JP4817778B2 - Battery case and battery, and electric double layer capacitor case and electric double layer capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent electrolyte leakage caused by gaps generated in a battery or an electrical double layer capacitor, prevent damage to an outside electric circuit board caused by the electrolyte leakage, and make easy the connection to the outside electric circuit board. <P>SOLUTION: This case for battery is equipped with a ceramic substrate 1 in which a recessed part 1a is formed in the central part of the upper surface and a step 1c is formed between an inside surface and a bottom surface of the recessed part 1a, a first metallized layer 1d formed on the upper surface of the step 1c, a second metallized layer 1b formed on the bottom surface of a hole part 10 formed on the bottom surface of the recessed part 1a, a first conductor layer 1f and a second conductor layer 1e installed on the lower surface of the ceramic substrate 1, a first inside conductor 2d formed from the first metallized layer 1d to the first conductor 2d, and a second inside conductor 2b formed from the second metallized layer 1b to the second conductor layer 1e, and a resin layer B-5 containing conductive particles is formed from the upper surface of the second metallized layer 1b to the bottom surface of the recessed part 1a. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is a thin battery case and battery, and an electric double layer that can be used for communication equipment such as a mobile phone and can be easily connected to an external electric circuit board and can effectively prevent leakage of electrolyte. The present invention relates to a capacitor case and an electric double layer capacitor.

  In recent years, as portable devices typified by mobile phones, laptop computer terminals, camera-integrated video tape recorders, and the like have developed remarkably, their size and weight have been reduced. In addition, the demand for batteries as power sources for these portable devices continues to increase, and research to increase the energy density of batteries is also actively conducted. In particular, lithium batteries have a small atomic weight and ionization energy. Since the battery uses a large amount of lithium, it has been actively studied as a battery that can obtain a high energy density and can be recharged, and has been widely used to date, including power supplies for portable devices.

  Such a battery has a structure in which a positive electrode and a negative electrode are inserted into a battery case can through a separator made of an insulating sheet, and an organic electrolyte is injected therein and sealed.

The positive electrode is generally made of, for example, a metal oxide as a positive electrode active material and a conductive material added thereto. As the positive electrode active material, lithium cobaltate (LiCoO ₂ ) or lithium manganate (LiMn ₂ O _4). In addition, examples of the conductive material include acetylene black (AB) and graphite. On the other hand, the negative electrode is obtained by adding a conductive material to a negative electrode active material, and as the negative electrode active material, for example, a carbon material such as coke or carbon fiber is used.

The charge / discharge voltage of the positive electrode active material made of LiCoO ₂ or LiMn ₂ O ₄ is about 4V. On the other hand, the charge / discharge voltage of the negative electrode active material made of a carbon material or the like is around 0 V. By combining these positive electrode active material, negative electrode active material, and electrolyte, the lithium battery has a high discharge voltage of about 3.5 V. Have achieved.

  The positive electrode and negative electrode of the battery are made into a slurry by adding the above conductive material to the positive electrode active material or the negative electrode active material, and further adding and mixing a binder such as polytetrafluoroethylene or polyvinylidene fluoride. In general, the sheet is formed into a sheet shape using a blade method, and then the sheet is cut into a circular shape, for example.

  Then, the positive electrode and the negative electrode thus produced are placed in the battery case through a separator made of a non-woven fabric made of polyolefin fiber having a heat resistant temperature of about 150 ° C. or a microporous membrane made of polyolefin. A battery is obtained by placing and injecting an electrolyte.

  Then, in order to further reduce the size and density of the battery thus manufactured, the development of a coin-type battery A has been advanced, and a disk-shaped positive electrode 11b is provided as shown in FIG. Further, for example, a positive electrode can 11 made of stainless steel and a negative electrode can 12 made of, for example, stainless steel provided with a disk-shaped negative electrode 12b are placed through a separator 14 impregnated with an electrolytic solution, and then made of, for example, an insulating polypropylene resin. A structure in which the periphery of the positive electrode can 11 and the periphery of the negative electrode can 12 are integrated through a gasket 15 is known. Charging / discharging in the positive electrode 11b and the negative electrode 12b is performed through lead portions of external connection terminal members attached to the positive electrode can 11 and the negative electrode can 12 (see, for example, Patent Documents 1 and 2 below).

  Further, in the electric double layer capacitor, in order to reduce the size and increase the density of the electric double layer capacitor, the first electrode can having the shape shown in FIG. A coin-type electric double layer capacitor A formed by crimping 11 and the second electrode can 12 has been developed.

The electric double layer capacitor A includes a first electrode can 11 made of, for example, stainless steel provided with a disk-shaped first electrode 11b, and a second electrode can 12 made of, for example, stainless steel provided with a second electrode 12b. In the state where the separator 14 containing the electrolyte is sandwiched between the first electrode 11b and the second electrode 12b, the edge of the first electrode can 11 and the edge of the second electrode can 12 are It is formed by caulking and joining to each other via a gasket 15. Charging / discharging in the first electrode 11b and the second electrode 12b is performed via an external connection terminal member attached to the first electrode can 11 and the second electrode can 12 (for example, Patent Document 3 below) 4).
JP 2000-106195 A (page 6-12, FIG. 1) JP 2002-198019 A (page 3-4, FIG. 1) Japanese Patent Laid-Open No. 2002-50551 JP 2003-100569 A

  However, when the conventional battery A as shown in Patent Documents 1 and 2 is exposed to a temperature cycle test (for example, −40 ° C. to 85 ° C.) having a temperature range of hundreds of degrees over a long period of time, When the gasket 15 made of polypropylene resin, the positive electrode can 11 and the negative electrode can 12 are different in thermal expansion coefficient, a gap is formed at the boundary between the gasket 15 and the caulked portion around the positive electrode can 11 and the negative electrode can 12. There is a problem that the liquid leaks, which causes the battery performance of battery A to deteriorate, and the leaked electrolyte causes corrosion and breakage of the copper (Cu) wiring on the external electric circuit board. Or, there has been a problem in that moisture enters the inside through this gap and deteriorates the battery performance.

  Also in the conventional electric double layer capacitor A as shown in Patent Documents 3 and 4, as in the conventional battery, a temperature cycle test (for example, −40 ° C. to When exposed to 85 ° C), there is a case where a gap is formed at the joint portion of the battery case that has been caulked in the same manner, so that the electrolyte may leak or moisture may enter, which deteriorates the performance of the electric double layer capacitor. Further, there has been a problem that the Cu wiring on the external electric circuit board is corroded and disconnected by the leaked electrolyte.

  In addition, in order to perform charging / discharging, the conventional battery A and electric double layer capacitor A must be connected to lead portions on the top and bottom and connected to the external electric circuit board. Had the problem that the connection of was complicated.

  In addition, the conventional battery A and electric double layer capacitor A must have a circular shape in plan view in order to securely caulk the periphery of the gasket 15, the positive electrode can 11 and the negative electrode can 12 without any gaps. Various shapes such as a square shape could not be obtained. In recent years, with the miniaturization of devices, the market demand for miniaturization and space saving of batteries and electric double layer capacitors has increased, for example, batteries and electric double layers for mounting on an external electric circuit board in a space-saving manner. It has not been possible to meet the demand for a square shape of the capacitor in plan view.

  Therefore, the present invention has been completed in view of the above problems, and its purpose is to cause a gap in the battery and the electric double layer capacitor due to long-term use, so that the electrolyte leaks and deteriorates the battery performance. The battery case and the battery and the electricity, which are easy to connect to the external electric circuit board without damaging the external electric circuit board, can be miniaturized, and have excellent mass productivity The object is to provide a case for a double layer capacitor and an electric double layer capacitor.

  The battery case of the present invention includes a ceramic base having a recess formed in the center of the upper surface and a step formed between one inner surface and the bottom of the recess, and a first formed on the upper surface of the step. A metallized layer; a second metallized layer formed on the bottom surface of the hole formed on the bottom surface of the recess; a first conductor layer and a second conductor layer formed on the bottom surface of the ceramic substrate; A first inner conductor formed from the first metallized layer to the first conductor layer, and a second inner conductor formed from the second metallized layer to the second conductor layer. And a resin layer containing conductive particles is formed from the upper surface of the second metallized layer to the bottom surface of the recess.

