JP5621824B2 - Battery electrode and manufacturing method thereof - Google Patents

Description

  The present invention relates to a battery electrode. In particular, the present invention relates to an improvement for improving output characteristics of a battery electrode.

  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 a secondary battery for driving a motor, a lithium ion secondary battery having the highest theoretical energy among all the batteries is attracting attention, and is currently being developed rapidly. Generally, a lithium ion secondary battery 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 a negative electrode current collector using a binder. However, it has the structure connected through the electrolyte layer and accommodated in a battery case (for example, refer patent document 1).

JP 2003-7345 A

  By the way, in recent years, in response to the demand for higher performance of batteries, development of batteries capable of charging and discharging at higher output has been actively conducted. As part of this, attempts have been made to increase the surface area of the active material that can contribute to the reaction by reducing the particle size of the electrode active material.

  However, if the particle size of the active material is too small, there is a possibility that the lithium ions present in the electrolyte layer are not sufficiently conducted to the active material. That is, if the particle diameter of the active material is too small, the active materials in the active material layer cannot be sufficiently in contact with each other, and thus the electron conduction in the active material layer is not sufficiently performed. In order to solve this problem, it is common to increase the amount of the conductive additive added. When the addition amount of the conductive auxiliary agent is increased, electronic conduction in the active material layer is ensured. However, an increase in the amount of conductive additive added may reduce the ratio of the active material in the electrode and reduce the output. In addition, from the viewpoint of improving the output density of the battery, the electrode may be pressed for the purpose of improving the contact between the active materials or the contact between the active material and the current collector. Therefore, if the density of the active material layer is uniformly increased, there may be a problem that a lithium ion conduction path is not sufficiently secured.

  As described above, in the active material layer of the battery electrode that can be used under high output conditions, it is currently required to sufficiently ensure the conduction of lithium ions. Note that the problems described above are significant in bipolar batteries that are being developed with higher output in mind.

The present inventors have conducted intensive research to solve the above problems. At that time, various attempts were made to control the thickness of the active material layer of the electrode. As a result, in the active material layer of the electrode, a thick part, a thin part, and a channel that reaches the thin part are present and the particle size of the active material is reduced, thereby solving the above problem. As a result, the present invention has been completed.

That is, the present invention is a battery including a battery electrode having a current collector and an active material layer containing an active material formed on the surface of the current collector, and the active material layer includes the active material. and other sites with small thin portion having a thickness in comparison layer includes a channel to reach the thin portion, the average particle size of the active material is Ru der less 10 [mu] m, a battery.

  That is, the present invention provides a battery electrode having a current collector and an active material layer including an active material formed on a surface of the current collector, wherein the active material layer includes: The battery electrode is characterized in that a thin portion having a smaller thickness than other portions is present.

  In the active material layer of the battery electrode of the present invention, there is a thin part having a smaller thickness than other parts of the active material layer. Due to the presence of such a thin part, lithium ion conduction can be sufficiently ensured. Therefore, the electrode of the present invention can contribute effectively to the improvement of the output characteristics of the battery.

It is a schematic sectional drawing which shows one Embodiment (1st Embodiment) of the battery electrode of this invention. It is sectional drawing which shows preferable one Embodiment of the bipolar battery of 2nd Embodiment. It is a perspective view which shows the assembled battery of 3rd Embodiment. It is the schematic of the motor vehicle of 4th Embodiment carrying the assembled battery of 3rd Embodiment. It is sectional drawing which shows the outline | summary of the lithium ion secondary battery which is not a bipolar type.

  Hereinafter, embodiments of the present invention will be described. However, the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following embodiments.

(First embodiment)
(Constitution)
1st of this invention is an electrode for batteries which has an electrical power collector and the active material layer containing the active material formed in the surface of the said electrical power collector, Comprising: In the said active material layer, the said active material The battery electrode is characterized in that a thin portion having a smaller thickness than other portions of the layer is present.

  As an electrode having a structure similar to the electrode of the present invention, a fine pattern in which a thin film made of a metal alloyed with Li or an alloy containing this metal is selectively formed in a predetermined pattern on a current collector A thin film electrode has been proposed (see Japanese Patent Application Laid-Open No. 2004-127561). This patent document discloses a technique using a photolithography method as an electrode manufacturing method. When such a patterned thin film electrode is used particularly for a negative electrode of a battery, when the battery is charged, a void in which no thin film is formed acts as an expansion allowance of an alloy that is an active material, and is accompanied by expansion of the active material. Generation of cracks in the active material can be effectively prevented. Therefore, the document 2 describes that the larger the interval between patterns, the better.

  However, the patterned thin film electrode described in the above patent document is limited to a thin film made of a metal alloyed with Li or an alloy containing this metal, and cannot be used when a carbon-based material is used as a negative electrode. In addition, active materials with a relatively large particle size are targeted. If the particle size is large, the reaction surface area is small, so it is not suitable for high-power batteries.

  Hereinafter, the structure of the battery electrode of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing one embodiment of a battery electrode of the present invention. In the battery electrode in the form shown in FIG. 1, a positive electrode active material layer 13 mainly composed of the positive electrode active material 3 is formed on one surface of the current collector 11, and the negative electrode active material 5 is mainly composed on the other surface. This is a bipolar electrode 1 in which a negative electrode active material layer 15 is formed. As will be described later, the active material layers (13, 15) may contain other components, but are not shown in FIG.

