JP6726503B2 - All-solid secondary battery and manufacturing method thereof - Google Patents

Description

The present invention relates to an all solid state secondary battery and a method for manufacturing the same.

Usually, in an all-solid secondary battery, a solid electrolyte layer is arranged between a positive electrode layer and a negative electrode layer, and a current collector is arranged on the outer surface of each of these electrode layers. By the way, as a method for manufacturing such an all-solid-state secondary battery, each of the constituent layers of the battery is formed by spraying a powder material onto a base material together with a carrier gas while charging and depositing the film by electrostatic force. There is a method of forming a battery, and then pressing (pressurizing) a laminate composed of these constituent layers to manufacture a battery (for example, Patent Document 1).

According to this method, since a constituent layer made of powder having a uniform thickness is formed, the pressing force is uniformly applied to the whole during pressure molding, that is, at the time of pressing. A battery is obtained.

JP, 2010-228803, A

However, an internal short circuit also occurred in the all-solid-state secondary battery obtained by the manufacturing method as described above.
As a result of examining the cause of this internal short circuit, the cause was the principal stress acting on the constituent layer (hereinafter referred to as the powder layer) made of powder by the force applied at the time of pressing and the shear stress caused by this principal stress. It turned out to be due to. That is, when a vertical force is applied to the powder layer, the maximum principal stress is generated in the vertical direction and the minimum principal stress is generated in the lateral direction, and the shear stress in the diagonal direction is generated by these both principal stresses. In other words, shearing force will work.

By the way, the powder layers are laminated with a predetermined thickness, and the central portion thereof is pressed and solidified, but the peripheral portion thereof becomes an inclined surface and is thin. Therefore, due to the shearing force, the peripheral portion of the powder layer collapsed, leading to an internal short circuit.

Therefore, an object of the present invention is to provide an all solid state secondary battery capable of suppressing an internal short circuit caused by pressing and a manufacturing method thereof.

The all-solid secondary battery according to the present invention is arranged between a pair of current collectors, a laminated body including a first electrode layer, a solid electrolyte layer and a second electrode layer, and arranged around the laminated body. An all-solid secondary battery comprising a plate-shaped insulating member that insulates both electrode layers from each other,
The inner edge of the insulating member contacts the outer edge of the first electrode layer or creates a gap of 2 mm or less,
The insulating member has a plate-shaped portion and a strip-shaped protruding portion that is thicker than the plate-shaped portion at an outer portion apart from the inner edge of the insulating member,
Further, the outer edge of the solid electrolyte layer covers at least the surface of the insulating member on the inner side of the protrusion and contacts the protrusion .

In addition, the method for manufacturing an all-solid-state secondary battery according to the present invention includes a laminated body including a first electrode layer, a solid electrolyte layer and a second electrode layer between a pair of current collectors, and a laminated body including the laminated body. A method for manufacturing an all-solid-state secondary battery provided with a plate-shaped insulating member which is arranged in the periphery and insulates the two electrode layers from each other,
The insulating member has a plate-shaped portion, an opening that can guide the first electrode layer, and a strip-shaped protruding portion that is thicker than the plate-shaped portion at an outer portion apart from an inner edge of the opening. And
The surface of one of the current collector, a step of bonding the insulating member,
Arranging the first electrode layer in the opening of the insulating member bonded in this step so that the inner edge of the insulating member contacts the outer edge of the first electrode layer or forms a gap of 2 mm or less ;
Arranging a solid electrolyte layer on the surface of the first electrode layer arranged in this step and on the surface of the insulating member at least inside the protruding portion and contacting the protruding portion ,
Arranging the second electrode layer on the upper surface of the solid electrolyte layer arranged in this step to obtain a laminate,
It is a manufacturing method including a step of arranging the other current collector on the upper surface of the laminate obtained in this step and then pressing.

