All-solid-state batteries

Abstract

To decrease the resistance increase rate.SOLUTION: An all-solid-state battery includes an electrode layer. The electrode layer includes an active material and a sulfide solid electrolyte. In the electrode layer, the sulfide solid electrolyte satisfies a relationship represented by formula (1): "C1 / (C1+C2+C3)>0.5". C1, C2 and C3 each represent an abundance ratio of a skeleton structure unit included in the sulfide solid electrolyte. C1 represents an abundance ratio of a PS43- unit. C2 represents an abundance ratio of a P2Sx unit. C3 represents an abundance ratio of a POx unit.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to all-solid-state batteries. [Background technology]

[0002] Japanese Patent Application Laid-Open No. 2020-173992 discloses a sulfide solid electrolyte. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2020-173992 Summary of the Invention [Problem to be solved by the invention]

[0004] The resistance of an all-solid-state battery gradually increases with repeated charge-discharge cycles. The resistance increase rate is calculated by dividing the resistance at a predetermined number of cycles by the initial resistance. The objective of the present disclosure is to reduce the resistance increase rate. [Means for solving the problem]

[0005] 1. In one aspect of the present disclosure, an all-solid-state battery includes an electrode layer. The electrode layer includes an active material and a sulfide solid electrolyte. In the electrode layer, the sulfide solid electrolyte satisfies the relationship of the following formula (1): C1 / (C1+C2+C3)>0.5 (1) In the above formula (1), C1, C2, and C3 represent the abundance ratios of the framework structural units contained in the sulfide solid electrolyte. C1 represents the ratio of the framework structural units contained in PS4 3- Indicates the ratio of units present. C2 is P2S x The ratio of the units is shown. C3 is PO x Indicates the ratio of units present.

[0006] Sulfide solid electrolytes are promising as ion conduction paths for bulk-type all-solid-state batteries. This is because sulfide solid electrolytes have both high ionic conductivity and excellent formability. Hereinafter, "solid electrolyte" may be abbreviated as "SE." For example, sulfide solid electrolyte may be abbreviated as "sulfide SE."

[0007] The sulfide SE may include multiple framework units. The sulfide SE may include, for example, PS4 3- Unit and P2S x The ratio of each unit can be determined by X-ray Photoelectron Spectroscopy (XPS). During charge-discharge cycles, sulfide SEs are exposed to a high potential, which can cause oxidative decomposition of the sulfide SEs. The oxidative decomposition of sulfide SEs results in the formation of PO x It is believed that units will occur. x The unit is a low ionic conductivity phase. x It is believed that the unit may facilitate increased resistance.

[0008] PS4 3- The unit is a highly ion-conducting phase. 3- When the unit presence ratio exceeds 50%, PO x Units tend to be hard to spawn. 3- It is thought that the oxidation resistance of sulfide SE is improved by the unit forming the basic skeleton of sulfide SE. 3- When the ratio of the unit exceeds 50%, a reduction in the rate of increase in resistance is expected. However, in the electrode layer of a conventional all-solid-state battery, the PS4 of sulfide SE 3- The unit's presence rate is less than 50%.

[0009] The sulfide SE is used in a powder state. To adjust the particle size, the sulfide SE is crushed after synthesis. That is, mechanical energy is applied to the sulfide SE. According to a further novel finding of the present disclosure, the sulfide SE to which mechanical energy is applied is dissolved in the electrode layer by the addition of PS4. 3-Therefore, for example, if sulfide SE that has not been subjected to crushing treatment is used, the abundance ratio of PS4 in the sulfide SE in the electrode layer may decrease to 50% or less. 3- The unit presence ratio can exceed 50%.

[0010] 2. In the all-solid-state battery described in the above item "1," the sulfide solid electrolyte may further satisfy the relationship of the following formula (2), for example. C2 / (C1+C2+C3)<0.3 (2)

[0011] 3. In the all-solid-state battery according to the above item "1" or "2," the sulfide solid electrolyte may further satisfy the relationship of the following formula (3), for example. C3 / (C1+C2+C3)<0.2 (3)

[0012] 4. In the all-solid-state battery according to any one of the above items "1" to "3," the sulfide solid electrolyte may further satisfy, for example, the relationship of the following formula (4). C2 / C1<0.4 (4)

[0013] 5. In one aspect of the present disclosure, the all-solid-state battery includes a positive electrode layer. The positive electrode layer includes an active material and a sulfide solid electrolyte. In the positive electrode layer, the sulfide solid electrolyte satisfies the relationships of the following formulas (1) to (4). C1 / (C1+C2+C3)>0.5 (1) C2 / (C1+C2+C3)<0.3 (2) C3 / (C1+C2+C3)<0.2 (3) C2 / C1<0.4 (4) In the above formulas (1) to (4), C1, C2, and C3 represent the abundance ratios of the framework structural units contained in the sulfide solid electrolyte. C1 represents the ratio of PS4 3- Indicates the ratio of units present. C2 is P2S x The ratio of the units is shown. C3 is PO x Indicates the ratio of units present.

