JP5845706B2 - Secondary battery and manufacturing method thereof - Google Patents

Description

  The present invention relates to a secondary battery and a manufacturing method thereof, for example, a secondary battery including a hard body in a positive electrode film or a negative electrode film and a manufacturing method thereof.

  The secondary battery can store and supply electric energy. For this reason, the secondary battery is applied to a hybrid vehicle, an electric vehicle, and the like. As a secondary battery, a lithium secondary battery has attracted attention. A secondary battery is formed by laminating a positive electrode, an electrolyte, and a negative electrode. From the viewpoint of improving the energy density, each film is being made thinner. Also, secondary batteries using solid electrolytes have been developed in order to form all-solid thin film secondary batteries. A lithium secondary battery in which zirconium oxide particles are incorporated in a solid electrolyte is known. It is known that a porous heat-resistant layer contains zirconia as an insulating filler on the surface of an electrode. An electrolyte including a reinforcing material is known.

JP 2002-280072 A JP 2007-42580 A International Publication No. 2007/13567 International Publication No. 2007/63943

  If the positive electrode, the electrolyte, and the negative electrode are thinned, the battery may be destroyed due to external impact or the like. For example, it is conceivable to package the entire secondary battery with a hard material. However, flexibility is sacrificed. The secondary battery and the manufacturing method thereof are intended to improve external impact resistance.

For example, a negative electrode film and a positive electrode film,
Wherein provided on the negative electrode membrane and at least one electrode film of cathode films, the rather hard than at least one electrode layer, and the at least one electrode film penetrates in the thickness direction of each of the at least one electrode film is filled A plurality of first hard bodies provided with a first hole, and at least one electrode film formed on one side, and a conductor plate provided with a first protrusion on the one side lower than the film thickness of the at least one electrode film The secondary battery is characterized in that the first protrusion is positioned in at least a part of the first hole of the plurality of first hard bodies .

For example, by applying a first paste containing at least one of a negative electrode material and a positive electrode material and including a plurality of first hard bodies on the conductor plate, and squeezing the first paste, the conductor plate wherein forming at least one electrode film of the corresponding negative electrode film and cathode film from at least one material above the plurality of first rigid body rather hard than the at least one electrode film, on one side of the conductor plate Is formed with a first protrusion lower than the thickness of the first hard body, and when the first paste is applied, the first paste is applied to the one surface and the at least one electrode film is formed. A method of manufacturing a secondary battery is used , wherein the first paste is squeezed so that movement of the plurality of first hard bodies is regulated by the first protrusions .

  According to this secondary battery and its manufacturing method, the impact resistance from the outside can be improved.

FIG. 1A is a cross-sectional view of the secondary battery according to Example 1, and FIG. 1B is a plan view showing the positive electrode film and the hard body. FIG. 2A and FIG. 2B are cross-sectional views showing a case where an object falls on the secondary battery. FIG. 3 is a plan view of the hard body and the positive electrode film of the secondary battery according to Example 2. FIG. 4A to FIG. 4D are cross-sectional views illustrating the manufacturing process of the secondary battery according to the third embodiment. FIG. 5A to FIG. 5D are diagrams showing a method for manufacturing a hard body. FIG. 6A to FIG. 6C are diagrams showing a method for forming a positive electrode film. FIG. 7A is a cross-sectional view of the secondary battery according to Example 4, and FIG. 7B is a plan view showing the solid electrolyte membrane and the hard body. FIG. 8 is a plan view of a hard body and a solid electrolyte membrane of a secondary battery according to Example 5. FIG. 9A to FIG. 9C are cross-sectional views illustrating the manufacturing process of the secondary battery according to the sixth embodiment. FIG. 10A to FIG. 10E are diagrams showing a method for manufacturing the hard body 20. FIG. 11A to FIG. 11D are diagrams showing a method for forming a positive electrode film and a solid electrolyte film.

  Embodiments will be described below with reference to the drawings.

