JP5762265B2 - Bonded body of ceramic body and metal body - Google Patents

Description

      The present invention relates to a joined body of a ceramic body and a metal body.

  For example, a battery such as a lithium ion battery uses an airtight terminal for taking out electricity to the outside while sealing a battery body containing an electrolytic solution inside. For example, Patent Document 1 below describes an example of a conventional hermetic terminal. As shown in a cross-sectional view in FIG. 5, an airtight terminal 100 described in Patent Document 1 below includes a sealing plate 102 made of metal having a through hole 102 a and a through hole penetrating from one main surface 104 α to the other main surface 104 β. A cylindrical ceramic body 104 provided with 104a and a columnar terminal body 106 made of metal and inserted through the through hole 104a are provided. In the sealing terminal 100, the sealing plate 102 and the ceramic body 104 are bonded via the bonding layer 110, and the terminal body 106 and the ceramic body 104 are bonded via the bonding layer 112. The bonding layer 110 and the bonding layer 112 are made of, for example, an aluminum brazing material. The ceramic body 104 has an enlarged diameter portion 120 surrounded by an inner peripheral surface 122 parallel to the side surface 106a of the terminal body 106 and a bottom surface 124 perpendicular to the side surface 106a at the end of the through hole 104a on the one main surface 104α side. It has. In the hermetic terminal 100 of Patent Document 1, the thickness of the bonding layer 112 is large in the enlarged diameter portion 120, and the bonding strength between the ceramic body 104 and the terminal body 106 is relatively high.

JP-A-11-167915

  In the ceramic body 104 in the hermetic terminal 100 described in Patent Document 1, the thickness of the bonding layer 112 in the enlarged diameter portion 120 is large and the bonding strength is sufficiently strong. On the other hand, when the bonding layer 112 is manufactured through a brazing process, for example, A large thermal stress is generated in the enlarged diameter portion 120 at the time of brazing, and there has been a problem that damage such as cracks is likely to occur in the ceramic body 104 due to the thermal stress at the time of brazing. Further, in the enlarged diameter portion 120, the thermal expansion and thermal contraction of the bonding layer 112 accompanying the temperature change during the use of the battery is relatively large, and the ceramic body 104 is damaged by repeated use. Or the bonding layer 112 is easily peeled off from the ceramic body 104. Further, the inner peripheral surface 122 and the bottom surface 124 of the enlarged diameter portion 120 are formed perpendicularly, and stress is easily concentrated on the corner portion of the boundary between the inner peripheral surface 122 and the bottom surface 124, and this is caused by the concentrated stress. There is also a problem that the ceramic body 104 is easily damaged.

  The present invention aims to solve this problem.

In order to solve the above problems, the present invention provides a ceramic body having one main surface and the other main surface, and a through-hole penetrating between the one main surface and the other main surface, and at least in the through-hole. The inner surface disposed in a gap between the metal body having a columnar portion having a side surface facing the inner surface of the through-hole, a part of which is disposed, and the inner surface of the through-hole and the side surface of the columnar portion. And a bonding layer that bonds the ceramic body and the metal body by bonding to the side surface, and a portion of the inner surface of the through hole that faces the side surface of the columnar portion is formed on the side surface. A parallel first inner surface portion, and arranged on the other main surface side of the first inner surface portion from the first inner surface portion side, to the other main surface side from the first inner surface portion side. As the distance from the side decreases, the distance from the side decreases. An inclined second inner surface portion, and a third inner surface portion parallel to the side surface, which is arranged on the side of the other main surface with respect to the second inner surface portion in succession to the second inner surface portion, The bonding layer is continuously bonded to the inner surface of the through hole from at least a part of the first inner surface part to the at least part of the third inner surface part through the entire second inner surface part. the end face of the one main surface side of the bonding layer between the inner surface of the through-hole and the side surface of the columnar section, Ri concave der recessed toward the side of the other main surface, wherein A ceramic body and a metal body , wherein the end surface of the bonding layer has a concave portion in which a portion closest to the other main surface is located in a region corresponding to the second inner surface portion in the gap. Provide a zygote with. In addition, a ceramic body having one main surface and the other main surface, and a through hole penetrating between the one main surface and the other main surface, and at least a part of the ceramic body is disposed in the through hole, Adhering to a metal body having a columnar portion having a side surface facing the inner surface of the through hole, and the inner surface and the side surface disposed in a gap between the inner surface of the through hole and the side surface of the columnar portion. A bonding layer that bonds the ceramic body and the metal body, and a portion of the inner surface of the through hole that faces the side surface of the columnar portion is a first inner surface portion parallel to the side surface; An interval between the first inner surface portion and the side surface as it is closer to the other main surface from the first inner surface portion side than the first inner surface portion. A second inner surface portion inclined with respect to the side surface so as to reduce A third inner surface portion parallel to the side surface, the third inner surface portion being arranged on the side of the other main surface with respect to the second inner surface portion. The inner surface is continuously bonded from at least a part of the first inner surface part to the at least part of the third inner surface part through the entire second inner surface part, and the inner surface of the through hole The end surface on the one main surface side of the bonding layer between the columnar portion and the side surface has a concave shape that is recessed toward the other main surface side, and the second inner surface portion includes the first inner surface portion. A first region that is continuous with the inner surface portion, and a first region that is continuous with the first region and is closer to the other main surface than the first region, and has a smaller inclination angle with respect to the side surface than the first region. Two regions and the second region continuous with the second main surface from the second region. And also provides conjugates of the ceramic body and the metal body, characterized in that it comprises a third region is larger inclination angle relative to the side as compared to the second region.

