Solid electrolyte, preparation method thereof and lithium secondary battery comprising electrolyte

Abstract

The invention relates to a solid electrolyte, a preparation method thereof and a lithium secondary battery comprising the solid electrolyte. The sulfide-based solid electrolyte according to the present invention is represented by the following Chemical Formula 1. [Chemical Formula 1] Li6 (1-y) A < 2 > y P < 1-y > S < 5-2y > X < 1-y > (In Chemical Formula 1, A is a boron group element, X is a halogen element, and 0 < y < = 1).

Description

Technical Field

[0001] The present invention relates to a solid electrolyte, a method for preparing the same, and a lithium secondary battery including the solid electrolyte. More specifically, the present invention relates to a sulfide-based solid electrolyte doped with a boron group element. Background Art

[0002] An all-solid-state battery is a battery in which an electrolyte is made solid. The all-solid-state battery replaces a flammable liquid electrolyte with a solid electrolyte, so it has a lower explosion risk and excellent stability. Therefore, the all-solid-state battery including a solid electrolyte is attracting attention as a next-generation battery.

[0003] In particular, compared with other solid electrolytes such as polymers and oxides, sulfide-based solid electrolytes exhibit excellent ionic conductivity. Since the ionic conductivity of sulfide-based solid electrolytes is similar to that of liquid electrolytes, the all-solid-state battery including a sulfide-based solid electrolyte is considered to be the material closest to practical use compared with other all-solid-state batteries.

[0004] In particular, Li6PS5X having an argyrodite structure exhibits high ionic conductivity and high stability, and thus is used as a solid electrolyte in many institutions.

[0005] In order to commercialize the battery, it is necessary to form a complete battery and evaluate it in the form of a battery. However, when a complete battery is formed using a solid electrolyte having an argyrodite structure and evaluated in the form of an all-solid-state battery, its performance is inferior to that of a conventional commercial lithium ion battery. This is because, compared with the currently used liquid electrolyte, the impedance generated by the solid electrolyte having an argyrodite structure is high, and it still has a low ionic conductivity. That is, due to the high impedance and low ionic conductivity, poor battery characteristics are exhibited.

[0006] Therefore, there is a current need to make efforts to improve the ionic conductivity of the solid electrolyte having an argyrodite structure. If the ionic conductivity characteristics of the solid electrolyte can be improved, the performance of the all-solid-state battery can be improved, thereby realizing the commercialization of the all-solid-state battery earlier. Summary of the Invention

[0007] The present invention aims to provide a solid electrolyte, a method for preparing the same, and a lithium secondary battery including the solid electrolyte. More specifically, the present invention aims to provide a sulfide-based solid electrolyte doped with a boron group element.

[0008] The sulfide-based solid electrolyte according to the present invention is represented by the following Chemical Formula 1.

[0009] [Chemical Formula 1]

[0010] Li 6(1-y) A2y P 1-y S 5-2y X 1-y

[0011] In Chemical Formula 1, A is an element of Group 13, X is a halogen element, and 0 < y ≤ 1.

[0012] A can be any one or more of boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Ta).

[0013] A can be boron (B).

[0014] y can be from 0.02 to 0.16.

[0015] X can be any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0016] X can be chlorine (Cl).

[0017] The sulfide-based solid electrolyte according to the present invention may include a crystalline phase having an argyrodite-type crystal structure.

[0018] A method for preparing a sulfide-based solid electrolyte according to the present invention includes: a step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing an element of Group 13; and a step of heat-treating the mixture.

[0019] In the step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing an element of Group 13, the compound containing an element of Group 13 may be B2S3.

[0020] In the step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing an element of Group 13, the concentration of the compound containing an element of Group 13 may be from 0.02 to 0.16 mol%.

[0021] In the step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing an element of Group 13, the sulfur compound may be phosphorus pentasulfide (P2S5).

[0022] In the step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing an element of Group 13, the halogen compound is LiX, and X can be any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0023] The lithium secondary battery according to the present invention includes a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and at least any one of the positive electrode, the negative electrode, and the solid electrolyte layer includes the aforementioned sulfide-based solid electrolyte according to the present invention.

[0024] The sulfide-based solid electrolyte according to the present invention is doped with boron, so the mobility of lithium ions is high, thereby having a high ionic conductivity and good battery capacity characteristics. Detailed Description

[0025] The terms first, second, third, etc. are used to describe various parts, components, regions, layers, and / or segments, but these parts, components, regions, layers, and / or segments should not be limited by these terms. These terms are only used to distinguish one part, component, region, layer, and / or segment from another part, component, region, layer, and / or segment. Therefore, without departing from the scope of the present invention, the first part, component, region, layer, and / or segment described below may also be described as the second part, component, region, layer, and / or segment.