  Example 1 is an example of a lithium secondary battery. FIG. 1A is a cross-sectional view of the secondary battery according to Example 1, and FIG. 1B is a plan view showing the positive electrode film and the hard body. As shown in FIG. 1A, the positive electrode film 10 including the hard body 20 (first hard body) is provided on the conductor plate 16. The hard body 20 is harder than the positive electrode film 10. The hard body 20 is an insulator such as zirconium oxide or aluminum oxide, for example. The hard body 20 may be a metal. The positive electrode film 10 includes, for example, a positive electrode active material such as lithium cobalt oxide. On the positive electrode film 10, for example, a solid electrolyte film 12 using a sulfide solid electrolyte is provided. A negative electrode film 14 is provided on the solid electrolyte film 12. The negative electrode film 14 includes, for example, a negative electrode active material such as lithium metal or lithium carbide. Thus, the negative electrode film 14 and the positive electrode film 10 are provided with the solid electrolyte film 12 interposed therebetween. A conductor plate 18 is provided on the negative electrode film 14. The conductor plates 16 and 18 are made of, for example, a metal such as a Ni—Cu alloy and function as current collectors. As shown in FIG. 1B, the hard body 20 is periodically or randomly provided in the positive electrode film 10.

  FIG. 2A and FIG. 2B are cross-sectional views showing a case where an object falls on the secondary battery. FIG. 2A shows a secondary battery according to a comparative example, in which the positive electrode film 10 does not include the hard body 20. FIG. 2B shows a cross section of the secondary battery according to the first embodiment. As shown in FIG. 2A, when the object 50 falls on the secondary battery, a recess 52 is formed in the conductor plate 18, the negative electrode film 14, the solid electrolyte film 12, and the positive electrode film 10 due to the impact. Thereby, the secondary battery is destroyed. For example, the positive electrode film 10 and the negative electrode film 14 are electrically short-circuited.

  As shown in FIG. 2B, in Example 1, a plurality of hard bodies 20 that are harder than the positive electrode film 10 are included in the positive electrode film 10. For this reason, even if the object 50 falls, the hollow 52 is small and the destruction of the secondary battery can be suppressed. In this way, a secondary battery that is resistant to external impact can be provided. Furthermore, since the plurality of hard bodies 20 are independently provided and not connected, the flexibility of the secondary battery can be maintained.

  Example 2 is an example in which a hard body includes a through hole. FIG. 3 is a plan view of the hard body and the positive electrode film of the secondary battery according to Example 2. As shown in FIG. 3, the hard body 20 is formed with a hole 22 (first hole) penetrating in the film thickness direction of the positive electrode film 10. The hole 22 is filled with the positive electrode film 10. Thereby, the positive electrode film 10 is formed in the hole 22. Therefore, the hard body 20 can suppress the area of the positive electrode film 10 from being reduced. In order to ensure the area of the positive electrode film 10, it is preferable that the hole 22 of the hard body 20 is large. For example, the size of the hole 22 is preferably 1/2 or more of the size of the hard body, and more preferably 3/4 or more. On the other hand, if the hole 22 is too large, the strength of the hard body 20 is lowered. Therefore, the size of the hole 22 can be set by the strength of the hard body 20. The shape of the hard body 20 can be, for example, a circle, an ellipse, or a polygon other than the quadrangle as in the first and second embodiments. A plurality of holes 22 may be provided in one hard body 20.

  Example 3 is an example of a method for manufacturing a secondary battery. FIG. 4A to FIG. 4D are cross-sectional views illustrating the manufacturing process of the secondary battery according to the third embodiment. As shown in FIG. 4A, for example, a Ni—Cu alloy conductor plate 16 having a thickness of about 100 μm is pressed. Thereby, the protrusion 24 (first protrusion) is formed on one surface of the conductor. The protrusions 24 can have a diameter of, for example, 100 μm, a height of, for example, 35 μm, and an interval of, for example, 1250 μm.

