All-solid-state battery and method for manufacturing the same

Abstract

To provide an all-solid-state battery that exhibits good Li-ion diffusibility during discharge.SOLUTION: An all-solid-state battery according to the present disclosure that utilizes a precipitation-dissolution reaction of metallic Li as a negative electrode reaction includes a positive electrode having a positive electrode current collector and a positive electrode active material layer, a negative electrode having at least a negative electrode current collector, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and the negative electrode has a compound layer containing a first compound represented by Li-Mg-X (X element is at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on a surface of the negative electrode current collector facing the solid electrolyte layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to an all-solid-state battery and a method for manufacturing an all-solid-state battery. [Background technology]

[0002] All-solid-state batteries are batteries that have a solid electrolyte layer between a positive electrode active material layer and a negative electrode active material layer, and have the advantage of being easier to simplify safety devices compared to liquid-based batteries that use electrolyte solutions containing flammable organic solvents. Among all-solid-state batteries, batteries that utilize the deposition and dissolution reaction of metallic lithium as the negative electrode reaction are known.

[0003] For example, Patent Document 1 discloses an all-solid-state battery that utilizes a deposition-dissolution reaction of metallic lithium as a negative electrode reaction, and that contains a β single-phase alloy of metallic lithium and metallic magnesium as a negative electrode active material, and that when the all-solid-state battery is fully charged, the elemental ratio of lithium element in the alloy is 81.80 atomic % or more and 99.97 atomic % or less.

[0004] Patent Document 2 discloses an all-solid-state battery having a protective layer containing a composite metal oxide represented by Li-MO (M is at least one metal element selected from the group consisting of Mg, Au, Al, and Sn) between a negative electrode layer containing at least one selected from the group consisting of metallic lithium and lithium alloys and a solid electrolyte layer.

[0005] Furthermore, Patent Document 3 discloses an all-solid-state battery that utilizes a deposition-dissolution reaction of metallic lithium as a reaction at the negative electrode, and that when the all-solid-state battery is fully charged, has, in this order, a negative electrode current collector, a negative electrode layer, a protective layer containing a Li-Zn-O composite metal oxide, a solid electrolyte layer, and a positive electrode layer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-184513 [Patent Document 2] Japanese Patent Publication No. 2020-184407 [Patent Document 3] Japanese Patent Publication No. 2021-034199 Summary of the Invention [Problem to be solved by the invention]

[0007] From the viewpoint of improving battery performance, it is preferable that the charge / discharge efficiency of the battery is good. As will be described in detail later, the present inventors have found that in all-solid-state batteries that utilize a deposition-dissolution reaction of metallic lithium as the negative electrode reaction, the diffusibility of Li ions decreases as discharge progresses. In particular, if the diffusibility of Li ions is low at the end of discharge, sufficient discharge capacity cannot be obtained, and the charge / discharge efficiency may decrease.

[0008] The present disclosure has been made in view of the above circumstances, and has as its main object to provide an all-solid-state battery in which Li ions have good diffusibility during discharge. [Means for solving the problem]

[0009] [1] An all-solid-state battery utilizing a deposition-dissolution reaction of metallic Li as an anode reaction, the all-solid-state battery comprising: a positive electrode having a positive electrode current collector and a positive electrode active material layer; a negative electrode having at least a negative electrode current collector; and a solid electrolyte layer disposed between the positive electrode and the negative electrode, wherein the negative electrode has a compound layer containing a first compound represented by Li-Mg-X (wherein X element is at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on a surface of the negative electrode current collector facing the solid electrolyte layer.

[0010] [2] The all-solid-state battery according to [1], wherein the element X is at least one selected from Zn, Sn, and Zr.

[0011] [3] The all-solid-state battery according to [1] or [2], wherein the compound layer contains a second compound consisting of Li element and Mg element.

[0012] [4] The all-solid-state battery according to [3], wherein in the second compound, a ratio of the Mg element to the Li element is 0.01 atomic % or more and 30 atomic % or less.

[0013] [5] [4] The all-solid-state battery according to any one of [1] to [4], wherein in the compound layer, a ratio of the number of atoms of the X element to the total number of atoms of the Mg element and the X element is 25 atomic % or more and 50 atomic % or less.