[0026] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. Unless otherwise clearly indicated to the contrary in the context, the singular forms used are also intended to include the plural forms. It should also be understood that the term "comprising" used in the specification may specifically refer to a certain characteristic, field, integer, step, action, element, and / or component, but does not exclude the existence or addition of other characteristics, fields, integers, steps, actions, elements, and / or components.

[0027] If a part is described as being on another part, there may be other parts directly on or between the other part. If a part is described as being directly on another part, there will be no other parts therebetween.

[0028] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. For terms defined in a dictionary, they should be interpreted as having a meaning consistent with the relevant technical literature and the content disclosed herein, and should not be interpreted in an idealized or overly formal sense.

[0029] The sulfide-based solid electrolyte according to the present invention has been invented to improve the low ionic conductivity of conventional undoped sulfide-based solid electrolytes and enhance the characteristics of batteries containing such solid electrolytes.

[0030] More specifically, this is to improve the ionic conductivity and battery characteristics of the solid electrolyte represented by Li6PS5X, where X refers to a halogen element.

[0031] The sulfide-based solid electrolyte according to the present invention is represented by Chemical Formula 1 below.

[0032] [Chemical Formula 1]

[0033] Li 6(1-y) A 2y P 1-y S 5-2y X 1-y

[0034] In Chemical Formula 1, A is a boron group element, X is a halogen element, and 0 < y ≤ 1.

[0035] The sulfide-based solid electrolyte according to the present invention may be a solid electrolyte in which a boron group element is doped in a solid electrolyte represented as Li6PS5X. More specifically, boron (B) may be doped in a solid electrolyte represented as Li6PS5Cl.

[0036] More specifically, A may be a boron group element, i.e., a Group 13 element. More specifically, A may be any one or more of boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Ta). More specifically, A may be boron (B).

[0037] The boron group element may be a doping element. "Doping" in this specification not only refers to replacing some elements of a compound with a new element, but may also refer to the doped element becoming a constituent element of the crystal phase of the compound.

[0038] Since a boron group element is doped in the solid electrolyte crystal, lithium ions in the existing crystal may be missing. If lithium ions are missing, vacancies will be generated at this position. Therefore, due to the multiple generated vacancies, lithium ions will migrate more smoothly. Thus, the ionic conductivity of the solid electrolyte can be increased.

[0039] In the solid electrolyte according to an embodiment of the present invention, lithium ions may be missing. Therefore, 6(1 - y) in Chemical Formula 1 above may be the molar number of lithium (Li), where 6(1 - y) may be 5 to 6. More specifically, 6(1 - y) may be 5 to 5.6. More specifically, 6(1 - y) may be 5 to 5.5. More specifically, 6(1 - y) may be 5.2 to 5.45.

[0040] On the other hand, in Chemical Formula 1 above, 2y is the doping amount of the boron group element expressed in molar number. At this time, y satisfies 0 < y ≤ 1.

[0041] More specifically, y can be from 0.02 to 0.16. If y is too small, it means that the doping amount of the boron group element is too small. If y is too large, it means that the doping amount of the boron group element is too large. When y is too small or too large, the ionic conductivity of the solid electrolyte is low, and the battery characteristics may be poor. More specifically, if the doping amount of the boron group element is too small, it will not deviate significantly from the basic Li6PS5Cl argyrodite component, the number of vacancy formations is small, and there is no doping effect. In addition, if the doping amount of the boron group element is too large, the crystal structure of the argyrodite of the sulfide-based solid electrolyte with ionic conductivity will be greatly deformed, and the migration of lithium ions may not be smooth.

[0042] More specifically, y can be from 0.07 to 0.16. More specifically, y can be from 0.08 to 0.16. More specifically, y can be from 0.09 to 0.13. More specifically, y can be from 0.1 to 0.12. More specifically, y can be from 0.11 to 0.13.

[0043] In the above Chemical Formula 1, X can be a halogen element, that is, any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0044] More specifically, X can be chlorine (Cl).

[0045] The sulfide-based solid electrolyte according to the present invention may include a crystalline phase having an argyrodite-type crystal structure. The advantage of the argyrodite-type crystal structure is high ionic conductivity.