  In the present embodiment, both the positive electrode active material layer 13 and the negative electrode active material layer 15 have a thin part having a smaller thickness than other portions of the active material layer. Specifically, channels (13 ′, 15 ′) exist in the thin portion. The channels (13 ′, 15 ′) exist in the same direction as the thickness direction of the active material layers (13, 15). In the present invention, the drawings are exaggerated for convenience of explanation, and the technical scope of the present invention is not limited to the forms shown in the drawings. Also, embodiments other than the drawings may be employed. For example, a form in which a channel exists in at least one of the positive electrode and the negative electrode can also be adopted. In FIG. 1, only three channels (13 ′, 15 ′) exist in each of the active material layers (13, 15), but an infinite number of channels exist originally.

  In the conventional battery electrode having a uniform thickness, due to the influence of the conductive additive added as the particle size of the active material decreases, the press treatment applied at the time of electrode preparation, etc., the broken line in FIG. As shown, the conduction of lithium ions in the active material layer (especially for the active material located on the side close to the current collector of the active material layer) is not sufficiently secured, and sufficient output characteristics cannot be obtained. was there.

  On the other hand, in the present invention, by adopting the configuration shown in FIG. 1, lithium ion conduction from the electrolyte layer can be sufficiently ensured at the channel (13 ′, 15 ′) site (solid line in FIG. 1).

  In the form shown in FIG. 1, as described above, channels (13 ′, 15 ′) exist in the same direction as the thickness direction of the active material layers (13, 15). However, it is not restricted only to such a form, The direction of a channel (13 ', 15') should just be a direction substantially the same as the thickness direction of an active material layer (13, 15). Note that “substantially the same direction” means that the directions of the channels (13 ′, 15 ′) may be inclined to the extent that the effects of the present invention can be obtained. Specifically, it is considered that the direction of the channels (13 ′, 15 ′) may be inclined by about 20 ° with respect to the thickness direction of the active material layers (13, 15). The presence and angle of such channels (13 ′, 15 ′), the shape and size of the channels described later, and the like can be confirmed by cross-sectional observation using an electron microscope. It may be confirmed by other methods. For example, cross-sectional observation using a focused ion beam (FIB) apparatus may be used.

  In the electrode of the present invention, the form in which the channels (13 ′, 15 ′) are not particularly limited. The channels (13 ′, 15 ′) may exist irregularly or regularly. In a preferred form of the invention, the channels (13 ′, 15 ′) exist regularly and periodically. Note that “exist regularly and periodically” means that the channels (13 ′, 15 ′) exist according to a certain rule, and the rule is repeated. In addition, in such a form, the specific shape in which the channel exists is not particularly limited, but for example, a shape such as a staggered arrangement or a grid arrangement may be exemplified.

  The specific value of the interval between adjacent channels is not particularly limited, but the adjacent average interval between adjacent channels (13 ′, 15 ′) is preferably the thickness of the active material layer (13, 15) (FIG. 1). 5) or less, more preferably 2 times or less, still more preferably 1 time or less, and particularly preferably 0.5 times or less. This is because if the average distance between adjacent channels is too large, the distance in the plane direction of the active material layer to which lithium ions should conduct becomes longer, and the significance of providing the channel may be lost. On the other hand, the lower limit value of the adjacent average interval of the channels (13 ′, 15 ′) is not particularly limited, but is 0.1 times or more the thickness of the active material layer (13, 15) from the viewpoint of easy production. It is good to do. The “average adjacent interval between channels” is an average value of adjacent intervals between channels (“X” shown in FIG. 1), and is a constant photograph of a direction perpendicular to the plane of the active material layer using an electron micrograph. Each of the adjacent intervals existing in the visual field is measured, and an arithmetic average thereof is calculated.

  The shape and size of the individual channels (13 ′, 15 ′) existing in the active material layer (13, 15) are not particularly limited, and the shape is a shape viewed from a direction perpendicular to the plane direction of the active material layer. For example, any shape such as a circular shape, a square shape, a rectangular shape, a triangular shape, a rhombus shape, and a star shape may be used. In some cases, other shaped channels may be present. The size of the channel is not particularly limited, and can be appropriately set according to the thickness of the active material layer, the interval between the channels, and the like.

  The total volume of the channels (13 ′, 15 ′) existing in the active material layers (13, 15) is not particularly limited, but is preferably relative to the total volume of the active material layers (13, 15). 1% or more, more preferably 2% or more, still more preferably 3% or more, and particularly preferably 4% or more. This is because if the total volume of the channel is too small, the distance in the plane direction of the active material layer through which lithium ions should be conducted becomes longer, and the significance of providing the channel may be lost. Because. On the other hand, the upper limit value of the total volume of the channel is not particularly limited, but is preferably 50% or less of the total volume of the active material layer from the viewpoint of preventing a decrease in capacity per unit volume.

  The battery electrode of the present invention can be employed in, for example, a bipolar lithium ion secondary battery (hereinafter also simply referred to as “bipolar battery”). Of course, it may be adopted for other batteries.