  The battery case of the present invention includes a ceramic base having a recess formed in the center of the upper surface, a first metallization layer formed around the recess on the upper surface of the ceramic base, and a bottom surface of the recess. A second metallized layer formed on the bottom surface of the formed hole, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and the first metallized layer to the first metallized layer. A first inner conductor formed over the conductor layer, and a second inner conductor formed from the second metallization layer to the second conductor layer, and the second metallization layer A resin layer containing conductive particles is formed from the upper surface to the bottom surface of the recess.

  The battery of the present invention includes a battery case having the above-described configuration, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the positive electrode plate. A negative electrode plate placed in close contact with an insulating sheet impregnated with a liquid and having one end electrically connected to the first metallized layer; and the upper surface of the ceramic substrate covering the recess. And a lid attached in contact with the negative electrode plate.

  The battery of the present invention includes a battery case having the above-described configuration, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the positive electrode plate. A negative electrode plate placed in close contact with an insulating sheet impregnated with an electrolyte solution, and bonded to the upper surface of the ceramic base so as to cover the recess, and at least the lower main surface is electrically conductive And a lid that is in contact with and electrically connected to the negative electrode plate.

  The electric double layer capacitor case of the present invention is formed on the upper surface of the step with a ceramic base having a recess formed at the center of the upper surface and a step formed between one inner side surface and the bottom surface of the recess. A first metallized layer; a second metallized layer formed on the bottom surface of the hole formed on the bottom surface of the recess; and a first conductor layer and a second conductor layer formed on the bottom surface of the ceramic substrate. And a first inner conductor formed from the first metallized layer to the first conductor layer, and a second inner conductor formed from the second metallized layer to the second conductor layer. And a resin layer containing conductive particles is formed from the top surface of the second metallization layer to the bottom surface of the recess.

  The case for an electric double layer capacitor of the present invention includes a ceramic base having a recess formed at the center of the upper surface, a first metallization layer formed around the recess on the upper surface of the ceramic base, and a bottom surface of the recess. A second metallization layer formed on the bottom surface of the hole formed in the first substrate, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and the first metallization layer to the first metallization layer. A first inner conductor formed over one conductor layer and a second inner conductor formed between the second metallization layer and the second conductor layer, the second metallization layer. A resin layer containing conductive particles is formed from the top surface to the bottom surface of the recess.

  The electric double layer capacitor of the present invention includes an electric double layer capacitor case having the above-described configuration, a first electrode placed on the upper surface of the resin layer and electrically connected to the second metallization layer, A second electrode mounted on an upper surface of the first electrode in close contact with an insulating sheet impregnated with an electrolyte and having one end electrically connected to the first metallized layer; and the ceramic A cover body is provided on the upper surface of the base so as to cover the recess and to be in contact with and attached to the second electrode.

  The electric double layer capacitor of the present invention includes an electric double layer capacitor case having the above-described configuration, a first electrode placed on the upper surface of the resin layer and electrically connected to the second metallization layer, A second electrode placed so as to be in close contact with the upper surface of the first electrode via an insulating sheet impregnated with an electrolyte, and is bonded to the upper surface of the ceramic base so as to cover the recess and at least The side main surface is conductive, and includes a lid body that is in contact with and electrically connected to the second electrode.

  The first battery case or the first electric double layer capacitor case according to the present invention includes a ceramic base body in which a recess is formed at the center of the upper surface and a step is formed between one inner side surface and the bottom surface of the recess. The first metallized layer formed on the upper surface of the step, the second metallized layer formed on the bottom surface of the hole formed on the bottom surface of the recess, and the first conductor layer formed on the lower surface of the ceramic substrate And a second conductor layer, a first inner conductor formed from the first metallization layer to the first conductor layer, and a second inner conductor formed from the second metallization layer to the second conductor layer And a resin layer containing conductive particles is formed from the top surface of the second metallization layer to the bottom surface of the recess, so that the electrolyte solution is formed by a ceramic substrate that is excellent in airtightness and heat resistance. Contained And for that, not that electrolyte leakage occurred gap even when exposed to a temperature cycle test, it is possible to satisfactorily accommodate the electrolyte. Further, even if the shape of the ceramic substrate in plan view is changed to various shapes such as a quadrangle, the hermeticity is maintained, so that the ceramic substrate can be formed in various shapes according to market demands, and the battery or electric double layer capacitor It is possible to prevent moisture, oxygen, or the like that deteriorates performance from entering the electrolyte from the outside.

  The second metallized layer is formed on the bottom surface of the hole formed on the bottom surface of the recess, and the resin layer containing conductive particles is formed from the top surface of the second metallized layer to the bottom surface of the recess. Therefore, the corrosive electrolyte is blocked by the resin layer containing conductive particles and does not come into contact with the second metallized layer, and the surface protection of the second metallized layer against the electrolyte can be simplified. it can.

  In addition, since the resin layer containing conductive particles is in contact with the corner between the hole and the bottom surface of the recess and the corner between the bottom surface and the side surface of the recess, the electrolytic solution is between the resin layer and the ceramic substrate. It is difficult to enter through a slight gap.

  In addition, since the electrolytic solution is less likely to enter the site where the second metallized layer is formed, it is possible to effectively prevent the electrolyte from leaking from the site where the second metallized layer is formed to the outside through the second internal conductor. it can.

  The second battery case or electric double layer capacitor case of the present invention includes a ceramic base having a recess formed in the center of the upper surface, and a first metallization layer formed around the recess on the upper surface of the ceramic base. The second metallization layer formed on the bottom surface of the hole formed on the bottom surface of the recess, the first conductor layer and the second conductor layer formed on the bottom surface of the ceramic base, and the first metallization layer. A first inner conductor formed over the first conductor layer, and a second inner conductor formed between the second metallization layer and the second conductor layer, and an upper surface of the second metallization layer. Since the resin layer containing conductive particles is formed from the bottom of the recess to the bottom of the recess, the electrolyte solution is accommodated by the ceramic substrate that is excellent in airtightness and heat resistance. Not be electrolyte leakage occurred gap even when exposed to, it can be satisfactorily accommodate the electrolyte. Further, even if the shape of the ceramic substrate in plan view is changed to various shapes such as a quadrangle, the hermeticity is maintained, so that the ceramic substrate can be formed in various shapes according to market demands, and the battery or electric double layer capacitor It is possible to effectively suppress moisture, oxygen, or the like that deteriorates performance from entering the electrolyte from the outside.

  Moreover, since it is not necessary to form a level | step difference between one inner side surface and bottom face of a recessed part, the volume of the battery case can be made still smaller.

  The second metallized layer is formed on the bottom surface of the hole formed on the bottom surface of the recess, and the resin layer containing conductive particles is formed from the top surface of the second metallized layer to the bottom surface of the recess. Therefore, the corrosive electrolyte is blocked by the resin layer containing conductive particles and does not come into contact with the second metallized layer, and the surface protection of the second metallized layer against the electrolyte can be simplified. it can.

  In addition, since the resin layer containing conductive particles is in contact with the corner between the hole and the bottom surface of the recess and the corner between the bottom surface and the side surface of the recess, the electrolytic solution is between the resin layer and the ceramic substrate. It is difficult to enter through a slight gap.

  In addition, since the electrolytic solution is less likely to enter the site where the second metallized layer is formed, it is possible to effectively prevent the electrolyte from leaking from the site where the second metallized layer is formed to the outside through the second internal conductor. it can.

  The battery of the present invention includes the first battery case of the present invention, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the positive electrode plate. A negative electrode plate that is placed in close contact with an insulating sheet impregnated with an electrolyte and electrically connected to the first metallized layer, and a negative electrode plate that covers the recess on the upper surface of the ceramic substrate. A lid that is in contact with and attached to the electrode plate, so that the first battery case of the present invention is highly airtight and reliable, with a predetermined battery performance that is normal over a long period of time. It can be operated stably.

  The battery of the present invention includes the second battery case of the present invention, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallized layer, and the positive electrode plate A negative electrode plate placed in close contact with an upper surface of the ceramic substrate through an insulating sheet impregnated with an electrolyte solution, and bonded to the upper surface of the ceramic base so as to cover the recess, and at least the lower main surface is electrically conductive And having a lid that is in contact with and electrically connected to the negative electrode plate, the airtight reliability using the second battery case according to the present invention is high, and is a predetermined value. The battery performance can be operated normally and stably over a long period of time.

