion secondary batteries according to the present embodiment are connected. FIG. 8A is a plan view of the assembled battery, and FIG. 8B is an assembled battery. FIG. 8C is a side view of the assembled battery.

  As shown in FIG. 8, the assembled battery 800 according to the embodiment of the present invention includes a small assembled battery 850 that can be attached and detached by connecting a plurality of lithium ion secondary batteries according to the embodiment of the present invention in series or in parallel. It is also possible to form a plurality of small assembled batteries 850 that can be attached and detached, connected in series or in parallel.

  As a result, it is possible to form the assembled battery 800 having a large capacity and a large output suitable for a vehicle driving power source and an auxiliary power source that require a high volume energy density and a high volume output density. In the assembled battery shown in FIG. 8, the small assembled battery 850 that can be attached and detached is connected to each other using an electrical connection means such as a bus bar. The assembled battery 850 is connected using a connection jig 810. Multiple layers are stacked. How many non-bipolar or bipolar secondary batteries are connected to form the assembled battery 850, and how many assembled batteries 850 are stacked to produce the assembled battery 800 depends on the vehicle ( It can be determined according to the battery capacity and output of the electric vehicle. That is, the capacity and voltage of the battery can be freely adjusted by serializing and paralleling the secondary batteries.

  FIG. 9 is a diagram showing an electric vehicle 900 equipped with a lithium ion secondary battery according to an embodiment of the present invention. As shown in FIG. 9, the lithium ion secondary battery 910 according to the present invention can be mounted under the seat 920 in the center of the vehicle body of the electric vehicle 900. If mounted under the seat 920, there is an advantage that a vehicle interior space and a trunk room can be widened. The place where the secondary battery 910 according to the present invention is mounted is not limited to the under-seat 920. That is, the secondary battery according to the present invention can be mounted in a lower part of the rear trunk room or an engine room in front of the vehicle. By using the lithium ion battery according to the present embodiment for a vehicle such as a hybrid vehicle or an electric vehicle, the vehicle can have a long life and high reliability.

Below, the effect of the lithium ion secondary battery which concerns on 1st Embodiment of this invention is shown.
-Even if the intensity of X-rays to be irradiated is lowered, a sufficiently strong transmitted X-ray image can be obtained, so that bubbles inside the electrode and foreign matters having a low X-ray absorption rate can be detected.
-It can be easily manufactured.

[Second Embodiment]
FIG. 10 is a diagram showing a part of a cross section of a lithium ion secondary battery according to the second embodiment of the present invention. The present embodiment is different from the first embodiment in that the surface 361 on the cutout structure portion 350 side of the part 360 to be inspected adjacent to the cutout structure portion 350 of the stacked structure 120 is disposed on the current collector 210 (for example, the positive electrode). (Current collector). Since the other points are the same as those in the first embodiment, redundant description is omitted.

  In general, it is well known that a laminated structure having a positive electrode and a negative electrode has a negative electrode larger than the positive electrode as the structure of the opposing portion of the negative electrode and the positive electrode. This is because, when the negative electrode is smaller than the positive electrode, in the charging process of the secondary battery, when lithium ions coming out of the positive electrode are occluded by the opposing negative electrode, lithium metal is deposited exceeding the lithium occlusion capacity of the negative electrode. This leads to deterioration of battery performance. In addition, when the negative electrode is the same size as the positive electrode, electric field concentration occurs at the electrode end, so that lithium is deposited on the current collector foil at the electrode end, resulting in deterioration of battery performance. In order to avoid such a problem, it is easy to take measures to dispose the negative electrode in the outermost layer of the laminated structure. However, since the outermost layer of the negative electrode that does not face the positive electrode does not operate, the battery capacity is useless and is not preferable.

  Such a problem also occurs in the opposite portions of the positive and negative electrodes of the single battery layer 340 that are left when the cutout structure portion 350 is provided in the laminated structure 120.

  Therefore, in the second embodiment, a part of the active material is applied to one side of the electrode that is the outermost layer of the unit cell layer 340 that is left when the notched structure portion 350 is provided in the multilayer structure 120. That is, in the lithium ion secondary battery according to the present embodiment, the adjacent portion of the surface of the unit cell layer 340 adjacent in the stacking direction of the notch structure portion 350 and the unit cell layer 340 is coated with an active material. First, expose the current collector. Such an active material pattern can be formed, for example, by inkjet.

  By setting it as such a structure, the lithium ion secondary battery which concerns on this embodiment can reduce the quantity of the active material used at the time of manufacture.