  As shown in FIG. 4B, the positive electrode film 10 having a film thickness of, for example, 50 μm is formed on one surface of the conductor plate 16. A plurality of hard bodies 20 are provided in the positive electrode film 10. The positive electrode film 10 includes, for example, lithium cobalt oxide as a positive electrode active material. In FIG. 4B, the left two hard bodies 20 show cross sections including the holes 22. The hard body 20 has a thickness of, for example, 500 μm × 500 μm as viewed from above, and a film thickness of, for example, 50 μm. The size of the hole 22 is, for example, 400 μm × 400 μm.

  As shown in FIG. 4C, the solid electrolyte film 12 having a film thickness of, for example, 50 μm is formed on the positive electrode film 10 by using, for example, a printing method. The solid electrolyte membrane 12 contains 97% by weight of a solid electrolyte such as a sulfide solid electrolyte and 3% by weight of a resin such as polyvinylidene fluoride. An intermediate layer having a thickness of 10 μm may be formed between the positive electrode film 10 and the solid electrolyte film 12, for example. For the intermediate layer, for example, a material containing 80% by weight of the positive electrode material and 20% by weight of the solid electrolyte material can be used. As shown in FIG. 4D, the negative electrode film 14 having a film thickness of, for example, 50 μm is formed on the solid electrolyte film 12. A conductor plate 18 is formed on the negative electrode film 14.

  FIG. 5A to FIG. 5D are diagrams showing a method for manufacturing a hard body. 5 (a) to 5 (c) are plan views, and FIG. 5 (d) is a perspective view. As shown in FIG. 5A, for example, a green sheet 30 containing 85% by weight of an insulator such as zirconium oxide and 15% by weight of a resin such as polyvinyl alcohol is manufactured. As shown in FIG. 5B, holes 22 are formed in the green sheet 30 by punching or the like. Thereafter, the green sheet 30 is fired. As shown in FIG. 5C, the fired green sheet is cut at the cutting line 32 using, for example, a dicing method. Thereby, the hard body 20 is separated into pieces. As shown in FIG. 5D, the hard body 20 includes a hole 22 penetrating in the film thickness direction.

  FIG. 6A to FIG. 6C are diagrams showing a method for forming the positive electrode film, and correspond to the step of FIG. 4B. 6B is a cross-sectional view taken along the line AA in FIG. 6C, and FIG. 6C is a top view. The positive electrode material contains 90% by weight of lithium cobalt oxide as a positive electrode active material, 5% by weight of a binder, and 5% by weight of a conductive material. An organic solvent is added to the positive electrode material to obtain a paste 26 (first paste) having viscosity. For example, polyvinylidene fluoride can be used as the binder, acetylene black or carbon black can be used as the conductive material, and n-methylpyrrolidone can be used as the organic solvent, for example. The hard body 20 is included in the paste 26. As shown in FIG. 6A, a paste 26 including a hard body 20 is applied on the conductor plate 16. For example, the paste 26 is applied using a printing method.

  As shown in FIG. 6B, the paste 26 is squeezed using a squeegee plate 28. Since the thickness of the hard body 20 is smaller than the vertical and horizontal dimensions as viewed from the top surface, the thickness direction of the hard body 20 is the normal direction of the top surface of the conductor plate 16 as shown in FIG. Is disposed on the conductor plate 16. Thereby, the positive electrode film 10 having substantially the same thickness as the hard body 20 is formed. The hard body 20 is disposed in the positive electrode film 10 almost uniformly. The restriction of the movement of the hard body 20 by the protrusion 24 is such that the protrusion 24 is caught in the hole 22 as in the leftmost hard body 20 of FIG. 6B, and the center hard body of FIG. 6B. 20, the protrusion 24 may be caught on the outside of the hard body 20.

