JP7120198B2 - ELECTRODE LAMINATE FOR ALL-SOLID BATTERY AND MANUFACTURING METHOD THEREOF - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to electrode laminates for all-solid-state batteries and methods of manufacturing the same.

BACKGROUND ART All-solid-state batteries are known in which electrode laminates for all-solid-state batteries are stacked, each having a current collector and a positive electrode active material layer or a negative electrode active material layer (hereinafter sometimes simply referred to as an active material layer).

In recent years, high-voltage and high-capacity all-solid-state batteries have been demanded, and there is an increasing demand for stacked-type all-solid-state batteries in which a plurality of the electrode laminates described above are stacked.
For example, in Patent Document 1, a current collector of one battery unit and another battery unit stacked adjacent to the current collector are adhered using a thermoplastic resin, thereby stacking each battery unit. An all-solid-state battery is disclosed that is fixed so as not to cause displacement. Patent Literature 1 exemplifies a form in which the current collector and another battery unit are bonded with a thermoplastic resin applied to a partial region of the surface of the current collector.

In addition, in the above-described stacked all-solid-state battery, it is required to fix the current collector and the active material layer in each electrode stack so as not to cause lamination misalignment between the current collector and the active material layer. ing. For example, Patent Literature 2 discloses a battery electrode plate in which a current collector and an active material layer are bonded with an adhesive layer made of polyamide-imide resin containing carbon. Patent Document 2 exemplifies a mode in which the current collector and the active material layer are adhered by the adhesive layer provided over the entire region between the current collector and the active material layer.

In recent years, a technique using laser light has been used to manufacture such a stacked all-solid-state battery.
For example, in Patent Document 3, by irradiating a laminate in which a first active material layer and a solid electrolyte layer are laminated with a laser beam of a predetermined wavelength, the first active material layer is formed while maintaining the solid electrolyte layer. A method for manufacturing a battery laminate is disclosed in which a portion of the is removed.

JP 2017-204377 A Japanese Patent Application Laid-Open No. 2004-273181 Japanese Unexamined Patent Application Publication No. 2016-213070

An electrode laminate produced by bonding a current collector and an active material layer with an adhesive (for example, the form exemplified in Patent Document 1) partially applied to the region between the current collector and the active material layer. When an all-solid-state battery is produced by stacking a plurality of the solid-state battery, when the charge-discharge cycle is repeated in the all-solid-state battery, cracks occur in the active material layer and the current collector, causing a short circuit. However, there is a problem that the durability is lowered.

Further, as exemplified in Patent Document 2, an electrode laminate in which an adhesive is applied to the entire region between the current collector and the active material layer and the current collector and the active material layer are bonded with the adhesive is produced. The all-solid-state battery has a problem that the resistance value becomes too high, so that the performance to function sufficiently as a battery cannot be obtained.

On the other hand, according to the technique described in Patent Document 3, a laminate in which a first active material layer and a solid electrolyte layer are laminated is irradiated with a laser beam, and the first active material layer is formed while maintaining the solid electrolyte layer. Although the battery laminate in which the occurrence of short circuits between the active material layers is suppressed can be efficiently manufactured by removing the Since this is not done, there is a problem that lamination misalignment cannot be suppressed.

In view of the above circumstances, the present disclosure is an all-solid battery capable of suppressing the occurrence of a short circuit, and / or suppressing a decrease in the durability of the all-solid-state battery, and suppressing an increase in the resistance value of the all-solid-state battery. An object of the present invention is to provide an electrode laminate for a solid-state battery.

An electrode laminate for an all-solid-state battery of the present disclosure includes a current collecting composite having a current collecting portion including at least a current collector and an adhesive portion, and an active material layer laminated on the current collecting composite. and a main surface of the current collecting portion on the active material layer side and a main surface of the adhesive portion on the active material layer side are formed to be flush with each other, and the current collecting portion and the active material layer are bonded by the adhesive portion.

A method for manufacturing an electrode laminate for an all-solid-state battery according to the present disclosure includes a current collecting portion including at least a current collector and an adhesive portion. a step of forming a current collecting composite having coplanar surfaces; forming an active material layer on the main surface of the current collecting composite on the side where the adhesive portion is exposed; and a step of bonding the current collector and the active material layer with the adhesive portion.

According to the present disclosure, it is possible to suppress the occurrence of a short circuit in an all-solid-state battery, and / or suppress the deterioration of the durability of the all-solid-state battery, and suppress the increase in the resistance value of the all-solid-state battery. can be provided.

1 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to a first embodiment of the present disclosure; FIG. FIG. 4 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to a second embodiment of the present disclosure; FIG. 10 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to a third embodiment of the present disclosure; FIG. 2 is a perspective view schematically explaining a process of an example of a method for manufacturing the electrode laminate 10 of the present disclosure shown in FIG. 1. FIG. FIG. 5 is a cross-sectional view taken along the line AA' of the steps shown in FIGS. 4B to 4D among the steps shown in FIG. 4; FIG. 3 is a perspective view schematically explaining a process of an example of a method for manufacturing the electrode laminate 20 of the present disclosure shown in FIG. 2. FIG. FIG. 7 is a cross-sectional view taken along the line AA' of the region β shown in FIG. 6A in the steps shown in FIG. 6; FIG. 4 is a perspective view schematically explaining the process of an example of a method for manufacturing the electrode laminate 30 of the present disclosure shown in FIG. 3 . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 100 including an electrode laminate 10 according to a first embodiment of the present disclosure; FIG. 2 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 200 including an electrode laminate 20 according to a second embodiment of the present disclosure; FIG. 3 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 300 including an electrode laminate 30 according to a third embodiment of the present disclosure; FIG. 10 is a cross-sectional view schematically showing a stacked all-solid-state battery in which a plurality of all-solid-state batteries shown in FIG. 9 are stacked. FIG. 2 is a cross-sectional view schematically showing the configuration of a stacked all-solid-state battery including a conventional electrode stack.

1. Electrode laminate for all-solid-state battery An electrode laminate for an all-solid-state battery of the present disclosure includes: a current collecting composite having a current collecting portion including at least a current collector; and an adhesive portion; and an active material layer laminated thereon, wherein the main surface of the current collecting portion on the active material layer side and the main surface of the adhesive portion on the active material layer side are flush with each other. and the current collecting portion and the active material layer are bonded by the adhesive portion.

FIG. 13 is a cross-sectional view schematically showing the configuration of a stacked all-solid-state battery including a conventional electrode stack.
A conventional electrode laminate 50 (positive electrode side) provided in the laminated all-solid-state battery shown in FIG. The positive electrode current collector 11 and the positive electrode active material layer 14 are bonded together with an adhesive 12 partially applied to the region between the positive electrode current collector 11 and the positive electrode active material layer 14 .
In the all-solid-state battery shown in FIG. 13 , each electrode laminate 50 (positive electrode side) is connected to the negative electrode laminate 60 via the solid electrolyte layer 15 . Each electrode laminate 50 is arranged such that the negative electrode laminate 60 is arranged in the order of the anode active material layer 19 and the anode current collector 18 from the cathode active material layer 14 side of the cathode electrode laminate 50 . (positive side).