[0014] [6] The all-solid-state battery according to any one of [1] to [5], wherein the negative electrode has a protective layer containing a composite oxide represented by Li-Mg-XO (wherein X is the X element) between the compound layer and the solid electrolyte layer.

[0015] [7] An all-solid-state battery utilizing a deposition-dissolution reaction of metallic Li as an anode reaction, the all-solid-state battery comprising: a positive electrode having a positive electrode current collector and a positive electrode active material layer; a negative electrode having at least a negative electrode current collector; and a solid electrolyte layer disposed between the positive electrode and the negative electrode, wherein the negative electrode has a modification layer containing a third compound containing Mg element and X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on a surface of the negative electrode current collector facing the solid electrolyte layer.

[0016] [8] A method for producing an all-solid-state battery that utilizes a deposition-dissolution reaction of metallic Li as an anode reaction, the method comprising: a preparation step of preparing a positive electrode having a positive electrode current collector and a positive electrode active material layer, a solid electrolyte layer, and a negative electrode having a negative electrode current collector and a modifying layer; and a laminate formation step of obtaining a laminate having the positive electrode, the solid electrolyte layer, and the negative electrode in this order, wherein the modifying layer contains a third compound containing Mg element and X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P).

[0017] [9] The method for producing an all-solid-state battery according to [8], further comprising an initial charging step of initially charging the laminate. [Effects of the Invention]

[0018] The present disclosure has an effect of providing an all-solid-state battery in which Li ions have good diffusibility during discharge. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating an example of an all-solid-state battery according to the present disclosure. [Figure 2] FIG. 1 is a flow diagram illustrating a method for manufacturing an all-solid-state battery according to the present disclosure. [Figure 3] 1 shows charge / discharge curves obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0020] The all-solid-state battery and the method for manufacturing the all-solid-state battery according to the present disclosure will be described in detail below.

[0021] A. All-solid-state battery FIG. 1 is a schematic cross-sectional view illustrating an example of an all-solid-state battery according to the present disclosure. FIG. 1(a) shows the all-solid-state battery before the first charge, FIG. 1(b) shows the all-solid-state battery after charge (after the first charge), and FIG. 1(c) shows the all-solid-state battery after discharge. The all-solid-state battery 10 shown in FIGS. 1(a) to 1(c) is a battery that utilizes a deposition-dissolution reaction of metallic Li as the anode reaction, and has the advantage of high energy density. The all-solid-state battery 10 includes a cathode CA having a cathode current collector 1 and a cathode active material layer 2, an anode AN having at least an anode current collector 3, and a solid electrolyte layer SE disposed between the anode AN and the cathode CA. In the all-solid-state battery according to the present disclosure, as shown in FIG. 1(b), the anode AN may include a compound layer 4 containing a first compound represented by Li-Mg-X (where X is at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on the surface of the anode current collector 3 facing the solid electrolyte layer SE. Furthermore, as shown in FIG. 1(a), in the all-solid-state battery 10, the negative electrode AN may have a modification layer 5 containing a third compound containing Mg element and X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on the surface of the negative electrode current collector 3 facing the solid electrolyte layer SE.

[0022] In the present disclosure, an embodiment including a compound layer 4, such as the all-solid-state battery shown in Figure 1(b), is referred to as a "first embodiment," and an embodiment including a modification layer 5, such as the all-solid-state battery shown in Figure 1(a), is referred to as a "second embodiment." As shown in Figures 1(a) and (b), when the all-solid-state battery of the second embodiment (Figure 1(a)) is initially charged, the all-solid-state battery of the first embodiment (Figure 1(b)) is obtained.

[0023] According to the present disclosure, since the negative electrode in the all-solid-state battery of the first embodiment contains a predetermined first compound, and since the negative electrode in the all-solid-state battery of the second embodiment contains a predetermined third compound, it is possible to provide an all-solid-state battery with good diffusibility of Li ions during discharge.