  According to the third embodiment, the protrusion 24 that is lower than the film thickness of the positive electrode film 10 (for example, lower than the film thickness of the hard body 20) is provided on one surface of the conductor plate 16. Thereby, it can suppress that the protrusion 24 penetrates the positive electrode film 10. Further, as shown in FIG. 6B, when the paste 26 is squeegeeed, the movement of the hard body 20 is restricted by the protrusions 24. Thereby, the hard body 20 can be disposed in the positive electrode film 10 almost uniformly. The restriction of the movement of the hard body 20 by the protrusion 24 may be the case where the protrusion 24 is caught in the hole 22 or the protrusion 24 is caught outside the hard body 20. In order to uniformly arrange the hard bodies 20, it is preferable that holes 22 are provided in the hard body 20 and protrusions 24 are provided in the conductor plate 16 in order to further restrict the movement of the hard body 20.

  In order to arrange the hard bodies 20 more uniformly, the interval between the protrusions 24 is preferably larger than the size of the hard bodies 20 (for example, the long side when the hard body 20 is rectangular, and the long axis when the hard body 20 is elliptic). This is because, when the interval between the protrusions 24 is narrower than the size of the hard body 20, the hard bodies 20 may be caught by the adjacent protrusions 24, and the hard bodies 20 may overlap during the squeegee. Furthermore, if the interval between the protrusions 24 is too large, the hard bodies 20 may not be arranged uniformly. In order to make the hard body 20 uniform, it is preferable that two or three hard bodies 20 are included in the interval between the protrusions 24. Therefore, the interval between the protrusions 24 is preferably 1.5 to 4 times the size of the hard body 20, and more preferably 2 to 3 times.

  Further, as shown in FIG. 6B, both surfaces of the hard body 20 in the film thickness direction of the positive electrode film 10 are flat. Thereby, the film thickness of the positive electrode film | membrane 10 can be made more uniform. Further, the plurality of hard bodies 20 have the same thickness. Thereby, the film thickness of the positive electrode film | membrane 10 can be made more uniform.

  In Example 1 to Example 3, instead of the solid electrolyte membrane 12, for example, an electrolyte in which an electrolyte such as an organic electrolyte is included in a separator such as a polyethylene porous separator may be used. In order to form an all-solid thin-film secondary battery, the electrolyte is preferably a solid electrolyte membrane.

  Example 4 is an example in which the solid electrolyte membrane includes a hard body. FIG. 7A is a cross-sectional view of the secondary battery according to Example 4, and FIG. 7B is a plan view showing the solid electrolyte membrane and the hard body. As shown in FIG. 7A, the solid electrolyte film 12 including the hard body 40 (second hard body) is provided on the positive electrode film 10. The hard body 40 is harder than the solid electrolyte membrane 12. The hard body 40 is an insulator such as zirconium oxide or aluminum oxide, for example. The hard body 40 is preferably an insulator in order to suppress an electrical short circuit between the positive electrode film 10 and the negative electrode film 14. The solid electrolyte membrane 12 is, for example, a sulfide solid electrolyte. In FIG.7 (b), the hard body 20 is shown with the dotted line, and the hard body 40 is shown with the continuous line. As shown in FIG. 7B, the hard body 40 is periodically or randomly provided in the solid electrolyte membrane 12. Other configurations are the same as those in FIG. 1A and FIG. 1B of the first embodiment, and a description thereof will be omitted.

  In Example 4, the solid electrolyte membrane 12 includes a plurality of hard bodies 40 in addition to the positive electrode membrane 10. For this reason, even if an object falls on the secondary battery as shown in FIG. 2B, the dent is small, and the destruction of the secondary battery can be further suppressed. In this way, a secondary battery that is resistant to external impact can be provided. Furthermore, since the plurality of hard bodies 40 are independently provided and not connected, the flexibility of the secondary battery can be maintained.