  In the joined body of the ceramic body and the metal body according to the present invention, the joining layer for joining the ceramic body and the metal body has a second inner surface from at least a part of the first inner surface portion with respect to the inner surface of the through hole of the ceramic body. Since it is continuously bonded to at least a part of the third inner surface portion through the entire portion, the bonding strength between the ceramic body and the metal body is relatively high, and between the inner surface of the through hole and the side surface of the columnar portion. Since the end surface on the one main surface side of the bonding layer has a concave shape that is recessed toward the other main surface side, the bonding layer itself is easily deformed in accordance with a temperature change or the like, and the bonding layer itself is deformed. Therefore, the stress can be relieved, and a stable bonding strength can be realized over a relatively long period.

It is a schematic sectional drawing of the terminal member 1 which is one Embodiment of the joined body of the ceramic body and metal body of this invention. (A) is sectional drawing which expands and shows a part of terminal member shown in FIG. 1, (b) is an electron micrograph of the cross section of the Example of the terminal member shown in FIG. It is a figure explaining the battery comprised by providing the terminal member shown in FIG.1 and FIG.2, (a) is a perspective view, (b) is sectional drawing. It is sectional drawing of the battery main body with which the battery shown in FIG. 3 is provided. It is sectional drawing of the airtight terminal 100 which is one Embodiment of the joined body of the conventional ceramic body and metal body.

  Embodiments of a joined body of a ceramic body and a metal body according to the present invention will be described below in detail with reference to the drawings. First, with reference to FIG. 1 and FIG. 2, the terminal member 1 which is one Embodiment of the joined body of the ceramic body and metal body of this invention is demonstrated. FIG. 1 is a schematic cross-sectional view of a terminal member 1 which is an embodiment of a joined body of a ceramic body and a metal body of the present invention. FIG. 2A is an enlarged cross-sectional view of a part of the terminal member 1. In FIG.2 (b), the electron micrograph of the cross section of the Example of the terminal member 1 is shown collectively.

  The terminal member 1 is a member used as a part of a battery 60 described later, for example. The terminal member 1 includes a ceramic body 16, a metal body 14, and a bonding layer 32 that bonds the ceramic body 16 and the metal body 14. The ceramic body 16 is made of, for example, a known alumina ceramic, and has one main surface 16α and the other main surface 16β, and a through hole 16a penetrating between the one main surface 16α and the other main surface 16β. The metal body 14 includes a columnar portion 15 at least a part of which is disposed in the through hole 16a, and a flange portion 13 protruding so as to face the other main surface 16β of the ceramic body 16. The columnar portion 15 has a side surface 19 that faces the inner surface 17 of the through hole 16a.