In such a stacked all-solid-state battery including the conventional electrode stack 50 (positive electrode side), when the charge/discharge cycle is repeated, cracks occur in the positive electrode active material layer 14 and/or the positive electrode current collector 11. There is a possibility that a short circuit may occur and a possibility that the durability of the all-solid-state battery may deteriorate.
It is considered that this is due to the reason explained below.
As shown in FIG. 13, the positive electrode current collector 11 and the positive electrode active material layer 14 are separated by partially applying the adhesive portion 12 to the region between the positive electrode current collector 11 and the positive electrode active material layer 14 . , the thickness of the electrode laminate 50 in the portion to which the adhesive portion 12 is applied (hereinafter sometimes referred to as the adhesive applied portion) and the thickness of the electrode laminate 50 in the portion to which the adhesive portion 12 is not applied are A step R is generated due to the difference in thickness. In a laminated structure in which a large number of such electrode laminates 50 are laminated, the total value of the step differences R is large, and the overall step is large.
For example, in each electrode laminate 50, even if the thickness of the adhesive part 12 that bonds between the positive electrode current collector 11 and the positive electrode active material layer 14 is suppressed to 2 μm, the electrode laminate 50 (positive electrode side) is For example, when 40 layers are stacked, the cumulative value of the steps is 80 μm.
In this way, in an all-solid-state battery having a laminated structure having a large step, when the charge-discharge cycle is repeated, an increase in the constraint pressure P due to expansion of the active material layer causes the application of the adhesive to form the step R described above. Stress concentrates on the portion (projection), and this stress tends to cause cracks in the positive electrode active material layer 14 and/or the positive electrode current collector 11, and short circuits are likely to occur.
In addition, in a laminated all-solid-state battery having a laminated structure having a large step, stress concentrates on the adhesive-applied portion (convex portion) forming the step R, as described above. At the interface between the positive electrode current collector 11 and the positive electrode active material layer 14 in the region of , the restraining pressure P by, for example, a restraining member or the like is not sufficiently applied, and the surface at the interface between the positive electrode current collector 11 and the positive electrode active material layer 14 Pressure distribution becomes uneven.
Due to such uneven surface pressure distribution, Li deposition (Li deposit) is likely to occur at the interface between the positive electrode current collector 11 and the positive electrode active material layer 14, and the durability as an all-solid-state battery is reduced. do.

However, as described below, the electrode laminate for an all-solid-state battery of the present disclosure can solve the above problems.

1-1. First Embodiment First, an electrode laminate for an all-solid-state battery according to a first embodiment of the present disclosure will be described.
FIG. 1 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to the first embodiment of the present disclosure.
FIG. 1(a) shows, for convenience of explanation, the carbon coat layer of the electrode laminate according to the first embodiment in order to explain the configuration of the electrode laminate for the all-solid-state battery according to the first embodiment. FIG. 1B is a perspective view showing a configuration before laminating a positive electrode active material layer, and FIG. 1B shows the first embodiment in which a positive electrode active material layer is laminated on the carbon coat layer shown in FIG. FIG. 1(a) shows a cross section of the electrode laminate taken along the line AA' in FIG. 1(a).

The electrode laminate 10 for an all-solid-state battery according to the first embodiment of the present disclosure includes a current collector 16 including a positive electrode current collector 11 and a carbon coat layer 13 formed on the positive electrode current collector 11, and carbon and an adhesive portion 12 formed on a portion of the coating layer 13 .
A positive electrode active material layer 14 is laminated on the current collecting composite 17 , and the positive electrode active material layer 14 and the current collecting portion 16 are bonded together by the adhesive portion 12 formed on the carbon coat layer 13 . ing.

In the example shown in FIG. 1( a ), the carbon coat layer 13 is formed on the positive electrode current collector 11 while leaving a region on one edge side in the longitudinal direction of the positive electrode current collector 11 .
In addition, when the electrode laminate 10 is viewed from above, the carbon coat layer 13 is formed between the positive electrode current collector 11 and the positive electrode active material on the main surface of the positive electrode current collector 11 facing the positive electrode active material layer 14 . The carbon coat layer 13 and the adhesive portions 12a to 12e described later may be placed on the positive electrode current collector 11 such that the entire region overlapping the layer 14 is covered.

In the example shown in FIG. 1A, the adhesive portions 12a to 12d are arranged at the four corner positions of the carbon coat layer 13, and the adhesive portion 12e is arranged at the center portion of the carbon coat layer 13. .
Specifically, the adhesive portions 12a to 12e are recessed portions 12a' to 12e' (see FIG. 4B), which are through holes formed at the four corner positions or the center position of the carbon coat layer 13 described above. It is formed as a solidified product of the composition for forming the adhesive portion filled in the space.
The adhesive portions 12a to 12e are arranged continuously with the carbon coat layer 13 without providing a gap between them.

In the electrode laminate 10 of the present disclosure, the main surface of the current collector 16 on the positive electrode active material layer 14 side (that is, the main surface of the carbon coat layer 13) and the adhesive portions 12a to 12e on the positive electrode active material layer 14 side are formed so as to be coplanar with the main surface of each. In addition, "formed so as to be in the same plane" can also be rephrased as being formed so as to be horizontal or flat.
In the electrode laminate 10 of the present disclosure, as shown in FIG. 1(a), the main surface of the carbon coat layer 13 and the main surfaces of the adhesive portions 12a to 12e are adjacent to each other to form a continuous surface. .
In the present disclosure, "the main surface of the carbon coat layer and the main surface of the adhesive part are adjacent to each other to form a continuous surface" means that the main surface of the carbon coat layer and the main surface of the adhesive part are It means that the main surface of the carbon coat layer and the main surface of the adhesive portion are formed so as to be flush with each other without having a gap that becomes a discontinuous portion.
Further, in the example shown in FIG. 1(a), the thickness of the adhesive portions 12a to 12e is the same as the thickness of the carbon coat layer 13. As shown in FIG.

In the example shown in FIG. 1, the positive electrode current collector 11 does not have recesses, and the through holes formed in the carbon coat layer 13 are filled with the solidified composition for forming the adhesive portion. Although an example in which the adhesive portion 12 is formed is shown (see FIG. 1B), the electrode laminate of the present disclosure is not limited to such a form.
For example, a recess may be formed in the positive electrode current collector 11 that exists directly under the through-hole formed in the carbon coat layer 13, and the through-hole and the adhesive part-forming composition filled in the recess may be An adhesive portion may be formed by the solidified material. In this case, the thickness of the adhesive portion is greater than the thickness of the carbon coat layer.
Further, in the carbon coat layer 13, recesses are formed that do not penetrate the carbon coat layer 13, and adhesive portions are formed by the solidified adhesive portion-forming composition filled in the recesses. good too. In this case, the thickness of the adhesive portion is thinner than the thickness of the carbon coat layer.

In the example shown in FIG. 1(a), the adhesive portions 12a to 12d are arranged at the four corner positions of the carbon coat layer 13, and the adhesive portion 12e is arranged at the central portion of the carbon coat layer 13. Although an example is shown, the position where the adhesive portion is arranged is not necessarily limited to the position described above.
For example, the adhesive portions may be arranged only at some of the four corner positions and the center position of the carbon coat layer 13 . For example, among the positions of the adhesive parts 12a to 12e in FIG. and 12e only.
Further, for example, the position between the adhesive portion 12a and the adhesive portion 12e and/or the position between the adhesive portion 12d and the adhesive portion 12e on the diagonal line of the carbon coat layer 13 in FIG. You may arrange|position an adhesive part to.
Further, for example, along the long side of the carbon coat layer 13 in FIG. , along the short side of the carbon coat layer 13 in FIG. An adhesive portion may be arranged between the portion 12c and the adhesive portion 12d.
Alternatively, the adhesive portion may be arranged at a position obtained by appropriately combining any of the arrangement positions of the adhesive portion described above.
However, in any of the above cases, the adhesive portion 12 is arranged so as to be continuous with the carbon coat layer 13 without providing a gap between the adhesive portion 12 and the carbon coat layer 13, and The main surface of the adhesive portion 12 and the main surface of the carbon coat layer 13 are arranged so as to be flush with each other.

1-2. Second Embodiment Next, an electrode laminate for an all-solid-state battery according to a second embodiment of the present disclosure will be described.
FIG. 2 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to the second embodiment of the present disclosure.
FIG. 2( a ) shows the positive current collector of the electrode laminate according to the second embodiment for convenience in order to explain the configuration of the electrode laminate for the all-solid-state battery according to the second embodiment. FIG. 2B is a perspective view showing the configuration before laminating a positive electrode active material layer on the positive electrode current collector shown in FIG. 2A, and FIG. FIG. 2(a) shows a cross section of the electrode laminate according to the embodiment, taken along the line AA' in FIG. 2(a).

