JP2012221580A - Solid-state battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid-state battery capable of applying a uniform pressure to unit cells in a container.SOLUTION: A solid-state battery comprises a plurality of unit cells including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer between the positive electrode layer and the negative electrode layer, and a container containing the unit cells. The surroundings of the unit cells and the inside of the container are filled with gas to apply pressure to the unit cells, separators are disposed between adjacent two unit cells and between the unit cells and the container, and the separators prevent contact between the adjacent two unit cells and contact between the unit cells and the container at least during the operation of the unit cells.

Description

  The present invention relates to a solid battery, and more particularly, to a solid battery having a structure in which a unit cell is isotropically pressurized.

  A lithium ion secondary battery (hereinafter sometimes referred to as a “lithium secondary battery”) has characteristics that it has a higher energy density than other secondary batteries and can operate at a high voltage. For this reason, it is used as a secondary battery that can be easily reduced in size and weight in information equipment such as a mobile phone, and in recent years, there is an increasing demand for large motive power such as for electric vehicles and hybrid vehicles.

  A lithium ion secondary battery includes a positive electrode layer and a negative electrode layer, and an electrolyte layer disposed therebetween. Examples of the electrolyte included in the electrolyte layer include non-aqueous liquid and solid substances. Used. When a liquid electrolyte (hereinafter referred to as “electrolytic solution”) is used, the electrolytic solution easily penetrates into the positive electrode layer and the negative electrode layer. Therefore, an interface between the active material contained in the positive electrode layer or the negative electrode layer and the electrolytic solution is easily formed, and the performance is easily improved. However, since the widely used electrolyte is flammable, it is necessary to mount a system for ensuring safety. On the other hand, when a solid electrolyte that is nonflammable (hereinafter referred to as “solid electrolyte”) is used, the above system can be simplified. Therefore, a lithium ion secondary battery (hereinafter referred to as “solid battery”) in a form provided with a layer containing a solid electrolyte that is nonflammable (hereinafter referred to as “solid electrolyte layer”) has been proposed. Yes.

  As a technique related to such a battery, for example, Patent Document 1 discloses an assembled battery in which a plurality of unit cells are combined and accommodated in an assembled battery case. Or the lithium secondary battery which pressurizes a unit cell using the hydrostatic pressure which arises in an assembled battery case by being filled with at least 1 sort (s) of solid powder, or these mixed substances is disclosed. Further, Patent Document 2 includes a pressurizing unit that pressurizes the battery elements in the stacking direction, and the pressurizing units are arranged at each of a plurality of positions with respect to the surface direction of the region corresponding to the battery element in the battery element. A bipolar battery is disclosed that is configured to be capable of energizing pressures of different strengths. Patent Document 3 discloses an inorganic solid electrolyte battery having a positive electrode and a negative electrode provided so as to mesh with the positive electrode while being spaced apart from each other. Patent Document 4 discloses that in a battery structure formed by laminating a plurality of unit cell layers, at least one unit cell layer and another unit cell among the plurality of unit cell layers forming the cell structure. A technique is disclosed in which a heat dissipating member having a function of preventing vibration received from the outside is disposed between the layers. Further, as a technique relating to a battery having a form different from that of a lithium ion secondary battery, Patent Document 5 discloses a sodium having a vacuum heat insulating container and a plurality of single cells accommodated in the vacuum heat insulating container with a space therebetween. -Sulfur batteries (NAS batteries) are disclosed.

JP-A-10-214638 JP 2008-159570 A JP 2006-261008 A JP 2007-31264 A JP 2000-48857 A

  In the technique disclosed in Patent Document 1, since the unit cell is pressurized using hydrostatic pressure, it is considered possible to suppress variation in unit cell performance due to application of non-uniform pressure. It is done. However, when a plurality of unit cells are accommodated in a form in contact with each other in the assembled battery case, the pressure applied to the part where the unit cells are in contact with each other and the part not in contact with the other unit cells There is a difference between the applied pressure. Therefore, in the technique disclosed in Patent Document 1, the effect of suppressing performance degradation due to application of non-uniform pressure tends to be insufficient. In addition, when a solid battery is arranged as disclosed in Patent Document 5, when the solid battery is used in a device that vibrates like a vehicle, vibration is easily transmitted to the solid battery, and the performance of the solid battery is reduced. There was a fear. These problems have been difficult to solve by simply combining the techniques disclosed in Patent Documents 1 to 5.

  Then, this invention makes it a subject to provide the solid battery which can improve performance.

In order to solve the above problems, the present invention takes the following means. That is,
The present invention comprises a unit cell having a positive electrode layer and a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, and a container for housing a plurality of unit cells, and the periphery of the unit cell The inside of the container is filled with gas to pressurize the unit cell, and a contact avoidance member is disposed between two adjacent unit cells and between the unit cell and the container, and the contact avoidance member is used. Thus, at least during operation of the unit cell, contact between two adjacent unit cells and contact between the unit cell and the container are avoided.

  Here, “when the unit cell is in operation” refers to charging and discharging when the unit cell is a secondary cell, and discharging when the unit cell is a primary cell.