  In addition, the inner surface of the concave portion of the base body is formed by bringing a lid whose at least the lower main surface is conductive into contact with the negative electrode plate to be electrically connected and joining the upper surface of the base body so as to cover the concave portion. The lid can function as the negative electrode of the battery without providing a step between the bottom surface and the bottom surface. As a result, the base can be reduced in size, and the battery element can be easily mounted inside the recess of the base.

  The electric double layer capacitor of the present invention includes the first electric double layer capacitor case of the present invention, a first electrode placed on the upper surface of the resin layer and electrically connected to the second metallization layer, A second electrode having an upper surface of the first electrode in close contact with an insulating sheet impregnated with an electrolyte and having one end electrically connected to the first metallized layer; and a ceramic substrate Airtight reliability using the first electric double layer capacitor case according to the present invention. Therefore, it is possible to operate normally and stably over a long period of time with a predetermined electric double layer capacitor performance.

  The electric double layer capacitor of the present invention includes a second electric double layer capacitor case of the present invention, a first electrode placed on the upper surface of the resin layer and electrically connected to the second metallization layer, A second electrode placed so as to be in close contact with the upper surface of the first electrode via an insulating sheet impregnated with an electrolyte, and is bonded to the upper surface of the ceramic substrate so as to cover the recess and at least the lower side Since the main surface is made conductive and includes a lid that is in contact with and electrically connected to the second electrode, the second electric double layer capacitor case of the present invention is used. It is possible to operate normally and stably over a long period of time with a predetermined electric double layer capacitor performance with high hermetic reliability.

  Further, at least one of the concave portions of the base body is formed by bringing a lid body having at least a lower main surface into contact with the second electrode to be electrically connected and joining the upper surface of the base body so as to cover the concave portion. The lid can function as the second electrode of the electric double layer capacitor without providing a step between the side surface and the bottom surface. As a result, the substrate can be reduced in size, and the electric double layer capacitor element can be easily mounted inside the recess of the substrate.

  The battery case or electric double layer capacitor case of the present invention will be described in detail below by taking the battery case as an example. 1A is a cross-sectional view showing an example of an embodiment of a battery case of the present invention, and FIG. 1B is a plan view of the battery case of FIG. 2A is a sectional view showing another example of the embodiment of the battery case of the present invention, and FIG. 2B is a plan view of the battery case of FIG. 3 shows still another example of the embodiment shown in FIGS. 1 and 2, and FIG. 3A is a cross-sectional view showing still another example of the embodiment of the battery case of the present invention. (B) shows a plan view of the battery case of (a). 4 shows still another example of the embodiment shown in FIGS. 1 and 2. In FIG. 4, (a) and (b) are still other examples of the embodiment of the battery case of the present invention. FIG. Hereinafter, the first embodiment of the battery case of the present invention is shown in FIG. 1, and the second embodiment of the battery case of the present invention is shown in FIG.

  In these drawings, 1 is a ceramic substrate, 1a is a recess, 1b is a second metallized layer, 1c is a step, 1d is a first metallized layer, 1e is a second conductor layer, 1f is a first conductor layer, 2b is a second inner conductor, 2d is a first inner conductor, 4 is a lid, 10 is a hole, and B-5 is a resin layer.

  In the first embodiment of the battery case of the present invention, a concave portion 1a having a rectangular parallelepiped shape, a prismatic shape, a cylindrical shape, or the like is formed at the center portion of the upper surface of the ceramic substrate 1, and one inner side surface and bottom surface of the concave portion 1a are formed. A step 1c is formed between the two. A first metallized layer 1d is formed on the upper surface of the step 1c, a hole 10 is formed on the bottom of the recess 1a, and a second metallized layer 1b is formed on the bottom of the hole 10. Furthermore, a first conductor layer 1f and a second conductor layer 1e are formed on the lower surface of the ceramic substrate 1, and a first inner layer formed from the first metallized layer 1d to the first conductor layer 1f. A conductor 2d and a second inner conductor 2b formed from the second metallized layer 1b to the second conductor layer 1e are formed. A resin containing conductive particles so as to cover the second metallized layer 1b and the upper surface of the recess 1a from the upper surface of the second metallized layer 1b on the bottom surface of the hole 10 formed on the bottom surface of the recess 1a to the recess 1a. Layer B-5 is formed.

Such a ceramic substrate 1 is made of ceramics such as an alumina sintered body and is manufactured as follows. For example, when the ceramic substrate 1 is made of an alumina sintered body, an organic material suitable for a raw material powder such as aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), magnesium oxide (MgO), calcium oxide (CaO), etc. A binder, a solvent, etc. are added and mixed to form a slurry. This slurry is made into a green sheet by a doctor blade method or a calender roll method and cut into a required size. Next, in order to form the recess 1a, the step 1c, the first and second inner conductors 2b and 2d, the first hole 10 and the like in a plurality of green sheets selected from them, an appropriate punching process is performed. .

  Then, through holes formed by drilling with a mold or the like in these green sheets are filled with a metal paste mainly composed of metal powder such as tungsten (W), or metal powder such as W is mainly composed. The first and second metallized layers 1d and 1b, the first and second inner conductors 2d and 2b, and the first and second conductor layers 1f and 1e are printed and applied to a predetermined portion. The ceramic substrate 1 is manufactured by forming a metal paste layer to be formed, then laminating green sheets on which these metal paste layers are formed, and firing at a temperature of about 1600 ° C.

  As shown in FIG. 1 (a), first and second conductor layers 1 f and 1 e are formed on the lower surface of the ceramic substrate 1. Since the first and second conductor layers 1f and 1e are formed on the lower surface of the ceramic substrate 1, the ceramic substrate 1 is easily placed on the upper surface of a flat external electric circuit board and soldered or the like. Since it can be connected to an electric circuit, the battery case is excellent in mass productivity of an external electric circuit board.

  As shown in FIG. 1 (a), a hole 10 is provided on the bottom surface of the recess 1a, a second metallized layer 1b is formed on the bottom surface of the hole 10, and the recess 1a is formed from the upper surface of the second metallized layer 1b. A resin layer B-5 containing conductive particles is formed so as to cover the top surface of the second metallized layer 1b and the bottom surface of the recess 1a.

  With this configuration, the corrosive electrolytic solution B-4 is blocked by the resin layer B-5 containing conductive particles and is not in direct contact with the second metallized layer 1b, and the electrolytic solution B of the second metallized layer 1b. Since surface protection such as plating for -4 can be simplified, the second metallized layer 1b can be formed at low cost by a simple process.

  Further, the path through which the electrolytic solution B-4 enters the second metallized layer 1b through a slight gap formed between the resin layer B-5 and the ceramic base 1 is the side surface of the concave portion 1a and the concave portion 1a. The length of the path extends along the bottom surface and the side surface of the hole portion 10, and the substantially perpendicular corner formed between the hole portion 10 around the hole portion 10 and the bottom surface of the recess portion 1a, and the recess portion 1a around the recess portion 1a. Since it passes through a substantially right angle formed between the bottom surface and the side surface, the path is bent, and the electrolytic solution B-4 hardly reaches the second metallized layer 1b.

  Further, since the electrolytic solution B-4 is less likely to enter the formation site of the second metallized layer 1b, the electrolytic solution B-4 passes through the second internal conductor 2b from the formation site of the second metallized layer 1b. It is possible to effectively prevent leakage to the outside.

  Further, when the battery element is installed so as to be embedded in the resin layer B-5, the battery element can be easily and efficiently installed at a predetermined position on the bottom surface of the battery case, and the battery element is difficult to be displaced after installation. Even when the battery is used over a long period of time or when it is used under a condition where an external force such as vibration is applied, the electrical connection between the battery element and the second metallized layer 1b is stable, and the battery is maintained at a predetermined battery performance for a long Can be operated normally and stably. Furthermore, since the contact area between the battery element and the resin layer B-5 is increased, the electrical resistance between the battery element and the resin layer B-5 can be reduced.

Further, since the resin layer B-5 has elasticity, even if the battery element is strongly pressed against the base body 1, it is buffered by the resin layer B-5, so that the base body 1 or the battery element is effectively prevented from being damaged. it can.