An electrode laminate 20 for an all-solid-state battery according to the second embodiment of the present disclosure includes a current collector 26 made of a positive electrode current collector 11 and an adhesive part 12 formed on a part of the positive electrode current collector 11. and a current collecting composite 27 having:
The positive electrode active material layer 14 is laminated on the current collector composite 27 , and the positive electrode active material layer 14 and the current collector 26 are bonded together by the adhesive part 12 formed on the positive electrode current collector 11 . It is

In the example shown in FIG. 2, the adhesive portions 12f to 12i are formed at the four corner positions of the positive electrode current collector 11, and the adhesive portion 12j is formed at the central portion of the positive electrode current collector 11. FIG.
Specifically, the adhesive portions 12f to 12j are filled in the concave portions 12f' to 12j' (see FIG. 6A) formed at the four corner positions or the center position of the positive electrode current collector 11 described above. It is formed as a solidified product of the composition for forming the adhesive portion.
The adhesive portions 12f to 12j are arranged continuously with the positive electrode current collector 11 without providing a gap between them.

In the electrode laminate 20 of the present disclosure, The main surfaces 12f to 12j on the positive electrode active material layer 14 side are formed to be flush with each other.
In the electrode laminate 20 of the present disclosure, as shown in FIG. 2(a), the main surface of the positive electrode current collector 11 and the main surfaces of the adhesive portions 12f to 12j are adjacent to each other to form a continuous surface. do.
In the present disclosure, "the main surface of the positive electrode current collector and the main surface of the adhesive part are adjacent to each other to form a continuous surface" means that the main surface of the positive electrode current collector and the main surface of the adhesive part However, it means that the main surface of the positive electrode current collector and the main surface of the adhesive portion are formed so as to be flush with each other without a gap that becomes a discontinuous portion.

In the example shown in FIG. 2(a), the adhesive portions 12f to 12i are arranged at the four corners of the positive electrode current collector 11, and the adhesive portion j is arranged at the central portion of the positive electrode current collector 11. However, the position where the adhesive portion is arranged is not necessarily limited to the position described above.
In the second embodiment, positions other than the positions of the adhesive parts 12f to 12j shown in FIG. In the electrode laminate according to the embodiment, the same position as described as the position where the adhesive portion may be formed in the carbon coat layer 13 can be used.
However, in any of the above cases, the adhesive portions 12f to 12j are arranged so as to be continuous with the positive electrode current collector 11 without providing a gap between them and the positive electrode current collector 11, In addition, the adhesive portions 12f to 12j and the main surface of the positive electrode current collector 11 are arranged so as to be flush with each other.

1-3. Third Embodiment Next, an electrode laminate for an all-solid-state battery according to a third embodiment of the present disclosure will be described.
FIG. 3 is a diagram for explaining an example of an electrode laminate for an all-solid-state battery according to a third embodiment of the present disclosure;
FIG. 3A shows, for convenience of explanation, the carbon coat layer of the electrode laminate according to the third embodiment in order to explain the configuration of the electrode laminate for the all-solid-state battery according to the third embodiment. FIG. 3B is a perspective view showing a configuration before laminating a positive electrode active material layer, and FIG. 3B is a third embodiment in which a positive electrode active material layer is laminated on the carbon coat layer shown in FIG. FIG. 3(a) shows a cross section of the electrode laminate taken along the line AA' in FIG. 3(a).

An electrode laminate 30 for an all-solid-state battery according to a third embodiment of the present disclosure includes a current collector 36 including a positive electrode current collector 11 and a carbon coat layer 13 formed on the positive electrode current collector 11; and an adhesive portion 12 formed on the main surface of the current collector 11 on which the carbon coat layer 13 is laminated.
The positive electrode active material layer 14 is laminated on the current collector composite 37, and the positive electrode active material layer 14 and the current collector 36 are formed by the adhesive part 12m formed on the positive electrode current collector 11 and the 12n.
That is, the electrode laminate 30 for an all-solid-state battery according to the third embodiment of the present disclosure includes a positive electrode current collector 11 and a positive electrode current collector 11 laminated on the positive electrode current collector 11 via adhesive portions 12m and 12n. It has a positive electrode active material layer 14 and a carbon coat layer 13 arranged between the positive electrode current collector 11 and the positive electrode active material layer 14 .

In the example shown in FIG. 3( a ), the adhesive portions 12 m and 12 n are formed as a pair of layers extending along the longitudinal direction of the positive electrode current collector 11 on both widthwise edge sides of the positive electrode current collector 11 . there is
In the present disclosure, the width direction of the positive electrode current collector 11 refers to a direction orthogonal to the longitudinal direction of the positive electrode current collector 11 .

The carbon coat layer 13 is arranged in the center portion in the width direction of the positive electrode current collector 11, that is, in the region between the adhesive portion 12m and the adhesive portion 12n.
As shown in FIG. 3B, the carbon coat layer 13 is arranged continuously with the adhesive portion 12m without providing a gap between the adhesive portion 12m and the adhesive portion 12m. 12n is also arranged continuously with the adhesive portion 12n without providing a gap.

In the electrode laminate 30 of the present disclosure, the main surface of the current collector 36 on the positive electrode active material layer 14 side, that is, the main surface of the carbon coat layer 13, and the main surface of the adhesive portion 12m on the positive electrode active material layer 14 side is formed so as to be coplanar, and the main surface of the carbon coat layer 13 and the main surface of the adhesive portion 12n on the side of the positive electrode active material layer 14 are formed so as to be coplanar. ing.
In the electrode laminate 30 of the present disclosure, as shown in FIG. 3B, the main surface of the carbon coat layer 13 is adjacent to the main surface of the adhesive portion 12m to form a continuous surface, and It is preferable to form a continuous surface adjacent to the main surface of the adhesive portion 12n.
The carbon coat layer 13 has the same thickness as the adhesive portions 12m and 12n.

The adhesive portions 12m and 12n and the carbon coat layer 13 are arranged such that, of the main surface of the positive electrode current collector 11 facing the positive electrode active material layer 14, when the electrode laminate 30 is viewed in plan, the positive electrode current collector It may be arranged on the positive electrode current collector 11 such that the entire region where the body 11 and the positive electrode active material layer 14 overlap is covered with the adhesive portions 12m and 12n and the carbon coat layer 13. .

In the example shown in FIG. 3, the adhesive portions 12m and 12n are arranged on both edge sides of the positive electrode current collector 11 in the width direction. It may be arranged on both lateral edge sides of the positive electrode current collector 11 , and may be arranged on both lateral and longitudinal end edges of the positive electrode current collector 11 . Further, the adhesive part 12 may be arranged only on one edge side of both edges of the positive electrode current collector 11 in the width direction, You may make it arrange|position only to one edge side. Alternatively, the adhesive part 12 may be arranged at the center in the width direction or the center in the longitudinal direction of the positive electrode current collector 11 .
However, in any of the above cases, the carbon coat layer 13 is arranged so as to be continuous with the adhesive portion 12 without providing a gap between the adhesive portion 12 and the The main surface of the carbon coat layer 13 and the main surface of the adhesive portion 12 are arranged so as to be flush with each other.