  Hereinafter, the configuration of the battery electrode of the present invention will be described by taking as an example a case where it is employed in a lithium ion secondary battery. The battery electrode of the present invention is characterized in that there is a thin portion having a smaller thickness in the active material layer than in other parts of the active material layer. In the battery electrode of the present invention, preferably, channels (13 ′, 15 ′) as shown in FIG. 1 exist. There is no particular limitation on the selection of the current collector, active material, binder, supporting salt (lithium salt), ion-conducting polymer, and other compounds added as necessary. Depending on the intended use, it may be selected by appropriately referring to conventionally known knowledge. The battery electrode of the present invention can be applied to both the positive electrode and the negative electrode. For example, when applied to the positive electrode, the current collector and the active material are used as the current collector and the positive electrode active material for the positive electrode. A compound known to act may be employed.

[Current collector]
The current collector 11 is made of a conductive material such as an aluminum foil, a nickel 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 size of the current collector is determined according to the intended use of the battery. If a large electrode used for a large battery is manufactured, a current collector having a large area is used. If a small electrode is produced, a current collector with a small area is used.

[Active material layer]
An active material layer (13, 15) is formed on the current collector 11. The active material layers (13, 15) are layers containing an active material that plays a central role in the charge / discharge reaction. When the electrode of the present invention is used as a positive electrode, the active material layer contains a positive electrode active material. On the other hand, when the electrode of the present invention is used as a negative electrode, the active material layer contains a negative electrode active material.

  As the positive electrode active material, a lithium-transition metal composite oxide is preferable, and examples thereof include a Li—Mn composite oxide such as LiMn 2 O 4 and a Li—Ni composite oxide such as LiNiO 2. In some cases, two or more positive electrode active materials may be used in combination.

  As the negative electrode active material, the above lithium transition metal-composite oxide or carbon is preferable. Examples of carbon include graphite-based carbon materials such as natural graphite, artificial graphite, and expanded graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, and hard carbon. In some cases, two or more negative electrode active materials may be used in combination.

  The average particle size of the active material is not particularly limited. However, if the average particle size is too large, the reaction surface area of the active material becomes small, making it difficult to increase the output, or the lithium ion conduction inside the active material particles determines the lithium ion conduction in the active material layer. As a result, the effects of the present invention may not be sufficiently obtained. From such a viewpoint, the average particle diameter of the active material is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less. However, forms outside these ranges can also be employed. In the present application, the average particle size of the active material is a value measured by a laser diffraction particle size distribution measuring device.

  The active material layers (13, 15) may contain other materials if necessary. For example, a binder, a conductive additive, a supporting salt (lithium salt), an ion conductive polymer, and the like can be included. When an ion conductive polymer is included, a polymerization initiator for polymerizing the polymer may be included.

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

  A conductive support agent means the additive mix | blended in order to improve the electroconductivity of an active material layer. Examples of the conductive aid include carbon powders such as graphite and carbon black, and various carbon fibers such as vapor grown carbon fiber (VGCF).

  The compounding ratio of the components contained in the active material layers (13, 15) is not particularly limited. The blending ratio can be adjusted by appropriately referring to known knowledge about lithium ion secondary batteries.

(Production method)
2nd of this invention is related with the manufacturing method of the electrode for batteries. That is, the second of the present invention is a current collector preparing step for preparing a current collector, an active material slurry preparing step for preparing an active material slurry containing an active material, and the active material slurry on the surface of the current collector. Is a coating film forming step of forming a coating film, and a channel forming step of forming a channel in a direction substantially the same as the thickness direction of the coating film. According to such a manufacturing method, the first battery electrode of the present invention can be manufactured. Hereinafter, although it demonstrates in detail in order of a process, it is not restrict | limited only to the following form.

[Current collector preparation process]
In this step, a current collector is prepared. The specific form of the current collector to be prepared is as described in the column of the configuration of the electrode of the present invention, and thus detailed description thereof is omitted here.

[Active material slurry preparation process]
In this step, an active material slurry is prepared by mixing a desired active material, a binder, and, if necessary, other components (for example, a conductive additive) in a solvent. Since the specific form of each component blended in the active material slurry is as described in the column of the configuration of the electrode of the present invention, detailed description is omitted here.

  The kind of solvent and the mixing means are not particularly limited, and conventionally known knowledge about electrode production can be appropriately referred to. As an example of the solvent, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide and the like can be used. When adopting polyvinylidene fluoride (PVdF) as a binder, NMP is preferably used as a solvent.

  There is no particular limitation on the blending ratio of each component contained in the active material slurry prepared in this step, and conventionally known knowledge can be appropriately referred to in the battery manufacturing field.

[Coating film forming process]
Subsequently, the active material slurry prepared above is applied to the surface of the current collector prepared as above. Thereby, the coating film which consists of an active material slurry is formed on the surface of an electrical power collector. This coating film is finally dried, and further, a channel is formed in a channel forming step described later to become an active material layer.

  The application means for applying the active material slurry is not particularly limited. For example, a commonly used means such as a coater can be adopted.

