JP4581384B2 - Battery and manufacturing method thereof - Google Patents

Description

  The present invention relates to a battery suitably used for a secondary battery as a power source for driving a motor of a vehicle.

  In recent years, there has been a strong demand for the introduction of electric vehicles (EV), hybrid vehicles (HEV), and fuel cell vehicles (FCV) against the background of the increasing environmental protection movement, and these motor drive batteries have been developed. Yes. As these motor drive batteries, rechargeable secondary batteries are used. Since EV, HEV, and FCV require high output and high energy density, it is virtually impossible to cope with a single large battery. Therefore, it is common to use a battery pack composed of a plurality of batteries connected in series. As one battery constituting such an assembled battery, for example, a thin laminate battery has been proposed (see, for example, Patent Document 1).

However, in view of improving the fuel efficiency of the vehicle and securing the interior space, it is desired to further increase the output per unit volume of the battery.
JP2003-151526A

  An object of the present invention is to provide a small and high output battery.

The present invention has a positive electrode active material part, a solid polymer electrolyte part adjacent to the positive electrode active material part, and a negative electrode active material part adjacent to the solid polymer electrolyte part, the positive electrode active material part, The solid polymer electrolyte part and the negative electrode active material part are juxtaposed on the same insulator , and a charge / discharge reaction part comprising the positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part is collected. It is a bipolar battery arranged repeatedly via an electric body . The battery of the present invention can be manufactured using an inkjet method.

  In the battery of the present invention, the positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part are juxtaposed on the surface of the insulator. For this reason, the thickness of the battery can be dramatically reduced.

  The battery of the present invention includes a positive electrode active material part, a solid polymer electrolyte part adjacent to the positive electrode active material part, and a negative electrode active material part adjacent to the solid polymer electrolyte part. The solid polymer electrolyte part and the negative electrode active material part are batteries that are juxtaposed on the same insulator.

  The effects of the present invention will be described in detail with reference to the drawings. FIG. 1 is a plan view of one embodiment of the battery of the present invention. FIG. 2 is a side view of the battery of FIG. 1 from the “II” direction. The batteries shown in FIGS. 1 and 2 are merely an embodiment, and the present invention is not limited to the illustrated batteries. For example, in the battery shown in FIG. 1, three charge / discharge reaction units 108 including a positive electrode active material unit 102, a solid polymer electrolyte unit 104, and a negative electrode active material unit 106 are connected in series via a current collector 110. Although it is a battery, the effect of this invention extends to the range which satisfy | fills the requirements described in the claim, and the range of its equivalent.

  The positive electrode active material part 102, the solid polymer electrolyte part 104, and the negative electrode active material part 106 are juxtaposed on the insulator 112. Conventional batteries have a configuration in which a positive electrode active material layer, a solid polymer electrolyte layer, and a negative electrode active material layer are laminated. When components are stacked, if the components are too thin, problems such as short-circuiting and deterioration of characteristics may occur, so each component needs to have a certain thickness. On the other hand, in the battery of the present invention, the constituent elements are arranged laterally on the insulator. That is, the positive electrode active material part 102, the solid polymer electrolyte part 104, and the negative electrode active material part 106 are juxtaposed on the insulator 112 so as to contact in this order. If it has such a structure, the thickness of a battery will become thin. Further, when the components are arranged side by side, it is easy to connect a large number of batteries in series, and a small and high-power battery can be formed.

  Next, components of the battery of the present invention will be described in detail.

  The positive electrode active material portion 102 includes at least a positive electrode active material, and is a portion where the positive electrode reaction proceeds by ions exchanged with the solid polymer electrolyte portion 104. The material constituting the positive electrode active material portion 102 is not limited as long as the electrode reaction proceeds. Conventionally, a material similar to the material used for forming the electrode layer can be used. Specifically, the active material part can include an active material, a conductive additive, a lithium salt, and the like. In order to improve ionic conductivity, a polymer electrolyte may be included. The contents of the active material, lithium salt, and the like in the positive electrode active material portion 102 are not particularly limited. What is necessary is just to determine suitably based on the knowledge already acquired regarding battery manufacture. Specific examples of the constituent elements of the battery will be exemplified below, but other substances may be used as a matter of course.

Examples of the positive electrode active material include Li—Mn complex oxides such as LiMn ₂ O ₄ and Li—Ni complex oxides such as LiNiO ₂ . In some cases, two or more positive electrode active materials may be used in combination.