[0024] As in Reference 1, a technique for providing a metallic Mg layer on the negative electrode current collector is known for all-solid-state batteries that utilize the deposition-dissolution reaction of metallic lithium as the negative electrode reaction. When metallic lithium is deposited in such an all-solid-state battery (when the all-solid-state battery is charged), Li and Mg form a body-centered cubic (BCC) structure at the negative electrode. Regarding this point, the inventors have found through simulations that when metallic lithium is dissolved (when the all-solid-state battery is discharged), the BCC structure undergoes a phase transition to a Mg-rich hexagonal close-packed (HCP) structure. Because the HCP structure has a higher packing density than the BCC structure, there is less room for Li to move within the crystal structure, resulting in a decrease in diffusibility, such as the Li diffusion rate. As a result, the Li diffusion rate decreases during discharge, which may reduce the battery's charging efficiency.

[0025] In contrast, in the all-solid-state battery of the present disclosure, in the all-solid-state battery of the first embodiment (all-solid-state battery after charging), the compound layer of the negative electrode contains a first compound containing an X element. Since the X element is an element that can form a BCC structure with both Li and Mg, it is presumed that the BCC structure can be maintained even if the Li element in the negative electrode (compound layer) decreases due to discharge. Therefore, it is possible to suppress a decrease in the diffusion rate of Li, particularly at the end of discharge, and as a result, it is possible to suppress a decrease in charge / discharge efficiency.

[0026] 1. First Aspect The all-solid-state battery of a first embodiment is an all-solid-state battery that utilizes a deposition-dissolution reaction of metallic Li as an anode reaction, and includes a positive electrode having a positive electrode current collector and a positive electrode active material layer, a negative electrode having at least a negative electrode current collector, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and the negative electrode has a compound layer containing a first compound containing Li-Mg-X (wherein X element is at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on a surface of the negative electrode current collector facing the solid electrolyte layer.

[0027] (1) Negative electrode The negative electrode in the first embodiment has at least a negative electrode current collector and a compound layer containing a first compound represented by Li-Mg-X (wherein X element is at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on the surface of the negative electrode current collector facing the solid electrolyte layer.

[0028] The first compound contains Li, Mg, and an X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P). The X element is an element that can form a BCC structure with both Li and Mg. The X element is more preferably at least one selected from Zn, Sn, and Zr. The first compound may be a compound containing Li, Mg, and one X element, or may be a compound containing Li, Mg, and two or more X elements.

[0029] Here, when the first compound contains only a metal element as the X element, i.e., when the first compound is an alloy, the electronic conductivity is faster than the ion conduction rate and ion diffusion rate, which is thought to make it difficult for Li ions to be exchanged at locations other than the interface between the solid electrolyte layer and the compound layer. On the other hand, when the first compound contains the nonmetallic element P as the X element, i.e., when the first compound is a semiconductor represented by Li-Mg-P, it is thought that the battery resistance can be reduced. This is because, although the inclusion of a semiconductor in the compound layer suppresses electronic conduction in the compound layer (electron conduction slows down), the slower electronic conduction is thought to allow for good exchange of Li ions even within the compound layer other than the interface, which is thought to result in a shorter diffusion distance of Li ions.

[0030] The first compound may be a metal compound (alloy) containing only a metal element as the X element. Preferably, the first compound has a crystalline phase (β phase) with a body-centered cubic structure. The crystalline phase of the first compound may be a single β phase or a mixed phase, with the former being preferred. In the latter case, the proportion of the β phase to the total crystalline phase in the first compound is preferably 50% or more. The crystalline phase (crystalline structure) can be confirmed by structural analysis such as XRD.

[0031] The compound layer may also contain a second compound consisting of Li and Mg. The second compound is a binary alloy containing only Li and Mg. The second compound preferably has a crystalline phase (β phase) with a body-centered cubic structure. The crystalline phase of the second compound may be a single β phase or a mixed phase, with the former being preferred. In the latter case, the proportion of the β phase relative to the total crystalline phase in the second compound is preferably 50% or more. In addition, the proportion of the Mg element relative to the Li element in the second compound is preferably 0.01 atomic% or more and 30 atomic% or less. When the proportion is within the above range, the second compound can exist as a single β phase alloy of Li and Mg, resulting in better charge / discharge efficiency. The proportion of the elements can be confirmed, for example, by removing the negative electrode from the all-solid-state battery after charging and subjecting it to inductively coupled plasma emission spectroscopy (ICP).