According to the all-solid-state secondary battery and the method for manufacturing the same of the present invention, the inner edge of the insulating member is brought into contact with or close to the outer edge of the first electrode layer, and the plate is formed on the outer portion apart from the inner edge of the insulating member. Since the strip-shaped projecting portion that is thicker than the projecting portion is provided, the outer edge of the first electrode layer contacts or approaches the insulating member and at least the outer edge of the solid electrolyte layer contacts the projecting portion. It is possible to prevent shear collapse that occurs at the periphery of the first electrode layer when pressing, and instead of covering the outer peripheral side surface of the first electrode layer with the solid electrolyte layer, contact the inner edge of the insulating member with the outer edge of the first electrode layer or By making them close to each other, it is possible to reduce the step portion due to the thin thickness of the solid electrolyte on the outer peripheral side surface of the first electrode layer when pressing the battery, and thus it is possible to prevent the occurrence of an internal short circuit.

1 is a cross-sectional view of an all solid state secondary battery according to an embodiment of the present invention. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 6 is a cross-sectional view illustrating the method for manufacturing the same all-solid-state secondary battery. FIG. 4 is a cross-sectional view of an essential part for explaining a step reducing function in the all-solid-state secondary battery. It is a principal part sectional drawing of the all-solid-state secondary battery which shows the modification of this invention.

Hereinafter, an all-solid-state secondary battery according to an embodiment of the present invention and a method for manufacturing the same will be described with reference to the drawings.
First, the configuration of the all solid state secondary battery will be described.

This all-solid-state secondary battery will be briefly described. A laminated body composed of a first electrode layer, a solid electrolyte layer and a second electrode layer is disposed between a pair of current collectors, and the laminated body is arranged around the laminated body. And a plate-shaped insulating member that insulates the two electrode layers from each other, wherein the inner edge of the insulating member is in contact with or close to the outer edge of the first electrode layer, and the insulating member is A strip-shaped protrusion that is thicker than the plate-shaped portion on the outer portion away from the inner edge, and the outer edge of the solid electrolyte layer covers at least the surface of the insulating member inside the protrusion. It is a thing.

Hereinafter, the all solid state secondary battery will be described in detail with reference to FIG.
This all-solid-state secondary battery 1 includes a positive electrode layer (an example of a first electrode layer) 12, a solid electrolyte layer 32, and a solid electrolyte layer 32 between a pair of current collectors, that is, a positive electrode current collector 11 and a negative electrode current collector 21. A laminated body X in which a negative electrode layer (an example of a second electrode layer) 22 is laminated in order, and a positive electrode layer 12 and a negative electrode layer which are arranged around the laminated body X and are in contact with at least the solid electrolyte layer 32. 22 is an all-solid-state secondary battery in which a plate-shaped insulating member 41 that electrically insulates the battery 22 is arranged, and an inner peripheral surface of an opening 41d formed in the center of the plate-shaped portion 41a of the insulating member 41 has While being in contact with the outer peripheral surface (outer peripheral side surface) of the positive electrode layer 12 and being thicker than the plate-shaped portion 41a with a predetermined width, the outer portion of the plate-shaped portion 41a separated from the inner peripheral surface of the opening 41d by a predetermined distance. The solid electrolyte layer 32 is provided on the surface of the positive electrode layer 12, and the outer periphery of the solid electrolyte layer 32 is at least the inner surface of the plate-like portion 41a inside the projecting portion 41b. It is sized to cover. In the following description, 41c is attached to the inner edge portion of the plate-shaped portion 41a.

The insulating member 41 and the positive electrode current collector 11 and the negative electrode current collector 21 are adhered to each other via the lower adhesive layer 51 and the upper adhesive layer 52. As the insulating member 41, for example, an insulating sheet made of a polymer material such as a PET film is used. Therefore, it can be said that the plate-shaped portion is the sheet portion, as well as the sheet-shaped insulating member. A pressure-sensitive adhesive such as a double-sided adhesive tape is used as each of the adhesive layers 51 and 52.