  A conductive support means the additive mix | blended in order to improve the electroconductivity of an active material part. Examples of the conductive aid include carbon powder such as graphite.

Examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ C ₂ F ₅ ) _{2 and the} like.

  Examples of the polymer electrolyte include a polymer having a heteroatom having a strong polarity such as an oxygen atom or a nitrogen atom in the molecule, such as polyether, polyester, polyamine, and polysulfide. More specifically, polyethylene oxide, polypropylene oxide, copolymers thereof, and the like can be used.

  The solid polymer electrolyte part 104 exists between the positive electrode active material part 102 and the negative electrode active material part 106, and is a solid polymer medium that mediates the movement of ions between the positive electrode active material part 102 and the negative electrode active material part 106. It is a member. The solid polymer electrolyte portion is made of a polymer electrolyte exhibiting ionic conductivity. If the electrolyte is liquid or gel, it is necessary to take measures to prevent liquid junction between the electrolytes. However, when the electrolyte disposed between the positive electrode active material part and the negative electrode active material part is solid, it is not necessary to prevent a liquid junction.

  The material constituting the solid polymer electrolyte part is not particularly limited as long as it is a material that can act as an electrolyte. As a polymer electrolyte, a polymer having a heteroatom having a strong polarity such as an oxygen atom or a nitrogen atom in the molecule, such as polyether, polyester, polyamine, and polysulfide is known. More specifically, polyethylene oxide, polypropylene oxide, copolymers thereof, and the like can be used. When the battery is a lithium secondary battery, a lithium salt may be contained in the solid polymer electrolyte part.

  The negative electrode active material part 106 includes at least a negative electrode active material, and is a part where a negative electrode reaction proceeds by ions exchanged with the solid polymer electrolyte part 104. The material constituting the negative electrode active material portion 106 is not limited as long as the electrode reaction proceeds. Conventionally, a material similar to the material used for forming the electrode layer can be used. Specifically, the active material part can include an active material, a conductive additive, a lithium salt, and the like. In order to improve ionic conductivity, a polymer electrolyte may be included. The content of the active material, lithium salt, and the like in the negative electrode active material portion 106 is not particularly limited. What is necessary is just to determine suitably based on the knowledge already acquired regarding battery manufacture. Specific examples of the constituent elements of the battery will be exemplified below, but other substances may be used as a matter of course.

  Examples of the negative electrode active material include a crystalline carbon material and an amorphous carbon material. Specific examples include natural graphite, artificial 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 conductive auxiliary agent and the lithium salt are the same as those described with respect to the positive electrode active material part, and thus description thereof is omitted here.

  A current collector 110 is disposed on both sides of the charge / discharge reaction unit 108 including the positive electrode active material unit 102, the solid polymer electrolyte unit 104, and the negative electrode active material unit 106. As shown in FIGS. 1 and 2, the current collector may be disposed on the insulator 112 in the same manner as the positive electrode active material portion 102, the solid polymer electrolyte portion 104, and the negative electrode active material 106. However, other modes may be adopted. For example, a plate-like current collector may be disposed on the side surface of the positive electrode active material portion 102 opposite to the solid polymer electrolyte portion 104 or the upper surface of the positive electrode active material 102 (not shown). The current collector 110 is made of a conductive material such as an aluminum foil, a copper foil, or a stainless steel foil. When the current collector 110 is manufactured by an inkjet method, the current collector 110 is composed of a large number of metal fine particles.

  In order to develop a high output, when it is necessary to connect a large number of batteries in series, the battery is preferably a bipolar battery. In the bipolar battery, one current collector functions as both a positive electrode current collector and a negative electrode current collector. A positive electrode active material portion is formed on one surface of the current collector, and a negative electrode active material portion is formed on the other surface. In other words, the positive electrode active material part, the current collector, and the negative electrode active material part have a structure juxtaposed in this order. In order to produce a high output battery using a normal battery, a positive electrode current collector in contact with the positive electrode active material part and a negative electrode current collector in contact with the negative electrode active material part are electrically connected via a connection part such as a wiring. Connect in series. Such batteries can be changed in parallel simply by adjusting the connection, and may be convenient in terms of design changes. However, although the resistance value of the connection portion is small, it naturally exists and causes a decrease in output. Further, considering the downsizing of the battery module, such a connecting portion is a factor that hinders downsizing. Bipolar electrodes solve such problems. That is, since there is no connection portion that interposes electrodes connected in series, there is no decrease in output due to the resistance of the connection portion. Moreover, since there is no connection part, the battery module can be reduced in size. As shown in FIG. 1, a battery in which a charge / discharge reaction unit is repeatedly arranged on a single insulator via a current collector has a small occupied volume and a very large output.