In the ceramic body 16 of the terminal member 1, a portion of the inner surface 17 of the through hole 16 a that faces the side surface 19 of the columnar portion 15 is continuous with the first inner surface portion 17 a parallel to the side surface 17 and the first inner surface portion 17 a. The first inner surface portion 17 is disposed closer to the other main surface 16β than the first inner surface portion 17a.
a second inner surface portion 17b that is inclined with respect to the side surface 19 so as to decrease the distance from the side surface 19 as it approaches the other main surface 16β side from the side a, and a second inner surface that is continuous with the second inner surface portion 17b. It has the 3rd inner surface part 17c parallel to the side surface 19 arrange | positioned rather than the part 17b at the other main surface 16 (beta) side. Note that “parallel to the side surface 17” means that the absolute value of the angle formed with the side surface 17 is 30 degrees or less in a cross-sectional view including the central axis of the columnar portion 15 (the cross section corresponding to FIGS. 1 and 2). Say.

  In the terminal member 1, the boundary between the first inner surface portion 17 a and the second inner surface portion 17 b is a smooth curved line in a cross-sectional view including a cross section including the central axis of the columnar portion 15. The second inner surface portion 17b is a first region 21a that is continuous with the first inner surface portion 17a, and a first region 21a that is continuous with the first region 21a and is disposed closer to the other main surface 16β than the first region 21a. Compared to the second region 21b having a smaller inclination angle with respect to the side surface 19 than the region 21a, and the second region 21b arranged on the other main surface 16β side of the second region 21b in succession to the second region 21b. And a third region 21c having a large inclination angle with respect to the side surface 19. In addition, in a cross-sectional view with a cross section including the central axis of the columnar portion 15, the boundary between the first region 21a and the second region 21b and the boundary between the second region 21b and the third region 21c are respectively smooth curved lines. It is.

If the ceramic body 16 is made of, for example, alumina ceramics, it is suitable for a raw material powder such as aluminum oxide (alumina: Al ₂ O ₃ ), silicon oxide (SiO ₂ ), calcium oxide (CaO), magnesium oxide (MgO). The raw material powder prepared by adding an organic binder is filled into a press mold having a predetermined shape and is molded by pressing it at a predetermined pressure, and then the obtained molded body is about 1600 ° C. in the atmosphere. It can manufacture by baking at the temperature of. In the ceramic body 16 including the through-hole 16 surrounded by the inner surface 17 described above, the cross-sectional area of the through-hole 16a is constant from the other main surface 16β toward the one main surface 16α or larger toward the one main surface 16α. It can be produced relatively easily by, for example, press molding.

The metal body 14 is made of, for example, an Al alloy that is electrochemically stable in a high electromotive force state, and preferably has an excellent corrosion resistance and is easily brazed (JIS H 4040 alloy number 3).
003) and the like. In the present embodiment, the columnar portion 15 has a columnar shape, and the through hole 16 a is formed in a columnar shape corresponding to the columnar portion 15. In the present invention, the shapes of the columnar part and the through hole are not limited to a cylindrical shape.

  The bonding layer 32 is continuously bonded to the inner surface 17 of the through hole 16a from at least a part of the first inner surface part 17a through the entire second inner surface part 17b to at least a part of the third inner surface part 17c. A layer 42, a plated layer 43 covering the surface of the metallized layer 42, and a brazing material layer 52 bonded to both the plated layer 43 and the columnar portion 15 of the metal body 14 are provided.

  The metallized layer 42 is made of a known metallized layer such as Mo-Mn. For example, a metal paste obtained by adding an appropriate organic binder and solvent to Mo powder, Mn powder and metal oxide powder is mixed with the ceramic body 16. It can be formed by applying to the inner surface 17 and baking at a temperature of about 1400 ° C. in a reducing atmosphere. The plating layer 43 is made of a known Ni plating layer. The brazing material layer 52 is made of an Al alloy containing Al as a main component, and uses an Al—Si based brazing material. Since the Al alloy has a relatively low brazing property due to its strong oxide film on its surface, a small amount of magnesium (Mg) having a getter action that improves the brazing property by removing the oxide film on the Al alloy surface. It is preferable to use the contained one.