  Further, in the present invention, the air blowing means is accommodated in the container, and a plurality of unit cells are stacked in the vertical direction, and the gas filled in the container is circulated using the air blowing means. A plurality of unit cells may be arranged so that the pressure decreases between adjacent unit cells on the upper side in the direction or between the unit cells and the container.

  Here, "the pressure decreases between adjacent unit cells on the upper side in the vertical direction or between the unit cells and the container" means that, for example, when two unit cells are accommodated in the container, The pressure of the region sandwiched between the upper surface of the unit cell disposed on the upper side in the vertical direction and the container is P1, the pressure of the region sandwiched between the two unit cells is P2, and the lower surface of the unit cell disposed on the lower side in the vertical direction When the pressure in the region sandwiched between the container and the container is P3, it means that P1 <P2 <P3.

  In the present invention, the contact avoidance member may have a hole.

  In the solid state battery of the present invention, the contact avoidance member is used to avoid contact between two adjacent unit cells and contact between the unit cell and the container at least during operation of the unit cell. By adopting such a configuration, the surface of the unit cell is uniformly pressurized using gas as compared to the case where two adjacent unit cells are in contact with each other or the unit cell and the container are in contact with each other. Is possible. By uniformly applying pressure, it is possible to suppress the performance degradation caused by the application of non-uniform pressure, so that the performance of the battery can be improved. Therefore, according to the present invention, it is possible to provide a solid state battery capable of improving performance. In the solid state battery of the present invention, the unit cell and the container are not in direct contact at least during operation of the unit cell. Therefore, even when the solid battery of the present invention is used in a vibrating device such as a vehicle, it is possible to reduce vibration transmitted to the unit cell, and as a result, the performance of the unit cell is reduced. It becomes possible to suppress. That is, according to the solid battery of the present invention, it is possible to improve the performance.

  Moreover, in this invention, when the gas with which the container was filled was circulated using the ventilation means, it is set as the form by which the several unit cell is arrange | positioned so that a pressure may become so small that it is the clearance gap of the upper direction of a perpendicular direction. Thus, it is possible to float a plurality of unit cells by sending wind from the blowing means. By floating a plurality of unit cells, it becomes easy to pressurize the entire surface of the unit cells uniformly, and it becomes easy to improve the performance of the solid state battery.

  Moreover, in this invention, when the contact avoidance member has a hole, the part of the unit cell which is contacting the contact avoidance member can also be pressurized using gas. Therefore, by setting it as this form, it becomes easy to apply a uniform pressure to the unit cell accommodated in the container, As a result, it becomes easy to improve the performance of a solid battery.

1 is a cross-sectional view illustrating a solid battery 10. 1 is a cross-sectional view illustrating a unit cell 1. 2 is a cross-sectional view illustrating a solid state battery 20. FIG. 2 is a cross-sectional view illustrating a solid battery 30. FIG. 2 is a cross-sectional view illustrating a solid state battery 40. FIG. 2 is a cross-sectional view illustrating a solid battery 50. FIG. It is sectional drawing explaining the unit cell 51. FIG. 2 is a cross-sectional view illustrating a solid battery 60. FIG.

  The present invention will be described below with reference to the drawings. In addition, the form shown below is an illustration of this invention and this invention is not limited to the form shown below. In order to make it easy to see, some reference numerals may be omitted in the drawings.

  FIG. 1 is a cross-sectional view illustrating a solid state battery 10 according to the first embodiment of the present invention. In FIG. 1, the solid state battery 10 is shown in a simplified manner. The direction from the upper side to the lower side in FIG. 1 is the direction of gravity (vertical direction). As shown in FIG. 1, the solid battery 10 includes a plurality of unit cells 1,..., And a container 2 that houses the unit cells 1, 1,. .. Around the unit cells 1,... And inside the container 2 are filled with an inert gas 3 that pressurizes the unit cells 1,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. The unit cells 1, 1,... Are arranged so that the ends thereof are in contact with the comb-like contact avoiding members 6, 6, so that the positions in the container 2 are determined. Thus, the contact between the adjacent unit cells 1 and 1 and the contact between the unit cell 1 and the container 2 are avoided. The gas flow path 4 is used when the inert gas 3 is filled in the container 2 containing the unit cells 1, 1,... Arranged so as to be in contact with the contact avoidance members 6, 6. When the filling is finished, the valve 5 is closed. By closing the valve 5, the leakage of the inert gas 3 is prevented and the inflow of air into the container 2 is prevented. In addition, although illustration is omitted, the container 2 is provided with an introduction portion such as a current terminal and a sensor typified by a temperature sensor. As shown in FIG. 1, the upper surface of the unit cell 1 arranged at the top in the direction of gravity (vertical direction) is not in contact with the container 2.