  In addition, the collector in a bipolar battery may be comprised from 2 or more types of members. For example, the current collector includes a portion mainly composed of aluminum in contact with the positive electrode active material portion side and a portion mainly composed of copper in contact with the negative electrode active material portion side.

  The shape of each component is not particularly limited. For example, as shown in FIG. 1, a mode in which the positive electrode active material part 102, the solid polymer electrolyte part 104, and the negative electrode active material part 106 are arranged in a strip shape on the insulator 112 can be considered. In the case where the current collector is also arranged on the insulator 112, it is preferable that the current collector has a strip shape as well. By making such a strip shape, the contact area between the components can be ensured. However, other arrangement modes may be used. For example, the contact portion of each component may be arranged in a saw-like or wavy manner to increase the contact area and improve battery characteristics.

  The size of each component should be determined according to the size of the battery. If a large-capacity battery is to be manufactured, it is preferable that the positive electrode active material portion 102 and the negative electrode active material portion 106 have a certain size. If a high-power battery is to be manufactured, it is preferable to reduce the width of each component and arrange the components on the insulator so that many batteries are connected in series. The thickness of each constituent element is generally about 5 to 30 μm if the constituent element is manufactured using an ink jet method described later. However, it is not excluded that the thickness is out of this range. Note that the components disposed on the insulator 112 may have different shapes or sizes.

  The insulator 112 in which the components of the battery are arranged is not particularly limited as long as the components are fixed and have insulating properties. For example, an insulating plate made of polypropylene, polyethylene, polyethylene terephthalate, polyimide, or the like is used. The insulator 112 only needs to have a size such that the structure of the battery can be arranged. The thickness of the insulator is not particularly limited. From the viewpoint of reducing the volume of the entire battery, the insulator 112 is preferably thinner. In some cases, the insulator 112 may be formed from a flexible material, and may be deformed according to the portion where the shape of the battery is arranged.

  In order to arrange the positive electrode active material part 102, the solid polymer electrolyte part 104, and the negative electrode active material part 106 in a desired shape, an inkjet method described in detail later is preferably used. That is, the positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part include a large number of liquids containing the constituent elements of the positive electrode active material part, the solid polymer electrolyte part, or the negative electrode active material part, or the raw materials of the constituent elements. It is formed by an ink jet method in which particles are ejected as particles and adhered to a predetermined position. For example, in order to form the positive electrode active material part on the insulator, a positive electrode ink including components of the positive electrode active material part is prepared, and the positive electrode ink is sprayed on a desired portion of the current collector using an ink jet method. And the formed coating film is dried and it is set as a positive electrode active material part.

  A voltage detection pattern 114 for detecting the voltage of each unit battery may be formed in the battery as needed (FIG. 3). The voltage detection pattern 114 may be connected to a current collector. Note that the battery detection pattern 114 can be formed by an ink jet method using a current collector ink used for producing a current collector. The pattern may be formed using a conductive material such as conductive carbon. Alternatively, an insulating plate in which a voltage detection pattern is previously formed on an insulating plate may be prepared, and a battery may be formed on the insulating plate.

  The battery of the present invention is preferably a lithium secondary battery in consideration of application to a vehicle. Further, the battery of the present invention may be used alone, or may be connected in series, in parallel, or a combination of series and parallel to constitute an assembled battery. The assembled battery may be further connected in series, in parallel, or a combination of series and parallel to form a composite assembled battery.

  The number of batteries and the manner of connection in the assembled battery and the composite assembled battery are determined according to the output and capacity required for the battery. When an assembled battery or a composite assembled battery is configured, the stability as a battery is increased as compared with a unit cell. By configuring the assembled battery or the composite assembled battery, the influence on the entire battery due to deterioration of one cell can be reduced.

  The battery of the present invention is preferably mounted on a vehicle. Since the battery of the present invention is small and has high output, the occupied volume of the power source in the vehicle is reduced, and it can contribute to the improvement of the fuel consumption of the vehicle.