[0046] The method for preparing a sulfide-based solid electrolyte according to the present invention includes: a step of preparing a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element; and a step of heat-treating the mixture.

[0047] Hereinafter, the method for preparing a sulfide-based solid electrolyte according to the present invention will be described according to each step.

[0048] First, a mixture including lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element is prepared. That is, lithium sulfide, a sulfur compound, a halogen compound, and a compound containing a boron group element are used as raw materials for the sulfide-based solid electrolyte according to the present invention.

[0049] At this time, the sulfur compound may be a mixture of sulfur (S) and an element selected from phosphorus (P), silicon (Si), germanium (Ge), aluminum (Al), boron (B), and mixtures thereof. More specifically, it may be diphosphorus pentasulfide (P2S5).

[0050] At this time, the halogen compound can be LiX. More specifically, X can be a halogen element, and X can be any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Therefore, X can be any one or more of LiF, LiCl, LiBr, and LiI.

[0051] On the other hand, the compound containing a boron group element can be A2S3. More specifically, A can be a boron group element, i.e., a Group 13 element. More specifically, A can be any one or more of boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Ta).

[0052] More specifically, the boron group element can be boron (B). That is, the compound containing a boron group element can be B2S3.

[0053] In addition, in this step, the concentration of the compound containing a boron group element can be 0.02 to 0.16 mol%.

[0054] If the doping amount of the boron group element is too small, it will not deviate significantly from the basic Li6PS5Cl argyrodite component, and the number of vacancy formations is small, without a doping effect. In addition, if the doping amount of the boron group element is too large, the crystal structure of the argyrodite of the sulfide-based solid electrolyte with ionic conductivity will be greatly deformed, and the migration of lithium ions may not be smooth.

[0055] More specifically, the concentration of the compound containing a boron group element can be such that y is 0.07 to 0.16 mol%. More specifically, it can be 0.08 to 0.16 mol%. More specifically, it can be 0.09 to 0.13 mol%. More specifically, it can be 0.1 to 0.12 mol%. More specifically, it can be 0.11 to 0.13 mol%.

[0056] For example, when preparing a sulfide-based solid electrolyte doped with B by adding B2S3 to Li6PS5X, a solid electrolyte can be prepared by reaction formulas such as the following reaction formula 1.

[0057] [Reaction formula 1]

[0058] (1-y)Li6PS5X + xB2S3 -> Li 6(1-y) B 2y P 1-y S 5-2y X 1-y

[0059] The mixing in this step can be carried out by a dry method or a wet method. More specifically, the mixing in this step can be carried out by dry grinding.

[0060] For dry grinding, specifically, a ball mill, a vibration mill, a turbo mill, a mechanical fusion machine, a disk mill, a bead mill, or a planetary mill can be used. More specifically, a planetary mill can be used.

[0061] The dry grinding in this step can be carried out for 5 to 12 hours. More specifically, it can be carried out for 6 to 10 hours. If the time is too short, there will be a problem of insufficient mixing. In addition, since the mixing is carried out for a certain period of time or more, even if the mixing is carried out for a long time, the mixing state will be the same. Therefore, from the perspective of productivity, it is preferable to carry out the mixing for an appropriate time.

[0062] In this step, the rotational speed of the planetary mill can be 150 rpm to 450 rpm. More specifically, it can be 200 rpm to 400 rpm. If the rotational speed is too slow, the spheres entering the planetary mill will not enter the interior of the powder, and the powder particles will not be fully mixed as a whole or the energy will be low, and there may be a problem of insufficient atomization of the powder particles. In addition, if the rotational speed is too fast, the powder will concentrate in one place, and there may be a problem of uneven mixing.

[0063] Next, a step of granulating the mixture can also be included.

[0064] The pressure in the step of granulating can be 150 MPa to 450 MPa. More specifically, it can be 200 MPa to 400 MPa. If the pressure is too low, the bonding (adhesion) between the powder particles is insufficient, and there is a defect of increased interfacial impedance. In addition, if the pressure in the step of granulating exceeds a certain level, the powder particles are completely bonded, and even if a higher pressure is applied, the bonding state will not change. Therefore, from the perspective of productivity, it is preferable to granulate under an appropriate pressure.

[0065] Next, the mixture is heat-treated to prepare a solid electrolyte.

[0066] The heat treatment can be carried out in the range of 200 to 700 °C. More specifically, it can be carried out in the range of 300 to 600 °C. If the heat treatment temperature is too low, the heat treatment effect is negligible. If the heat treatment temperature is too high, the elements constituting the solid electrolyte are vaporized, and there is a problem of loss of the solid electrolyte.