  Preferably, when the resin layer B-5 is provided on the upper surface of the first metallized layer 1b, as shown in FIG. 3, a groove 11 is provided around the hole 10 on the bottom surface of the concave portion 1a, and the resin layer B It is preferable to form −5 from the upper surface of the first metallized layer 1 b to the bottom surface of the recess 1 a so as to fill the hole 10 and the groove 11. With this configuration, it is possible to more reliably block the electrolytic solution B-4 that attempts to reach the first metallized layer 1b through a slight gap at the boundary surface between the ceramic substrate 1 and the resin layer B-5. That is, the distance of the path from the bottom surface of the recess 1a to the first metallized layer 1b via the boundary surface between the ceramic substrate 1 and the resin layer B-5 is increased, and the electrolytic solution B-4 is effectively blocked. In addition, a protrusion is formed between the hole 10 and the groove 11 on the bottom surface of the recess 1a, and the curved path formed by the protrusion is a boundary surface between the bottom surface of the recess 1a and the resin layer B-5. This is because the electrolytic solution B-4 that is about to reach the first metallized layer 1b through the above is surely blocked. As a result, the corrosive electrolyte B-4 is less likely to touch the first metallized layer 1b, and the electrolyte B-4 is more reliably prevented from leaking outside the battery B through the first internal conductor 2b. Can do.

  The first and second inner conductors 2d and 2b are formed only by through connection conductors perpendicular to the first and second conductor layers 1f and 1e in FIG. An internal wiring layer parallel to the second conductor layers 1f and 1e is formed in the middle, and the through wiring conductor perpendicular to the first and second conductor layers 1f and 1e is changed to the internal wiring layer and the vertical through wiring conductor. May be formed from the first metallized layer 1d to the first conductor layer 1f and from the second metallized layer 1b to the second conductor layer 1e, whereby an electric circuit is formed in the ceramic substrate 1. The first and second conductor layers 1 f and 1 e can be formed at suitable positions on the bottom surface of the ceramic substrate 1.

  Further, since the first and second inner conductors 2d and 2b are through-connection conductors formed inside the ceramic substrate 1, the upper end surfaces of the first and second inner conductors 2d and 2b are made of the same material. Since the first and second metallized layers 1d and 1b are connected to and covered with the first and second metallized layers 1d and 1b, the electrolyte enters even if a slight gap is generated between the first and second inner conductors 2d and 2b and the ceramic substrate 1. The risk of doing so is reduced.

  Further, the first and second metallized layers 1d and 1b are led out to the outer surface of the ceramic substrate 1 by an internal wiring layer formed between the layers of the ceramic green sheet, not the through-connection conductors, and the side conductor layers of the ceramic substrate 1 Is connected to the first and second conductor layers 1f and 1e via delamination at the portion of the ceramic green sheet where the internal wiring layer is formed (peeling caused by weak bonding force between the stacked green sheets) The electrolytic solution B-4 sealed in the concave portion 1a of the ceramic substrate 1 may enter a gap between the ceramic green sheets sandwiching the internal wiring layer generated thereby. However, since the first and second inner conductors 2d and 2b are formed by through connection conductors, there is no possibility of this.

  A first inner conductor 2d is formed from the first metallized layer 1d to the first conductor layer 1f, and a second inner conductor 2b is formed from the second metallized layer 1b to the second conductor layer 1e. However, preferably, a plurality of first inner conductors 2d and second inner conductors 2b are formed. With this configuration, it is possible to suppress an increase in resistance between the first metallized layer 1d and the first conductor layer 1f and between the second metallized layer 1b and the second conductor layer 1e. Connection reliability can be increased, and battery performance can be prevented from deteriorating.

  More preferably, the number of the second inner conductors 2b is smaller than the number of the first inner conductors 2d, and the total cross-sectional area of the second inner conductor 2b is larger than the total cross-sectional area of the first inner conductor 2d. Since the second inner conductor 2b is formed to be smaller than the first inner conductor 2d, it is preferable that the second inner conductor 2b is smaller than the first inner conductor 2d. The heat transmitted to the electrolyte in the concave portion can be suppressed. Therefore, even when the temperature of the bottom surface of the battery rises, the temperature change of the electrolytic solution can be suppressed as much as possible, and desired battery performance can always be exhibited. In addition, the resistance value of the first inner conductor 2d can be made closer to the resistance value of the second inner conductor 2b.

  The sum of the cross-sectional areas of the plurality of second inner conductors 2b is smaller than the sum of the cross-sectional areas of the plurality of first inner conductors 2d, but the cross-sectional areas of the individual second inner conductors 2b are smaller than the individual first inner conductors 2b. Since the cross-sectional area is slightly larger than the cross-sectional area of the internal conductor 2d and the number of the second internal conductors 2b is smaller than the number of the first internal conductors 2d, the total cross-sectional area of the plurality of second internal conductors 2b May be smaller than the sum of the cross-sectional areas of the plurality of first inner conductors 2d, or the cross-sectional areas of the individual first inner conductors 2d may be smaller than the cross-sectional areas of the individual second inner conductors 2b. Are the same or slightly larger in cross-sectional area, and the number of the first inner conductors 2d is not so much larger than that of the second inner conductor 2b, the total of the sectional areas of the plurality of second inner conductors 2b is the plurality of first inner conductors 2b. To be smaller than the total cross-sectional area of the inner conductor 2d It may be.

  Preferably, the cross-sectional area of each of the first inner conductors 2d is the same as or slightly larger than the cross-sectional area of each of the second inner conductors 2b. The temperature change of the liquid can be effectively suppressed, and the resistance value of the first inner conductor 2d longer than the second inner conductor 2b can be made closer to the resistance value of the second inner conductor 2b.

  Preferably, the first and second metallized layers 1d and 1b, the first and second inner conductors 2d and 2b, and the first and second conductor layers 1f and 1e are made of copper (Cu). It is good to contain. With this configuration, the electrical resistance values of the first and second metallized layers 1d and 1b, the first and second inner conductors 2d and 2b, and the first and second conductor layers 1f and 1e are lowered. It is possible to effectively prevent the battery performance from deteriorating.

  More preferably, the first and second metallized layers 1d and 1b, and the first and second conductor layers 1f and 1e are formed of a conductor layer containing 10% by volume to 70% by volume of Cu and 30% by volume to 90% of W. The first and second inner conductors 2d and 2b preferably contain 20% by volume to 80% by volume of Cu and W at a rate of 20% by volume to 80% by volume. It is preferable that the Cu content in the first and second inner conductors 2d and 2b is larger than that of the conductor layers to be the first and second metallized layers 1d and 1b and the first and second conductor layers 1f and 1e. . As a result, the first and second metallized layers 1d, 1b and the first and second conductive layers 1f, 1e can be effectively prevented from being corroded by the electrolytic solution, and the battery performance is deteriorated. Therefore, a battery that functions stably over a long period of time can be obtained.

The method for containing Cu in these conductor layers will be specifically described in the case of using ceramics mainly composed of Al ₂ O ₃ for the ceramic substrate 1. First, in order to form the ceramic substrate 1, a powder having an average particle size of 0.5 to 2.5 μm, preferably 0.5 to 2 μm is used as the Al ₂ O ₃ raw material powder as a main component. This is because if the average particle size is smaller than 0.5 μm, it is difficult to handle the powder, and the cost of the powder becomes higher. If it is larger than 2.5 μm, it becomes difficult to fire at a temperature of 1500 ° C. or less. This is because the Cu component of the conductor layer is evaporated.

Then, with respect to the _Al 2 _{O 3} powder, as a second component, the MnO ₂ 2 to 6% by weight, preferably added in a proportion of 3-5 wt%. In addition, as appropriate, as a third component, 0.4 to 8% by mass of SiO ₂ , MgO, CaO powder or the like, and as a fourth component, a metal powder or oxide powder of a transition metal such as W or Mo is used as a coloring component. It is added at a rate of 2% by mass or less in terms of conversion.

  And the sheet-like molded object (green sheet) for forming an insulating layer using this mixed powder is produced. The sheet-like molded body can be produced by a known molding method. For example, after preparing a slurry by adding an organic binder or solvent to the above mixed powder, it is formed by a doctor blade method, or an organic binder is added to the mixed powder, and sheet-like molding with a predetermined thickness is performed by press molding, rolling molding, etc. Or make a body.