  Then, the manufacturing method of the battery of this invention is demonstrated.

  The battery manufacturing method according to the present invention includes ejecting a positive electrode ink containing a positive electrode active material, an electrolyte ink containing a polymer electrolyte or a polymer electrolyte raw material, and a negative electrode ink containing a negative electrode active material as a large number of particles using an inkjet method. In this way, the positive electrode active material part, the solid polymer electrolyte part and the negative electrode active material part are formed on the same insulator.

  Conventionally, electrodes have been formed using a doctor blade or a coater. However, it is difficult to arrange a desired component at a desired location with high accuracy using these. If the inkjet method is used, a battery having a shape as shown in FIG. 1 or a battery having a more complicated shape can be easily manufactured.

  The ink jet method means a printing method in which liquid ink is ejected from a nozzle and ink is attached to an object. For example, the active material portion is formed by ejecting a liquid containing an active material as a large number of particles and attaching it to a predetermined location. 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.

  The piezo method is a method in which ink is ejected from nozzles by deformation of a piezo element that is arranged at the bottom of an ink chamber that stores ink and deforms when an electric current flows. The thermal ink jet method is a method in which ink is heated by a heat-generating heater, and the ink is ejected with the energy of steam explosion when the ink is vaporized. The bubble jet (registered trademark) method is a method in which ink is ejected by the energy of steam explosion when the ink is vaporized, similarly to the thermal ink jet method. The thermal ink jet method and the bubble jet (registered trademark) method are different in the portion to be heated, but the basic principle is the same. The ink jet method is a very well-known technique at present. If an ink jet system is used, a battery with a precise pattern can be manufactured. Moreover, design changes can be made freely on the computer.

  In order to form a battery using the inkjet method, ink for forming each component of the battery is prepared. If the positive electrode active material part is to be formed, a positive electrode ink containing components of the positive electrode active material part is prepared. If the negative electrode active material part is to be formed, a negative electrode ink containing components of the negative electrode active material part is prepared. If the solid polymer electrolyte part is to be formed, an electrolyte ink containing a polymer electrolyte or a polymer electrolyte raw material is prepared. For example, the positive electrode ink contains at least a positive electrode active material. In addition, the positive electrode ink may contain a conductive additive, a lithium salt, a solvent, and the like. In order to improve the ionic conductivity of the positive electrode, a polymer electrolyte raw material that becomes a polymer electrolyte by polymerization and a polymerization initiator may be included in the positive electrode ink.

The active material is not particularly limited in the present application. Examples of the positive electrode active material include Li—Mn complex oxides such as LiMn ₂ O ₄ and Li—Ni complex oxides such as LiNiO ₂ . In some cases, two or more positive electrode active materials may be used in combination. Examples of the negative electrode active material include a crystalline carbon material and an amorphous carbon material. Specific examples include natural graphite, artificial 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.

  A conductive support means the additive mix | blended in order to improve the electroconductivity of an active material part. Examples of the conductive aid include carbon powder such as graphite.

Examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (SO ₂ C ₂ F ₅ ) _{2 and the} like.

  Examples of the solvent include acetonitrile. When blending the polymer electrolyte raw material, a compound capable of dissolving the polymer electrolyte raw material is used. In order to improve the energy density of the formed battery, the lower the solvent content, the better.

  Examples of the polymer electrolyte include a polymer having a heteroatom having a strong polarity such as an oxygen atom or a nitrogen atom in the molecule, such as polyether, polyester, polyamine, and polysulfide. More specifically, polyethylene oxide, polypropylene oxide, copolymers thereof, and the like can be used. When the battery is a lithium secondary battery, a lithium salt may be contained in the solid polymer electrolyte part. However, since the polymer electrolyte is a polymer, if the polymer electrolyte is contained in the ink, the viscosity of the ink increases, and there is a possibility that printing using the ink jet apparatus cannot be performed. In that case, a polymer electrolyte raw material that becomes a polymer electrolyte by polymerization may be blended in the ink, a coating film may be formed, polymerized, and then synthesized with the polymer electrolyte. Examples of the polymer electrolyte raw material include macromers of ethylene oxide and propylene oxide.