Of course, the laminated body X is arranged in the opening 41d of the insulating member 41. The thickness of the protrusion 41b is thicker (higher) than the total thickness of the positive electrode layer 12 and the solid electrolyte layer 32, for example.

A powder electrode mixture is used as the positive electrode layer 12 and the negative electrode layer 22, and a powder material is also used as the solid electrolyte layer 32. As the electrode mixture, a mixture of an electrode active material and a solid electrolyte is used, but in some cases, only the electrode active material may be used.

Here, the shape and size of the all-solid secondary battery 1 will be described. The shape in plan view is square (may be circular or polygonal), and the length of one side thereof is in the range of 30 to 300 mm. It is proper that the thickness is in the range of 50 to 500 μm. Therefore, the planar view shape of the laminated body X is also square, and the planar view shape of the opening 41d for guiding the positive electrode layer 12 and the solid electrolyte layer 32 of the laminated body X is also square.

In FIG. 1, the all-solid-state secondary battery is placed on a horizontal surface, and the positive electrode side is located below and the negative electrode side is located above. However, of course, the negative electrode side is located below and the positive electrode side is located below. It may be arranged above.

The constituent materials of the main part of the all-solid-state secondary battery will be described collectively after the manufacturing method is described.
Hereinafter, a method for manufacturing the all-solid secondary battery will be described in detail with reference to FIGS.

As shown in FIG. 2, the surface of the positive electrode current collector 11 has an opening 41d capable of guiding the positive electrode layer 12, and an outer protruding portion 41b separated from the opening 41d by a predetermined distance is formed from the plate-shaped portion 41a. The thickened insulating member 41 is adhered via the lower adhesive layer 51. The predetermined distance is a value determined by how much the area of the solid electrolyte layer 32 is increased in view of safety, and the smaller the film formation area, the more compact and less raw material the lighter the weight. That is, the predetermined distance is preferably in the range of 0.1 to 5 mm, more preferably in the range of 0.5 to 5 mm. Further, the width of the protruding portion 41b is preferably in the range of 0.5 to 20 mm, more preferably in the range of 1.0 to 20 mm, depending on the strength of the material and the easiness of manufacturing the member. Further, regarding the height of the protrusions 41b, if the protrusions 41b are too high, the protrusion 41b may not be sufficiently pressed, so that the laminated body (the positive electrode layer, the solid electrolyte layer, the negative electrode layer) X after the pressure is pressed. It is desirable that the thickness is smaller than the thickness, and the range of 50 to 500 μm is preferable.

In addition, here, it is assumed that the thickened protruding portion 41b is bonded to the upper surface of the plate-shaped main insulating member 41A close to the inner periphery with the band-shaped sub-insulating member 41B having a predetermined width via the adhesive layer 53. explain.

Next, as shown in FIG. 3, the positive electrode layer 12 is disposed on the surface of the positive electrode current collector 11 inside the opening 41d provided in the insulating member 41, that is, the main insulating member 41A.
Next, as shown in FIG. 4, the solid electrolyte layer 32 is arranged on the upper surface of the positive electrode layer 12 with a predetermined thickness. In this case, the outer peripheral portion of the solid electrolyte layer 32 is arranged so as to cover above the band-shaped sub-insulating member 41B having a width of 1 mm, for example. The surface height of the solid electrolyte layer 32 above the positive electrode layer 12 is the same as or slightly lower than the surface of the protrusion 41b (sub-insulating member 41B).

Next, as shown in FIG. 5, the negative electrode layer 22 is arranged on the upper surface of the solid electrolyte layer 32 with a predetermined thickness to obtain a laminated body X.
Next, as shown in FIGS. 6 and 7, the negative electrode current collector 21 around which the upper adhesive layer 52 is attached is arranged on the upper surface of the negative electrode layer 22 and air is sucked in at a low pressure of about 5000 Pa. Then, temporary pressing (temporary pressing) is performed, and the negative electrode current collector 21 is bonded to the upper surface of the insulating member 41 by the upper adhesive layer 52.