In the terminal member 1, the bonding layer 32 continues from the at least part of the first inner surface part 17 a to the at least part of the third inner surface part 17 c through the entire second inner surface part 17 b with respect to the inner surface 17 of the through hole 16 a. The end surface 32a on the one main surface 16α side of the bonding layer 32 between the inner surface 17 of the through hole 16a and the side surface 19 of the columnar portion 15 is recessed toward the other main surface 16β side. It has become. That is, in the terminal member 1, the bonding layer 32 is continuously bonded from at least a part of the first inner surface part 17a to the at least part of the third inner surface part 17c through the entire second inner surface part 17b. The bonding area between the layer 32 and the ceramic body 16 is relatively large. On the other hand, the end surface 32a of the bonding layer 32 has a concave shape, and the volume of the bonding layer 32 itself is relatively small. Such a concave shape of the end surface 32a of the bonding layer 32 is formed along the second inner surface portion 17b inclined so as to gently connect the first inner surface portion 17a to the third inner surface portion 17c when the bonding layer 32 is formed. It is formed by wetting the brazing material. By providing the inner surface 17 including the first inner surface portion 17a, the second inner surface portion 17b, and the third inner surface portion 17c, it is possible to stably form the concave end surface 32a when forming the bonding layer 32. It has become.

  In addition, since the cross section of the end surface 32a is concave, the vicinity of the end surface 32a of the bonding layer 32 has a side bonded to the side surface 19 of the columnar portion 15 and a side bonded to the inner surface 17 of the through hole 16a. It tends to be deformed in a direction approaching or moving away (a direction indicated by an arrow in FIGS. 1 and 2). For this reason, for example, even when the bonding layer 32 or the metal body 14 is thermally expanded or contracted due to a temperature change, a portion near the end surface 32a of the bonding layer 32 that is relatively easily deformed is selectively deformed. Thereby, the excess stress accompanying a temperature change is relieved and the damage of the ceramic body 16 and the metal body 14 accompanying a temperature change is suppressed. In the terminal member 1, the end surface 32 a of the bonding layer 32 is located in a region corresponding to the second inner surface portion 17 b in the gap between the inner surface 17 and the side surface 19, of the concave shape. Therefore, the portion corresponding to the first inner surface portion 17a is easily deformed, and the stress relaxation effect is relatively high.

  Further, since the terminal member 1 includes the first region 21a, the second region 21b, and the third region 21c, it is possible to obtain the bonding layer 32 having a sufficiently high bonding strength and a high stress relaxation effect. Can do. That is, a relatively large amount of the bonding layer 32 is disposed in the gap between the side surface 19 and the portion corresponding to the third region 21c and the second region 21b, and a relatively high bonding strength is achieved. By forming the concave end face 32a having a relatively large radius of curvature along the first region 21a having a relatively large angle, the stress relaxation effect can be made relatively high.

  In the terminal member 1, as described above, the boundary between the first inner surface portion 17 a and the second inner surface portion 17 b is a smooth curved line in a cross-sectional view with a cross section including the central axis of the columnar portion 15. . In addition, in a cross-sectional view with a cross section including the central axis of the columnar portion 15, the boundary between the first region 21a and the second region 21b and the boundary between the second region 21b and the third region 21c are respectively smooth curved lines. It is. In the terminal member 1, there is no corner portion where excessive stress is concentrated on the inner surface 17 of the ceramic body 16, and the force applied from the outside and the stress generated according to the temperature change are concentrated in one place. The ceramic body 16 is prevented from being broken.

Next, the battery 60 provided with the terminal member 1 will be described. 3A and 3B are diagrams for explaining the battery 60 configured to include the terminal member 1, wherein FIG. 3A is a perspective view and FIG. 3B is a cross-sectional view. As shown in FIG. 3, the terminal member 1 includes a battery body 61, a long cylindrical metal container 62 in which the battery body 61 is accommodated, a sealing plate 12, and the joined body 1 shown in FIG. It is configured. The sealing plate 12 includes a through hole 12a, the terminal member 1 is disposed in the through hole 12a, and the inner peripheral surface of the through hole 12a and the inner surface 17 of the ceramic body 16 are bonded via a bonding layer 34. ing. The sealing plate 12 is preferably made of, for example, an Al alloy (JIS H 4040 alloy number 3003) that is excellent in corrosion resistance to an electrolytic solution containing lithium ions and is easy to braze. The bonding layer 34 includes a metallization layer (not shown) such as Mo—Mn and a brazing material layer (not shown) mainly composed of Al. Similarly to the metallized layer 42, the metallized layer of the bonding layer 34 is obtained by adding, for example, a metal paste obtained by adding and mixing an appropriate organic binder and solvent to Mo powder, Mn powder, and metal oxide powder. It can be formed by applying to the surface 16α and baking it at a temperature of about 1400 ° C. in a reducing atmosphere. Similarly to the brazing filler metal layer 52, the brazing filler metal layer of the bonding layer 34 is made of an Al alloy containing Al as a main component, and an Al-Si based composition may be used. The peripheral portion of the sealing plate 12 is welded to the open end 62 a of the metal container 62.