  The polymerization initiator is blended in order to act on the crosslinkable group of the polymer electrolyte raw material and advance the crosslinking reaction. Depending on the external factor for acting as an initiator, it is classified into a photopolymerization initiator, a thermal polymerization initiator and the like. Examples of the polymerization initiator include benzyl dimethyl ketal.

  The compounding ratio of the components contained in the ink is not particularly limited. However, the viscosity of the ink should be low enough to apply the inkjet method. Examples of the method for keeping the viscosity low include a method for increasing the amount of the solvent and a method for increasing the temperature of the ink. You may improve a polymer electrolyte raw material and another compound so that a viscosity may become low. Preferably, the viscosity of each ink supplied to the ink jet apparatus is adjusted to about 0.1 to 50 cP. However, if the amount of the solvent is increased too much, the amount of the active ingredient per unit volume decreases, so the amount of the solvent should be minimized. For example, when the positive electrode active material part is formed, the positive electrode active material is preferably contained in an amount of 15 to 60% by mass with respect to the total mass of the positive electrode ink. When a polymer electrolyte raw material is blended, the preferable content of the polymer electrolyte raw material is 10 to 60% by mass.

  The current collector may also be manufactured by an inkjet method. In order to form the current collector by an ink jet method, a current collector ink containing conductive metal particles is ejected onto the insulator as a large number of particles using the ink jet method. The current collector ink is made of metal fine particles, an ion insulating polymer, a solvent, and the like. The metal fine particles are used to ensure the electronic conductivity of the current collector. Specifically, the metal fine particles are made of the material exemplified above as a current collector, such as aluminum, copper, and stainless steel. The particle size of the metal fine particles is generally about 10 to 30 μm. The ion insulating polymer is blended so that ions that mediate movement of electrons do not pass through the current collector. Specifically, the ion insulating polymer is made of a material in which an acrylic resin is dissolved. An ion insulating polymer raw material may be blended and ejected onto an insulator, and then the raw material may be polymerized to obtain an ion insulating polymer. Examples of the solvent contained in the current collector ink include acetonitrile. When blending the polymer electrolyte raw material, a compound capable of dissolving the polymer electrolyte raw material is used. In order to improve the energy density of the formed battery, the lower the solvent content, the better.

  The blending amount of each component in the current collector ink is not particularly limited, but the metal fine particles are preferably contained in an amount of 2 to 20% by mass with respect to the total mass of the current collector ink. When the ion insulating polymer or its raw material is blended, the total amount of the ion insulating polymer and its raw material is preferably 5 to 30% by mass.

  When ink is prepared, a battery is produced using these. The ejection order of each ink is not particularly limited. For example, when forming the pattern shown in FIG. 1, the ink may be ejected in the order of the current collector 110, the positive electrode active material portion 102, the solid polymer electrolyte portion 104, and the negative electrode active material portion 106. If there is no problem even if a plurality of inks are ejected at a time, a plurality of inks may be ejected simultaneously.

  When the battery is manufactured, the active material portion, the solid polymer electrolyte portion, and the current collector pattern are determined in advance as required. If a system in which the active material part and the solid polymer electrolyte part are formed on the basis of an image created on a computer, the design can be easily changed. Pattern determination using a computer and production of an active material portion and a solid polymer electrolyte portion are basically the same as image creation and printout operations using computers and printers that are generally widely known.

  First, the insulator 112 is supplied to the inkjet device. The ink jet method is not particularly limited. As described in the examples, necessary improvements may be made depending on the ink used. When it is difficult to supply the insulator 112 alone to the ink jet apparatus, a method of attaching the insulator 112 to a medium such as paper and supplying the same to the ink jet apparatus may be used. Then, ink is ejected to the insulator 112 by an ink jet method and attached to the insulator 112. The amount of ink ejected from the nozzles of the ink jet apparatus is very small, and an approximately equal volume can be ejected. Usually, the volume of the particles ejected from the ink jet apparatus is in the range of 1 to 100 picoliters.

  If the thickness of the component is insufficient by only attaching the particles once by the ink jet apparatus, the thickness may be increased by attaching the particles twice or more at the same location. That is, it is a repeated coating with the same material. By using such a method, the thickness of each component can be increased.

  After the ink coating is formed by the inkjet method, the solvent is removed by drying. If a polymer electrolyte raw material is blended, a polymerization treatment is performed in order to form a polymer electrolyte by polymerization. For example, when a photopolymerization initiator is added, for example, ultraviolet rays are irradiated to initiate polymerization.