[0067] The heat treatment can be carried out in an inert gas environment. More specifically, it can be carried out in an argon (Ar) environment.

[0068] Furthermore, after the synthesized solid electrolyte is crushed into a pellet shape, a battery can be fabricated using a working electrode.

[0069] The lithium secondary battery according to the present invention includes a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and at least any one of the positive electrode, the negative electrode, and the solid electrolyte layer contains the aforementioned sulfide-based solid electrolyte according to the present invention.

[0070] The positive electrode may contain a positive electrode active material, a conductive material, a binder, and any one or more of the aforementioned solid electrolytes.

[0071] The negative electrode may be a metal negative electrode or a composite negative electrode. The composite negative electrode may contain a negative electrode active material, a conductive material, a binder, and any one or more of the aforementioned solid electrolytes.

[0072] The detailed content regarding the sulfide-based solid electrolyte has been described above, and the specific content is omitted below.

[0073] Hereinafter, embodiments of the present invention will be described in detail. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. The scope of the present invention is defined by the claims.

[0074] Comparative Example 1 - Without adding B2S5

[0075] (1) Synthesis of solid electrolyte

[0076] The solid electrolyte was synthesized by a dry grinding method.

[0077] Lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium chloride (LiCl) were mixed using a planetary mill at 300 rpm for about 8 hours.

[0078] Then, pellets were formed at 300 MPa.

[0079] Then, heat treatment was performed at 500 °C in an argon (Ar) environment to synthesize Li6PS5Cl.

[0080] (2) Measuring the ionic conductivity of the battery

[0081] After the synthesized solid electrolyte was pulverized, pellets were formed at 300 MPa. Then, a battery was fabricated using sus as the working electrode.

[0082] The ionic conductivity of the battery was measured by impedance.

[0083] The measurement results are shown in Table 1 below.

[0084] Example 1 - Adding 0.02 mol% of B2S5

[0085] In addition to further adding 0.02 mol% of B2S5 to the mixing process of Comparative Example 1, synthesis was carried out under the same conditions as in Comparative Example 1.

[0086] After fabricating a battery using the synthesized B-doped solid electrolyte in the same manner as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0087] Example 2 - Adding 0.04 mol% of B2S5

[0088] In addition to further adding 0.04 mol% of B2S5 to the mixing process of Comparative Example 1, synthesis was carried out under the same conditions as in Comparative Example 1.

[0089] After fabricating a battery using the synthesized B-doped solid electrolyte in the same manner as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0090] Example 3 - Adding 0.06 mol% of B2S5

[0091] In addition to further adding 0.06 mol% of B2S5 to the mixing process of Comparative Example 1, synthesis was carried out under the same conditions as in Comparative Example 1.

[0092] After fabricating a battery using the synthesized B-doped solid electrolyte in the same manner as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0093] Example 4 - Adding 0.08 mol% of B2S5

[0094] In addition to further adding 0.08 mol% of B2S5 to the mixing process of Comparative Example 1, synthesis was carried out under the same conditions as in Comparative Example 1.

[0095] After fabricating a battery using the synthesized B-doped solid electrolyte in the same manner as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0096] Example 5 - Adding 0.1 mol% of B2S5

[0097] In addition to further adding 0.1 mol% of B2S5 to the mixing process of Comparative Example 1, synthesis was carried out under the same conditions as in Comparative Example 1.

[0098] After fabricating a battery using the synthesized B-doped solid electrolyte in the same manner as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0099] Example 6 - Adding 0.12 mol% of B2S5

[0100] Synthesis was carried out under the same conditions as in Comparative Example 1, except that 0.12 mol% of B2S5 was further added to the mixing process of Comparative Example 1.

[0101] After fabricating a battery using the synthesized B-doped solid electrolyte by the same method as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0102] Example 7 - Adding 0.14 mol% of B2S5

[0103] Synthesis was carried out under the same conditions as in Comparative Example 1, except that 0.14 mol% of B2S5 was further added to the mixing process of Comparative Example 1.

[0104] After fabricating a battery using the synthesized B-doped solid electrolyte by the same method as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0105] Example 8 - Adding 0.16 mol% of B2S5

[0106] Synthesis was carried out under the same conditions as in Comparative Example 1, except that 0.16 mol% of B2S5 was further added to the mixing process of Comparative Example 1.