  Containing 10 to 80% by volume of Cu powder having an average particle size of 1 to 10 μm and 20 to 90% by volume of W powder having an average particle size of 1 to 10 μm with respect to the sheet-like molded body thus prepared A conductor paste to be prepared is prepared, and this paste is printed and applied to each sheet-like molded body by a method such as screen printing or gravure printing, whereby Cu can be contained in these conductor layers.

  Further, the exposed surface of these conductor layers formed on the ceramic substrate 1 thus produced has a metal excellent in corrosion resistance and wettability with solder, specifically having a thickness of 1 to 12 μm. A nickel (Ni) layer and a gold (Au) layer having a thickness of 0.3 to 5 μm are preferably sequentially deposited by a plating method or the like. Thereby, in particular, it is possible to effectively suppress the first and second metallized layers 1d and 1b formed inside the battery case from being easily eluted into the electrolytic solution by the voltage due to charging and discharging. Further, the first and second conductor layers 1f and 1e have better wettability with solder, and the bonding strength with the wiring conductor on the external electric circuit board becomes stronger.

  If the thickness of the Ni layer is less than 1 μm, it becomes difficult to prevent the oxidative corrosion of each conductor layer made of metallization and to effectively prevent the metal component from eluting from each conductor layer. Tends to deteriorate. On the other hand, if the thickness of the Ni layer exceeds 12 μm, it takes a long time to form the plating, so that the mass productivity is likely to be lowered and the electric resistance is likely to be increased.

  Further, if the thickness of the Au layer is less than 0.3 μm, it is difficult to form an Au layer having a uniform thickness, and a portion where the Au layer is extremely thin or a portion where the Au layer is not formed is likely to occur. The effect of preventing oxidative corrosion and the wettability with solder are likely to decrease. On the other hand, if the thickness of the Au layer exceeds 5 μm, it takes a long time to form the plating, and the mass productivity tends to decrease.

  The first and second metallization layers 1d and 1b located inside the recess 1a are preferably formed with aluminum (Al) layers, and the electrolytic solution B-4 sealed inside the recess 1a. It can be difficult to be affected by. The aluminum layer is formed by a plating method such as an electrolytic plating method or an electroless plating method, or a vapor deposition method such as sputtering. The thickness is preferably 0.1-5 μm. If the thickness is less than 0.1 μm, it is difficult to form an aluminum layer having a uniform thickness, and it is easy to generate a portion where the aluminum layer is extremely thin or a portion where the aluminum layer is not formed. The wettability of the glass tends to decrease. On the other hand, if the thickness of the aluminum layer exceeds 5 μm, it takes a long time to form the plating or vapor deposition, and the mass productivity tends to be lowered.

  When the aluminum layer is vapor-deposited on the second metallized layer 1b, the vertical and horizontal dimensions of the hole 10 in plan view should be gradually increased toward the upper side of the hole 10. With this configuration, an aluminum layer can be easily formed by vapor deposition on the second metallized layer 1b, and an aluminum layer having a uniform thickness can be reliably formed. By protecting the surface of the second metallized layer 1b with such an aluminum layer and the like, and further forming the resin layer B-5, the second metallized layer 1b is more reliably protected against the electrolytic solution B-4. It will be a thing.

  Preferably, as shown in FIG. 3, a metal frame member 3 made of iron (Fe) -Ni-cobalt (Co) alloy, aluminum or the like is silver on the upper surface of the ceramic substrate 1 so as to surround the recess 1a. It is preferable to braze via (Ag) brazing, aluminum (Al) brazing or the like. With this configuration, by placing a metal lid 4 on the frame-like member 3 and adopting a welding method such as a seam welding method for the lid 4, the concave portion 1 a of the ceramic substrate 1 can be reliably and efficiently operated. The inside can be hermetically sealed.

  Further, in this case, a metallized layer made of W or the like is formed on a portion where the frame-like member 3 on the upper surface of the ceramic substrate 1 is brazed, and the surface thereof is preferably plated with Ni or the like. With this configuration, the wettability with the brazing material on the upper surface of the ceramic substrate 1 is improved, and the bonding strength between the upper surface of the ceramic substrate 1 and the frame-shaped member 3 becomes stronger. Moreover, the frame-shaped member 3 may be one in which an aluminum layer is formed on the surface of an iron-nickel-cobalt alloy, and can be made difficult to be affected by the electrolytic solution by the aluminum layer.

  More preferably, the frame-shaped member 3 has a rectangular shape whose section is long in the vertical direction. When the lid 4 is welded and joined to the frame-like member 3, the outer periphery of the lid 4 is thermally expanded, resulting in a difference in thermal expansion between the base body 1 and the lid body 4. The difference in thermal expansion from the lid 4 can be easily absorbed by the frame member 3, and it is possible to effectively prevent the thermal stress due to the thermal expansion difference from the lid 4 from being applied to the ceramic base 1. As a result, it is possible to prevent breakage such as cracks from occurring in the ceramic substrate 1, and to securely hold the inside of the recess 1a.

  In FIG. 3, the lid 4 made of metal such as Fe—Ni—Co alloy or Al alloy is welded or ultrasonically bonded to the frame-shaped member 3 to cover the concave portion 1 a of the ceramic base 1, thereby The inside of the substrate 1 can be surely hermetically sealed. Accordingly, it is possible to more effectively suppress moisture, oxygen, and the like from entering the electrolyte solution inside the ceramic substrate 1 through the interface between the ceramic substrate 1 and the lid 4 from the outside.

  A lid 4 made of ceramic such as an alumina sintered body, a metal such as an Fe-Ni-Co alloy or an Al alloy, or a resin such as an epoxy resin is placed on the upper surface of the ceramic substrate 1. The inside of the ceramic substrate 1 can be reliably hermetically sealed by covering the concave portion 1a of the ceramic substrate 1 by bonding through an adhesive material made of a material or resin or by ultrasonic bonding.

Next, a second embodiment of the battery case of the present invention will be described with reference to FIG.
In the second embodiment of the battery case of the present invention, a rectangular parallelepiped recess 1a is formed at the center of the upper surface of the ceramic substrate 1, and the first metallization layer is formed around the recess 1a on the upper surface of the ceramic substrate 1. 1d is formed, a hole 10 is formed on the bottom surface of the recess 1a, and a second metallized layer 1b is formed on the bottom surface of the hole 10. Furthermore, a first conductor layer 1f and a second conductor layer 1e are formed on the lower surface of the ceramic substrate 1, and a first inner layer formed from the first metallized layer 1d to the first conductor layer 1f. A conductor 2d and a second inner conductor 2b formed from the second metallized layer 1b to the second conductor layer 1e are formed. A resin containing conductive particles so as to cover the second metallized layer 1b and the upper surface of the recess 1a from the upper surface of the second metallized layer 1b on the bottom surface of the hole 10 formed on the bottom surface of the recess 1a to the recess 1a. In the second embodiment of the battery case of the present invention in which the layer B-5 is formed, the difference from the first embodiment is a step between one side surface and the bottom surface of the recess 1a of the ceramic substrate 1. 1c is not formed, and only the first metallized layer 1d is formed around the recess 1a on the upper surface of the ceramic substrate 1, and the first implementation is performed according to the difference in shape and position. The battery case of the second embodiment can be obtained by changing the forming method of the embodiment. The same characteristics as those of the battery case of the first embodiment can be obtained except that the formation position of the first metallized layer 1d is different. Therefore, the description other than the first metallized layer 1d is omitted below.

  In the second embodiment, the first metallized layer 1d is formed around the recess 1a on the upper surface of the ceramic substrate 1 as shown in FIGS. 2 (a), 2 (b), and 4 (a) (b). ing. By electrically connecting a lid 4 having at least a lower surface conductive to the first metallized layer 1d on the upper surface of the base body 1, FIG. 1 and FIG. It is possible to function as a battery without providing the step 1c as shown in FIG. As a result, the substrate 1 can be reduced in size, and the battery element can be easily mounted inside the recess 1 a of the substrate 1.

  In FIG. 2, the first metallized layer 1d is formed around the entire periphery of the recess 1a on the upper surface of the ceramic substrate 1, but is formed only on a portion electrically connected to the first inner conductor 2d. May be. However, the formation over the entire circumference around the recess 1a is preferable in that the connection resistance with the lid 4 can be lowered.