  In an industrial production process, in order to improve productivity, an electrode larger than the final battery size may be produced and a step of cutting the electrode into a predetermined size may be employed.

Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, the following materials were used as a polymer electrolyte raw material, a lithium salt, a positive electrode active material, a negative electrode active material, a photopolymerization initiator, and an ion insulating polymer unless otherwise specified.
Polymer electrolyte raw material: Macromer of ethylene oxide and propylene oxide Lithium salt: LiN (SO ₂ C ₂ F ₅ ) ₂ (hereinafter abbreviated as “BETI”)
Positive electrode active material: spinel type LiMn ₂ O ₄ (average particle size: 0.6 μm)
Negative electrode active material: pulverized graphite (average particle size: 0.7 μm)
Photopolymerization initiator: benzyl dimethyl ketal Ion insulating polymer: acrylic resin The polymer electrolyte raw material was synthesized according to the method described in JP-A No. 2002-110239. The preparation, printing, and battery assembly of the negative electrode ink, the positive electrode ink, the electrolyte ink, and the current collector ink were performed in a dry atmosphere with a dew point of −30 ° C. or lower.

<Preparation of positive electrode ink>
Positive electrode active material (7% by mass), acetylene black (2% by mass) as a conductive material, polymer electrolyte material (4% by mass), lithium salt (2% by mass), and photopolymerization initiator (based on polymer electrolyte material) 0.1 wt%) was prepared, and acetonitrile (85 wt%) was added as a solvent thereto. This was sufficiently stirred to prepare a slurry as a positive electrode ink. The viscosity of this ink was about 3 cP.

<Preparation of negative electrode ink>
A negative electrode active material (9% by mass), a polymer electrolyte raw material (4% by mass), a lithium salt (2% by mass), and a photopolymerization initiator (0.1% by mass with respect to the polymer electrolyte raw material) were prepared, Acetonitrile (85 mass%) was added to these as a solvent. This was sufficiently stirred to prepare a slurry as negative electrode ink. The viscosity of this ink was about 3 cP.

<Preparation of electrolyte ink>
A polymer electrolyte raw material (15% by mass), a lithium salt (8% by mass), and a photopolymerization initiator (0.1% by mass with respect to the polymer electrolyte raw material) were prepared, and acetonitrile (77% by mass) was used as a solvent. ) Was added. This was sufficiently stirred to prepare a slurry as an electrolyte ink. The viscosity of this ink was 2 cP.

<Preparation of positive electrode current collector ink>
Aluminum fine particles (5% by mass; average particle size 50 nm) and an ion insulating polymer (10% by mass) were prepared, and acetone (85% by mass) was added as a solvent thereto. This was sufficiently stirred to prepare a slurry as a positive electrode current collector ink.

<Preparation of negative electrode current collector ink>
Copper fine particles (5% by mass; average particle size 50 nm) and an ion insulating polymer (10% by mass) were prepared, and acetone (85% by mass) was added thereto as a solvent. This was sufficiently stirred to prepare a slurry as a negative electrode current collector ink.

<Example 1>
A battery was prepared according to the following procedure using the prepared ink and a commercially available ink jet printer. The inkjet printer was controlled by a commercially available computer and software. In preparing the negative electrode active material part, the polymer electrolyte part, the positive electrode active material part, and the current collector, the prepared negative electrode ink, electrolyte ink, positive electrode ink, positive electrode current collector ink, and negative electrode current collector ink were prepared. Each was used. The negative electrode active material part, the polymer electrolyte part, and the positive electrode active material part were produced by printing a pattern created on a computer using an inkjet printer.

  When the above ink is used, there is a problem that acetonitrile as a solvent dissolves plastic parts in the ink introduction portion of the ink jet printer. Therefore, the parts in the ink introduction part were replaced with metal parts, and ink was supplied directly from the ink reservoir to the metal parts. Further, since there was a concern that the viscosity of the ink was low and the active material was precipitated, the ink reservoir was always stirred using a rotary blade.

  A positive ink, negative ink, electrolyte ink, and current collector ink are introduced into the modified ink jet printer, and a predetermined pattern created on a computer is formed on a polypropylene plate (thickness: 1 mm) as an insulator. Printed on. After printing, in order to dry the solvent, drying was performed in a vacuum oven at 60 ° C. for 2 hours. In order to polymerize the polymer electrolyte raw material, ultraviolet rays were irradiated for 20 minutes in a vacuum after drying.