  FIG. 2 is a cross-sectional view illustrating the unit cell 1. As shown in FIG. 2, the unit cell 1 has a laminate 1x, and the laminate 1x is wrapped in a laminate film 1y. The laminated body 1x includes a positive electrode current collector 1a, a positive electrode layer 1b connected to the positive electrode current collector 1a, a solid electrolyte layer 1c disposed so as to be in contact with the positive electrode layer 1b, and a solid electrolyte layer 1c. And a negative electrode layer 1d disposed on the opposite side of the positive electrode layer 1b so as to be in contact with the solid electrolyte layer 1c, and a negative electrode current collector 1e connected to the negative electrode layer 1d. A terminal 1f is connected to the positive electrode current collector 1a, and a terminal 1g is connected to the negative electrode current collector 1e. One end of each of the terminal 1f and the terminal 1g is located outside the laminate film 1y. In the solid battery 10, a plurality of terminals 1f, 1f,... Are connected to a positive electrode connection terminal (not shown), and one end of the positive electrode connection terminal is connected to a positive electrode terminal (not shown) located outside the container 2. Has been. Similarly, the plurality of terminals 1g, 1g,... Are connected to a negative electrode connection terminal (not shown), and one end of the negative electrode connection terminal is connected to a negative electrode terminal (not shown) located outside the container 2. Yes.

  As described above, in the solid battery 10, the contact avoiding members 6 and 6 avoid contact between the adjacent unit cells 1 and 1 and contact between the unit cell 1 and the container 2. The surface of the unit cells 1, 1,... Is uniformly pressurized using the inert gas 3 by avoiding the contact between the adjacent unit cells 1, 1 and the contact between the unit cell 1 and the container 2. Can do. Here, in the solid battery 10, the end portions of the unit cells 1, 1,... Are in contact with the contact avoidance member 6. As described above, the unit cell 1 is configured such that the laminate 1x is wrapped with the laminate film 1y, and the laminate film 1y is sealed, for example, by heat-sealing the edges. Therefore, by adopting a form in which the edge of the sealed laminate film 1y and the contact avoiding members 6 and 6 are brought into contact with each other, according to the solid battery 10, both end surfaces in the stacking direction of the stacked body 1x (upper and lower in FIG. 1). The side surface) can be evenly pressurized. Therefore, according to the present invention, since it becomes possible to apply a uniform pressure to the laminates 1x, 1x,... Accommodated in the container 2, performance degradation due to the application of a non-uniform pressure. Can be suppressed. Therefore, according to this invention, the solid battery 10 which can improve performance can be provided.

  Further, in the solid battery 10, the container 2 and the unit cells 1, 1,... Are not in direct contact. Therefore, even when the solid battery 10 is used for a vibrating device, the vibration transmitted to the unit cells 1, 1,... Is reduced as compared with the case where the unit cell and the container are in direct contact. be able to. By reducing the vibration transmitted to the unit cells 1, 1,..., It is possible to suppress the performance degradation caused by the vibration. Therefore, according to the solid battery 10, the performance can be improved.

  In the solid battery 10, the positive electrode current collector 1a and the negative electrode current collector 1e can be formed of a known conductive material that can be used as a positive electrode current collector or a negative electrode current collector of a lithium ion secondary battery. Examples of such a conductive material include one or more elements selected from the group consisting of Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. Examples of the metal material to be included can be given. Moreover, the positive electrode current collector 1a and the negative electrode current collector 1e can be formed into a shape such as a metal foil or a metal mesh, for example.

Moreover, as a positive electrode active material contained in the positive electrode layer 1b, the well-known active material which can be contained in the positive electrode layer of a lithium ion secondary battery can be used suitably. Examples of such a positive electrode active material include lithium cobaltate (LiCoO ₂ ). As the solid electrolyte contained in the positive electrode layer 1b, a known solid electrolyte that can be contained in the positive electrode layer of the lithium ion secondary battery can be appropriately used. Such solid electrolyte, _Li 3 PO ₄ addition of the oxide-based solid electrolytes such as, _Li 3 PS _{4 and, Li 2 S: P 2 S} 5 = 50: 50~100: 0 become as Li ₂ A sulfide-based solid electrolyte prepared by mixing S and P ₂ S ₅ (for example, mixing Li ₂ S and P ₂ S ₅ so that the mass ratio is Li ₂ S: P ₂ S ₅ = 75: 25) Examples thereof include a sulfide solid electrolyte produced in the above manner. In addition, the positive electrode layer 1b may contain a binder for binding the positive electrode active material and the solid electrolyte and a conductive material for improving conductivity. Examples of the binder that can be contained in the positive electrode layer 1b include butylene rubber, and examples of the conductive material that can be contained in the positive electrode layer 1b include carbon black. Moreover, as a solvent used when manufacturing the positive electrode layer 1b, the well-known solvent which can be used when adjusting the slurry used at the time of preparing the positive electrode layer of a lithium ion secondary battery can be used suitably. As such a solvent, heptane and the like can be exemplified.

  Examples of the solid electrolyte contained in the solid electrolyte layer 1c include the solid electrolyte that can be contained in the positive electrode layer 1b. Examples of the solvent used when producing the solid electrolyte layer 1c include the above-mentioned solvents that can be used when producing the positive electrode layer 1b.