[0032] The compound layer may also contain compounds other than the first compound and the second compound and elemental metals. Examples of compounds other than the first compound and the second compound include ternary alloys such as Li-Mg-Z (where Z is a metal element other than Li, Mg, and X) and binary alloys such as Mg-X and Li-X. Examples of elemental metals include elemental Li, elemental Mg, elemental X, and elemental Z, which are metal elements.

[0033] In the compound layer, the first compound may be in a particle state. When the first compound is an alloy, the first compound may be in a solid solution state. In the latter case, the compound layer can be considered to have an alloy phase, such as a Li-Mg-X alloy phase. The same applies to the second compound.

[0034] The total proportion of the first compound and the second compound to all compounds and elemental metals in the compound layer may be 100% or less. In the latter case, the proportion is, for example, 50% or more, 80% or more, 90% or more, or 99% or more.

[0035] In the compound layer, the proportion of the X element may be the same as or different from the proportion of the Mg element. In the latter case, the proportion of the X element may be greater or less than the proportion of the Mg element. The proportion of the number of atoms of the X element to the total number of atoms of the Mg element and the X element (atomic ratio) is, for example, 25 atomic % or more, 30 atomic % or more, or 35 atomic % or more. On the other hand, the proportion is, for example, 50 atomic % or less, 45 atomic % or less, or 40 atomic % or less. The atomic ratio can be confirmed by the ICP.

[0036] The compound layer in the present disclosure functions as a negative electrode active material layer. That is, the first compound and the second compound function as a negative electrode active material. When an all-solid-state battery having the compound layer is discharged, Li dissolves from the first compound and the second compound, and the compound layer becomes a layer containing Mg elemental, X elemental, and an Mg-X compound as main components. Meanwhile, the compound layer after discharge may also contain the first compound and the second compound.

[0037] The thickness of the compound layer is not particularly limited, but is, for example, 30 nm or more and 5000 nm or less.

[0038] Examples of materials for the negative electrode current collector include copper, SUS, nickel, and carbon. Examples of the shape of the negative electrode current collector include foil. The thickness of the negative electrode current collector is, for example, 1 nm or more and 1 mm or less.

[0039] 1(b), in the all-solid-state battery of the first embodiment, the negative electrode AN may have a protective layer 6 containing a composite oxide represented by Li-Mg-XO (wherein X is the X element) between the compound layer 4 and the solid electrolyte layer SE. The presence of the protective layer can prevent the interface between the negative electrode (compound layer) and the solid electrolyte layer from becoming high in resistance.

[0040] The composite oxide is more stable than metallic lithium, functions as a protective layer that suppresses the reaction between metallic lithium and the solid electrolyte, and contains lithium elements, so that the lithium ion conductivity is high. Therefore, as shown in Figures 1(b) and 1(c), once the protective layer 6 is formed, the protective layer 6 usually does not disappear even after discharging the all-solid-state battery 10.

[0041] The thickness of the protective layer is not particularly limited, but is, for example, 1 nm or more and 5 nm or less.

[0042] (2) Positive electrode The positive electrode in the present disclosure has a positive electrode current collector and a positive electrode active material layer.

[0043] The positive electrode active material layer contains at least a positive electrode active material, and may also contain at least one of a solid electrolyte, a conductive material, and a binder, as necessary.

[0044] The positive electrode active material is not particularly limited, but examples thereof include oxide active materials and sulfur-based active materials. Examples of oxide active materials include LiCoO2, LiMnO2, LiNiO2, LiVO2, and LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, etc., rock salt layered active materials, LiMn2O4, Li4Ti5O 12 , Li(Ni 0.5 Mn 1.5)Spinel-type active materials such as O4, olivine-type active materials such as LiFePO4, LiMnPO4, LiNiPO4, and LiCoPO4 can be mentioned. Also, as the oxide active material, Li 1+x Mn 2-x-y M y O4 (M is at least one of Al, Mg, Co, Fe, Ni, Zn, 0 < x + y < 2), a LiMn spinel active material represented by, lithium titanate, etc. may be used.