  Example 5 is an example in which a hard body includes a through hole. FIG. 8 is a plan view of a hard body and a solid electrolyte membrane of a secondary battery according to Example 5. In FIG. 8, the hard body 20 is indicated by a dotted line, and the hard body 40 is indicated by a solid line. As shown in FIG. 8, a hole 42 (second hole) penetrating in the thickness direction of the solid electrolyte membrane 12 is formed in the hard body 40. The holes 42 are filled with the solid electrolyte membrane 12. Thereby, the solid electrolyte membrane 12 is formed in the hole 42. Therefore, the hard body 40 can suppress the area of the solid electrolyte membrane 12 from being reduced. In order to ensure the area of the solid electrolyte membrane 12, it is preferable that the hole 42 of the hard body 40 is large. For example, the size of the hole 42 is preferably 1/2 or more of the size of the hard body 40 and more preferably 3/4 or more. On the other hand, if the hole 42 is too large, the strength of the hard body 40 decreases. Therefore, the size of the hole 42 can be set by the strength of the hard body 40. The shape of the hard body 40 may be, for example, a circle, an ellipse, or a polygon other than the quadrangular shape as in the fourth and fifth embodiments. A plurality of holes 42 may be provided in one hard body 40.

  Example 6 is an example of a method for manufacturing a secondary battery. FIG. 9A to FIG. 9C are cross-sectional views illustrating the manufacturing process of the secondary battery according to the sixth embodiment. As shown in FIG. 9A, the conductor plate 16 including the protrusions 24 is formed in the same manner as in FIG. For example, the positive electrode film 10 having a film thickness of 50 μm is formed on one surface of the conductor plate 16. A plurality of hard bodies 20 are provided in the positive electrode film 10. The plurality of hard bodies 20 include protrusions 44 in the film thickness direction of the positive electrode film 10 or the penetration direction of the holes 22. The protrusions 44 are formed on both surfaces of the hard body 20. At least a part of the protrusion 44 protrudes from the positive electrode film 10 to the upper surface.

  As shown in FIG. 9B, the solid electrolyte film 12 having a film thickness of, for example, 50 μm is formed on the positive electrode film 10 by using, for example, a printing method. The solid electrolyte membrane 12 includes a plurality of hard bodies 40. The hard body 40 does not have to be formed with the projection 44 like the hard body 20. Note that the intermediate layer described in the third embodiment may be provided between the positive electrode film 10 and the solid electrolyte film 12. In this case, the protrusion 44 protrudes from at least the upper surface of the intermediate layer. As shown in FIG. 4C, the negative electrode film 14 is formed on the solid electrolyte film 12. A conductor plate 18 is formed on the negative electrode film 14.

  FIG. 10A to FIG. 10E are diagrams showing a method for manufacturing the hard body 20. 10 (a), 10 (b) and 10 (d) are plan views, FIG. 10 (c) is a cross-sectional view taken along line AA of FIG. 10 (b), and FIG. 10 (e) is a perspective view. As shown in FIG. 10A, a green sheet 30 including a plurality of holes 22 is produced in the same manner as in FIG. As shown in FIG. 10B, grooves are formed in the arrangement direction of the holes 22 of the green sheet 30 using, for example, a dicing blade. A groove is formed in the region 62 and the surface is shaved. In the region 60, no groove is formed and a projection is formed. As shown in FIG. 10C, protrusions are formed on both sides of the green sheet 30. Thereafter, the green sheet 30 is fired. As shown in FIG. 10D, the fired green sheet is cut at the cutting line 32 using, for example, a dicing method. Thereby, the hard body 20 is separated into pieces. As shown in FIG. 10E, the hard body 20 includes a hole 22 penetrating in the film thickness direction. Further, protrusions 44 are formed on the four corners of the front and back surfaces. The formation of the hard body 40 is performed in the same manner as in Example 3 and FIGS. 5 (a) to 5 (d). Thereby, no protrusion is formed on the hard body 40.

  FIG. 11A to FIG. 11D are diagrams showing a method of forming the positive electrode film and the solid electrolyte film, and correspond to the steps of FIG. 10A and FIG. 10B. Referring to FIG. 11A, an organic solvent is added to the positive electrode material to obtain a paste 26 (first paste) having viscosity. The hard body 20 is included in the paste 26. A paste 26 including a hard body 20 is applied on the conductor plate 16. For example, the paste 26 is applied using a printing method. As shown in FIG. 11 (b), the paste 26 is squeezed using a squeegee plate 28. Since the thickness of the hard body 20 is smaller than the vertical and horizontal dimensions as viewed from the top surface, the thickness direction of the hard body 20 is the normal direction of the top surface of the conductor plate 16 as shown in FIG. Is disposed on the conductor plate 16. Thereby, the positive electrode film 10 having substantially the same thickness as the hard body 20 is formed. Since the movement of the hard body 20 is restricted by the protrusions 24, the hard body 20 is disposed in the positive electrode film 10 almost uniformly. The restriction of the movement of the hard body 20 by the protrusion 24 may be caused when the protrusion 24 is caught in the hole 22 or when the protrusion 24 is caught outside the hard body 20.