  Moreover, as a negative electrode active material contained in the negative electrode layer 1d, the well-known active material which can be contained in the negative electrode layer of a lithium ion secondary battery can be used suitably. Examples of such an active material include graphite. Moreover, as a solid electrolyte contained in the negative electrode layer 1d, a known solid electrolyte that can be contained in the negative electrode layer of the lithium ion secondary battery can be appropriately used. Examples of such a solid electrolyte include the solid electrolyte that can be contained in the positive electrode layer 1b. In addition, the negative electrode layer 1d may contain a binder for binding the negative electrode active material and the solid electrolyte, and a conductive material for improving conductivity. Examples of the binder and conductive material that can be contained in the negative electrode layer 1d include the binder and conductive material that can be contained in the positive electrode layer 1b. Moreover, as a solvent used when producing the negative electrode layer 1d, the said solvent etc. which can be used when producing the positive electrode layer 1b can be illustrated.

  In addition, the laminate film 1y is not particularly limited, and a film that can withstand the environment during use of the lithium ion secondary battery, has a property of not allowing gas to permeate, and can be sealed is used. Can do. Examples of the constituent material of such a film include not only resins represented by polyethylene, polyvinyl fluoride, polyvinylidene chloride, and the like, but also metal-deposited films obtained by depositing a metal such as aluminum on these surfaces. .

  Moreover, the terminal 1f and the terminal 1g can be comprised with the material which has the favorable electronic conductivity which can endure the environment at the time of use of the solid battery 10, and can respond also to the external force provided at the time of use of the solid battery 10. It is preferable that the material is composed of a material having strength and flexibility. Examples of such materials include carbon fibers typified by carbon fiber reinforced plastic (CFRP).

  Further, the container 2, the gas flow path 4, and the contact avoidance member 6 can withstand the environment when the solid battery 10 is used, and the pressure of the inert gas 3 that pressurizes the unit cell 1 (for example, 1 It can be made of a known material having a strength that can withstand a pressure of about 200 atm or more. Examples of such a material include thermosetting resins represented by polyether ether ketone (PEEK) and the like in addition to metals such as aluminum and stainless steel. In addition, the container 2, the gas flow path 4, and the contact avoidance member 6 can be made of the same material as that of the laminate film 1y.

  Further, as the inert gas 3, for example, nitrogen gas, argon gas, or the like can be used. In addition, as the gas to pressurize the unit cells 1, 1,..., A fluorine-based gas that can be used as a refrigerant (for example, a hydrofluorocarbon mixed refrigerant (R410A, R407C, etc.)), isobutane, carbon dioxide, or dry air. Etc. can also be used.

  Further, the form of the valve 5 is particularly limited as long as the valve 5 has a function of blocking the movement of the fluid through the gas flow path 4 and is made of a material that can withstand the environment when the solid battery 10 is used. Not. As the valve 5, in addition to a valve whose operation is electronically controlled, a valve that manually opens and closes can be used.

  FIG. 3 is a cross-sectional view for explaining the solid state battery 20 of the present invention according to the second embodiment. The direction from the upper side to the lower side in FIG. 3 is the direction of gravity (vertical direction). In FIG. 3, the same components as those of the solid battery 10 are denoted by the same reference numerals as those used in FIG. 1, and the description thereof is omitted as appropriate. In FIG. 3, the solid state battery 20 is shown in a simplified manner.

  As shown in FIG. 3, the solid battery 20 includes a plurality of unit cells 1, 1,... Arranged in parallel in the vertical direction, and a container 2 that houses the unit cells 1, 1,. Have. .. Around the unit cells 1,... And inside the container 2 are filled with an inert gas 3 that pressurizes the unit cells 1,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. On the inner side of the container 2 (the side facing the unit cells 1, 1,...), The position of the unit cells 1, 1,. Positioning pieces 22 and 22, positioning pieces 23 and 23, positioning pieces 24 and 24, positioning pieces 25 and 25, positioning pieces 26 and 26, and positioning for preventing contact with 2 and adjacent unit cells 1 and 1 The pieces 27 and 27 (hereinafter, these may be collectively referred to as “positioning pieces”) are provided. Here, the distance between the upper surface of the unit cell 1 disposed so as to be in contact with the positioning pieces 23 and 23 and the container 2 at the time of manufacturing the solid battery 20 is L1, and the lower surface of the unit cell 1 and the positioning pieces 24 and 24 are arranged. L2 is the distance between the upper surface of the unit cell 1 disposed so as to be in contact with the upper surface of the unit cell 1, and L3 is the distance between the lower surface of the unit cell 1 and the upper surface of the unit cell 1 disposed so as to be in contact with the positioning pieces 25, 25. The distance between the lower surface of the unit cell 1 and the upper surface of the unit cell 1 arranged so as to contact the positioning pieces 26, 26 is L4, and the lower surface of the unit cell 1 is arranged so as to contact the positioning pieces 27, 27. In the solid battery 20, L1> L2> L3> L4> L5> L6, where the distance between the upper surface of the unit cell 1 is L5 and the distance between the lower surface of the unit cell 1 and the container 2 is L6. .