  Further, as compared with the first embodiment, the length of the first inner conductor 2d is increased, so that the electric resistance of the first inner conductor 2d is increased. Preferably, a plurality of first inner conductors 2d are used. It is possible to prevent the electrical resistance from becoming too large by increasing the number or increasing the total cross-sectional area.

  Also in the second embodiment, as shown in FIG. 3, a metal frame-like member 3 may be brazed to the first metallized layer 1 d on the upper surface of the ceramic substrate 1, and the lid 4 is In addition to being able to be joined efficiently, the inside of the recess 1a can be surely hermetically sealed.

  Moreover, as shown to Fig.4 (a) (b), it is good to provide the recess 40 in the center part of the main surface by the side of the base | substrate 1 of the cover body 4. As shown in FIG. With this configuration, when a battery element is installed inside the recess 1a, a battery element can be installed in the recess 40, and the lid 4 can be brought into contact with the battery element in the recess 40. The battery element can be easily and efficiently installed at a predetermined position of the lid 4. That is, the battery performance can be a predetermined performance, and the battery element can be installed easily and efficiently. In addition, the first and second inner conductors 2d and 2b are formed inside, and the height of the ceramic base 1 which has a complicated structure can be reduced, so that the ceramic base 1 can be easily manufactured.

  In the first embodiment as well, as shown in FIGS. 4A and 4B, a recess 40 may be provided at the center of the main surface of the lid 4 on the base 1 side. With this configuration, the battery performance can be set to a predetermined performance, and the battery element can be installed easily and efficiently.

  Next, the battery of the present invention will be described in detail below. 5A is a cross-sectional view showing a battery (referred to as battery B) using the battery case according to the first embodiment of FIG. 1 as an example of the embodiment of the battery of the present invention, FIG. FIG. 6B is a cross-sectional view showing an example of the embodiment in which the groove 11 is provided around the hole portion 10 in the battery B, and FIG. 6A shows another example of the embodiment of the battery according to the present invention. FIG. 6B is a cross-sectional view showing a battery using the battery case according to the second embodiment (referred to as battery C), and FIG. 6B shows a case where the groove 11 is provided around the hole 10 in the battery C. It is sectional drawing which shows an example of embodiment, B-1 is a positive electrode board, B-2 is a negative electrode board, B-3 is an insulation sheet, B-4 is electrolyte solution, B-5 is a resin layer, B Or C is a battery.

  The battery B of the present invention includes a battery case according to the first embodiment and a positive electrode plate B placed on the upper surface of the resin layer B-5 and electrically connected to the second metallized layer 1b. -1 and the upper surface of the positive electrode plate B-1 are placed in close contact with each other via an insulating sheet B-3 impregnated with an electrolytic solution B-4, and one end is electrically connected to the first metallized layer 1d. The negative electrode plate B-2 connected in general, and the cover 4 attached to the upper surface of the ceramic substrate 1 so as to cover the concave portion 1a and to be in contact with and attached to the negative electrode plate B-2.

  The battery C of the present invention includes a battery case according to the second embodiment and a positive electrode plate placed on the upper surface of the resin layer B-5 and electrically connected to the second metallized layer 1b. B-1, negative electrode plate B-2 placed so as to be in close contact with the upper surface of positive electrode plate B-1 via insulating sheet B-3 impregnated with electrolyte B-4, and recess 1a The lid 4 is joined to the upper surface of the ceramic base 1 so as to cover and at least the lower main surface is conductive, and is in contact with and electrically connected to the negative electrode plate B-2. Yes.

  Thereby, the airtight reliability and heat resistance using the battery case of the present invention are excellent, and the shape in plan view can be made to meet various market demands such as a quadrangle. Further, the first and second metallized layers 1d and 1b can be connected to the negative electrode plate B-2 and the positive electrode plate B-1, respectively, and the batteries B and C function as excellent batteries.

  The positions of the positive electrode plate B-1 and the negative electrode plate B-2 are switched, and the negative electrode plate B-2 is electrically connected to the upper surface of the second metallized layer 1b via the resin layer B-5. The positive electrode plate B-1 may be arranged on the upper surface of the negative electrode plate B-2 via the insulating sheet B-3.

The positive electrode plate B-1 is a plate or sheet having a positive electrode active material such as LiCoO ₂ or LiMn ₂ O ₄ and a conductive material such as acetylene black or graphite, and the negative electrode plate B-2 is It is a plate or sheet containing a negative electrode active material made of a carbon material such as coke or carbon fiber.

  The positive electrode plate B-1 and the negative electrode plate B-2 are prepared by adding the conductive material to the positive electrode active material or the negative electrode active material, and adding and mixing a binder such as polytetrafluoroethylene or polyvinylidene fluoride to form a slurry. The sheet is formed into a sheet using a well-known doctor blade method, and the sheet is then cut into, for example, a circle.

  The insulating sheet B-3 is made of a non-woven fabric made of polyolefin fiber, a microporous membrane made of polyolefin, and the like, impregnated with the electrolytic solution B-4, and between the positive electrode plate B-1 and the negative electrode plate B-2. By being placed between, the contact between the positive electrode plate B-1 and the negative electrode plate B-2 is prevented, and the electrolytic solution B- between the positive electrode plate B-1 and the negative electrode plate B-2. 4 can be moved to allow current to flow.

  The resin layer B-5 containing conductive particles is composed of conductive particles and a binder resin that binds the conductive particles. When the resin layer B-5 containing conductive particles contains the conductive particles and the binder resin, the resin layer B-5 does not react with the electrolytic solution B-4 and has electrical conductivity. That is, the conductive particles have high electrical conductivity and properties such as being chemically stable, and the resin layer B-5 containing the conductive particles has electrical conductivity. .

  The mixing ratio of the conductive particles and the binder resin is not particularly limited. That is, when the batteries B and C are formed, the content of the conductive particles is too small so that the electric resistance does not increase too much, and the binder resin may be mixed in a range of a mixing ratio that can sufficiently bind the conductive particles. . When the content of the conductive particles increases, the conductivity of the resin layer B-5 increases, and when the content of the conductive particles decreases, the conductivity decreases. Further, when the content of the conductive particles increases, the content of the binder resin relatively decreases, and the conductive particles cannot be sufficiently bound and supported by the binder resin.

  The binder resin is not particularly limited as long as the conductive particles can be bound, and examples thereof include phenol resins, polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and the like.

  The type of conductive particles is not particularly limited, and is composed of metal particles that do not react with the electrolytic solution B-4 such as carbon particles or aluminum powder. When the conductive particles are made of carbon particles, it is preferable to contain at least one of carbon black and graphite. By containing at least one of carbon black and graphite, sufficient electrical conductivity is ensured for the resin layer B-5.

  Then, the conductive particles and the binder resin are mixed to form a paste, which is applied from the top surface of the second metallized layer 1b to the bottom surface of the concave portion 1a, and then dried and bonded to form the resin layer B-5. Form. Alternatively, the paste-like mixture is formed into a sheet shape using a well-known doctor blade method or the like, and cut into a size that can cover the second metallized layer 1b and its periphery before being completely dried, and then this The sheet is sufficiently adhered over the bottom surfaces of the second metallized layer 1b and the recess 1a to form the resin layer B-5.

  Preferably, the resin layer B-5 may be provided so as to cover the lower surface of the lid 4 and the surface of the first metallized layer 1d, and the negative electrode plate B-2 is formed of the resin layer B-5. It may be electrically connected to the first metallized layer 1d or the conductive portion on the lower surface of the lid body 4 via the via. With this configuration, the lower surface of the lid 4 and the surface of the first metallized layer 1d can be prevented from coming into direct contact with the corrosive electrolytic solution B-4, and the negative electrode plate B-2 is interposed via the resin layer B-5. And can be elastically held by the lid 4. As a result, the battery element including the positive electrode plate B-1, the negative electrode plate B-2, and the insulating sheet B-3 inside the batteries B and C is displaced without damaging the negative electrode plate B-2 due to cracks or the like. You can detain not to.