  A coating film is formed according to the desired arrangement | positioning form of the electrical power collector and active material layer in the electrode manufactured. For example, when the manufactured electrode is a bipolar electrode, a coating film containing a positive electrode active material is formed on one surface of the current collector, and a coating film containing a negative electrode active material is formed on the other surface. On the other hand, when manufacturing a non-bipolar electrode, a coating film containing either the positive electrode active material or the negative electrode active material is formed on both surfaces of one current collector.

[Channel formation process]
Then, a channel is formed with respect to the coating film formed above. Thereby, the battery electrode (for example, the first battery electrode of the present invention shown in FIG. 1) is completed.

  The method for forming a channel in this step is not particularly limited. This step includes, for example, a step of laminating and pressing a mold (mold) on the coating film formed above (mold pressing step), a step of drying the coating film (drying step), and removing the mold. The process (mold removal process) to perform.

  First, a mold is laminated on the coating film formed as described above. There is no restriction | limiting in particular about the specific form of the mold used here, The mold which has a pattern corresponding to the shape and size of the channel which formation is desired can be used suitably.

  About a mold, when goods are marketed, what purchased the goods concerned may be used, and what was produced itself may be used. As a method for producing the mold itself, for example, a nano-imprinting method can be cited. The “nanoimprinting method” is a technique for transferring a fine structure by pushing a mold into a resin, and is roughly divided into a thermal nanoimprinting method and an optical nanoimprinting method. Since the nanoimprinting method is a widely known method, detailed description is omitted here, but by adopting this method, a nano-level extremely fine mold corresponding to the desired channel shape and size can be obtained. Can be made.

  After lamination of the mold, the laminate of the coating film and the mold is pressed in the lamination direction. Thereby, the pattern which a mold has is transcribe | transferred to a coating film, and a channel can be formed in a coating film. The pressure at the time of pressing is not particularly limited, and can be set as appropriate.

  Thereafter, the coating film on which the channel is formed is dried. Thereby, the solvent in the coating film is removed, and the coating film is solidified into a shape having a channel.

  The drying means for drying the coating film is not particularly limited, and conventionally known knowledge can be appropriately referred to in the field of battery production. For example, heat treatment is exemplified. Drying conditions (drying time, drying temperature, etc.) can be appropriately set according to the application amount of the active material slurry and the volatilization rate of the solvent of the slurry. An example of heat treatment for the purpose of drying is exemplified by heat treatment at a temperature of about 110 to 130 ° C. for about 1 to 5 minutes.

  When a coating film contains a polymerization initiator, the ion conductive polymer in a coating film is bridge | crosslinked by a crosslinkable group by performing a superposition | polymerization process further.

  The polymerization treatment in the polymerization step is not particularly limited, and conventionally known knowledge may be referred to as appropriate. For example, when the coating film contains a thermal polymerization initiator (AIBN or the like), the coating film is subjected to heat treatment. Moreover, when a coating film contains a photoinitiator (BDK etc.), light, such as an ultraviolet light, is irradiated. In addition, the heat processing for thermal polymerization may be performed simultaneously with said drying process, and may be performed before or after the said drying process. Further, the heat treatment may be performed simultaneously with the press treatment described above. According to such a form, a channel can be formed by a simple method.

  Finally, the mold is removed from the laminate of the coating film and the mold. Thereby, the battery electrode is completed. The removal of the mold may be performed manually or at a mass production level by an automated machine.

  Hereinafter, another preferred embodiment of the second production method of the present invention will be described. In this embodiment, the coating film is formed by ink jet printing in the coating film forming step. Thereby, a channel can be formed simultaneously with the formation of the coating film. That is, the channel forming process is performed simultaneously with the coating film forming process. Therefore, this embodiment can also contribute to the reduction of the man-hour at the time of electrode preparation.

  “Inkjet printing” means a printing method in which liquid ink is ejected from nozzles and ink is adhered to an object. The ink jet method is classified into a piezo method, a thermal ink jet method, and a bubble jet (registered trademark) method according to a method of ejecting ink. Inkjet printing is a very well-known technique at present, and a detailed description of inkjet printing is omitted.

  In order to produce a coating film by ink jet printing in the coating film forming step of this embodiment, first, an active material slurry for forming a coating film is prepared. Since the preparation of the active material slurry is performed in the same manner as the above-described active material slurry preparation step, detailed description is omitted here.

  Subsequently, a current collector for forming a coating film is prepared. Since the form of the current collector to be prepared has also been described above, detailed description thereof is omitted here.

  Subsequently, the current collector is supplied to an ink jet apparatus capable of printing the active material slurry. Then, an active material slurry is ejected from the current collector by an ink jet method and attached to the current collector. The amount of the slurry ejected from the nozzles of the ink jet apparatus is very small, and it is possible to eject an approximately equal volume. Therefore, the coating film formed by the adhesion of the active material slurry is very thin and uniform. Moreover, if inkjet printing is used, the thickness and shape of the coating film can be precisely controlled. Furthermore, when ink jet printing is used, a predetermined pattern is designed on a computer, and a coating film having a desired shape is formed simply by printing the pattern. When the thickness of the coating film is insufficient in one printing, the printing may be repeated twice or more on the same surface. That is, the same active material slurry may be printed over the same current collector. Thereby, a coating film having a desired thickness is formed.