In the electrode laminate of the present disclosure described above, the main surface of the current collecting portion including at least the current collector on the positive electrode active material layer side and the main surface of the adhesive portion on the positive electrode active material layer side are flush with each other. The positive electrode active material layer laminated on the current collecting composite and the current collecting portion are adhered by the adhesive portion.
That is, the main surface of the current collecting composite on the side in contact with the positive electrode active material layer forms a flat surface without steps.
Therefore, in an all-solid-state battery having a laminated structure in which a plurality of the electrode laminates are laminated, even if the confining pressure increases due to repeated charge-discharge cycles, stress is locally generated inside the laminated structure. Concentration phenomenon can be suppressed. Therefore, it is possible to prevent cracks in the positive electrode active material layer 14 and the positive electrode current collector 11 and short circuits associated therewith.
In addition, the electrode laminate of the present disclosure has the above-described configuration, so that when the confining pressure increases due to repeated charge-discharge cycles in an all-solid-state battery including a laminate structure in which a large number of the electrode laminates are laminated, Since the phenomenon in which the stress is locally concentrated inside the laminated structure is suppressed, the phenomenon that the surface pressure distribution between the positive electrode current collector 11 and the positive electrode active material layer 14 becomes uneven (positive electrode collector) is suppressed. It is possible to suppress the phenomenon that the surface pressure at the interface between the conductor 11 and the positive electrode active material layer 14 varies. Therefore, it is possible to suppress the occurrence of Li deposition (Li deposit) and the accompanying decrease in durability of the all-solid-state battery.
In addition, since the electrode laminate of the present disclosure does not employ a configuration in which an adhesive portion is formed in the entire region between the positive electrode current collector 11 and the positive electrode active material layer 14, the resistance value of the all-solid-state battery Excessive rise of the can be suppressed.

Further, the electrode laminate 10 (see FIG. 1) according to the first embodiment of the present disclosure and the electrode laminate 30 (see FIG. 3) according to the third embodiment include the positive electrode current collector 11 and the positive electrode active material layer 14, the carbon coat layer 13 controls the adhesion between the positive electrode active material layer 14 and the current collector 16 and the adhesion between the positive electrode active material layer 14 and the current collector. 36 can be improved, and high conductivity can be obtained between the positive electrode current collector 11 and the positive electrode active material layer 14 .

On the other hand, the electrode laminate 20 according to the second embodiment of the present disclosure does not have a carbon coat layer, thereby reducing the thickness of the electrode laminate and the entire laminate structure obtained by laminating a plurality of the electrode laminates. can be used and costs can be reduced.

In addition, in the electrode laminate of the present disclosure, the number of adhesive parts included in the current collector composite may be singular or plural.
For example, as shown in FIGS. 1 to 3, when the current collecting composite has a plurality of adhesive parts, the main surface of each of the plurality of adhesive parts is flush with the main surface of the current collecting part. It should be arranged so that

In the examples described above, the positive electrode active material layer is laminated on the collector composite including the current collecting portion having the positive electrode current collector, and the positive electrode active material layer and the current collecting portion are adhered by the adhesive portion. Although examples of electrode laminates have been shown, the electrode laminates of the present disclosure are not limited to the forms shown in FIGS.
That is, in the electrode laminate of the present disclosure, a negative electrode active material layer is laminated on a current collecting composite having a current collecting portion having a negative electrode current collector, and the negative electrode active material layer and the current collecting portion are bonded together by an adhesive portion. (not shown).
The structure of the electrode laminates in which the negative electrode active material layer is laminated on the current collecting composite having the current collecting portion having the negative electrode current collector is the electrode laminates 10 to 30 shown in FIGS. 1 to 3, respectively, The configuration can be the same as the configuration shown in FIGS. Therefore, detailed description is omitted.

Materials for the electrode laminate for the all-solid-state battery of the present disclosure are described in detail below.
The electrode laminate of the present disclosure has an active material layer and a current collector composite.

(Active material layer)
The active material layer may be a positive electrode active material layer or a negative electrode active material layer.

The positive electrode active material layer contains at least a positive electrode active material and, if necessary, a conductive material, a binder, and a solid electrolyte.
Conventionally known materials can be used as the positive electrode active material. Examples of positive electrode active materials include metallic lithium (Li), lithium alloys, LiCoO ₂ , LiNi _x Co _1-x O ₂ (0<x<1), LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiMnO ₂ , heteroelement-substituted Li—Mn spinels (eg LiMn _1.5 Ni _0.5 O ₄ , LiMn _1.5 Al _0.5 O ₄ , LiMn _1.5 Mg _0.5 O ₄ , LiMn _1.5 Co _0.5O4 , _{LiMn1.5Fe0.5O4} , and _{LiMn1.5Zn0.5O4} , etc.), _{lithium titanate ( e.g. Li4Ti5O12} ), _lithium metal phosphate _{( e.g. LiFePO4} , _LiMnPO4 , _{LiCoPO4 ,} and _LiNiPO4 , etc.), lithium compounds such as _LiCoN , _Li2SiO3 , and _Li4SiO4 , transition metal oxides (such as _V2O5 and _MoO3 , etc.), _{TiS 2} , Si, SiO ₂ , and lithium-storing intermetallic compounds (such as Mg ₂ Sn, Mg ₂ Ge, Mg ₂ Sb, and Cu ₃ Sb).
Lithium alloys include Li-Au, Li-Mg, Li-Sn, Li-Si, Li-Al, Li-B, Li-C, Li-Ca, Li-Ga, Li-Ge, Li-As, Li -Se, Li-Ru, Li-Rh, Li-Pd, Li-Ag, Li-Cd, Li-In, Li-Sb, Li-Ir, Li-Pt, Li-Hg, Li-Pb, Li-Bi , Li—Zn, Li—Tl, Li—Te, and Li—At.
The shape of the positive electrode active material is not particularly limited, and may be particulate, plate-like, or the like.
As the solid electrolyte to be contained in the positive electrode active material layer _, a known _{solid electrolyte can} be _{appropriately} used. A sulfide solid electrolyte prepared by mixing Li ₂ S and P ₂ S ₅ at a ratio of 50:50 to 100:0 (preferably Li ₂ S:P ₂ S ₅ =70:30 by mass) A sulfide solid electrolyte prepared by mixing Li ₂ S and P ₂ S ₅ can be used.
The shape of the solid electrolyte is not particularly limited, and may be particulate, plate-like, or the like.
The binder is not particularly limited, and includes fluorine-containing resins such as polyvinylidene fluoride (PVDF), butadiene rubber (BR), styrene-butadiene rubber (SBR), and the like.
The conductive material is not particularly limited, and examples thereof include carbon materials such as acetylene black, ketjen black, carbon nanotubes and carbon fibers, and metal materials.
The carbon nanotube and carbon nanofiber may be VGCF (vapor grown carbon fiber).
The thickness of the positive electrode active material layer is not particularly limited, but may be, for example, 0.1 μm or more and 1000 μm or less, especially 10 μm or more and 250 μm or less.
The content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but may be, for example, 50% by mass to 90% by mass.

The negative electrode active material layer contains at least a negative electrode active material and, if necessary, a conductive material, a binder, and a solid electrolyte.
Conventionally known materials can be used as the negative electrode active material, and examples thereof include Li simple substance, lithium alloys, carbon materials, Si simple substances, Si alloys, and Li ₄ Ti ₅ O ₁₂ (LTO).
Examples of the lithium alloy include the lithium alloys exemplified as the lithium alloy used for the positive electrode active material.
Examples of Si alloys include alloys with metals such as Li, and may be alloys with at least one metal selected from the group consisting of Sn, Ge, and Al.
The carbon material may be, for example, at least one selected from the group consisting of graphite, graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon).
The shape of the negative electrode active material is not particularly limited, and examples thereof include a particulate shape and a plate shape.
The content of the negative electrode active material in the negative electrode active material layer is not particularly limited, but may be, for example, 20% by mass to 90% by mass.
As the solid electrolyte used for the negative electrode active material layer, the same solid electrolyte as that usable for the positive electrode active material layer can be used.
As the conductive material and binder used for the negative electrode active material layer, the same materials as those usable for the positive electrode active material layer can be used.
The thickness of the negative electrode active material layer is not particularly limited, but may be, for example, 0.1 μm or more and 1000 μm or less.

(Current collector composite)
The current collecting composite has a current collecting portion and an adhesive portion.
The current collector may be a laminate of a current collector and a carbon coat layer, which includes at least a current collector and optionally has a carbon coat layer laminated on at least one surface of the current collector. .
The current collector may be a positive electrode current collector or a negative electrode current collector, but when the active material layer is a positive electrode active material layer, the current collector is a positive electrode current collector, When the active material layer is the negative electrode active material layer, the current collector is the negative electrode current collector.