  Further, if the outermost layer of the single cell layer left when the cut-off structure portion is provided in the laminated structure is a positive electrode, it is necessary to dispose the negative electrode facing this on both sides, and the positive electrode It is impossible to have one opposing surface of the negative electrode. However, when the positive electrode is applied on one side of the active material, the part to be inspected can have one opposing surface of the positive electrode and the negative electrode. Therefore, in the lithium ion secondary battery according to the present embodiment, the opposite surfaces of the positive electrode and the negative electrode of the part to be inspected can be one which is the minimum necessary for inspection, so that the transmitted X-ray image becomes clear. The detection sensitivity of bubbles can be improved.

  Also in this embodiment, it is desirable to fill the notch structure portion 350 with the resin material 400 as in the first embodiment. FIG. 9 is a view showing a part of a cross-sectional view of the lithium ion secondary battery according to this embodiment in which the notch structure portion 350 is filled with a resin material.

The fuel cell operating method according to the second embodiment of the present invention has the following effects in addition to the effects of the first embodiment.
-The amount of active material used during production can be reduced.
-The transmitted X-ray image can be made clear and the detection sensitivity of bubbles can be improved.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, the following materials were used as the positive electrode material and the negative electrode material unless otherwise specified.

<Positive electrode material>
The following materials were mixed at the following predetermined ratio to produce a positive electrode slurry.
Positive-electrode active material: LiMn ₂ O ₄ (85 wt%)
-Conductive auxiliary agent: Acetylene black (5 wt%)
・ Binder: PVDF (10% by weight)
-The viscosity for coating was adjusted using NMP as the slurry viscosity adjusting solvent.
-The positive electrode was produced by apply | coating the said slurry on both surfaces of aluminum foil (20 micrometers), and making it dry.

<Negative electrode material>
The following materials were mixed at the following predetermined ratio to produce a negative electrode slurry.
・ Negative electrode active material: Hard carbon (85% by weight)
-Conductive auxiliary agent: Acetylene black (5 wt%)
・ Binder: PVDF (10% by weight)
-The viscosity for coating was adjusted using NMP as the slurry viscosity adjusting solvent.
-The positive electrode was produced by apply | coating the said slurry on both surfaces of copper foil (15 micrometers), and making it dry.

  The electrode structure manufacturing process and the battery manufacturing process were performed in the following order.

<Electrode structure manufacturing process>
-Roll press of the positive electrode and the negative electrode, respectively.
Cut the positive electrode to 90 × 90 mm, the negative electrode to 91 × 91 mm, and the separator to 95 × 95 mm.
A hole having a diameter of 2 mm is formed on 9 sheets of positive electrodes, a diameter of 1.5 mm is formed on 9 sheets of negative electrodes, and a diameter of 1 mm is formed on 17 sheets of separators.
-Laminate in order of negative electrode, separator, positive electrode, and separator so that the holes are aligned.
-An electrode structure is obtained by laminating a non-perforated separator, a negative electrode, a separator, a positive electrode, a separator, and a negative electrode in this order.
-The total number of negative electrode layers is 11.

<Battery production process>
A tab was welded to each of the positive electrode and the negative electrode, and the aluminum laminate was sealed together with an electrolyte (PC + EC + DEC (1: 1: 2) 1M LiPF ₆ ).
-It was set as the laminated type lithium ion secondary battery which charged with predetermined current value and did not add a degassing process, and contained bubbles between electrodes.

  The evaluation method was performed as follows.

<Evaluation method>
-The inside of the manufactured battery was inspected with an X-ray inspection apparatus.
-Monochromatic radiation was used for X-rays, and X-rays were incident from a direction parallel to the stacking direction of the battery to be evaluated.
-A BM manufactured by Hamamatsu Photonics and a CCD camera C4880 were used for X-ray detection.
・ The optimum values of X-ray energy and detector accumulation time were searched for while viewing the images.
An image (C) for inspection when the transmitted X-ray image data (S), direct beam data (D), and dark noise data (N) of the battery is C = (S−N) / ( DN) and digital processing.
-Ten batteries of Examples 1 to 3 and Comparative Example were prepared, and the number of detected bubbles was compared.

  Compared to the comparative example, the bubble detection evaluation results of Examples 1 to 3 were as follows.

[Comparative example]
<Battery structure>
It is a normal electrode structure (laminated structure) having no holes (notch structure portion).

<Evaluation>
As shown in Table 1 below, even when the X-ray energy was 30 keV, no bubbles could be detected for all 10 batteries with an exposure time of 2 minutes.