  In order to form a coating film having a channel as described above, for example, the coating film is formed by ejecting the active material slurry several times over the entire surface of the current collector, and then the part where the channel is located. If the coating pattern is designed so that the active material slurry is not ejected, and the coating film having the desired thickness (channel of the desired depth) is formed with this pattern, the active material slurry is applied by ink jet printing. Good.

  Then, the obtained coating film is dried. When a coating film contains a polymerization initiator, the ion conductive polymer in a coating film is bridge | crosslinked by a crosslinkable group by performing a superposition | polymerization process further. Thereby, an active material layer is completed. About the specific form of a drying process or a superposition | polymerization process, since the form similar to what was mentioned above may be employ | adopted, detailed description is abbreviate | omitted here.

  According to the manufacturing method of this embodiment, a channel having a desired pattern can be easily produced by adopting ink jet printing. In addition, since an active material layer having an extremely uniform thickness can be produced, it is possible to effectively prevent the occurrence of problems such as uneven current density due to the non-uniformity of the thickness of the active material layer, and an electrode having excellent durability. Can be manufactured.

(Second Embodiment)
In 2nd Embodiment, a battery is comprised using the battery electrode of said 1st Embodiment.

  That is, a third aspect of the present invention is a battery having at least one single cell layer in which a positive electrode, an electrolyte layer, and a negative electrode are laminated in this order, and at least one of the positive electrode and the negative electrode is an electrode of the present invention. There is a battery. The electrode of the present invention can be applied to any of a positive electrode, a negative electrode, and a bipolar electrode. A battery including the electrode of the present invention as at least one electrode belongs to the technical scope of the present invention. However, preferably, all of the electrodes constituting the battery are the electrodes of the present invention. By adopting such a configuration, the durability of the battery can be effectively improved.

  The battery of the present invention may be a bipolar lithium ion secondary battery (hereinafter also referred to as “bipolar battery”). FIG. 2 is a cross-sectional view showing a battery of the present invention which is a bipolar battery. Hereinafter, the bipolar battery shown in FIG. 2 will be described in detail as an example, but the technical scope of the present invention is not limited to such a form.

  The bipolar battery 10 of this embodiment shown in FIG. 2 has a structure in which a substantially rectangular battery element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior.

  As shown in FIG. 2, the battery element 21 of the bipolar battery 10 of this embodiment has a plurality of bipolar electrodes of the first embodiment shown in FIG. In FIG. 2, there are channels as shown in FIG. 1 in the active material layer of the electrode, but each active material layer is shown as a single layer. Each bipolar electrode is laminated via an electrolyte layer 17 to form a battery element 21. At this time, each bipolar electrode and electrolyte layer are arranged so that the positive electrode active material layer 13 of one bipolar electrode and the negative electrode active material layer 15 of another bipolar electrode adjacent to the one bipolar electrode face each other through the electrolyte layer 17. 17 are stacked.

  The adjacent positive electrode active material layer 13, electrolyte layer 17, and negative electrode active material layer 15 constitute one unit cell layer 19. Therefore, it can be said that the bipolar battery 10 has a configuration in which the single battery layers 19 are stacked. In addition, an insulating layer 31 for insulating adjacent current collectors 11 is provided on the outer periphery of the unit cell layer 19. The current collector (outermost layer current collector) (11a, 11b) located in the outermost layer of the battery element 21 has a positive electrode active material layer 13 (positive electrode side outermost layer current collector 11a) or a negative electrode only on one side. One of the active material layers 15 (negative electrode side outermost layer current collector 11b) is formed.

  Further, in the bipolar battery 10 shown in FIG. 2, the positive electrode side outermost layer current collector 11a is extended to form a positive electrode tab 25, which is led out from a laminate sheet 29 which is an exterior. On the other hand, the negative electrode side outermost layer current collector 11 b is extended to form a negative electrode tab 27, which is similarly derived from the laminate sheet 29.

  Hereinafter, members constituting the bipolar battery 10 of the present embodiment will be briefly described. However, since the components constituting the electrode are as described above, the description thereof is omitted here. Further, the technical scope of the present invention is not limited to the following forms, and conventionally known forms can be similarly adopted.

[Electrolyte layer]
A liquid electrolyte or a polymer electrolyte can be used as the electrolyte constituting the electrolyte layer 17.

  The liquid electrolyte (electrolyte salt and plasticizer) is not particularly limited, and various conventionally known electrolytic solutions can be appropriately used. For example, at least selected from inorganic acid anion salts such as LiPF6, LiBF4, LiClO4, LiAsF6, LiTaF6, LiAlCl4, and Li2B10Cl10, organic acid anion salts such as LiCF3SO3, Li (CF3SO2) 2N, and Li (C2F5SO2) 2N 1 type of lithium salt (electrolyte salt), cyclic carbonates such as propylene carbonate and ethylene carbonate; chain carbonates such as dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; tetrahydrofuran, 2-methyltetrahydrofuran, 1,4- Ethers such as dioxane, 1,2-dimethoxyethane, 1,2-dibutoxyethane; lactones such as γ-butyrolactone; nitriles such as acetonitrile; esters such as methyl propionate; Amides such as muamide; those using a plasticizer (organic solvent) such as an aprotic solvent in which at least one selected from methyl acetate and methyl formate or a mixture of two or more thereof can be used. However, it is not necessarily limited to these.