The positive electrode current collector has a function of collecting current for the positive electrode active material layer. Examples of materials for the positive electrode current collector include metallic materials such as SUS, Ni, Cr, Au, Pt, Al, Fe, Ti and Zn.
In addition, examples of the shape of the positive electrode current collector include foil, plate, mesh, and the like.
The positive electrode current collector may have a positive electrode lead for connection with an external terminal.
The thickness of the positive electrode current collector is not particularly limited, but may be, for example, 0.1 μm or more and 1000 μm or less.

The negative electrode current collector has a function of collecting current for the negative electrode active material layer. Examples of materials for the negative electrode current collector include metal materials such as SUS, Cu, Ni, Fe, Ti, Co, and Zn. Further, examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh shape.
The negative electrode current collector may have a negative electrode lead for connection with an external terminal.
The thickness of the negative electrode current collector is not particularly limited, but may be, for example, 0.1 μm or more and 1000 μm or less.

The carbon coat layer contains at least a carbon material and, if necessary, a binder.
Examples of the carbon material contained in the carbon coat layer include carbon black such as acetylene black, furnace black, and ketjen black, and graphite powder.
As the binder contained in the carbon coat layer, the same binder as that contained in the positive electrode active material layer can be used.
The content of the carbon material in the carbon coat layer is not particularly limited, but may be, for example, 10% by mass to 90% by mass. Also, the content of the binder in the carbon coat layer is not particularly limited, but may be, for example, 10% by mass to 90% by mass.
As the carbon coat layer, for example, one containing 15% by mass of a carbon material and 85% by mass of a binder can be used.
The thickness of the carbon coat layer is not particularly limited, but may be, for example, 5 μm or more and 50 μm or less. The thickness of the carbon coat layer may be, for example, 10 μm.
The carbon coating layer may have a volume resistivity of 1×10 ³ Ωcm to 10×10 ³ Ωcm. The volume resistivity of the carbon coat layer may be, for example, 5×10 ³ Ωcm.

The adhesive portion contains at least resin.
As the resin used for the adhesive portion, a thermoplastic resin having a melting point or softening point lower than the deterioration temperature of the battery material may be used. Examples of thermoplastic resins used in the adhesive portion include polyolefin resins, and specific examples include low density polyethylene (LDPE) and ethylene-vinyl acetate copolymer resin (EVA).
Examples of the thermoplastic resin used for the adhesive portion include ethylene-vinyl acetate copolymer resin (manufactured by Hitachi Chemical Co., Ltd.).
As the resin used for the adhesive part, considering the temperature dependence of each resin, a resin that can be used at a temperature below the deterioration temperature of the battery material and having a resin viscosity that allows adhesion is appropriately selected and used. be able to.
Moreover, as the adhesive portion, the above-described thermoplastic resin may be applied in layers and dried, but it is not necessarily limited to such a form. For example, a commercially available double-sided tape may be used as the adhesive portion, or a commercially available adhesive may be applied in layers and dried to be used as the adhesive portion. .
If the thickness of the adhesive portion is formed so that the main surface of the current collecting portion on the side of the active material layer and the main surface of the adhesive portion on the side of the active material layer are flush with each other, It is not particularly limited.

2. Method for manufacturing electrode laminate for all-solid-state battery A method for manufacturing an electrode laminate for an all-solid-state battery according to the present disclosure includes a current collector including at least a current collector and an adhesive part, and the current collector includes the current collector. a step of forming a current collecting composite formed so that the main surface of the adhesive portion and the main surface of the adhesive portion are flush with each other (current collecting composite forming step); and the adhesive of the current collecting composite. forming an active material layer on the main surface on the side where the portion is exposed to bond the current collecting portion and the active material layer with the adhesive portion (adhesion step); characterized by

The method of manufacturing the electrode laminate of the present disclosure includes, for example, (1) a current collector composite forming step, (2) an adhesion step, and optionally (3) a pressing step and the like.

(1) Current-collecting composite forming step The current-collecting composite forming step includes:
A current collector composite having a current collector portion including at least a current collector and an adhesive portion, wherein the main surface of the current collector portion and the main surface of the adhesive portion are formed in the same plane. It is a step of forming
Hereinafter, (1A) an example of the first embodiment and the second embodiment, and (1B) an example of the third embodiment of the current collecting composite forming step will be described in order.

(1A) First Embodiment and Second Embodiment In the method for manufacturing the electrode laminate according to the first embodiment and the electrode laminate according to the second embodiment, (1) current collector composite forming step includes: (1-1) recess forming step and (1-2) first adhesive portion forming step.
FIG. 4 is a perspective view schematically explaining the process of an example of the method for manufacturing the electrode laminate 10 according to the first embodiment of the present disclosure shown in FIG. ) are sectional views taken along the line AA' of the steps shown in FIGS. 4B to 4D among the steps shown in FIG. 5(b) is a cross-sectional view of region α in FIG. 4(b), FIG. 5(c) is a cross-sectional view of region α in FIG. 4(c), and FIG. ) is a cross-sectional view of the region α in FIG. 4(d).
6 is a perspective view schematically explaining the process of an example of the method for manufacturing the electrode laminate 20 according to the second embodiment of the present disclosure shown in FIG. 2, and FIG. 6A is a cross-sectional view taken along the line AA' of the region β shown in FIG. 6A in the process shown in FIG.

(1-1) Recess Forming Step The recess forming step is a step of forming a recess for forming an adhesive portion on the surface of the current collecting portion on which the active material layer is laminated (Fig. 4(b), Fig. 6 ( a) see).
The current collector forming the concave portion may be a laminate of a current collector and a carbon coat layer (see FIG. 4(b)), or may be a current collector alone (see FIG. 6(a) )reference).

When a laminate of a current collector and a carbon coat layer is used as the current collector, the carbon coat layer can be formed on the surface of the current collector, for example, as follows.
First, a slurry of a composition for forming a carbon coat layer containing a carbon material and a binder is applied onto the positive electrode current collector 11 and dried to form the carbon coat layer 13 (FIG. 4). (a)).
As the carbon material and the binder contained in the composition for forming the carbon coat layer, the materials described above as the material for the carbon coat layer can be used.

The position where the carbon coat layer 13 is formed is not particularly limited. For example, as shown in FIG. 11 may be formed as a layer covering one surface.
In the step shown in FIG. 4( a ), when the positive electrode current collector 11 is viewed from above, the main surface of the positive electrode current collector 11 (2) bonding step described later ( FIG. 4( d ) )), the entire region overlapping with the positive electrode active material layer 14 formed in (1-2) described later is the adhesive portions 12a to 12e formed in the first adhesive portion forming step (1-2) (Fig. The carbon coat layer 13 may be formed so as to be covered with 4(c)).

The method of forming the recesses on the surface of the current collector is not particularly limited, but for example, it can be carried out by irradiating a laser beam to the positions where the recesses are to be formed.

As the laser light, for example, an ultrashort pulse laser with a pulse width of 10 ⁻⁹ seconds or less may be used.
As the ultrashort pulse laser, a nanosecond pulse laser (1×10 ⁻⁹ ), a picosecond pulse laser (1×10 ⁻¹² ) and a femtosecond pulse laser (1×10 ⁻¹⁵ ) may be used.
Among them, when a femtosecond pulse laser is used, it has an arbitrary hole diameter and depth at an arbitrary position with respect to the current collector, regardless of the material properties of the current collector to be irradiated. It becomes possible to form a concave portion.
The wavelength, output value, and frequency of the laser light can be appropriately adjusted according to the hole diameter of the hole formed by laser irradiation, the thickness of the current collecting portion, and/or the material properties.