  The battery body 61 includes a housing 70 provided with a positive electrode terminal body 72 and a negative electrode terminal body 73, and a battery body 80 accommodated inside the housing 70. FIG. 4 is a cross-sectional view of the battery main body 80. The main body 80 includes a separator 79, and a positive electrode plate 77 and a negative electrode plate 78 that are disposed in close proximity to each other with the separator 79 interposed therebetween, and an electrolyte solution (not shown) is filled in the gap between the members. Yes. In the present embodiment, a so-called overlapping structure shown in FIG. 4 is adopted as a structure in which the positive electrode plate 77 and the negative electrode plate 78 are laminated. The overlapping structure of the positive electrode plate 77 and the negative electrode plate 78 may employ a so-called folding structure or a winding structure, and is not particularly limited. The positive electrode plate 77 and the negative electrode plate 78 are obtained by applying an active material to a current collector (electrode base material). The active material in the positive electrode plate 77 can be used without being limited to oxides of transition metals such as cobalt, manganese, nickel, chalcogen compounds, composite compounds thereof, and various additive elements. As the active material in the negative electrode plate 78, a carbonaceous material is preferably used, but a material containing an oxide of boron and tin is also used. The shape is usually granular and the particle size is preferably from 0.3 μm to 20 μm, and more preferably from 1 μm to 5 μm. It is also possible to use metallic lithium as the active material. In the case of metallic lithium, it may be either granular or foil-like. The positive electrode plate 77 and the negative electrode plate 78 are made of an electrochemically stable metal. The positive electrode plate 77 is preferably made of aluminum and the negative electrode plate 78 is preferably made of copper. The current collector can be any shape such as foil, net, expanded metal, etc., but foil is often used. The positive electrode terminal body 72 provided in the housing 70 is a plate-like member formed of aluminum metal or the like, and is connected to the positive electrode plate 7 of the battery main body 80 accommodated in the housing 70. Further, the negative electrode terminal body 73 is a plate-like member formed of nickel, copper or the like, and is connected to the negative electrode plate 78 of the battery main body 80 accommodated in the housing 70. The connection between the positive electrode plate 77 and the positive electrode terminal body 72 and the connection between the negative electrode plate 78 and the negative electrode terminal body 73 include various connection forms such as welding, but are configured so that current can be efficiently extracted from the battery body 80. If it is, it will not be specifically limited.

  The terminal member 1 fixed to the sealing plate 12 is disposed so as to close the open end 62a of the metal container 62 in which the battery body 61 is accommodated. Specifically, in a state where the metal body 14 of one joined body 1 is in contact with the positive electrode terminal body 72 and the metal body 14 of the other joined body 1 is in contact with the negative electrode terminal body 73, The peripheral portion is welded to the open end 102 a of the metal container 102.

  The battery 60 configured to include the terminal member 1 has high bonding strength between the ceramic body 16 and the metal body 14 and suppresses damage to the bonding portion due to temperature change and applied external force. High reliability over time.

  As mentioned above, although one Embodiment of this invention was described, the joined body of the ceramic body and metal body of this invention is not limited to the said embodiment. For example, the ceramic body and metal body of the present invention can be used for various applications such as electrodes and insulators in various measuring apparatuses. The present invention is not limited to the above-described embodiment, and various improvements and modifications may be made without departing from the scope of the present invention.