  The electrolyte solution B-4 is injected into the batteries B and C from the upper surface of the recess 1a using an injection means such as a syringe in a container filled with, for example, argon (Ar) gas that hardly contains moisture. Then, the inside of the batteries B and C can be hermetically sealed by airtightly bonding the lid 4 to the upper surface of the ceramic base 1 or the frame-like member 3 after the injection.

  The electrolytic solution B-4 is obtained by, for example, dissolving a lithium salt such as lithium tetrafluoroborate or an acid such as hydrochloric acid, sulfuric acid, or nitric acid in an organic solvent such as dimethoxyethane or propylene carbonate. Such an electrolytic solution B-4 is highly corrosive and soluble, but by using the battery case of the present invention, the ceramic substrate 1 is excellent in chemical resistance. It is difficult to be attacked by the electrolyte solution B-4 containing the above, and the battery solution is maintained well without the impurities dissolved from the battery case being mixed in the electrolyte solution B-4 and degrading the electrolyte solution B-4. can do.

  5A and 5B, on the upper surface of the ceramic substrate 1, ceramics such as an alumina sintered body, metals such as Fe-Ni-Co alloys and Al alloys, and resins such as epoxy resins. The lid body 4 made of, for example, is joined via a brazing material such as Ag brazing or Al brazing, or an adhesive made of a resin, or is joined by an ultrasonic joining method to cover the concave portion 1a of the ceramic base 1 so that the inside of the ceramic base 1 Is hermetically sealed to form a battery B.

  When the battery case of FIG. 3 is used in the battery B, the lid 4 made of metal such as Fe—Ni—Co alloy or Al alloy is welded to the frame member 3, and the recess 1 a of the ceramic base 1 is formed. By covering, the inside of the ceramic substrate 1 can be surely hermetically sealed. Accordingly, it is possible to more effectively suppress moisture, oxygen, and the like from entering the electrolyte solution inside the ceramic substrate 1 through the interface between the ceramic substrate 1 and the lid 4 from the outside.

  Moreover, in the battery C of FIGS. 6A and 6B, the lid 4 is specifically made of a metal such as an Fe—Ni—Co alloy or an Al alloy, or a ceramic or epoxy resin such as an alumina sintered body. In the case where the lid 4 is made of an insulator, a metal layer 4a formed by depositing a metal such as Ni or Al by vapor deposition or the like is formed on at least the lower main surface. The body 4 is joined via a brazing material such as Ag brazing or Al brazing or a resin conductive adhesive containing a metal such as Ag, and the metal layer 4a on the lower main surface of the lid 4 is joined to the first metallization layer. The battery C is formed by hermetically sealing the inside of the ceramic substrate 1 by being electrically connected to 1d and covering the recess 1a of the ceramic substrate 1.

  Preferably, at least the lower main surface of the lid 4 is made of aluminum. With this configuration, the cover 4 can form a passive film having excellent corrosion resistance on the surface, effectively preventing the cover 4 from being corroded by the electrolyte B-4 or the external atmosphere, and the inside of the batteries B and C. The airtight reliability can be made very excellent.

  The lid body 4 whose lower main surface is made of aluminum is a plate material made of aluminum, a plate material in which an aluminum layer is formed on the lower main surface of a ceramic plate material, Fe-Ni-Co alloy, Fe-Ni alloy, etc. An aluminum layer may be formed on the lower main surface of the plate material. Further, it is preferable that a protrusion (a portion protruding linearly) is formed on the outer peripheral portion of the lower main surface of the lid body 4 over the entire periphery. If the lid 4 is a plate material made of aluminum, the ridges are formed simultaneously when the lid 4 is punched with a press, or after so-called coining method (restraining the side of the workpiece). By limiting the escape area of the meat and transferring the concave / convex pattern of the mold onto the surface of the workpiece by overlapping the mold with the irregularities formed on the mold surface and pressing the workpiece from above and below) For example, it is provided by forming it into a triangular shape with a height of about 0.1 mm and a cross section projecting downward.

  Further, if the lid 4 is made of a plate material in which an aluminum layer is formed on the lower main surface of an Fe—Ni—Co alloy or the like, these metal ingots are rolled to have a thickness of 0.2 to 0.5, for example. For example, an aluminum plate having a thickness of 0.1 mm is clad-bonded to the surface of the plate when the plate is made of mm, and then the protrusion is formed by the coining method.

  Then, an aluminum layer is formed on the upper surface of the metallization layer for metal bonding, the frame-shaped member 3 or the first metallization layer 1d provided around the recess 1a on the upper surface of the ceramic substrate 1, and the lid 4 The protrusion formed on the outer peripheral portion of the cover 4 is placed in contact with the cover 4, and by applying ultrasonic waves of about several tens of kHz from the upper surface of the cover 4, the protrusion on the lower surface of the cover 4 is It is joined to the aluminum layer on the ceramic substrate 1 side while being crushed along the unevenness of the aluminum layer on the upper surface on the ceramic substrate 1 side. At this time, even when the upper surface of the ceramic substrate 1 is warped or undulated, the ceramic base 1 is joined due to the different size of the protrusions. Then, according to this ultrasonic bonding method, the lid 4 can be firmly bonded without impairing the airtightness in the recesses 1a of the batteries B and C.

  More specifically, the ultrasonic bonding method is performed as follows, for example. That is, the ceramic base body 1 and the lid 4 that are the objects to be joined are set between a horn (square-shaped fixing base) having a chip serving as a vibration medium at the lower end of the tip and an anvil (anvil), and the chip is mounted. For example, a horizontal ultrasonic vibration of 15 to 30 kHz is applied while continuously moving along the outer periphery of the lid 4 while applying a pressure of about 30 to 50 N vertically. Alternatively, a method may be used in which bonding of a certain length is performed in a short time by increasing the pressure in the vertical direction with the shape of the chip as a line.

  In the ultrasonic bonding method, at the initial stage when ultrasonic vibration is applied, an oxide film or dirt on the surface of the bonded portion is pushed out toward the outer side of the bonded portion, and the aluminum crystal grains of the aluminum layer on the lid 4 and the ceramic substrate 1 side. By approaching each other until the interatomic distance is reached, a mutual attractive force acts between the atoms to obtain a strong bond. At this time, a temperature of 1/3 or less of the melting point of the metal in the method of melting and joining ordinary metals is locally generated, but with such a heat, the electrolyte solution B-4 hardly changes, Thus, the battery life can be extended.

  Furthermore, according to the ultrasonic bonding method, other metals hardly diffuse into aluminum, and therefore, a bonded portion having further corrosion resistance to the electrolytic solution B-4 can be formed.

  Further, in the metal case that has been conventionally used, as shown in FIG. 7, the positive electrode can 11 and the negative electrode can 12 are integrated by caulking them with a gasket 15 made of polypropylene resin or the like. The thickness of the caulked portion is about 2 mm in total of the positive electrode can 11, the negative electrode can 12, and the separator 14, whereas according to the present invention, the thickness is 1 mm or less because there is no need for caulking. This can greatly contribute to downsizing of portable devices and the like.

  Next, the electric double layer capacitor case and the electric double layer capacitors B and C of the present invention have the same configuration and operational effects as the battery case and the batteries B and C.

  That is, the electric double layer capacitor case of the present invention shown in FIG. 1 has a ceramic substrate 1 in which a recess 1a is formed at the center of the upper surface and a step 1c is formed between one inner side surface and the bottom surface of the recess 1a. The first metallized layer 1d formed on the top surface of the step 1c, the second metallized layer 1b formed on the bottom surface of the hole 10 formed on the bottom surface of the recess 1a, and the bottom surface of the ceramic substrate 1. The first conductor layer 1f and the second conductor layer 1e, the first inner conductor 2d formed from the first metallized layer 1d to the first conductor layer 1f, and the second metallized layer 1b to the second And a second inner conductor 2b formed over the conductor layer 1e, and a resin layer B-5 containing conductive particles is formed from the upper surface of the second metallized layer 1b to the bottom surface of the recess 1a. It is what.

  Further, the electric double layer capacitor B of the present invention shown in FIG. 5 is placed on the upper surface of the first electric double layer capacitor case of the present invention and the resin layer B-5, and is applied to the second metallized layer 1b. The first electrode B-1 that is electrically connected and the upper surface of the first electrode B-1 are placed so as to be in close contact via an insulating sheet B-3 impregnated with the electrolytic solution B-4. The second electrode B-2 whose one end is electrically connected to the first metallized layer 1d, and the upper surface of the ceramic substrate 1 covers the recess 1a and is in contact with and attached to the second electrode B-2. The lid 4 is provided.