Next, as shown in FIG. 8, main pressing (main pressing) is performed with a high pressure of about 10 ton/cm ² in a state where air inside is sucked.
When the negative electrode current collector 21 is pressed from above, an elastic member such as a rubber plate is arranged between the negative electrode current collector 21 and the pressing member (not shown).

Then, finally, after sandwiching the battery in which the laminate X is arranged between the current collectors 11 and 21 with a pair of stainless plates, it is sandwiched with a laminate film provided with a tab lead for electrical extraction, and under vacuum, A laminate pack is performed by heat-sealing the periphery.

As a result, a single all-solid secondary battery can be obtained. Usually, an all-solid secondary battery is constructed by stacking a plurality of single batteries in series or arranging them in parallel.
The main parts of the above manufacturing method are described below in process form.

That is, this manufacturing method includes a laminate including a positive electrode layer (first electrode layer), a solid electrolyte layer, and a negative electrode layer (second electrode layer) between a pair of current collectors, and the periphery of the laminate. A method for manufacturing an all-solid-state secondary battery, which comprises a plate-shaped insulating member for insulating the two electrode layers from each other, wherein a positive electrode layer is provided on the surface of the positive electrode current collector (one current collector). A strip-shaped protrusion having a predetermined width and having a predetermined width was provided at an outer portion having a guideable opening (so as to have the opening) and a predetermined distance from the inner edge of the opening. The step of adhering the insulating member (so as to have the protruding portion), the step of disposing the positive electrode layer in the opening of the insulating member adhered in this step, the surface of the positive electrode layer disposed in this step and the protrusion The step of arranging the solid electrolyte layer on the surface of the insulating member at least on the inner side of the cylindrical portion, the step of arranging the negative electrode layer on the upper surface of the solid electrolyte layer arranged in this step to obtain a laminate, and the step obtained The step of arranging the negative electrode current collector (the other current collector) on the upper surface of the obtained laminated body, and then pressing the same.

The materials of the main constituent members of the all-solid secondary battery 1 will be described.
As the positive electrode current collector 11 and the negative electrode current collector 21, copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn). ), aluminum (Al), germanium (Ge), indium (In), lithium (Li), tin (Sn), alloys thereof, or the like, or a thin plate-like body or a foil-like body is used. Here, the thin plate-shaped body and the foil-shaped body have a thickness within a range of 5 μm to 100 μm. In the present embodiment, an aluminum foil is used as the positive electrode current collector 11 and a copper foil is used as the negative electrode current collector 21. Furthermore, it is preferable that the surface of each of the current collectors 11 and 21 is subjected to a roughening treatment from the viewpoint of improving the adhesion to the powder laminate X. The roughening treatment is a treatment for increasing the surface roughness by etching or the like. In the present embodiment, as the positive electrode current collector 11, an etched aluminum foil (also referred to as an etched aluminum foil) is used. Further, as the negative electrode current collector 21, an etched copper foil (also referred to as a roughened copper foil) is used, but a copper foil that is not etched may be used. An insulating sheet made of a polymer material such as a PET film is used as the insulating member 41 (41A, 41B).

By using the current collector that has been subjected to the etching treatment as described above, the holes formed by the etching are crushed by the pressure during the production of the all-solid secondary battery, and the electrode layers, that is, the positive electrode layer 12 and the negative electrode layer 22. It becomes easy to bite on the surface of, and the current collector and these electrode layers are easily integrated.

The electrode layer is a layer made of a mixture material in which an electrode active material that secures an electron conduction path between particles to transfer electrons and a solid electrolyte having ion conductivity are mixed at a predetermined ratio. By thus mixing the electrode active material with the solid electrolyte having lithium ion conductivity, it is possible to impart ion conductivity in addition to electron conductivity and secure an ion conduction path between particles.