  Referring to FIG. 11C, an organic solvent is added to the solid electrolyte to obtain a paste 46 (second paste) having viscosity. The solid electrolyte contains 97% by weight of a solid electrolyte such as a sulfide solid electrolyte and 3% by weight of a resin such as polyvinylidene fluoride. For example, n-methylpyrrolidone can be used as the organic solvent. The hard body 40 is included in the paste 46. A paste 26 including a hard body 20 is applied on the positive electrode film 10. When the paste 26 is dried, the volume of the positive electrode film 10 is reduced. Thereby, at least a part of the protrusion 44 protrudes from the upper surface of the positive electrode film 10. For example, the paste 46 is applied using a printing method. As shown in FIG. 11 (e), the paste 46 is squeezed using the squeegee plate 28. Since the film thickness of the hard body 40 is smaller than the vertical and horizontal sizes as viewed from the top surface, the film thickness direction of the hard body 40 is the normal direction of the top surface of the positive electrode film 10 as shown in FIG. Is disposed on the positive electrode film 10. Thereby, the solid electrolyte membrane 12 having substantially the same thickness as the hard body 40 is formed. Since the movement of the hard body 40 is restricted by the protrusions 44, the hard body 40 is disposed in the solid electrolyte membrane 12 almost uniformly. The restriction of the movement of the hard body 40 by the protrusion 44 may be caused when the protrusion 44 is caught in the hole 42 or when the protrusion 44 is caught outside the hard body 40.

  According to Example 6, the hard body 20 included in the positive electrode film 10 includes protrusions 44 that are lower than the film thickness of the solid electrolyte film 12 (for example, lower than the film thickness of the hard body 40). Thereby, it can suppress that the protrusion 44 penetrates the solid electrolyte membrane 12. FIG. Further, the protrusion 24 is higher than the protrusion 44. Thereby, in FIG.11 (b), the hard body 20 becomes easy to be controlled by the protrusion 24. FIG. Further, as shown in FIG. 11D, when the paste 46 is squeegeeed, the movement of the hard body 40 is restricted by the protrusions 44. Thereby, the hard body 40 can be disposed in the solid electrolyte membrane 12 almost uniformly. The restriction of the movement of the hard body 40 by the protrusion 44 may be caused when the inside of the hole 42 is caught by the protrusion 44 or when the outside of the hard body 40 is caught by the protrusion 44. In order to arrange the hard body 40 uniformly and further restrict the movement of the hard body 40, it is preferable that the hole 42 is provided in the hard body 40 and the protrusion 44 is provided in the hard body 20. Further, the protrusion 44 may be formed only on the upper surface of the upper surface and the lower surface of the hard body 20. Further, in FIG. 10 (e), four protrusions 44 are formed on one surface of the hard body 20, but one or a plurality of protrusions may be formed.

  In order to arrange the hard bodies 40 more uniformly, the interval between the protrusions 44 is preferably larger than the size of the hard bodies 40 (for example, the long side when the hard body 40 is rectangular and the long axis when the hard body 40 is elliptic). This is because when the distance between the protrusions 44 is narrower than the size of the hard body 40, the hard bodies 20 may be caught by the adjacent protrusions 44, and the hard body 40 may overlap during the squeegee. Furthermore, if the interval between the protrusions 44 is too large, the hard bodies 40 may not be arranged uniformly. In order to make the hard body 40 uniform, it is preferable that two or three hard bodies 40 are included in the interval between the protrusions 44.