[0045] Also, a coating layer containing a Li-ion conductive oxide may be formed on the surface of the oxide active material. This is because the reaction between the oxide active material and the solid electrolyte can be suppressed. Examples of the Li-ion conductive oxide include LiNbO3, Li4Ti5O 12 , Li3PO4. The thickness of the coating layer is, for example, 0.1 nm or more, and may be 1 nm or more. On the other hand, the thickness of the coating layer is, for example, 100 nm or less, and may be 20 nm or less. The coverage rate of the coating layer on the surface of the oxide active material is, for example, 70% or more, and may be 90% or more.

[0046] Also, the sulfur-based active material is an active material containing at least the S element. The sulfur-based active material may or may not contain the Li element. Examples of the sulfur-based active material include elemental sulfur, lithium sulfide (Li2S), polysulfide lithium (Li2Sx, 2 ≤ x ≤ 8).

[0047] The proportion of the positive electrode active material in the positive electrode active material layer is, for example, 50% by weight or more and 99% by weight or less.

[0048] The solid electrolyte is described in "(3) Solid Electrolyte Layer." Examples of conductive materials include carbon materials. Examples of carbon materials include particulate carbon materials such as acetylene black (AB) and ketjen black (KB), and fibrous carbon materials such as carbon fiber, carbon nanotubes (CNT), and carbon nanofibers (CNF). Examples of binders include rubber-based binders such as butylene rubber (BR) and styrene butadiene rubber (SBR), and fluoride-based binders such as polyvinylidene fluoride (PVDF).

[0049] The thickness of the positive electrode active material layer is, for example, 0.1 μm or more and 1000 μm or less.

[0050] The positive electrode current collector is a member that collects electrons from the positive electrode active material layer. Examples of materials for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. Examples of the shape of the positive electrode current collector include foil and mesh. The thickness of the positive electrode current collector is, for example, 1 μm or more and 1 mm or less.

[0051] (3) Solid electrolyte layer The solid electrolyte layer is disposed between the positive electrode and the negative electrode. The solid electrolyte layer contains at least a solid electrolyte and may further contain a binder. The binder is the same as that described in "(2) Positive electrode," and therefore will not be described here.

[0052] Examples of solid electrolytes include inorganic solid electrolytes such as sulfide solid electrolytes, oxide solid electrolytes, nitride solid electrolytes, and halide solid electrolytes. The sulfide solid electrolyte preferably contains sulfur (S) as the main anion element. The oxide solid electrolyte preferably contains oxygen (O) as the main anion element. The nitride solid electrolyte preferably contains nitrogen (N) as the main anion element. The halide solid electrolyte preferably contains halogen (N) as the main anion element. Among these, sulfide solid electrolytes are preferred.

[0053] Examples of sulfide solid electrolytes include Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, and Li2S-P2S5-Z m S n (where m and n are positive numbers. Z is Ge, Zn, or Ga.), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li x MO y (where x and y are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, and In.)

[0054] The composition of the sulfide solid electrolyte is not particularly limited, but examples thereof include yLiI·zLiBr·(100-yz)Li3PS4 (0≦y≦30, 0≦z≦30).

[0055] The thickness of the solid electrolyte layer is, for example, not less than 0.1 μm and not more than 1000 μm.

[0056] (4) All-solid-state battery The all-solid-state battery according to the present disclosure may further include a restraining jig that applies a restraining pressure to the positive electrode, the solid electrolyte layer, and the negative electrode in the thickness direction. A known jig can be used as the restraining jig. The restraining pressure is, for example, 0.1 MPa or more and 50 MPa or less.

[0057] The all-solid-state battery in the present disclosure is typically a Li-ion secondary battery. The all-solid-state battery may be a single cell or a stacked battery. The stacked battery may be a monopolar stacked battery (a parallel-connected stacked battery) or a bipolar stacked battery (a series-connected stacked battery). Examples of the shape of the battery include a coin type, a laminate type, a cylindrical type, and a prismatic type.