  On the other hand, the polymer electrolyte is classified into a gel electrolyte containing an electrolytic solution and an intrinsic polymer electrolyte containing no electrolytic solution.

  A gel electrolyte is a solid polymer electrolyte having ion conductivity and containing an electrolytic solution used in a conventionally known lithium ion secondary battery. Further, a polymer skeleton having no lithium ion conductivity is used. Some of them contain an electrolyte solution. Examples of the solid polymer electrolyte having ion conductivity include known solid polymer electrolytes such as polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof. These solid polymer electrolytes can be suitably used for intrinsic (all solid) polymer electrolytes.

  Examples of the polymer having no lithium ion conductivity used for the gel electrolyte include polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), polyacrylonitrile (PAN), and polymethyl methacrylate (PMMA). However, it is not necessarily limited to these. PAN, PMMA, and the like, which are in a class with little ion conductivity, can be used as the above polymer having ion conductivity, but are used here as a polymer gel electrolyte. It was exemplified as a polymer having no lithium ion conductivity.

  In the case where the electrolyte layer 17 is composed of a liquid electrolyte or a gel electrolyte, a separator may be used for the electrolyte layer 17. Specific examples of the separator include a microporous film made of polyolefin such as polyethylene or polypropylene.

  The intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the above-described solid polymer electrolyte (matrix polymer) having ion conductivity, and does not include an organic solvent that is a plasticizer. Therefore, when the electrolyte layer 17 is composed of an intrinsic polymer electrolyte, there is no fear of liquid leakage from the battery, and the reliability of the battery can be improved.

[Insulation layer]
In the bipolar battery 10, an insulating layer 31 is usually provided around each unit cell layer 19. The insulating layer 31 is provided for the purpose of preventing the adjacent current collectors 11 in the battery from contacting each other and short-circuiting due to a slight unevenness at the end of the battery cell layer 19 in the battery element 21. It is done. The installation of such an insulating layer 31 ensures long-term reliability and safety, and can provide a high-quality bipolar battery 10.

  The insulating layer 31 only needs to have insulating properties, sealing properties against falling off of the solid electrolyte, sealing properties against moisture permeation from the outside (sealing properties), heat resistance under battery operating temperature, etc. Urethane resin, epoxy resin, polyethylene resin, polypropylene resin, polyimide resin, rubber and the like can be used. Of these, urethane resins and epoxy resins are preferred from the viewpoints of corrosion resistance, chemical resistance, ease of production (film forming properties), economy, and the like.

[tab]
In the bipolar battery 10, the tab (positive electrode tab 25 and negative electrode tab 27) electrically connected to the outermost layer current collector (11a, 11b) is used for taking out the current outside the battery. Take out to the outside. Specifically, the positive electrode tab 25 electrically connected to the positive electrode outermost layer current collector 11 a and the negative electrode tab 27 electrically connected to the negative electrode outermost layer current collector 11 b are formed on the laminate sheet 29. Take out to the outside.

  The material of the tabs (the positive electrode tab 25 and the negative electrode tab 27) is not particularly limited, and a known material conventionally used as a tab for a bipolar battery can be used. Examples thereof include aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof. Note that the same material may be used for the positive electrode tab 25 and the negative electrode tab 27, or different materials may be used. As in the present embodiment, the outermost layer current collectors (11a, 11b) may be extended to form tabs (25, 27), or a separately prepared tab may be connected to the outermost layer current collector. Good.

[Exterior]
In the bipolar battery 10, the battery element 21 is preferably housed in an exterior such as a laminate sheet 29 in order to prevent external impact and environmental degradation during use. The exterior is not particularly limited, and a conventionally known exterior can be used. A polymer-metal composite laminate sheet or the like excellent in thermal conductivity can be preferably used in that heat can be efficiently transferred from a heat source of an automobile and the inside of the battery can be rapidly heated to the battery operating temperature.

  According to the bipolar battery 10 of the present embodiment, a bipolar electrode in which the electrode of the present invention is formed on both surfaces of the current collector 11 is employed. For this reason, the bipolar battery of this embodiment is excellent in output characteristics.

  Here, the operational effects of the present invention as described above can be particularly remarkably exhibited in a secondary battery used under high output conditions. Therefore, the secondary battery of the present invention is preferably used under high output conditions. Specifically, the secondary battery of the present invention is used under conditions that require an output of preferably 20 C or higher, more preferably 50 C or higher, and even more preferably 100 C or higher.

(Third embodiment)
In the third embodiment, a plurality of the bipolar batteries of the second embodiment are connected in parallel and / or in series to constitute an assembled battery.

  FIG. 3 is a perspective view showing the assembled battery of the present embodiment.

  As shown in FIG. 3, the assembled battery 40 is configured by connecting a plurality of the bipolar batteries of the second embodiment. Specifically, each bipolar battery 10 is connected by connecting the positive electrode tab 25 and the negative electrode tab 27 of each bipolar battery 10 using a bus bar. On one side surface of the assembled battery 40, electrode terminals (42, 43) are provided as electrodes of the entire assembled battery 40.