The concave portion for forming the adhesive portion is formed on the surface of the current collecting portion on which the active material layer is laminated.
In the case of forming a concave portion in the current collector, which is a laminate of a current collector and a carbon coat layer, for example, as shown in FIG. After fabricating the current collector 16 (see FIG. 4(a)), the surface of the carbon coat layer 13 is irradiated with a laser beam to form concave portions 12a′ to 12e′ (FIG. 4(b), FIG. 5 ( b) see). At this time, through holes may be formed in the carbon coat layer 13 as shown in FIG. 5(b). Further, at this time, recesses may be formed in a portion of the positive electrode current collector 11 that exists directly under the through holes formed in the carbon coat layer 13 to such an extent that the positive electrode current collector 11 does not have through holes. good.

Further, in the case of forming a concave portion in a current collecting portion constituted by a current collector alone, one main surface of the positive electrode current collector 11 is irradiated with a laser beam as shown in FIG. Concave portions 12f' to 12j' having a predetermined depth are formed so that the current collector 11 does not penetrate (FIG. 6(a)).

The method of forming recesses on the surface of the current collector is not limited to the method of irradiating the laser beam described above. For example, the concave portion may be formed by bringing the tip of a needle-like member into contact with the position where the concave portion is to be formed on the main surface of the current collecting portion on the side of the active material layer, and scooping out the surface of the current collecting portion. .

The position where the recess is formed is not particularly limited. For example, as shown in FIGS. 4(b) and 6(a), the recesses are formed at the four corner positions and the central position of the surface of the current collecting portion on which the active material layer is laminated. good too.
The position where the concave portion is formed is not limited to the position described above, and can be formed at any position on the main surface of the current collector on the side where the active material layer is laminated.

As described above, by adopting a method of irradiating the current collector with a laser beam as a method of forming the concave portion for forming the adhesive portion, the concave portion can be formed at an arbitrary position on the current collector. The number of recesses can be formed.
Therefore, it is possible to form the recesses in the current collecting portion by appropriately adjusting the position and the number of the recesses according to the adhesive force required in each electrode laminate. Therefore, it is possible to minimize the reduction in the power generation effective area due to the presence of the adhesive portion.

(1-2) First Adhesive Portion Forming Step The first adhesive portion forming step is a step of filling the recess with the adhesive portion forming composition.
Specifically, the recesses formed in the (1-1) recess forming step are filled with the composition for forming the adhesive portion containing, for example, the thermoplastic resin described above, and the solidified composition for forming the adhesive portion is obtained. You may form the adhesive part which consists of (refer FIG.4(c), FIG.6(b)).

As the resin component such as a thermoplastic resin contained in the composition for forming the adhesive portion, the materials described above as the material for the adhesive portion can be used.

As a method for filling the concave portion with the composition for forming the adhesive portion, a conventionally known filling method can be used.

When forming a plurality of the adhesive portions, the main surface of each adhesive portion is formed so as to be flush with the main surface of the current collecting portion.
For example, as shown in FIG. 4, when a current collector 16 made of a laminate of a positive electrode current collector 11 and a carbon coat layer 13 is used as the current collector, an adhesive formed at least in part of the carbon coat layer 13 The principal surfaces of the agent portions 12a to 12e are formed so as to be flush with the principal surface of the current collecting portion 16, that is, the principal surface of the carbon coat layer 13 (see FIG. 4(c)). Thus, a current collecting composite 17 is obtained. In this case, the adhesive part 12 is formed so that the adhesive part 12 is arranged continuously with the carbon coat layer 13 without providing a gap between the adhesive part 12 and the carbon coat layer 13 .
Further, for example, as shown in FIG. The surface is formed so as to be flush with the main surface of the current collector 26, that is, the main surface of the positive electrode current collector 11 (see FIG. 6B). Thus, a collector composite 27 is obtained. In this case, the adhesive part 12 is formed so that the adhesive part 12 is arranged continuously with the positive electrode current collector 11 without providing a gap between the adhesive part 12 and the positive electrode current collector 11 .

That is, the adhesive portion 12 is formed such that the main surface of the adhesive portion 12 is adjacent to the main surface of the current collector portion 11 on which the positive electrode active material layer 14 is laminated to form a continuous surface. Form.
Specifically, it is preferable to fill the entire concave portion with the composition for forming the adhesive portion without gaps.

(1B) Third Embodiment In the method for manufacturing an electrode laminate according to the third embodiment, (1) a current collector composite forming step includes (1-3) a carbon coat layer forming step, and (1-4) You may have a 2nd adhesive bond part formation process.
FIG. 8 is a perspective view schematically explaining the process of an example of the method of manufacturing the electrode laminate 30 of the present disclosure shown in FIG.
A method for manufacturing an electrode laminate according to a third embodiment of the present disclosure will be described with reference to FIG.

(1-3) Carbon coat layer forming step The carbon coat layer forming step is a step of forming a carbon coat layer on at least one surface of a current collector to produce a current collector having a current collector and a carbon coat layer ( See FIG. 8(a)).
The carbon coat layer can be formed using the same composition for forming a carbon coat layer as described in step (1-1) above.

In the step (1-3), the position where the carbon coat layer 13 is formed is not particularly limited. For example, as shown in FIG. It may be formed as a strip-shaped layer extending along the longitudinal direction of the positive electrode current collector 11 .

(1-4) Second Adhesive Portion Forming Step The second adhesive portion forming step is a step of forming an adhesive portion on the surface of the current collector on which the carbon coat layer is formed.
In the second adhesive portion forming step, the adhesive portion forming composition may be applied onto the positive electrode current collector 11 to form the layered adhesive portions 12m and 12n (FIG. 8B). reference). Thus, a collector composite 37 is obtained.
As the adhesive part-forming composition, the same composition as the adhesive part-forming composition used in (1-2) the first adhesive part-forming step can be used.
The position where the adhesive portion 12 is laminated is not particularly limited. However, the adhesive part 12 is formed so that the adhesive part 12 is arranged continuously with the carbon coat layer 13 without providing a gap between the carbon coat layer 13 and the positive electrode current collector. The adhesive part 12 may be laminated on the entire area of the main surface of the body 11 where the carbon coat layer 13 is not laminated.
For example, as shown in FIG. 8( a ), when the carbon coat layer 13 is formed in the central portion of the positive electrode current collector 11 in the width direction, the adhesive portion 12 is formed on the main surface of the positive electrode current collector 11 . Of these, in the regions on both widthwise edge sides of the positive electrode current collector 11 where the carbon coat layer 13 is not laminated (regions indicated by 11α and 11β in FIG. 8A), the longitudinal direction of the positive electrode current collector 11 may be formed as a pair of layers extending along the

The adhesive portions 12m and 12n are formed so that their main surfaces are flush with the main surface of the carbon coat layer 13, which is the main surface of the current collecting portion .
Further, the adhesive portions 12m and 12n are arranged such that the main surface of the adhesive portion 12m and the main surface of the adhesive portion 12n are adjacent to the main surface of the carbon coat layer 13, respectively, to form a continuous surface. to form.
Such a configuration may be formed, for example, by setting the thickness of the adhesive portions 12m and 12n to be the same as the thickness of the carbon coat layer 13 .

In the step shown in FIG. 8(b), when the positive electrode current collector 11 is viewed from above, the (2) bonding step described later (see FIG. 8(c)) among the main surfaces of the positive electrode current collector 11 ), the adhesive portions 12m and 12n are preferably formed such that the entire region overlapping the positive electrode active material layer 14 is covered with the adhesive portions 12m and 12n and the carbon coat layer 13.

(2) Bonding Step The bonding step includes forming an active material layer on the main surface of the collector composite on which the adhesive portion is exposed, thereby separating the current collector and the active material layer. This is a step of bonding with the adhesive portion.
In the adhesion step, for example, a slurry of a composition for forming a positive electrode active material layer containing a positive electrode active material, a solid electrolyte, a binder and, if necessary, a conductive material is applied to the adhesive portion of the current collector composite. may be applied to the exposed surface and dried to form a positive electrode active material layer on the current collecting composite. As a result, the current collecting portion and the active material layer are adhered by the adhesive portion, and an electrode laminate can be obtained (see FIGS. 4(d), 6(c), and 8(c)). ).
As the positive electrode active material, the solid electrolyte, the binder, and the conductive material contained in the positive electrode active material layer-forming composition, the materials described above as the material for the positive electrode active material layer can be used.