[0058] Examples of applications of the all-solid-state battery according to the present disclosure include power sources for vehicles such as hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), electric vehicles (BEVs), gasoline-powered automobiles, diesel-powered automobiles, etc. The all-solid-state battery according to the present disclosure may also be used as a power source for mobile objects other than vehicles (for example, trains, ships, and aircraft), and may also be used as a power source for electrical appliances such as information processing devices.

[0059] 2. Second Aspect The all-solid-state battery of the second embodiment is an all-solid-state battery that utilizes a deposition-dissolution reaction of metallic Li as an anode reaction, and includes a positive electrode having a positive electrode current collector and a positive electrode active material layer, a negative electrode having at least a negative electrode current collector, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and the negative electrode has a modification layer containing a third compound containing Mg element and X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P) on a surface of the negative electrode current collector facing the solid electrolyte layer.

[0060] The positive electrode and the solid electrolyte layer in the all-solid-state battery of the second embodiment are the same as those in the all-solid-state battery of the first embodiment described above.

[0061] (1) Negative electrode The negative electrode in the second embodiment has at least a negative electrode current collector, which is the same as that in the first embodiment.

[0062] The negative electrode in the second embodiment has a modification layer on the surface of the negative electrode current collector facing the solid electrolyte layer, the modification layer containing a third compound containing Mg element and X element (at least one element selected from Zn, Sn, Ag, Al, Zr, Ni, and P). The X element is usually the same as in the first embodiment.

[0063] The third compound may be a metal compound (alloy) containing only a metal element as the X element. The third compound may be a binary alloy consisting of Mg and one type of X element, which is a metal element, or a multi-component alloy consisting of Mg and two or more types of X elements, which are metal elements. The third compound may also be an alloy containing Mg, an X element, which is a metal element, and the Z element. In the modified layer, the third compound may be in a particle state. When the third compound is an alloy, the third compound may be in a solid solution state. In the latter case, the modified layer can be considered to have an alloy phase, such as an Mg-X alloy phase.

[0064] The ratio (atomic ratio) of Mg element and X element in the modified layer usually coincides with the ratio of Mg element and X element in the alloy layer of the first embodiment.

[0065] In addition to the third compound, the modification layer may contain simple substances such as Mg and X. The modification layer may also contain an alloy containing the above-mentioned Z element, such as an Mg-XZ alloy.

[0066] Here, the surface of the modification layer is usually covered with an oxide film. Therefore, as shown in Figures 1(a) and 1(b), the oxide film on the surface of the modification layer reacts with lithium ions during initial charging of the all-solid-state battery, forming a layer of the above-mentioned composite oxide (protective layer) at the interface between the negative electrode and the solid electrolyte layer. Therefore, the all-solid-state battery of the second embodiment usually does not have the above-mentioned protective layer.

[0067] The thickness of the modification layer is not particularly limited, but is, for example, 30 nm or more and 5000 nm or less.

[0068] B. Manufacturing method of all-solid-state batteries FIG. 2 is a flow diagram illustrating a method for producing an all-solid-state battery according to the present disclosure. As shown in FIG. 2, in the method for producing an all-solid-state battery according to the present disclosure, a positive electrode having a positive electrode current collector and a positive electrode active material layer, a solid electrolyte layer, and a negative electrode having a negative electrode current collector and a modifying layer are prepared (preparation step). The modifying layer contains a third compound containing Mg element and X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P). Next, a laminate having the positive electrode, the solid electrolyte layer, and the negative electrode in this order is obtained (laminate formation step). As shown in FIG. 2, the method for producing an all-solid-state battery according to the present disclosure may also include an initial charging step in which the laminate is initially charged.

[0069] According to the present disclosure, in the laminate before the first charge, the negative electrode has a modified layer containing a third compound containing an Mg element and an X element (at least one selected from Zn, Sn, Ag, Al, Zr, Ni, and P), and therefore an all-solid-state battery with good diffusibility of Li ions during discharge can be manufactured.