The positive electrode active material suitable for the positive electrode layer 12 is not particularly limited as long as it can insert and release lithium ions. For example, as the positive electrode active material, a lithium nickel composite oxide (LiNi _x M _1-x O ₂ , where M is Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo and W) is used. At least one element), layered oxides such as lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium iron phosphate having an olivine structure (LiFePO ₄₎ ), a solid solution such as lithium manganate (LiMn ₂ O ₄ , Li ₂ MnO ₃ or LiMO ₂ ) having a spinel structure, or a mixture thereof, and a sulfide such as sulfur (S) or lithium sulfide (Li ₂ S). It can also be used. In the present embodiment, a lithium/nickel/cobalt/aluminum composite oxide (LiNi _0.8 Co _0.15 Al _0.05 O ₂ , hereinafter referred to as NCA-based composite oxide) is used as the positive electrode active material. ..

On the other hand, as the negative electrode active material suitable for the negative electrode layer 22, for example, a carbon material such as natural graphite, artificial graphite, graphite carbon fiber, resin-fired carbon, or an alloy-based material that is mixed with a solid electrolyte is used. Examples of the alloy-based material include lithium alloys (LiAl, LiZn, Li ₃ Bi, Li ₃ Cd, Li ₃ Sb, Li ₄ Si, Li _4.4 Pb, Li _4.4 Sn, Li _0.17 C, LiC. _6, etc.), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), metal oxides such as Zn, and the like. In the present embodiment, natural or artificial graphite is used as the negative electrode active material.

In addition, zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), lithium niobate (Li ₄ NbO ₃ ), carbon are formed on the surfaces of the positive electrode active material and the negative electrode active material. Those coated with (C) or the like can be used as the electrode active material.

The solid electrolyte is roughly classified into an organic polymer electrolyte (also referred to as an organic solid electrolyte), an inorganic inorganic solid electrolyte, and the like, but any solid electrolyte may be used. Inorganic solid electrolytes are roughly classified into oxide-based materials and sulfide-based materials, but either may be used. Furthermore, the inorganic solid electrolyte can be appropriately selected from crystalline and amorphous ones. That is, the solid electrolyte can be appropriately selected from materials composed of organic compounds, inorganic compounds, or mixtures thereof. Specifically, examples of the material that can be used as the solid electrolyte include lithium-containing metal oxides (one or more kinds of metal) such as Li ₂ —SiO ₂ , Li ₂ —SiO ₂ —P ₂ O ₅ , and Li _x. lithium-containing metal nitride such as _{P y O 1-z N 2} , Li 2 S-P 2 S 5 _based, Li ₂ S-SiS 2 _{system, Li 2 S-B 2 S} 3 _system, Li ₂ S-GeS 2 _system, Li 2 _S-SiS 2 -LiI _{system, Li 2 S-SiS 2 -Li} 3 PO 4 _{based, Li 2 S-Ge 2 S} 2 _{system, Li 2 S-GeS 2 -P} 2 S 5 based, Li _{2 S-GeS} 2 -ZnS-based lithium-containing sulfide-based glass such as, and PEO (polyethylene oxide), PVDF (polyvinylidene fluoride), lithium phosphate _(Li 3 _PO 4), lithium-containing transition metal, such as lithium titanium oxide An oxide is mentioned. In the present embodiment, Li ₂ S-P ₂ S ₅ based glass is used as the solid electrolyte among the sulfide based inorganic solid electrolytes based on sulfide based glass having high ion conductivity. The solid electrolyte suitable for the solid electrolyte layer 32 may be the same as or different from the solid electrolytes used for the positive electrode layer 12 and the negative electrode layer 22.

In the above-described embodiment, a pressure-sensitive adhesive material such as a double-sided adhesive tape is used as the adhesive layer for easy handling, but an adhesive agent such as liquid or solid may be used.
Further, in the above embodiment, the inner edge of the insulating member 41 was described as being in contact with the outer edge of the positive electrode layer 12, but due to manufacturing error, for example, 2 mm or less between the inner edge of the insulating member 41 and the positive electrode layer 12. Gaps may occur. That is, the inner edge of the insulating member 41 may be close to the outer edge of the positive electrode layer 12.