Here, the pressure in the region having the interval L1 is P1, the pressure in the region having the interval L2 is P2, the pressure in the region having the interval L3 is P3, the pressure in the region having the interval L4 is P4, and the interval is L5. Let P5 be the pressure in the region, and P6 be the pressure in the region where the interval is L6. In the solid battery 20, since L1>L2>L3>L4>L5> L6, when air is sent from the blowing means 21 to the unit cells 1, 1,. It is possible to satisfy <P2 <P3 <P4 <P5 <P6. In the solid battery 20, for example, when the unit cells 1, 1,... Have a weight of 3 g and the area of the air receiving surface is 50 cm ² , when 0.5 m / s of wind is sent from the blowing means 21. It becomes possible to float the unit cells 1, 1,. The floating unit cells 1, 1,... Remain in a position where the force received from the upper surface and the force received from the lower surface are balanced. By setting it as this state, it becomes possible to pressurize the surface of unit cell 1,1, ... uniformly. Moreover, even if it is a case where the solid battery 20 is used for the apparatus which vibrates by floating the unit cells 1, 1,..., It is possible to make the vibration transmitted to the unit cells 1, 1,. Become. Therefore, according to the solid battery 20, the performance can be improved.

  In the solid battery 20, the degree of floating of the unit cells 1,... Can be changed by changing the strength of the wind sent from the blowing unit 21. 1, 1,... Can be raised high. As described above, since the positioning piece is provided in the solid battery 20, even when the unit cells 1, 1,... Contact between the unit cell 1 and the container 2 is prevented.

  In the solid battery 20, the form of the air blowing means 21 is not particularly limited as long as it is a device capable of sending wind to the unit cells 1, 1,. As the air blowing means 21, for example, a known blower used for the purpose of cooling a lithium ion secondary battery can be used.

  Further, the positioning piece can exhibit a function of defining a region in which the unit cell 1 can move so that the adjacent unit cells 1, 1 and the unit cell 1 and the container 2 do not come into contact with each other, and the solid state battery 20. If it is comprised by the substance which can endure the environment at the time of use, the form will not be specifically limited. The positioning piece can be formed of the same material as that of the container 2, for example.

  FIG. 4 is a cross-sectional view for explaining a solid state battery 30 according to the third embodiment of the present invention. The direction from the upper side to the lower side in FIG. 4 is the direction of gravity (vertical direction). 4, the same reference numerals as those used in FIG. 3 are attached to the same components as those of the solid battery 20, and the description thereof is omitted as appropriate. In FIG. 4, the solid state battery 30 is shown in a simplified manner.

  As shown in FIG. 4, the solid battery 30 includes a plurality of unit cells 1, 1,... Arranged in parallel in the vertical direction, and a container 2 that houses the unit cells 1, 1,. Have. .. Around the unit cells 1,... And inside the container 2 are filled with an inert gas 3 that pressurizes the unit cells 1,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. On the inner side of the container 2 (the side facing the unit cells 1, 1,...), The position of the unit cells 1, 1,. Positioning pieces for preventing contact with 2 and contact between adjacent unit cells 1 and 1 are provided. In the solid battery 30, the wings 31 are in contact with the positioning pieces 24, 24 at the time of manufacturing the solid battery 30 at the end face of the unit cell 1 arranged so as to be in contact with the positioning pieces 23, 23 at the time of manufacturing the solid battery 30. The wings 32 are provided on the end face of the unit cell 1 arranged in the above, and the wings 33 are provided on the end face of the unit cell 1 arranged so as to be in contact with the positioning pieces 25, 25 when the solid battery 30 is manufactured. Sometimes the wings 34 are on the end face of the unit cell 1 arranged so as to be in contact with the positioning pieces 26, 26, and the end surface of the unit cell 1 arranged so as to be in contact with the positioning pieces 27, 27 when the solid battery 30 is manufactured. Each has a wing 35 attached thereto. The areas of the surface 31z of the wing 31 that receives the wind sent from the blower means 21, the surface 32z of the wing 32, the surface 33z of the wing 33, the surface 34z of the wing 34, and the surface 35z of the wing 35 are respectively S1 and S2. , S3, S4, and S5, the solid battery 30 satisfies S1> S2> S3> S4> S5.

Here, the pressure in the region sandwiched between the upper surface of the unit cell 1 to which the wing 31 is attached and the container 2 is P1, and the lower surface of the unit cell 1 to which the wing 31 is attached and the unit to which the wing 32 is attached. The pressure in the region sandwiched between the upper surface of the battery 1 is P2, and the pressure in the region sandwiched between the lower surface of the unit cell 1 to which the wing 32 is attached and the upper surface of the unit cell 1 to which the wing 33 is attached is P3. The pressure in the region sandwiched between the lower surface of the unit cell 1 to which the wing 33 is attached and the upper surface of the unit cell 1 to which the wing 34 is attached is P4, and the lower surface of the unit cell 1 to which the wing 34 is attached The pressure in the region sandwiched between the upper surface of the unit cell 1 to which the wings 35 are attached is P5, and the pressure in the region sandwiched between the lower surface of the unit cell 1 to which the wings 35 are attached and the container 2 is P6. To do. In the solid battery 30, since S1>S2>S3>S4> S5, when the air is sent from the blowing means 21 to the unit cells 1, 1,... When the unit cells 1, 1,. It is possible to satisfy <P3 <P4 <P5 <P6. In the solid battery 30, for example, when the unit cell 1 to which the wings 31 are attached has a weight of 3 g and the area of the air receiving surface is 50 cm ² , the air blown from the air blowing means 21 is 0.3 m / s. To send the unit cell 1 to the floating position. As described above, the unit cells 1, 1,... Therefore, according to the solid battery 30, the performance can be improved as in the solid battery 20.