Specifically, in the example of the first embodiment shown in FIG. The positive electrode active material layer 14 is formed on the surface (see FIG. 4(c)), and the current collecting portion 16 and the positive electrode active material layer 14 are adhered by the adhesive portions 12a to 12e, thereby forming an electrode laminate. 10 may be obtained (see FIG. 4(d)).
In addition, in the example of the second embodiment shown in FIG. 6, the main surface of the collector composite 27 on the side where the adhesive portions 12f to 12j are exposed, that is, the adhesive portion of the positive electrode current collector 11 A positive electrode active material layer 14 is formed on the main surface (see FIG. 6B) on the side where 12f to 12j are exposed, and the collector portion 26 and the positive electrode active material layer 14 are attached to the adhesive portion 12f. 12j, the electrode stack 20 may be obtained (see FIG. 6(c)).
Furthermore, in the example of the third embodiment shown in FIG. 8, a positive electrode is formed on the main surface of the collector composite 37 on the side where the adhesive portions 12m and 12n are exposed (see FIG. 8(b)). The electrode laminate 30 may be obtained by forming the active material layer 14 and bonding the collector portion 36 and the positive electrode active material layer 14 with the adhesive portions 12m and 12n (see FIG. 8C). ).

(3) Pressurization step The pressurization step is a step of pressurizing the electrode laminate produced in the above-described (2) bonding step in the stacking direction (not shown). The means for applying pressure to the electrode laminate in the pressure step is not particularly limited, and any known means can be used. In the pressurizing step, it is preferable to pressurize under heating.

A method for pressurizing the electrode laminate is not particularly limited, and examples thereof include mechanical pressurization and gas pressurization.
Examples of mechanical pressurization include a method of driving a motor to pressurize the electrode stack in the stacking direction via a ball screw, and a method of driving a motor to pressurize the electrode stack in the stacking direction via hydraulic pressure. be able to. At this time, after pressurizing or depressurizing to a desired pressure, by fixing the moving part of the press using a mechanical stopper, the consumption of energy required for driving the motor can be minimized.
Gas pressurization includes, for example, a method of pressurizing the electrode laminate via a pressurized gas supplied from a gas cylinder or the like.
The pressure when pressing the electrode laminate may be, for example, 1 MPa, and the heating temperature may be, for example, 140.degree.

In the examples shown in FIGS. 4 to 8, a positive electrode active material layer is formed on the main surface of the current collecting composite having a current collecting portion having a positive electrode current collector on the side where the adhesive portion is exposed. Although an example of a manufacturing method for forming and obtaining an electrode laminate has been shown, the method for manufacturing an electrode laminate of the present disclosure includes the adhesive portion of a current collecting composite comprising a current collecting portion having a negative electrode current collector. It is also possible to form a negative electrode active material layer on the main surface of the exposed side to obtain an electrode laminate.
In the case of the manufacturing method, a negative electrode current collector is used instead of the positive electrode current collector 11, and a negative electrode active material, a solid electrolyte, a binder and, if necessary, a 4 to 8, except that the composition for forming a negative electrode active material layer containing a conductive material is used.
As the negative electrode active material, the solid electrolyte, the binder, and the conductive material contained in the negative electrode active material layer-forming composition, the materials used for the negative electrode active material layer can be used.

3. All-solid-state battery 3-1. First Embodiment FIG. 9 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 100 including the electrode laminate 10 according to the first embodiment of the present disclosure.
The all-solid-state battery 100 includes a current collector 16 including a positive electrode current collector 11 and a carbon coat layer 13, and a current collector composite 17 having adhesive portions 12a to 12e formed on a part of the carbon coat layer 13. and a cathode active material layer 14 laminated on the current collecting composite 17, and a negative electrode laminate including a negative electrode active material layer 19 and a negative electrode current collector 18. 40, and a solid electrolyte layer 15 disposed between the electrode laminate 10 on the positive electrode side and the electrode laminate 40 on the negative electrode side.

Since the electrode laminate 10 on the positive electrode side provided in the all-solid-state battery 100 is the electrode laminate for the all-solid-state battery according to the first embodiment of the present disclosure (see FIG. 1), the positive electrode side here Description of the electrode laminate 10 is omitted.

3-2. Second Embodiment FIG. 10 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 200 including an electrode laminate 20 according to a second embodiment of the present disclosure.
The all-solid-state battery 200 is an all-solid-state battery provided with the positive electrode-side electrode laminate 20 shown in FIG. 2 instead of the positive electrode-side electrode laminate 10 in the all-solid-state battery 100 shown in FIG.
Since the electrode laminate 20 on the positive electrode side provided in the all-solid-state battery 200 is the electrode laminate 20 (see FIG. 2) for the all-solid-state battery according to the second embodiment of the present disclosure, the positive electrode side here The description of the electrode laminate 20 is omitted.

3-3. Third Embodiment FIG. 11 is a cross-sectional schematic diagram showing an example of an all-solid-state battery 300 including an electrode laminate 30 according to a third embodiment of the present disclosure.
The all-solid-state battery 300 is an all-solid-state battery provided with the positive electrode-side electrode laminate 30 shown in FIG. 3 instead of the positive electrode-side electrode laminate 10 in the all-solid-state battery 100 shown in FIG.
Since the electrode laminate 30 on the positive electrode side provided in the all-solid-state battery 300 is the electrode laminate 30 (see FIG. 3) for the all-solid-state battery according to the third embodiment of the present disclosure, the positive electrode side here The description of the electrode laminate 30 is omitted.

The negative electrode active material layer of the electrode laminate 40 on the negative electrode side provided in the all-solid-state batteries 100 to 300 can be used as the negative electrode active material layer provided as the active material layer of the electrode laminate for the all-solid-state battery of the present disclosure described above. can be used.
In addition, the negative electrode current collector of the electrode laminate 40 on the negative electrode side provided in the all-solid-state batteries 100 to 300 is the negative electrode current collector provided as the current collector of the electrode laminate for the all-solid-state battery of the present disclosure described above. Anything similar to what can be used can be used.

The solid electrolyte layer provided in the all-solid-state battery of the present disclosure contains at least a solid electrolyte, and may contain a binder or the like as necessary.
The solid electrolyte used for the solid electrolyte layer can be used without particular limitation as long as it is a known solid electrolyte that can be used for all-solid-state batteries. Anything similar can be used.
The shape of the solid electrolyte is not particularly limited, and may be particulate, plate-like, or the like.
As the binder used for the solid electrolyte layer, the same binder as used for the positive electrode active material layer can be used.
The thickness of the solid electrolyte layer varies depending on the type of electrolyte, the structure of the battery, etc., and is not particularly limited. may be

The all-solid-state battery of the present disclosure optionally includes an exterior body that houses the positive electrode layer, the negative electrode layer, and the solid electrolyte layer.
The material of the exterior body is not particularly limited as long as it is stable in the electrolyte, and examples thereof include resins such as polypropylene, polyethylene, and acrylic resin.

In addition, the all-solid-state battery of the present disclosure includes a restraining member that presses and restrains the laminated structure having the positive electrode laminate, the negative electrode laminate, and the solid electrolyte layer in the stacking direction, if necessary. good too.

When the all-solid-state battery of the present disclosure is used as a power source, the pressure applied to the electrode portion (region where the positive electrode active material layer and the negative electrode active material layer exist) may be 1 MPa or more and 45 MPa or less. The pressure applied to the electrode portion when the battery is not in use may be 0 MPa or more and 1 MPa or less.

Examples of all-solid-state batteries include lithium batteries, sodium batteries, magnesium batteries, calcium batteries, and the like. Among them, lithium batteries may be used.
The shape of the all-solid-state battery including the electrode laminate of the present disclosure includes, for example, a coin shape, a laminate shape, a cylindrical shape, a rectangular shape, and the like.