  Moreover, as shown in FIG. 11D, both surfaces of the solid electrolyte membrane 12 of the hard body 40 in the film thickness direction are flat. Thereby, the film thickness of the solid electrolyte membrane 12 can be made more uniform. Further, the thicknesses of the plurality of hard bodies 40 are the same. Thereby, the film thickness of the solid electrolyte membrane 12 can be made more uniform.

  In the first to sixth embodiments, the positive electrode film 10 is described as an example of the film including the hard body 20, but the hard body 20 may be included in the negative electrode film 14. Further, the hard body 20 may be provided in both the negative electrode film 14 and the positive electrode film 10. As described above, it is sufficient that a plurality of hard bodies 20 are provided in at least one of the negative electrode film 14 and the positive electrode film 10. Moreover, although the example of the lithium secondary battery has been described, other secondary batteries may be used.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.

The following appendices are further disclosed with respect to the embodiments including Examples 1 to 6.
Appendix 1:
A secondary comprising: a negative electrode film and a positive electrode film; and a plurality of first hard bodies provided in at least one electrode film of the negative electrode film and the positive electrode film and harder than the at least one electrode film. battery.
Appendix 2:
The secondary according to claim 1, wherein each of the plurality of first hard bodies includes a first hole penetrating in a film thickness direction of the at least one electrode film and filled with the at least one electrode film. battery.
Appendix 3:
The secondary battery according to claim 2, wherein the at least one electrode film is formed on one side, and a conductive plate having a first protrusion lower than the film thickness of the at least one electrode film is provided on the one side. .
Appendix 4:
The secondary battery according to any one of supplementary notes 1 to 3, wherein both surfaces of the at least one electrode film of each of the plurality of first hard bodies are flat.
Appendix 5:
The secondary battery according to supplementary note 1, comprising: a solid electrolyte film provided between the negative electrode film and the positive electrode film; and a plurality of second hard bodies provided in the solid electrolyte film and harder than the solid electrolyte.
Appendix 6:
A solid electrolyte membrane provided between the negative electrode membrane and the positive electrode membrane; and a plurality of second hard bodies provided in the solid electrolyte membrane and harder than the solid electrolyte membrane, wherein the first hard body is The second hard body has a second hole filled with the solid electrolyte membrane, and has a second protrusion in the penetration direction of the first hole, and the second hard body penetrates in the film thickness direction of the solid electrolyte membrane. The secondary battery as set forth in Appendix 3.
Appendix 7:
The secondary battery according to appendix 6, wherein the first protrusion is higher than the second protrusion.
Appendix 8:
The secondary battery according to appendix 4, wherein each of the plurality of first hard bodies has the same thickness.
Appendix 9:
The secondary battery according to any one of appendices 1 to 4, further comprising a solid electrolyte membrane sandwiched between the negative electrode membrane and the positive electrode membrane.
Appendix 10:
The secondary battery according to appendix 5 or 6, wherein both surfaces of the at least one electrode film of each of the plurality of second hard bodies are flat.
Appendix 11:
The secondary battery according to appendix 5 or 6, wherein each of the plurality of second hard bodies has the same thickness.
Appendix 12:
The secondary battery according to any one of appendices 1 to 11, wherein the at least one electrode film is the positive electrode film.
Addendum 13:
The secondary battery according to any one of appendices 1 to 12, wherein the secondary battery is a lithium secondary battery.
Appendix 14:
A first paste containing at least one of a negative electrode material and a positive electrode material and including a plurality of first hard bodies is applied on the conductor plate, and the first paste is squeegeeed to squeeze the first paste on the conductor plate. A method for manufacturing a secondary battery, wherein at least one electrode film of a corresponding negative electrode film and positive electrode film is formed from the at least one material, and the plurality of first hard bodies are harder than the at least one electrode film. .
Appendix 15:
A first protrusion lower than the film thickness of the first hard body is formed on one surface of the conductor plate, and when applying the first paste, the first paste is applied to the one surface, and the at least one electrode 15. The method of manufacturing a secondary battery according to appendix 14, wherein when forming the film, the first paste is squeezed so that movement of the plurality of first hard bodies is restricted by the first protrusions.
Appendix 16:
On the at least one electrode film, a second paste containing a solid electrolyte material and including a plurality of second hard bodies is applied, and the second paste is squeezed to form the second paste on the at least one electrode film. 15. The method of manufacturing a secondary battery according to appendix 14, wherein a solid electrolyte membrane is formed, and the plurality of second hard bodies are harder than the solid electrolyte membrane.
Addendum 17:
The first hard body has second protrusions lower than the thickness of the second hard body, and when the solid electrolyte membrane is formed, movement of the plurality of second hard bodies is restricted by the second protrusions. The method of manufacturing a secondary battery according to appendix 16, wherein the second paste is squeegeeed as described above.