  In the solid battery 30 as well as the solid battery 20, the degree of floating of the unit cells 1,... Can be changed by changing the strength of the wind sent from the blower unit 21. When the wind is sent, the unit cells 1, 1,... As described above, since the positioning piece is provided in the solid battery 30, even if the unit cells 1, 1,... Contact between the unit cell 1 and the container 2 is prevented.

  In the solid battery 30, the wings 31, 32, 33, 34, and 35 have a strength capable of receiving a wind sent from the air blowing means 21 and generating lift, and when the solid battery 30 is used. The form is not particularly limited as long as it is made of a material that can withstand the environment. From the viewpoint of easily floating the unit cells 1, 1,..., It is preferably formed of a lightweight material. The wings 31, 32, 33, 34, and 35 can be made of a resin such as polyethylene terephthalate (PET).

  FIG. 5 is a cross-sectional view illustrating a solid state battery 40 of the present invention according to the fourth embodiment. The direction from the upper side to the lower side in FIG. 5 is the direction of gravity (vertical direction). In FIG. 5, the same components as those of the solid battery 20 are denoted by the same reference numerals as those used in FIG. 3, and the description thereof is omitted as appropriate. In FIG. 5, the solid state battery 40 is shown in a simplified manner.

  As shown in FIG. 5, the solid battery 40 includes a plurality of unit cells 1, 1,... Arranged in parallel in the vertical direction, and a container 2 that houses the unit cells 1, 1,. Have. .. Around the unit cells 1,... And inside the container 2 are filled with an inert gas 3 that pressurizes the unit cells 1,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. On the inner side of the container 2 (the side facing the unit cells 1, 1,...), The position of the unit cells 1, 1,. Positioning pieces for preventing contact with 2 and contact between adjacent unit cells 1 and 1 are provided. In the solid battery 40, wings 41, 41,... Are attached to end faces of all the unit cells 1, 1,. In the solid battery 40, the wing 41 attached to the unit cell 1 disposed so as to be in contact with the positioning pieces 23, 23 at the time of manufacturing the solid battery 40 receives the wind sent from the blowing means 21 and the unit cell 1. 1 is an angle formed by the stacking direction of θ 1, and the wing 41 attached to the unit cell 1 disposed so as to be in contact with the positioning pieces 24, 24 at the time of manufacturing the solid battery 40 is sent from the blowing means 21. The angle between the receiving surface and the stacking direction of the unit cells 1, 1,..., Is θ 2, and the wing 41 attached to the unit cell 1 arranged so as to contact the positioning pieces 25, 25 when the solid battery 40 is manufactured. The cell formed by the surface that receives the wind sent from the blower 21 and the stacking direction of the cells 1, 1,..., Is θ3, and is disposed so as to be in contact with the positioning pieces 26, 26 when the solid battery 40 is manufactured. Wings 41 attached to 1 The cell formed by the surface that receives the wind sent from the wind means 21 and the stacking direction of the cells 1, 1,... When the angle formed between the surface of the wing 41 attached to 1 that receives the wind sent from the blowing means 21 and the stacking direction of the cells 1, 1,... Is θ5, in the solid battery 40, θ1> θ2>. θ3> θ4> θ5.

Here, the pressure in the region sandwiched between the upper surface of the unit cell 1 disposed at the top in the vertical direction and the container 2 is P1, and the bottom surface of the unit cell 1 disposed at the top in the vertical direction is perpendicular to the bottom surface. The pressure in the region sandwiched between the upper surface of the unit cell 1 arranged second from the top is P2, and the lower surface of the unit cell 1 arranged second from the top in the vertical direction is third from the top in the vertical direction. The pressure of the region sandwiched between the upper surfaces of the arranged unit cells 1 is P3, the lower unit cell 1 arranged third from the top in the vertical direction, and the unit cell 1 arranged second from the bottom in the vertical direction The pressure in the region sandwiched between the upper surface of the cell is P4, and is sandwiched between the lower surface of the unit cell 1 disposed second from the bottom in the vertical direction and the upper surface of the unit cell 1 disposed at the bottom in the vertical direction. The pressure of the region is P5, the lower surface of the unit cell 1 arranged at the bottom in the vertical direction and the container The pressure in the region flanked by and P6, to. In the solid battery 40, θ1>θ2>θ3>θ4> θ5 is satisfied. Therefore, when air is sent from the blowing unit 21 to the unit cells 1, 1,... When the unit cells 1, 1,. It is possible to satisfy <P3 <P4 <P5 <P6. In the solid battery 40, for example, when the unit cell 1 to which the wings 41 are attached has a weight of 3 g and the area of the air receiving surface is 50 cm ² , the air blown from the air blowing means 21 is 0.3 m / s. To send the unit cell 1 to the floating position. As described above, the unit cells 1, 1,... Therefore, according to the solid battery 40, the performance can be improved in the same manner as the solid battery 20 and the solid battery 30.