According to the all-solid-state secondary battery and the manufacturing method thereof, the inner edge of the insulating member is brought into contact with or close to the outer edge of the positive electrode layer (first electrode layer), and the outer edge of the insulating member is separated from the inner edge thereof. Since the strip-shaped protrusions that are thicker than the plate-shaped portion are provided, the outer edge of the positive electrode layer contacts or approaches the insulating member and at least the outer edge of the solid electrolyte layer contacts the protrusions, and the state is held respectively. Therefore, it is possible to prevent the collapse of the laminate that occurs in the peripheral portion at the time of pressing, and instead of covering the outer peripheral side surface of the positive electrode layer with the solid electrolyte layer, by bringing the inner edge of the insulating member into contact with or close to the outer edge of the positive electrode layer, Again, when the battery is pressed, the stepped portion due to the thin thickness of the solid electrolyte layer on the outer peripheral side surface of the positive electrode layer can be reduced, so that an internal short circuit can be more reliably prevented from occurring.

More specifically, since the protruding portion 41b, which is a contact portion with the laminated body X in the insulating member 41, is made thicker than the outer plate-like portion 41a, collapse due to shearing force generated at the peripheral portion when the battery is pressed is prevented. Therefore, an internal short circuit (electrical short circuit) can be prevented from occurring. That is, the protruding portion 41b of the insulating member 41 functions as a collapse prevention block capable of preventing shear collapse that occurs when the laminated body X is pressed.

For example, if the positive electrode layer 12, the solid electrolyte layer 32, and the negative electrode layer 22 are simply laminated, the central portion becomes thickest and the peripheral portion becomes thin. In this state, even if pressed with high pressure, little force acts on the peripheral portion, so that the powder particles are not firmly fixed to each other at the peripheral portion, and the layer structure is formed by impact or deformation of the current collector. Although it is easily destroyed, such a situation can be avoided.

Further, by providing an inner edge portion 41c inside the protruding portion 41b of the insulating member 41 to eliminate a step portion generated when the periphery of the positive electrode layer 12 is covered with the solid electrolyte layer 32, a step reducing function (step reducing area) ) Is provided. For example, as shown in FIG. 9, when the inner edge portion that contacts the outer peripheral surface of the positive electrode layer 12 is not provided inside the protruding portion 41b, the solid electrolyte layer 32 that covers the positive electrode layer 12 is indicated by a broken line. As shown in the drawing, since a shoulder portion, that is, a step portion is generated, this shoulder portion collapses when the laminated body X is pressed, and a short circuit easily occurs. Such a situation can be avoided.

Here, the result of charging and discharging the actually manufactured all-solid-state secondary battery will be described.
In this all-solid secondary battery, a roughened aluminum foil (etched aluminum) having a thickness of 20 μm is used as the positive electrode current collector 11, and a copper foil having a thickness of 18 μm is used as the negative electrode current collector 21. Using. As the insulating member 41, a PET film (polyethylene terephthalate film) having a thickness of 50 μm was used. Further, as the lower adhesive layer 51 and the upper adhesive layer 52, a pressure-sensitive adhesive film (double-sided adhesive tape) having a thickness of 30 μm and a width of 2 mm is used, and the adhesive layer 53 of the protrusion 41b has the same width. Of 1 mm was used.

Further, as the positive electrode layer 12, an NCA-based composite oxide that is a positive electrode active material and a glass ceramic made of Li ₂ S (80 mol%)-P ₂ S ₅ (20 mol%) as a solid electrolyte were mixed at a ratio of 7:3. The mixture was used. As the negative electrode layer 22, graphite powder, which is a negative electrode active material, and a glass ceramic made of Li ₂ S (80 mol %)-P ₂ S ₅ (20 mol %), which is a solid electrolyte, were mixed at a ratio of 6:4. I used one. As the solid electrolyte in the solid electrolyte layer 32, a glass ceramic made of Li ₂ S (80 mol%)-P ₂ S ₅ (20 mol%) was used.