[0070] 1. Preparation process The preparation step in the present disclosure is a step of preparing a positive electrode having a positive electrode current collector and a positive electrode active material layer, a solid electrolyte layer, and a negative electrode having a negative electrode current collector and a modification layer. These components are as described in "A. All-Solid-State Battery."

[0071] The positive electrode and the solid electrolyte layer can each be formed by a coating method. The positive electrode can be formed, for example, by applying a positive electrode composite containing at least a positive electrode active material to a positive electrode current collector and drying the applied material. The solid electrolyte layer can also be formed by applying a composite containing at least a solid electrolyte to a substrate and drying the applied material. The solid electrolyte layer can also be formed by a pressure molding method as shown in the examples described below. The negative electrode can be prepared by forming the above-mentioned modification layer on the negative electrode current collector using, for example, physical vapor deposition (PVD) such as ion plating or chemical vapor deposition (CVD) such as plasma CVD.

[0072] 2.Laminate formation process The laminate formation step in the present disclosure is a step of obtaining a laminate having the positive electrode, the solid electrolyte layer, and the negative electrode in this order. The laminate has the positive electrode current collector, the positive electrode active material, the solid electrolyte layer, the modification layer, and the negative electrode current collector in this order. The laminate can be considered as the all-solid-state battery of the second embodiment, as shown in FIG. 1(a).

[0073] 3. Initial charging process Furthermore, the method for producing an all-solid-state battery according to the present disclosure may include an initial charging step of initially charging the laminate. By performing the initial charging, an all-solid-state battery as shown in FIG. 1(b) is obtained. Specifically, by initially charging the laminate, the precipitated Li reacts with the third compound in the modification layer, and the modification layer becomes a compound layer containing the first compound described above. The conditions for the initial charging are not particularly limited and can be adjusted as appropriate.

[0074] 4.All-solid-state battery The all-solid-state battery manufactured by the above-described method is similar to the content described in "A. All-solid-state battery," and therefore will not be described here.

[0075] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present disclosure and that provides similar effects is included within the technical scope of the present disclosure. [Example]

[0076] [Example 1] (Preparation of negative electrode) By ion plating, Mg and Zn elements were deposited on Ni foil in a 50:50 atomic ratio. This resulted in a negative electrode with a Mg-Zn binary alloy layer formed on the Ni foil as a modified layer. The modified layer was 1 μm thick.

[0077] (Fabrication of Li half-cell) 101.7 mg of sulfide solid electrolyte (LiBr-LiI-Li2S-P2S5) was placed in a pressed cell with a diameter of 11.28 mm. It was then left to stand for one minute under a 6-ton press pressure to obtain a solid electrolyte layer (sulfide solid electrolyte layer). Lithium metal foil was then placed on the sulfide solid electrolyte layer and left to stand for one minute under a 1-ton press pressure. The above-mentioned negative electrode, punched to a diameter of 11.28 mm, was then placed on the surface of the sulfide solid electrolyte layer opposite the Li metal foil to obtain a laminate. This laminate was then restrained using three bolts with a torque of 2 N m. This resulted in a battery for evaluation (Li half cell).

[0078] [Examples 2 to 5] A negative electrode and a battery for evaluation were fabricated in the same manner as in Example 1, except that the Zn element and atomic ratio were changed as shown in Table 1.

[0079] [Comparative Example 1] A battery for evaluation was fabricated in the same manner as in Example 1, except that a negative electrode in which only Mg element was vapor-deposited on Ni foil was used.

[0080] [evaluation] (Proliferation resistance evaluation) First, each of the fabricated evaluation batteries was charged at 0.6 mA / cm 2 at a current density of 3mAh / cm 2 The battery was then discharged at 0.6 mA / cm to deposit Li metal. 2 The battery was charged at a current density of 1 V (vs. Li / Li) for 30 minutes to dissolve the deposited Li metal. Then, charging was stopped for 90 minutes to allow the diffusion resistance to decrease. + ) was reached. In this way, the charge-discharge curve shown in Fig. 3 was obtained. Note that Fig. 3 shows the charge-discharge curve in Example 1.