  The basic pattern of the formed battery was such that six cells were joined in series in the pattern of FIG. That is, the charging / discharging reaction part 108 was repeated 6 times through the current collector 110, and the current collector was arranged at both ends. The positive electrode active material part 102, the solid polymer electrolyte part 104, the negative electrode active material part 106, and the current collector 110 were each 1 cm wide × 20 cm long × 20 μm thick. The size of the entire portion where the positive electrode active material part, the solid polymer electrolyte part, the negative electrode active material part, and the current collector are formed is 25 cm wide × 20 cm long × 20 μm thick. Therefore, the battery volume is 1 cc. The current collector existing between the positive electrode active material part and the negative electrode active material part is a two-layered structure including a positive electrode current collector adjacent to the positive electrode active material part and a negative electrode current collector adjacent to the negative electrode active material part. The structure. The positive electrode current collector was formed using a positive electrode current collector ink, and the negative electrode current collector was formed using a negative electrode current collector ink. The size of the positive electrode current collector and the negative electrode current collector was 0.5 cm wide × 20 cm long × 20 μm thick, respectively.

  Leads were attached to the current collectors at both ends, and charging / discharging was performed. In addition, charge / discharge was performed in a dry atmosphere with a dew point of −50 ° C. or lower. The charging / discharging conditions were charging: 25.2 V, 10 μA, discharging: 15.0 V, 10 μA. The battery capacity at this time was 12 mAh.

<Example 2>
A voltage detection pattern was formed on the battery produced in Example 1 using a positive electrode current collector ink or a negative electrode current collector ink by an inkjet method, and a battery of the type shown in FIG. 3 was obtained. Using the voltage detection pattern of this battery, charging / discharging was performed while measuring the voltage.

  At the end of charging, the voltage of each single cell was 4.2V, and it was confirmed that the voltage of the entire battery was 25.2V. Moreover, at the time of discharge, it has confirmed that the voltage of each single cell was 2.5V, and the voltage of the whole battery was 15.0V.

  Thus, by using the present invention, a battery having a small volume and a high voltage of 25.2 V was obtained. By using the present invention, the volume can be reduced to 1/100 or less as compared with the case of producing a battery having an equivalent voltage by using a battery generally known at present. Therefore, the present invention is very useful in applications where there is a strong demand for downsizing of batteries such as vehicles.

It is a top view of one Embodiment of the battery of this invention. It is a side view from the "II" direction of the battery of FIG. It is a top view of the battery in which the pattern for voltage detection was formed.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 102 ... Positive electrode active material part, 104 ... Solid polymer electrolyte part, 106 ... Negative electrode active material part, 108 ... Charge / discharge reaction part, 110 ... Current collector, 112 ... Insulator, 114 ... Voltage detection pattern.

Claims (5)

A positive electrode active material part;
A solid polymer electrolyte part adjacent to the positive electrode active material part;
A negative electrode active material part adjacent to the solid polymer electrolyte part,
The positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part are juxtaposed on the same insulator ,
A bipolar battery in which a charge / discharge reaction part composed of the positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part is repeatedly arranged via a current collector .   The battery according to claim 1, wherein the positive electrode active material part, the solid polymer electrolyte part, and the negative electrode active material part have a band shape. Is a lithium secondary battery, battery according to claim 1 or 2. It is a manufacturing method of the battery according to any one of claims 1 to 3,
A positive electrode ink containing a positive electrode active material, an electrolyte ink containing a polymer electrolyte or a polymer electrolyte raw material, and a negative electrode ink containing a negative electrode active material are ejected as a large number of particles using an ink jet method on the same insulator. A battery manufacturing method for forming a positive electrode active material part, a solid polymer electrolyte part, and a negative electrode active material part. A positive electrode ink containing a positive electrode active material, an electrolyte ink containing a polymer electrolyte or a polymer electrolyte raw material, and a negative electrode ink containing a negative electrode active material are ejected as a large number of particles using an ink jet method on the same insulator. , the positive electrode active material portion, and forming a solid polymer electrolyte portion and the negative electrode active material portion,
A step of further forming a current collector on the insulator by ejecting a current collector ink containing conductive metal particles as a large number of particles using an inkjet method; and
A method for producing a battery.

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