The all-solid-state battery provided with the electrode laminate of the present disclosure may be a primary battery or a secondary battery, and may be a secondary battery among others. This is because it can be repeatedly charged and discharged, and is useful, for example, as a vehicle battery.
When the all-solid-state battery comprising the electrode laminate of the present disclosure is used as a vehicle battery, target vehicles include electric vehicles equipped with a battery and no engine, hybrid vehicles equipped with both a battery and an engine, and the like. mentioned.

In the all-solid-state batteries 100 to 300 shown in FIGS. 9 to 11, a positive electrode active material layer is formed on a current collecting composite having a current collector having a positive electrode current collector, and the positive electrode active material layer and the current collector are formed. Although an example in which the electrode laminates 10 to 30 are attached to each other with an adhesive portion has been shown, the all-solid-state battery of the present disclosure is not limited to these. That is, in the all-solid-state battery of the present disclosure, a negative electrode active material layer is formed on a current collecting composite including a current collecting portion having a negative electrode current collector, and the negative electrode active material layer and the current collecting portion are bonded to each other by an adhesive portion. It may be a configuration including an electrode laminate adhered by.

4. Manufacturing method of all-solid-state battery 4-1. First Embodiment The all-solid-state battery 100 according to the first embodiment shown in FIG. 9 can be manufactured, for example, through the steps shown below.
First, the positive electrode current collector 11 and the carbon coat layer are performed in the same manner as described in (1) the current collector composite forming step and (2) the bonding step in the method for manufacturing the electrode laminate for the all-solid-state battery described above. 13, a current collecting composite 17 having adhesive portions 12a to 12e formed on a part of the carbon coat layer 13, and a positive electrode active layer laminated on the current collecting composite 17 A positive electrode laminate 10 (see FIG. 4D) having a material layer 14 is produced.
Next, a slurry of a composition for forming a negative electrode active material layer containing a negative electrode active material, a solid electrolyte, a binder, and optionally a conductive material is applied onto the negative electrode current collector 18 and dried. Then, the negative electrode active material layer 19 is formed, and a bonded body (not shown) having the negative electrode active material layer 19 and the negative electrode current collector 18 is manufactured.
As the negative electrode active material, the solid electrolyte, the binder, and the conductive material contained in the negative electrode active material layer-forming composition, the materials described above as the material for the negative electrode active material layer can be used.
Next, a composition for forming a solid electrolyte layer containing a solid electrolyte and a binder is applied to the positive electrode active material layer 14 and the negative electrode active material layer 19, respectively, and the positive electrode active material layer 14 and the negative electrode active material layer 19 are coated. A part of the solid electrolyte layer 15 is laminated on each of . After that, the solid electrolyte layer 15 is overlapped so that parts of the solid electrolyte layer 15 are aligned with each other, and if necessary, the obtained laminated structure is pressed in the lamination direction to obtain the positive electrode current collector 11, the carbon coat layer 13, An all-solid-state battery 100 according to the first embodiment having a laminated structure in which the cathode active material layer 14, the solid electrolyte layer 15, the anode active material layer 19, and the anode current collector 18 are laminated in this order is produced. be able to.
The pressurizing method and pressurizing conditions can be performed in the same manner as described in (3) the pressurizing step.

4-2. Second Embodiment An all-solid-state battery 200 according to a second embodiment shown in FIG. 10 can be manufactured, for example, through the steps shown below.
First, in the same manner as described in the (1) current collector composite forming step and (2) bonding step in the method for manufacturing an electrode laminate for an all-solid-state battery described above, a current collector composed of the positive electrode current collector 11 a current collecting composite 27 having a portion 26 and adhesive portions 12f to 12j formed on a part of the positive electrode current collector 11; and a positive electrode active material layer 14 laminated on the current collecting composite 27. , is prepared on the positive electrode side (see FIG. 6(c)). Subsequent steps can be performed in the same manner as in the method for manufacturing the all-solid-state battery 100 according to the first embodiment, thereby producing the all-solid-state battery 200 according to the second embodiment.

4-3. Third Embodiment An all-solid-state battery 300 according to a third embodiment shown in FIG. 11 can be manufactured through the following steps, for example.
First, the positive electrode current collector 11 and the carbon coat layer are performed in the same manner as described in (1) the current collector composite forming step and (2) the bonding step in the method for manufacturing the electrode laminate for the all-solid-state battery described above. 13, adhesive portions 12m and 12n formed on the main surface of the positive electrode current collector 11 on which the carbon coat layer 13 is laminated; A cathode-side electrode laminate 30 (see FIG. 8C) having a cathode active material layer 14 laminated on a collector composite 37 is produced. Subsequent steps are the same as the manufacturing method of the all-solid-state battery 100 according to the first embodiment, and the all-solid-state battery 300 according to the third embodiment can be produced.

5. Stacked All-Solid-State Battery FIG. 12 is a cross-sectional view schematically showing a stacked-type all-solid-state battery in which a plurality of the all-solid-state batteries shown in FIG. 9 are stacked.
The laminated all-solid-state battery shown in FIG. It has a current collecting composite 17 formed so that the main surface on the 14 side is flush with the current collecting composite 17, and the positive electrode active material layer 14 laminated on the current collecting composite 17 and the current collecting part 16 are adhered by the adhesive portion 12 .
For this reason, the entire surface of the collector composite 16 that contacts the positive electrode active material layer 14 is a flat surface without steps.
Therefore, the stacked all-solid-state battery shown in FIG. 12 does not have a large step as the stacked all-solid-state battery shown in FIG. 13 has. It is possible to suppress the generation of cracks in the positive electrode current collector 11 and the occurrence of a short circuit, and the deterioration of the durability of the all-solid-state battery.

The stacked all-solid-state battery shown in FIG. 12 can be manufactured, for example, as follows.
First, a laminated structure is produced by laminating the negative electrode active material layer 19, the solid electrolyte layer 15, and the positive electrode active material layer 14 in this order on both sides of the negative electrode current collector 18. FIG. The manufacturing process of each layer can be performed in the same procedure as described in the manufacturing method of the all-solid-state battery described above, so detailed description thereof will be omitted. Next, the current collector composite 17 is produced in the same procedure as described in (1) current collector composite formation step in the method for manufacturing the electrode laminate according to the first embodiment. Next, the main surface of the current collecting composite 17 on which the adhesive portion 12 is exposed is superimposed on the positive electrode active material layer 14 of the laminated structure described above, and the above Laminate the laminated structure. By repeating this procedure, the stacked all-solid-state battery shown in FIG. 12 can be obtained.

10, 20, 30 Electrode laminate 11 for all-solid-state battery Positive electrode current collectors 12, 12a to 12n Adhesive portions 12a' to 12j' Concave portion 13 Carbon coat layer 14 Positive electrode active material layer 15 Solid electrolyte layer 16, 26, 36 Current collectors 17, 27, 37 Current collector composite 18 Negative electrode current collector 19 Negative electrode active material layer 40 Negative electrode laminate 50 Conventional electrode laminate (positive electrode side)
60 Conventional electrode laminate (negative electrode side)
100, 200, 300 All-solid battery R Step P Confining pressure

Claims (2)

a current collecting composite having a current collecting portion including at least a current collector and an adhesive portion;
an active material layer laminated on the current collecting composite,
The main surface of the current collector on the active material layer side and the main surface of the adhesive part on the active material layer side are formed to be flush with each other, and the current collector and the active material layer are formed in the same plane. An electrode laminate for an all-solid-state battery, wherein the electrode laminate is adhered by the adhesive portion. A current collector composite having a current collector portion including at least a current collector and an adhesive portion, wherein the main surface of the current collector portion and the main surface of the adhesive portion are formed in the same plane. forming a
forming an active material layer on the main surface of the current collector composite on which the adhesive portion is exposed, thereby bonding the current collector and the active material layer with the adhesive portion; A method for manufacturing an electrode laminate for an all-solid-state battery, comprising:

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