[0107] After fabricating a battery using the synthesized B-doped solid electrolyte by the same method as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0108] Example 9 - Adding 0.18 mol% of B2S5

[0109] Synthesis was carried out under the same conditions as in Comparative Example 1, except that 0.18 mol% of B2S5 was further added to the mixing process of Comparative Example 1.

[0110] After fabricating a battery using the synthesized B-doped solid electrolyte by the same method as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0111] Example 10 - Adding 0.2 mol% of B2S5

[0112] Synthesis was carried out under the same conditions as in Comparative Example 1, except that 0.2 mol% of B2S5 was further added to the mixing process of Comparative Example 1.

[0113] After fabricating a battery using the synthesized B-doped solid electrolyte by the same method as in Comparative Example 1, the ionic conductivity was measured by the same method. The measurement results are shown in Table 1 below.

[0114] [Table 1]

[0115]

[0116] The ionic conductivities of the batteries containing sulfide-based solid electrolytes fabricated in Comparative Example 1 and Examples 1 to 10 were compared.

[0117] For the solid electrolyte of Example 1 doped with B by adding 0.02 mol% of B2S5, it was found that the ionic conductivity was higher than that of Comparative Example 1 without B doping. With only a small amount of B doping, the ionic conductivity was higher than that without B doping, indicating that B doping fundamentally improved the ionic conductivity of the battery.

[0118] Furthermore, up to Example 5 doped with B by adding 0.1 mol% of B2S5, the higher the doping concentration of B, the higher the ionic conductivity.

[0119] In particular, for Example 4 doped with B by adding 0.08 mol% of B2S5, Example 5 doped with B by adding 0.1 mol% of B2S5, Example 6 doped with B by adding 0.12 mol% of B2S5, Example 7 doped with B by adding 0.14 mol% of B2S, and Example 8 doped with B by adding 0.16 mol% of B2S5, their ionic conductivities exceeded 4 mS / cm.

[0120] Meanwhile, for Example 5 doped with B by adding 0.1 mol% of B2S5, its ionic conductivity was 4.75 mS / cm, which was the highest.

[0121] The present invention can be implemented in various different ways and is not limited to the described embodiments. Those of ordinary skill in the technical field to which the present invention pertains can understand that the present invention can be implemented in other specific ways without changing the technical idea or essential features of the present invention. Therefore, it should be understood that the above embodiments are exemplary in all aspects and are not intended to limit the present invention.

Claims

1. A sulfide-based solid electrolyte represented by the following Chemical Formula 1: [Chemical Formula 1] Li 6(1-y) A 2y P 1-y S 5-2y X 1-y In Chemical Formula 1 above, A is a boron group element, X is a halogen element, and 0 < y ≤ 1.

2. The sulfide-based solid electrolyte according to Claim 1, wherein the A is any one or more of boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Ta).

3. The sulfide-based solid electrolyte according to Claim 2, wherein the A is boron (B).

4. The sulfide-based solid electrolyte according to Claim 1, wherein the y is from 0.02 to 0.

16.

5. The sulfide-based solid electrolyte according to Claim 1, wherein the X is any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

6. The sulfide-based solid electrolyte according to Claim 5, wherein the X is chlorine (Cl).

7. The sulfide-based solid electrolyte according to Claim 1, wherein the sulfide-based solid electrolyte contains a crystalline phase having an argyrodite-type crystal structure.

8. A method for preparing a sulfide-based solid electrolyte, comprising: a step of preparing a mixture containing lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element; and a step of heat-treating the mixture.

9. The method for preparing a sulfide-based solid electrolyte according to Claim 8, wherein in the step of preparing a mixture containing lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element, the compound containing a boron group element is B2S3.

10. The method for preparing a sulfide-based solid electrolyte according to Claim 8, wherein in the step of preparing a mixture containing lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element, the concentration of the compound containing a boron group element is from 0.02 to 0.16 mol%.

11. The method for preparing a sulfide-based solid electrolyte according to Claim 8, wherein in the step of preparing a mixture containing lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element, the sulfur compound is phosphorus pentasulfide (P2S5).

12. The method for preparing a sulfide-based solid electrolyte according to Claim 8, wherein in the step of preparing a mixture containing lithium sulfide (Li2S), a sulfur compound, a halogen compound, and a compound containing a boron group element, the halogen compound is LiX, wherein X is any one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

13. A lithium secondary battery, wherein the lithium secondary battery includes a positive electrode, a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode, and at least any one of the positive electrode, the negative electrode, and the solid electrolyte layer contains the solid electrolyte according to Claim 1.

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