  The connection method when connecting the plurality of bipolar batteries 10 constituting the assembled battery 40 is not particularly limited, and a conventionally known method can be appropriately employed. For example, a technique using welding such as ultrasonic welding or spot welding, or a technique of fixing using rivets, caulking, or the like can be employed. According to such a connection method, the long-term reliability of the assembled battery 40 can be improved.

  According to the assembled battery 40 of the present embodiment, each bipolar battery 10 constituting the assembled battery 40 is excellent in output characteristics, and therefore, an assembled battery excellent in output characteristics can be provided.

  The connection of the bipolar batteries 10 constituting the assembled battery 40 may be all connected in parallel, all may be connected in series, or a combination of series connection and parallel connection may be used. Also good.

(Fourth embodiment)
In the fourth embodiment, the bipolar battery 10 of the second embodiment or the assembled battery 40 of the third embodiment is mounted as a motor driving power source to constitute a transportation system. As a transportation system using the bipolar battery 10 or the assembled battery 40 as a motor power source, for example, a complete electric vehicle that does not use gasoline, a hybrid vehicle such as a series hybrid vehicle or a parallel hybrid vehicle, and a fuel cell vehicle, a wheel motor is used. In addition to cars driven by, trains, motorcycles, ships, aircraft and the like.

  For reference, FIG. 4 shows a schematic diagram of an automobile 50 on which the assembled battery 40 is mounted. The assembled battery 40 mounted on the automobile 50 has the characteristics as described above. For this reason, the automobile 50 equipped with the assembled battery 40 has excellent output characteristics and can provide sufficient output even after being used for a long period of time.

  As described above, some preferred embodiments of the present invention have been described. However, the present invention is not limited to the above embodiments, and various modifications, omissions, and additions can be made by those skilled in the art. . For example, in the above description, a bipolar lithium ion secondary battery (bipolar battery) has been described as an example. However, the technical scope of the battery of the present invention is not limited to a bipolar battery. A non-type lithium ion secondary battery may be used. For reference, FIG. 5 is a cross-sectional view showing an outline of a lithium ion secondary battery 60 that is not bipolar. In the lithium ion secondary battery 60 shown in FIG. 5, the negative electrode active material layer 15 is slightly smaller than the positive electrode active material layer 13, but is not limited to such a form. A negative electrode active material layer 15 that is the same as or slightly larger than the positive electrode active material layer 13 may also be used.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to only the forms shown in the following examples.

<Example 1>
<Preparation of positive electrode>
Spinel type lithium manganate (LiMn 2 O 4) (average particle size: 5 μm) (90 parts by mass) which is a positive electrode active material, acetylene black (5 parts by mass) which is a conductive additive, and polyvinylidene fluoride (PVdF) which is a binder ( 5 parts by mass) was mixed, and then an appropriate amount of N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent was added to prepare a positive electrode active material slurry.

  On the other hand, an aluminum foil (thickness: 20 μm) was prepared as a positive electrode current collector. The positive electrode active material slurry prepared above was applied to one surface of the prepared current collector by a self-propelled coater to form a coating film. Next, the coating film was dried and pressed to form a coating film (200 μm) composed of a positive electrode active material slurry.

  On the surface of the coating film formed as described above, a channel was formed using a sword mountain having needles in a grid arrangement (length: 3 mm, diameter: 200 μm, interval between adjacent needles: 1 mm) to complete a test positive electrode.

<Production of negative electrode>
Hard carbon (average particle size: 6 μm) (95 parts by mass) as a negative electrode active material and polyvinylidene fluoride (PVdF) (5 parts by mass) as a binder are mixed, and then N-methyl- as a slurry viscosity adjusting solvent. An appropriate amount of 2-pyrrolidone (NMP) was added to prepare a negative electrode active material slurry.

  On the other hand, a copper foil (thickness: 20 μm) was prepared as a current collector for the negative electrode. The negative electrode active material slurry prepared above was applied to one surface of the prepared current collector with a self-propelled coater to form a coating film. Next, the coating film was dried and pressed to form a coating film (thickness: 200 μm) made of a negative electrode active material slurry.

  On the surface of the coating film formed as described above, a channel was formed using a sword mountain having needles in a grid arrangement (length: 3 mm, diameter: 200 μm, interval between adjacent needles: 1 mm) to complete a test negative electrode.

<Example 2>
A test positive electrode and a test negative electrode were prepared in the same manner as in Example 1 except that a sword was used having a needle having a length of 3 mm, a diameter of 50 μm, and an adjacent needle interval of 0.4 mm. Produced.

<Example 3>
As the sword mountain, the same as in the above Example 2 was used, except that the holes were made four times while being shifted by 0.2 mm, and a channel with a grid arrangement with a channel spacing of 0.2 mm was formed. A test positive electrode and a test negative electrode were produced in the same manner as in Example 1.

<Example 4>
As the sword mountain, the same as in Example 2 above was used, except that 16 holes were made while shifting by 0.1 mm each, and a channel with a grid arrangement with 0.1 mm spacing between adjacent channels was formed. A test positive electrode and a test negative electrode were produced in the same manner as in Example 1.

<Comparative Example 1>
Each electrode was produced by the same method as in Example 1 except that the channel was not formed.