[0081] Next, the diffusion resistance of each evaluation battery was calculated using the following formula: A diffusion resistance of 5Ω or less was determined to be high diffusion (high diffusion rate). Diffusion resistance [Ω] = [Voltage before rest V1 (mV) - Voltage after rest V2 (mV)] / Current density (0.6 mA)

[0082] The range of SOC (State of Charge) in which the diffusion resistance calculated by the above formula was 5Ω or less was then read. The results are shown in Table 1.

[0083] [Table 1]

[0084] As shown in Table 1, all of the Examples had a wider range of SOC with high diffusion during discharge than the Comparative Examples. This is presumably because the inclusion of Mg and X elements in the modification layer made it easier to maintain the BCC structure formed in the negative electrode by Li precipitation even after the amount of lithium was reduced by Li dissolution, thereby suppressing a decrease in the diffusion rate of lithium ions. These results confirmed that the all-solid-state battery of the present disclosure had good Li ion diffusibility even at the end of discharge, and also had good charge / discharge efficiency. [Explanation of symbols]

[0085] 1...Positive electrode current collector 2...Cathode active material layer 3...Negative electrode current collector 4…Compound layer 5...Modification layer 6...protective layer CN…Positive electrode AN…Negative electrode SE…Solid electrolyte layer 10...All-solid-state battery

Claims

1. An all-solid-state battery that utilizes a deposition-dissolution reaction of metallic Li as a negative electrode reaction, a positive electrode having a positive electrode current collector and a positive electrode active material layer, a negative electrode having at least a negative electrode current collector, and a solid electrolyte layer disposed between the positive electrode and the negative electrode; the negative electrode has a compound layer on a surface of the negative electrode current collector facing the solid electrolyte layer, the compound layer containing a first compound that is an alloy represented by Li—Mg—X (wherein X element is at least one element selected from Zn, Sn, Ag, Al, Zr, and Ni); The compound layer has a thickness of 30 nm or more and 5000 nm or less.

2. 2. The all-solid-state battery according to claim 1, wherein the element X is at least one selected from the group consisting of Zn, Sn, and Zr.

3. The all-solid-state battery according to claim 1 , wherein the compound layer contains a second compound that is an alloy composed of Li element and Mg element.

4. 4. The all-solid-state battery according to claim 3, wherein in the second compound, a ratio of the Mg element to the Li element is 0.01 atomic % or more and 30 atomic % or less.

5. 2. The all-solid-state battery according to claim 1, wherein in the compound layer, a ratio of the number of atoms of the X element to the total number of atoms of the Mg element and the X element is 25 atomic % or more and 50 atomic % or less.

6. 6. The all-solid-state battery according to claim 1, wherein the negative electrode has a protective layer between the compound layer and the solid electrolyte layer, the protective layer containing a composite oxide represented by Li—Mg—X—O (wherein X is the X element).

7. An all-solid-state battery that utilizes a deposition-dissolution reaction of metallic Li as a negative electrode reaction, a positive electrode having a positive electrode current collector and a positive electrode active material layer, a negative electrode having at least a negative electrode current collector, and a solid electrolyte layer disposed between the positive electrode and the negative electrode; the positive electrode active material layer contains a positive electrode active material containing Li element, the negative electrode has a modification layer containing a third compound that is an alloy containing an Mg element and an X element (at least one element selected from Zn, Sn, Ag, Al, Zr, and Ni) on a surface of the negative electrode current collector facing the solid electrolyte layer.

8. A method for manufacturing an all-solid-state battery using a deposition-dissolution reaction of metallic Li as a negative electrode reaction, a preparation step of preparing a positive electrode having a positive electrode current collector and a positive electrode active material layer, a solid electrolyte layer, and a negative electrode having a negative electrode current collector and a modification layer; a laminate forming step of obtaining a laminate having the positive electrode, the solid electrolyte layer, and the negative electrode in this order, the positive electrode active material layer contains a positive electrode active material containing Li element, the modification layer contains a third compound that is an alloy containing an Mg element and an X element (at least one selected from Zn, Sn, Ag, Al, Zr, and Ni).

9. The method for producing an all-solid-state battery according to claim 8 , further comprising an initial charging step of initially charging the laminate.

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