DESCRIPTION OF SYMBOLS 10 Positive electrode film | membrane 12 Solid electrolyte membrane 14 Negative electrode film | membrane 16 Electric conductor board 20, 40 Hard body 22, 42 Hole 24, 44 Protrusion 26, 46 Paste

Claims (7)

A negative electrode film and a positive electrode film;
Provided in at least one of the negative electrode film and the positive electrode film, harder than the at least one electrode film, penetrating in the film thickness direction of the at least one electrode film, and filled with the at least one electrode film A plurality of first hard bodies provided with first holes;
The at least one electrode film is formed on one side, and a conductor plate provided with a first protrusion on the one side lower than the film thickness of the at least one electrode film;
Comprising
The secondary battery, wherein the first protrusion is positioned in at least a part of the first hole of the plurality of first hard bodies. A solid electrolyte membrane provided between the negative electrode membrane and the positive electrode membrane;
A plurality of second hard bodies provided in the solid electrolyte membrane and harder than the solid electrolyte membrane;
The secondary battery according to claim 1, comprising: A negative electrode film and a positive electrode film;
A plurality of first hard bodies provided in at least one of the negative electrode film and the positive electrode film and harder than the at least one electrode film;
The at least one electrode film is formed on one side, and a conductor plate provided with a first protrusion on the one side lower than the film thickness of the at least one electrode film;
A solid electrolyte membrane provided between the negative electrode membrane and the positive electrode membrane;
A plurality of second hard bodies provided in the solid electrolyte membrane and harder than the solid electrolyte membrane;
Comprising
The first hard body includes a first hole penetrating in the film thickness direction of the at least one electrode film and filled with the at least one electrode film, and a second protrusion in the penetrating direction of the first hole,
The secondary battery includes a second hole penetrating in a film thickness direction of the solid electrolyte membrane and having a second hole filled with the solid electrolyte membrane.   The secondary battery according to claim 3, wherein the first protrusion is higher than the second protrusion. On the conductor plate, a first paste including at least one of a negative electrode material and a positive electrode material and including a plurality of first hard bodies is applied,
By squeezing the first paste, a corresponding negative electrode film and a positive electrode film are formed on the conductor plate from the at least one material,
The plurality of first hard bodies are harder than the at least one electrode film,
A first protrusion lower than the thickness of the first hard body is formed on one surface of the conductor plate,
When applying the first paste, apply the first paste on the one side;
A method of manufacturing a secondary battery, wherein when forming the at least one electrode film, the first paste is squeezed so that movement of the plurality of first hard bodies is restricted by the first protrusions. A second paste containing a solid electrolyte material and a plurality of second hard bodies is applied onto the at least one electrode film,
By squeezing the second paste, a solid electrolyte membrane is formed on the at least one electrode membrane,
6. The method of manufacturing a secondary battery according to claim 5, wherein the plurality of second hard bodies are harder than the solid electrolyte membrane. Second protrusions lower than the film thickness of the second hard body are formed on the first hard body,
The secondary battery according to claim 6, wherein when forming the solid electrolyte membrane, the second paste is squeezed so that movement of the plurality of second hard bodies is restricted by the second protrusions. Production method.

Images