<Production of test cell>
In order to use as a positive electrode and a negative electrode of a test cell, the positive electrode and the negative electrode prepared in each of the above examples and comparative examples were punched into 50 mm squares using punches, and current extraction terminals (for the positive electrode) An aluminum terminal and a nickel terminal were connected to the negative electrode.

  Furthermore, a polypropylene microporous film (thickness: 20 μm) was prepared as a separator. Moreover, what melt | dissolved LiPF6 which is lithium salt in the density | concentration of 1M in the equal volume mixed liquid of ethylene carbonate (EC) and propylene carbonate (PC) was prepared as electrolyte solution.

  The negative electrode, separator, and positive electrode obtained above were laminated in this order, and the battery element was placed in an aluminum laminate film so that the current extraction terminal was exposed to the outside. Thereafter, several drops of the electrolytic solution prepared above were dropped and then sealed in a vacuum to prepare a test cell.

<Evaluation of battery characteristics of test cell>
In each of the above Examples and Comparative Examples, each test cell was charged with a constant current of 0.2 C to a potential of 4.2 V and held at this potential for 1 hour. Thereafter, it was paused for 10 minutes and discharged to a potential of 3.0 V at a constant current of 0.5C. Subsequently, a hole was made in the laminate film, the gas resulting from the first charge / discharge was removed, and the laminate film was sealed again in vacuum.

  Thereafter, the battery was charged again to a potential of 4.2 V with a constant current of 0.2 C and held at this potential for 1 hour. Thereafter, it was paused for 10 minutes and discharged to a potential of 3.0 V at a constant current of 10C. The discharge capacity at the time of this discharge was measured, and the discharge efficiency was calculated as a percentage of the theoretical capacity. The calculated results are shown in Table 1 below.

  From the comparison between each example and the comparative example, when the active material layer of the electrode has a thin portion having a smaller thickness than other parts of the active material layer (specifically, the thickness of the active material layer) It is shown that the discharge efficiency is excellent even under a high power condition of 10C (when there is a channel formed in substantially the same direction as the direction). This is considered to be because lithium ion conduction is sufficiently ensured in the thin part (channel part).

  Thus, according to the battery electrode of the present invention, sufficient conduction of lithium ions in the active material layer can be ensured even under high output conditions. As a result, it can contribute effectively to the improvement of the output characteristics of the battery.

1 Bipolar electrode,
3 positive electrode active material,
5 negative electrode active material,
10 Bipolar battery,
11 Current collector,
11a, 11b outermost layer current collector,
13 positive electrode active material layer,
13 'channel existing in the positive electrode active material layer,
15 negative electrode active material layer,
15 ′ a channel present in the negative electrode active material layer,
17 electrolyte layer,
19 cell layer,
21 battery elements,
25 positive electrode tab,
27 negative electrode tab,
29 Laminate sheet,
31 insulating layer,
33 positive electrode current collector,
35 negative electrode current collector,
40 battery packs,
42, 43 electrode terminals,
50 cars,
60 Lithium ion secondary battery that is not bipolar,
X channel adjacent spacing,
Y The thickness of the active material layer.

Claims (7)

A positive electrode having a current collector and a positive electrode active material layer containing a positive electrode active material formed on a surface of the current collector, an electrolyte layer having a liquid electrolyte or a gel electrolyte as an electrolyte, a current collector, and the current collector In a battery having at least one unit cell layer in which a negative electrode having a negative electrode active material layer containing a negative electrode active material formed on the surface of a body is laminated in this order,
The positive electrode and / or negative electrode active material layer includes a thin part having a smaller thickness than other parts of the active material layer, and a channel reaching the thin part, and the channel is an active material layer A battery which is scattered on the surface, has an average particle diameter of the active material in the active material layer of 10 μm or less, and a diameter of the channel of 50 to 200 μm. The battery according to claim 1, wherein an adjacent average interval between adjacent channels is not more than 5 times the thickness of the active material layer. The battery according to claim 1 or 2 , wherein a total volume of the channels is 1% or more with respect to a total volume of a positive electrode and / or a negative electrode active material layer including the channel. The battery according to any one of claims 1 to 3 , which is a bipolar lithium ion secondary battery. A method for producing a battery having a positive electrode, an electrolyte layer having a liquid electrolyte or a gel electrolyte as an electrolyte, and at least one unit cell layer in which a negative electrode is laminated in this order,
A current collector preparing step in which at least one of the positive electrode or the negative electrode prepares a current collector; and
An active material slurry preparation step of preparing an active material slurry containing the active material;
Applying the active material slurry to the surface of the current collector to form a coating film,
Channel formation for ensuring lithium ion conduction in the active material layer, the channel being formed so as to be scattered on the surface of the active material layer in substantially the same direction as the thickness direction of the coating film A process,
The average particle size of the active material is 10 μm or less,
The diameter of the channel is 50-200 μm;
A method for producing a battery, wherein the channel forming step is a battery electrode obtained by a method for producing a battery electrode, wherein the channel forming step includes a step of laminating and pressing a mold on at least the coating film. The battery manufacturing method according to claim 5 , wherein an adjacent average interval between the adjacent channels is 5 times or less of a thickness of the active material layer. The battery manufacturing method according to claim 5 or 6 , wherein a total volume of the channels is 1% or more with respect to a total volume of a positive electrode and / or a negative electrode active material layer including the channel.

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