1 Terminal member (joint)
13 flange part 14 metal body 15 columnar part 16 ceramic body 16a through hole 16α one main surface 16β other main surface 17 inner surface 17a first inner surface portion 17b second inner surface portion 17c third inner surface portion 19 side surface 21a first region 21b second region 21c 3rd area | region 32 Joining layer 42 Metallizing layer 43 Plating layer 52 Brazing material layer 60 Battery 61 Battery body 70 Housing | casing 72 Positive electrode terminal body 73 Negative electrode terminal body 79 Separator 80 Main body 100 Airtight terminal 102 Sealing plate 102a Through-hole 104 Ceramic body 104α One main surface 104β Other main surface 104a Through hole 106 Terminal body 110 Bonding layer 112 Bonding layer 120 Expanded portion 122 Inner peripheral surface 124 Bottom surface

Claims (5)

A ceramic body having one main surface and the other main surface, and a through-hole penetrating between the one main surface and the other main surface;
A metal body provided with a columnar portion having a side surface opposed to the inner surface of the through hole, at least part of which is disposed in the through hole;
A bonding layer that is disposed in a gap between the inner surface of the through-hole and the side surface of the columnar portion, and is bonded to the inner surface and the side surface to bond the ceramic body and the metal body;
Of the inner surface of the through hole, the portion facing the side surface of the columnar portion is:
A first inner surface portion parallel to the side surface;
An interval between the first inner surface portion and the side surface as it is closer to the other main surface from the first inner surface portion side than the first inner surface portion. A second inner surface portion inclined with respect to the side surface so as to reduce
A third inner surface portion parallel to the side surface and disposed on the side of the other main surface with respect to the second inner surface portion continuously to the second inner surface portion;
The bonding layer is continuously bonded to the inner surface of the through hole from at least a part of the first inner surface part to the at least part of the third inner surface part through the entire second inner surface part. cage, the end face of the one main surface side of the bonding layer in between the side surface of said inner surface and said columnar portion of said through hole, Ri concave der recessed toward the side of the other main surface,
The end face of the bonding layer has a concave portion in which a portion closest to the other main surface is located in a region corresponding to the second inner surface portion in the gap. A joint with the body. 2. The ceramic body according to claim 1, wherein a boundary between the first inner surface portion and the second inner surface portion has a smooth curved shape in a cross-sectional view including a central axis of the columnar portion. Bonded body with metal body. A ceramic body having one main surface and the other main surface, and a through-hole penetrating between the one main surface and the other main surface;
A metal body provided with a columnar portion having a side surface opposed to the inner surface of the through hole, at least part of which is disposed in the through hole;
A bonding layer that is disposed in a gap between the inner surface of the through-hole and the side surface of the columnar portion, and is bonded to the inner surface and the side surface to bond the ceramic body and the metal body;
Of the inner surface of the through hole, the portion facing the side surface of the columnar portion is:
A first inner surface portion parallel to the side surface;
An interval between the first inner surface portion and the side surface as it is closer to the other main surface from the first inner surface portion side than the first inner surface portion. A second inner surface portion inclined with respect to the side surface so as to reduce
A third inner surface portion parallel to the side surface and disposed on the side of the other main surface with respect to the second inner surface portion continuously to the second inner surface portion;
The bonding layer is continuously bonded to the inner surface of the through hole from at least a part of the first inner surface part to the at least part of the third inner surface part through the entire second inner surface part. And the end surface on the one main surface side of the bonding layer between the inner surface of the through hole and the side surface of the columnar portion is a concave shape recessed toward the other main surface side,
The second inner surface portion is
A first region continuous to the first inner surface portion;
A second region having a smaller inclination angle with respect to the side surface than the first region, the second region being arranged on the side of the other main surface with respect to the first region continuously to the first region;
And a third region that is arranged on the side of the other main surface with respect to the second region, and that has a larger inclination angle with respect to the side surface than the second region. conjugates of Rousset ceramic body and the metal body. In a cross-sectional view including a central axis of the columnar portion, a boundary between the first region and the second region and a boundary between the second region and the third region are respectively smooth curves. The joined body of a ceramic body and a metal body according to claim 3 . The bonding layer includes a metallized layer deposited on the inner surface of the through hole, a plated layer covering the surface of the metallized layer, and a brazing material layer bonded to both the plated layer and the columnar portion of the metal body. The joined body of the ceramic body and the metal body according to any one of claims 1 to 4 .