Regarding the predetermined thickness of each component, after the main pressing, the thickness of the positive electrode layer 12 is about 70 μm, the thickness of the negative electrode layer 22 is about 100 μm, and the thickness of the solid electrolyte layer 32 is about 70 μm. Was applied by, for example, an electrostatic screen coating method.

The battery thus obtained was sandwiched between a pair of stainless steel plates each having a side of 70 mm and a thickness of 0.3 mm, and then sandwiched by a laminate film provided with tab leads for electrical extraction, and the surroundings were heat-sealed under vacuum. Then, the laminate pack was applied, and then pressed (main press) with a pressure of 100 MPa, for example, for 30 seconds to produce an all solid state secondary battery 1.

For example, four all-solid-state secondary batteries 1 were produced and charged and discharged at 0.1 C and 4 to 2 V, respectively, and all were able to be charged and discharged without abnormality.
By the way, in the said embodiment, although a part of insulating member arrange|positioned around a laminated body was demonstrated as a strip|belt-shaped protrusion, for example, as shown in FIG. 10, the negative electrode collector 21 shown in FIG. On the side, a ring-shaped outer insulating member 42 that can be arranged along the outer side of the band-shaped sub-insulating member 41B is adhered via an upper adhesive layer 52, and when pressed (indicated by arrow a), this outer insulating member The member 42 may be adhered to the upper surface of the plate-shaped portion 41A (41a) of the insulating member 41 via the adhesive layer 54. In other words, the total thickness of the insulating members 41, 42 may be increased so as to be located above the lower surface of the solid electrolyte layer 32 of the laminated body X after pressing.

X Laminated body 1 All-solid-state secondary battery 11 Positive electrode collector 12 Positive electrode layer 21 Negative electrode collector 22 Negative electrode layer 32 Solid electrolyte layer 41 Insulating member 41a Plate part 41b Projecting part 41c Inner edge part 41d Opening part 41A Main insulating member 41B Sub-insulating member 51 Lower adhesive layer 52 Upper adhesive layer 53 Adhesive layer

Claims (2)

Between the pair of current collectors, a laminated body composed of the first electrode layer, the solid electrolyte layer and the second electrode layer, and a plate-shaped body arranged around the laminated body to insulate the two electrode layers from each other. An all-solid-state secondary battery including an insulating member,
The inner edge of the insulating member contacts the outer edge of the first electrode layer or creates a gap of 2 mm or less,
The insulating member has a plate-shaped portion and a strip-shaped protruding portion that is thicker than the plate-shaped portion at an outer portion apart from the inner edge of the insulating member,
An all-solid secondary battery , wherein the outer edge of the solid electrolyte layer covers at least the surface of the insulating member inside the protrusion and contacts the protrusion . Between the pair of current collectors, a laminated body composed of the first electrode layer, the solid electrolyte layer and the second electrode layer, and a plate-shaped body arranged around the laminated body to insulate the two electrode layers from each other. A method for manufacturing an all-solid secondary battery including an insulating member, comprising:
The insulating member has a plate-shaped portion, an opening that can guide the first electrode layer, and a strip-shaped protruding portion that is thicker than the plate-shaped portion at an outer portion apart from an inner edge of the opening. And
The surface of one of the current collector, a step of bonding the insulating member,
Arranging the first electrode layer in the opening of the insulating member bonded in this step so that the inner edge of the insulating member contacts the outer edge of the first electrode layer or forms a gap of 2 mm or less ;
Arranging a solid electrolyte layer on the surface of the first electrode layer arranged in this step and on the surface of the insulating member at least inside the protruding portion and contacting the protruding portion ,
Arranging the second electrode layer on the upper surface of the solid electrolyte layer arranged in this step to obtain a laminate,
The upper surface of the laminate obtained in this step, after placing the other current collector, the production method of the all-solid secondary battery, characterized by comprising the step of pressing.

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