  The electric double layer capacitor cases B and C of the present invention have the same configuration as the battery cases B and C described above, and thereby have the same effects as the battery cases B and C. , C. Accordingly, the detailed description of the electric double layer capacitor case of the present invention will be omitted because it overlaps with the battery cases B and C described above.

The first electrode B-1 and the second electrode B-2 are obtained by, for example, carbonizing activation of phenol resin fibers (novoloid fibers), and the activation is performed in a high temperature atmosphere of 800 to 1000 ° C. It is carried out by bringing it into contact with an activation gas such as high-temperature steam, and gasifies volatile components or part of carbon atoms in the carbide, mainly developing a fine structure of 1 to 10 nm to increase the internal surface area to 1 × 10 ⁶ m ^2. / Kg or more. The electric double layer capacitors B and C of the present invention have no polarity in the first and second conductor layers 1d and 1e, and can use the first conductor layer 1f side as an anode and the second conductor layer 1e side as a cathode. However, it can be used with the opposite polarity.

The electrolytic solution B-4 is, for example, a lithium salt such as lithium hexafluorophosphate (LiPF ₆ ) or a quaternary ammonium salt such as tetraethylammonium tetrafluoroborate ((C ₂ H ₅ ) ₄ NBF ₄ ) using propylene carbonate. It is dissolved in a solvent such as (PC) or sulfolane (SLF).

  Further, for the insulating sheet B-3, for example, a resin having heat resistance such as glass fiber, polyphenylene sulfide, polyethylene terephthalate, and polyamide is used.

  In the electric double layer capacitor B, the first electrode B-1, the insulating sheet B-3, the second electrode B-2, and the lid 4 are in close contact with each other on the upper surface of the first metallized layer 1d. After placing and injecting the electrolytic solution B-4, the concave portion 1a is formed on the upper surface of the substrate 1 by a method such as brazing using Al brazing, Ag brazing, Au—Sn solder or the like, or bonding using a resin adhesive or the like. The electric double layer capacitors B and C are joined so as to cover them.

  Note that the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the present invention. For example, in the present invention, the material of the ceramic substrate 1 of the battery case or the electric double layer capacitor case has been described as an alumina sintered body, but it is made of other ceramics such as an aluminum nitride sintered body or glass ceramics. In the case of the aluminum nitride sintered body, the batteries B and C or the electric double layer capacitors B and C that can efficiently dissipate heat during operation to the outside can be obtained.

  In addition, the battery case B or C or the electric double layer capacitor B or C using the battery case having one recess 1a or the electric double layer capacitor case has been described. The case may be a multilayer capacitor case, in which case the lid 3 is a single lid 3 that covers all the recesses 1a, or a plurality of lids 3 that cover the respective recesses 1a are attached. do it. When a battery case having a plurality of recesses 1a is used in this way, the batteries B, C or the electric double layer capacitors B, C produced in the respective recesses 1a are connected in parallel to thereby provide a high-capacity battery B, C or electric double layer capacitors B and C, or batteries B and C capable of supplying a high voltage by being connected in series, or electric double layer capacitors B and C having a high withstand voltage. .

(A) is sectional drawing which shows an example of embodiment of the case for batteries of this invention, or the case for electric double layer capacitors, (b) is a top view of (a). (A) is sectional drawing which shows the other example of embodiment of the case for batteries of this invention, or the case for electric double layer capacitors, (b) is a top view of (a). (A) is sectional drawing which shows the other example of embodiment of the case for batteries of this invention, or the case for electric double layer capacitors, (b) is a top view of (a). (A) (b) is sectional drawing which shows the other example of embodiment of the case for batteries of this invention, or the case for electric double layer capacitors. (A) (b) is sectional drawing which shows an example of embodiment of the battery or electric double layer capacitor of this invention. (A) (b) is sectional drawing which shows the other example of embodiment of the battery or electric double layer capacitor of this invention. It is sectional drawing which shows the example of the conventional battery or an electrical double layer capacitor.

Explanation of symbols

1: Ceramic substrate 1a: Concavity 1b: Second metallized layer 1c: Step 1d: First metallized layer 1e: Second conductor layer 1f: First conductor layer 2b: Second inner conductor 2d: First Inner conductor 3: Frame-shaped member 4: Lid
10: Hole
40: recess B: battery or electric double layer capacitor B-1: positive electrode plate or first electrode B-2: negative electrode plate or second electrode B-3: insulating sheet B-4: electrolyte B- 5: Resin layer C: Battery or electric double layer capacitor

Claims (8)

A ceramic base in which a recess is formed in the center of the upper surface and a step is formed between one inner side surface and the bottom surface of the recess, a first metallized layer formed on the upper surface of the step, and a bottom surface of the recess A second metallization layer formed on the bottom surface of the hole formed in the first substrate, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and the first metallization layer to the first metallization layer. A first inner conductor formed over one conductor layer and a second inner conductor formed between the second metallization layer and the second conductor layer, the second metallization layer. A battery case containing a conductive layer containing conductive particles is formed from the top surface to the bottom surface of the recess. Formed on the bottom surface of the ceramic substrate having a recess formed in the center of the upper surface, the first metallization layer formed around the recess on the upper surface of the ceramic substrate, and the hole formed in the bottom surface of the recess. A second metallized layer, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and a first metal layer formed from the first metallized layer to the first conductor layer. An inner conductor and a second inner conductor formed from the second metallized layer to the second conductor layer, and conductive particles extending from the upper surface of the second metallized layer to the bottom surface of the recess. A battery case, wherein a resin layer containing is formed. The battery case according to claim 1, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the positive electrode plate impregnated with an electrolyte. A negative electrode plate placed in close contact with an insulating sheet and having one end electrically connected to the first metallization layer; and the upper surface of the ceramic substrate covering the recess and the negative electrode plate And a lid attached in contact with the battery. The battery case according to claim 2, a positive electrode plate placed on the upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the positive electrode plate impregnated with an electrolyte. A negative electrode plate placed in close contact with an insulating sheet; and a negative electrode plate that is joined to the upper surface of the ceramic base so as to cover the recess, and at least the lower main surface is made conductive. And a lid that is in contact with and electrically connected to the battery. A ceramic base in which a recess is formed in the center of the upper surface and a step is formed between one inner side surface and the bottom surface of the recess, a first metallized layer formed on the upper surface of the step, and a bottom surface of the recess A second metallization layer formed on the bottom surface of the hole formed in the first substrate, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and the first metallization layer to the first metallization layer. A first inner conductor formed over one conductor layer and a second inner conductor formed between the second metallization layer and the second conductor layer, the second metallization layer. A case for an electric double layer capacitor, wherein a resin layer containing conductive particles is formed from the top surface to the bottom surface of the recess. Formed on the bottom surface of the ceramic substrate having a recess formed in the center of the upper surface, the first metallization layer formed around the recess on the upper surface of the ceramic substrate, and the hole formed in the bottom surface of the recess. A second metallized layer, a first conductor layer and a second conductor layer formed on the lower surface of the ceramic base, and a first metal layer formed from the first metallized layer to the first conductor layer. An inner conductor and a second inner conductor formed from the second metallized layer to the second conductor layer, and conductive particles extending from the upper surface of the second metallized layer to the bottom surface of the recess. An electric double layer capacitor case, wherein a resin layer containing is formed. The case for an electric double layer capacitor according to claim 5, a first electrode placed on an upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the first electrode A second electrode placed in close contact with an insulating sheet impregnated with an electrolytic solution and having one end electrically connected to the first metallized layer; and the recess on the upper surface of the ceramic substrate. An electric double layer capacitor comprising: a cover body that covers and is attached in contact with the second electrode. The case for an electric double layer capacitor according to claim 6, a first electrode placed on an upper surface of the resin layer and electrically connected to the second metallization layer, and an upper surface of the first electrode A second electrode placed so as to be in close contact via an insulating sheet impregnated with an electrolytic solution, and joined to the upper surface of the ceramic base so as to cover the recess, and at least the lower main surface is conductive. And a lid that is in contact with and electrically connected to the second electrode.

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