  In the solid battery 40 as well as the solid battery 20 and the solid battery 30, the degree of floating of the unit cells 1, 1,... When strong wind is sent from the means 21, the unit cells 1, 1,... As described above, since the positioning piece is provided in the solid battery 40, even if the unit cells 1, 1,... Contact between the unit cell 1 and the container 2 is prevented.

  In the solid battery 40, the wing 41 can have the same form as the wings 31, 32, 33, 34, and 35.

  In the above description regarding the solid batteries 20, 30, and 40 of the present invention using the air blowing means 21, the solid battery 20 and the wind in the form in which the interval between the container 2 and the unit cell 1 and the interval between the adjacent unit cells 1 and 1 are changed. Although the solid battery 30 in the form in which the area of the receiving surface is changed and the solid battery 40 in the form in which the angle for attaching the wings is changed are mentioned, the solid battery of the present invention using the air blowing means is not limited to these forms. When the solid battery of the present invention is configured to be provided with a blowing means, a group consisting of (1) changing the interval, (2) changing the area of the wing, and (3) changing the angle of the wing. It is also possible to adopt a combination of two or three more selected.

  FIG. 6 is a cross-sectional view illustrating a solid state battery 50 of the present invention according to a fifth embodiment. The direction from the upper side to the lower side in FIG. 6 is the gravity direction (vertical direction). In FIG. 6, the same components as those of the solid battery 10 are denoted by the same reference numerals as those used in FIG. 1, and the description thereof is omitted as appropriate. In FIG. 6, the solid state battery 50 is shown in a simplified manner.

  As shown in FIG. 6, the solid battery 50 includes a plurality of unit cells 51, 51,... Stacked in the vertical direction, and a container 2 that houses the unit cells 51, 51,. . .. Around the unit cells 51, 51,... And inside the container 2 are filled with an inert gas 3 to pressurize the unit cells 51, 51,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. As shown in FIG. 6, the upper surface of the unit cell 51 disposed at the top in the direction of gravity (vertical direction) is not in contact with the container 2.

  FIG. 7 is a cross-sectional view illustrating the unit cell 51. In FIG. 7, the same components as those of the unit cell 1 are denoted by the same reference numerals as those used in FIG. 2, and the description thereof is omitted as appropriate.

  As shown in FIG. 7, the unit cell 51 includes a laminated body 1x and convex pieces 52, 52,... Attached to edges (ends) of the laminated body 1x. The pieces 52, 52,... Are wrapped in the laminate film 1y. By adopting such a configuration, on both end surfaces of the unit cell 51 in the stacking direction (upper and lower surfaces in FIG. 6), the portion of the stacked body 1x to which the protruding pieces 52 and 52 are not attached, and the protruding pieces 52 and 52. Concavities and convexities can be produced at the site where the is attached. For example, according to the solid battery 50, the positive electrode layer 1b is formed in a part other than the edge of the positive electrode current collector 1a, and the negative electrode layer 1d is formed in a part other than the edge of the negative electrode current collector 1e. The part in which the layer 1b and the negative electrode layer 1d are formed can be uniformly pressed. Therefore, according to the present invention, it is possible to apply a uniform pressure to the positive electrode layer 1b and the negative electrode layer 1d. As a result, it is possible to suppress a decrease in performance due to the nonuniform pressure being applied. Is possible. Therefore, according to the present invention, it is possible to provide the solid battery 50 capable of improving the performance.

  Moreover, in the solid battery 50, the convex pieces 52 and 52 (and the laminate film 1y) are interposed between the container 2 and the laminated body 1x. Therefore, even when the solid battery 50 is used for a vibrating device, the vibration transmitted to the laminated body 1x is reduced as compared with the case where only the laminated film is interposed between the laminated body and the container. can do. By reducing the vibration transmitted to the laminated body 1x, it is possible to suppress a decrease in performance due to the vibration. Therefore, according to the solid battery 50, the performance can be improved.

  In the solid battery 50, the convex piece 52 can be made of a material having good electronic conductivity that can withstand the environment when the solid battery 50 is used, and is preferably made of a substance that can absorb vibration. The convex piece 52 can be made of, for example, carbon fiber typified by carbon fiber reinforced plastic (CFRP) or the like.

  FIG. 8 is a cross-sectional view for explaining a solid state battery 60 of the present invention according to a sixth embodiment. The direction from the upper side to the lower side in FIG. 8 is the direction of gravity (vertical direction). In FIG. 8, the same components as those of the solid battery 10 are denoted by the same reference numerals as those used in FIG. 1, and the description thereof is omitted as appropriate. In FIG. 8, the solid state battery 60 is shown in a simplified manner.

  As shown in FIG. 8, the solid battery 60 includes a battery stack 62 formed by alternately stacking porous members 61, 61,... And unit cells 1, 1,. And a container 2 that accommodates the body 62. The porous member 61 is disposed at the bottom of the battery stack 62 in the stacking direction, and the unit cell 1 is disposed at the top of the battery stack 62 in the vertical direction. .. Around the unit cells 1,... And inside the container 2 are filled with an inert gas 3 that pressurizes the unit cells 1,. The container 2 is provided with a gas flow path 4, and a valve 5 is connected to the gas flow path 4. As shown in FIG. 8, the upper surface of the unit cell 1 disposed at the top in the direction of gravity (vertical direction) is not in contact with the container 2.