[Example 1]
<Battery structure>
A hole was provided near the center of the electrode structure.

<Evaluation>
As shown in Table 1 below, the optimum value of X-ray energy was 18 keV, and air bubbles could be detected in 9 out of 10 batteries with an exposure time of 1 minute.

[Example 2]
<Battery structure>
Example 1 was repeated except that polyethylene was inserted into the hole.

<Evaluation>
As shown in Table 1 below, the same results as in Example 1 were obtained.

[Example 3]
<Battery structure>
Example 2 was the same as Example 2 except that there was only one opposing surface of the positive electrode and the negative electrode of the part adjacent to the hole and the electrode structure in the stacking direction (inspected part).

<Evaluation>
As shown in Table 1 below, 15 keV, which is lower than those of Examples 1 and 2, was the optimum value for the X-ray energy, and bubbles could be detected in all 10 batteries with an exposure time of 1 minute. Even if the energy of X-rays is low, the bubble detection rate is improved because the effect of refraction by an X-ray irradiation object is larger for low-energy X-rays, and the present invention also uses the effect of X-ray refraction. Because it can.

It is an external view of a lithium ion secondary battery. It is sectional drawing of a lithium ion secondary battery. It is the figure which showed a part of sectional drawing of the lithium ion secondary battery which concerns on 1st Embodiment of this invention. It is the figure which showed a part of sectional drawing of the lithium ion secondary battery which concerns on the 1st Embodiment of this invention with which the notch structure part was filled with the resin material. The figure which showed a part of sectional drawing of the lithium ion secondary battery which concerns on 1st Embodiment of this invention which has a laminated structure which formed the notch part of the cell layer in the part containing the outer periphery of a cell layer. is there. It is the figure which showed a part of sectional drawing of the lithium ion secondary battery which filled the notch structure part of the lithium ion secondary battery which concerns on 1st Embodiment of this invention shown in FIG. 5 with the resin material. It is explanatory drawing for detecting the bubble which exists in the inside of the lithium ion secondary battery which concerns on embodiment of this invention by X-ray irradiation. It is an external view of an embodiment of an assembled battery in which a plurality of lithium ion secondary batteries according to this embodiment are connected. It is a figure which shows the electric vehicle carrying the lithium ion secondary battery which concerns on embodiment of this invention. It is a figure which shows a part of cross section of the lithium ion secondary battery which concerns on 2nd Embodiment of this invention. It is the figure which showed a part of sectional drawing of the lithium ion secondary battery which filled the resin material in the notch structure part of the lithium ion secondary battery which concerns on 2nd Embodiment of this invention shown in FIG.

Explanation of symbols

100 lithium ion secondary battery (non-aqueous electrolyte secondary battery),
120 power generation element (laminated structure),
130 exterior material,
210 positive electrode current collector,
211 positive electrode active material layer,
220 negative electrode current collector,
221 negative electrode active material layer,
230 electrolyte layer,
340 cell layer,
350 notch structure part,
351 Notch,
360 inspected part,
400 resin material,
700 X-ray source,
710 detector,
800 batteries,
900 Electric car (vehicle).

Claims (8)

A laminated structure having a single battery layer in which a positive electrode active material layer formed on the surface of a current collector, an electrolyte layer, and a negative electrode active material layer formed on the surface of the current collector are laminated in this order A non-aqueous electrolyte secondary battery comprising:
The laminated structure includes a first unit cell layer having a notch, a second unit cell layer not having a notch in a position that is the same position as the notch of the first unit cell layer, and A non-aqueous electrolyte secondary battery comprising:   The non-aqueous electrolyte secondary battery according to claim 1, wherein the notched portion is a hole penetrating the single battery layer.   The non-cutting structure according to claim 1 or 2, wherein a notch structure portion formed by laminating the first cell layer on the second cell layer is filled with a resin material. Water electrolyte secondary battery.   The non-aqueous electrolyte 2 according to claim 3, wherein the resin material includes at least one selected from the group consisting of polyethylenes, polypropylenes, polyvinylidene fluorides, and polyethylene oxides. Next battery.   The nonaqueous electrolyte secondary battery according to any one of claims 1 to 4, wherein the first single battery layer and the second single battery layer are laminated via a current collector.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the single cell layer has a planar shape.   An assembled battery formed by connecting a plurality of the nonaqueous electrolyte secondary batteries according to claim 1.   A vehicle equipped with the nonaqueous electrolyte secondary battery according to any one of claims 1 to 6 or the assembled battery according to claim 7.

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