  In the solid battery 60, the porous member 61 is in contact with the substantially entire surface of the cell 1 in the stacking direction (the upper surface and / or the lower surface in FIG. 8), and the porous members 61, 61,. The contact between the adjacent unit cells 1 and 1 and the contact between the unit cell 1 and the container 2 are avoided. Further, the inert gas 3 can pass through the porous members 61, 61,. By the porous members 61, 61,... Through which the inert gas 3 can pass, the contact between the adjacent unit cells 1, 1 and the contact between the unit cell 1 and the container 2 are avoided. The surface of the unit cells 1, 1,... Can be uniformly pressurized using the gas 3. By uniformly pressurizing the surfaces of the unit cells 1, 1,..., It is possible to suppress performance degradation due to application of uneven pressure. Therefore, according to the present invention, it is possible to provide a solid state battery 60 capable of improving performance.

  Further, in the solid battery 60, the container 2 and the unit cells 1, 1,... Are not in direct contact. Therefore, even when the solid battery 60 is used as a vibrating device, the vibration transmitted to the unit cells 1, 1,... Is reduced as compared with the case where the unit cell and the container are in direct contact. be able to. By reducing the vibration transmitted to the unit cells 1, 1,..., It is possible to suppress the performance degradation due to the vibration. Therefore, according to the solid battery 60, the performance can be improved.

  In the solid battery 60, the porous member 61 can withstand the environment when the solid battery 60 is used, and can be composed of a porous material that allows the inert gas 3 to pass therethrough, and can absorb vibration. It is preferable that it is made of a material. The porous member 61 can be formed of a porous metal typified by a metal mesh or a foam metal. In addition, it can be formed of a known porous plastic or the like.

  In the above description regarding the solid battery 60, the battery stack 62 in which the unit cell 1 is arranged on the top in the vertical direction is mentioned, but the present invention is not limited to this form. When a porous member is used in the solid battery of the present invention, it is also possible to dispose a porous member on the upper surface of the uppermost unit cell in the vertical direction.

  In the above description regarding the present invention, the unit cells 1 and 51 in which the laminate 1x and 51x are accommodated in the laminate film 1y have been described, but the present invention is not limited to this form. The unit cell provided in the solid state battery of the present invention may have one or more battery cells. When a unit cell is provided with two or more battery cells, these battery cells can be electrically connected in series and / or in parallel.

  Moreover, in the said description regarding this invention, although the substantially square column-shaped unit cells 1 and 51 were illustrated, this invention is not limited to the said form. The unit cell provided in the solid state battery of the present invention can have other forms such as a columnar shape.

  Moreover, in the said description regarding this invention, although the unit cells 1 and 51 of the form wrapped in the laminate film 1y were illustrated, this invention is not limited to the said form. The unit cell provided in the solid state battery of the present invention does not allow fluid to pass through, can withstand the environment during use of the solid state battery, and can transmit pressure applied from the outside to the inside. It can be in a wrapped form. As such a substance, metal foils, such as aluminum foil, can be illustrated.

  Moreover, in the said description regarding this invention, although the form with which the unit cells 1 and 51 which are lithium ion secondary batteries were provided was mainly illustrated, the battery which can apply this invention is not limited to the said form. The unit cell in the present invention can be configured such that ions other than lithium ions move between the positive electrode layer and the negative electrode layer. Examples of such ions include sodium ions and potassium ions. In the case where ions other than lithium ions move, the positive electrode active material, the solid electrolyte, and the negative electrode active material may be appropriately selected according to the moving ions. The unit cell provided in the solid state battery of the present invention may be a primary battery.

DESCRIPTION OF SYMBOLS 1, 51 ... Unit cell 1a ... Positive electrode collector 1b ... Positive electrode layer 1c ... Solid electrolyte layer 1d ... Negative electrode layer 1e ... Negative electrode collector 1f, 1g ... Terminal 1x ... Laminate 1y ... Laminate film 2 ... Container 3 ... Unsatisfactory Active gas 4 ... Gas flow path 5 ... Valve 6 ... Contact avoidance member 10, 20, 30, 40, 50, 60 ... Solid battery 21 ... Air blowing means 22, 23, 24, 25, 26, 27 ... Positioning pieces 31, 32 , 33, 34, 35, 41 ... feather 52 ... convex piece 61 ... porous member (contact avoidance member)
62 ... Battery stack

Claims (3)

A unit cell having a positive electrode layer and a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, and a container for accommodating a plurality of the unit cells,
A gas to pressurize the unit cell is filled around the unit cell and inside the container,
A contact avoidance member is disposed between two adjacent unit cells and between the unit cell and the container, and at least when the unit cell is operated, the two contact avoidance members are used. A solid state battery characterized in that contact between the unit cells and contact between the unit cells and the container are avoided. The container contains air blowing means, and a plurality of the unit cells are stacked in a vertical direction,
When the gas filled in the container is circulated using the blowing means, the pressure is smaller between the adjacent unit cells on the upper side in the vertical direction or between the unit cells and the container. The solid battery according to claim 1, wherein a plurality of the unit cells are arranged. The solid battery according to claim 1, wherein the contact avoiding member has a hole.