[0014] The positive electrode layer has a higher potential than the negative electrode layer. In the positive electrode layer, sulfide SE tends to be easily oxidized and deteriorated. In the positive electrode layer, PS4 3- A high ratio of units is expected to reduce the rate of increase in resistance.

[0015] Hereinafter, an embodiment of the present disclosure (hereinafter may be abbreviated as "the present embodiment") and an example of the present disclosure (hereinafter may be abbreviated as "the present example") will be described. However, the present embodiment and the example do not limit the technical scope of the present disclosure. The present embodiment and the example are illustrative in all respects. The present embodiment and the example are non-restrictive. The technical scope of the present disclosure encompasses all modifications within the meaning and scope equivalent to the claims. For example, it is originally intended that any configuration may be extracted from the present embodiment and the example and that they may be arbitrarily combined.

[0016] The terms "comprise," "include," "have," and variations thereof (e.g., "consisting of") are open-ended. Open-ended terms may or may not include additional elements in addition to the required elements. The term "consisting of" is closed-ended. However, even closed-ended terms do not exclude additional elements that are normally incidental impurities or unrelated to the disclosed technology. The term "consisting essentially of..." is semi-closed. Semi-closed terms allow for the addition of elements that do not substantially affect the basic and novel characteristics of the disclosed technology.

[0017] Unless otherwise specified, numerical ranges such as "m to n%" include the upper and lower limits. That is, "m to n%" indicates a numerical range of "m% or more and n% or less." "m% or more and n% or less" includes "more than m% but less than n%."

[0018] The measured value may be the average value of multiple measurements. The number of measurements may be three or more, five or more, or ten or more. In general, the more measurements there are, the more reliable the average value is expected to be. The measured value may be rounded off based on the number of significant figures. The measured value may include errors, for example, due to the detection limit of the measuring device. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a first conceptual diagram of an all-solid-state battery according to this embodiment. [Figure 2] FIG. 2 is a second conceptual diagram of the all-solid-state battery according to this embodiment. [Figure 3] Figure 3 shows the abundance ratio of skeletal structural units in Nos. 1 and 8. DETAILED DESCRIPTION OF THE INVENTION

[0020] <All-solid-state battery> FIG. 1 is a first conceptual diagram of an all-solid-state battery according to this embodiment. FIG. 1 conceptually illustrates a cross section parallel to the thickness direction of a first battery 100. The first battery 100 includes a first power generating element 150. The first battery 100 may include, for example, an exterior body (not shown). The exterior body may house the first power generating element 150. The exterior body may be, for example, a pouch made of a metal foil laminate film or a metal case. The first battery 100 may include a single first power generating element 150 or multiple first power generating elements 150. The multiple first power generating elements 150 may form, for example, a series circuit or a parallel circuit.

[0021] The first power generating element 150 includes a first electrode layer 110, a separator layer 130, and a second electrode layer 120. The first power generating element 150 may include a plurality of first electrode layers 110, a plurality of separator layers 130, and a plurality of second electrode layers 120. For example, the first power generating element 150 shown in FIG. 1 includes two first electrode layers 110, two separator layers 130, and two second electrode layers 120. The separator layer 130 is interposed between the first electrode layer 110 and the second electrode layer 120. The separator layer 130 separates the first electrode layer 110 from the second electrode layer 120. The separator layer 130 may include, for example, a sulfide SE. The separator layer 130 may have a thickness of, for example, 1 to 100 μm.

[0022] The second electrode layer 120 has a polarity different from that of the first electrode layer 110. For example, when the first electrode layer 110 is a positive electrode layer, the second electrode layer 120 is a negative electrode layer. The first power generating element 150 may further include a first current collector 111 and a second current collector 121. The first current collector 111 is in contact with the first electrode layer 110. The second current collector 121 is in contact with the second electrode layer 120. For example, when the first electrode layer 110 is a positive electrode layer, the first current collector 111 is a positive electrode current collector. For example, when the second electrode layer 120 is a negative electrode layer, the second current collector 121 is a negative electrode current collector. The first current collector 111 and the second current collector 121 may each independently have a thickness of, for example, 5 to 50 μm. First current collector 111 and second current collector 121 may each independently include, for example, Al foil, Al alloy foil, Cu foil, Ni foil, stainless steel foil, or the like.

[0023] 《Electrode layer》 The first electrode layer 110 and the second electrode layer 120 are collectively referred to as "electrode layers." That is, the electrode layer may be a positive electrode layer or a negative electrode layer. The electrode layer may have a thickness of, for example, 1 to 1000 μm, 5 to 500 μm, or 10 to 100 μm. The electrode layer includes an active material and a sulfide SE. The electrode layer may further include, for example, a conductive material, a binder, etc. The electrode layer may include, for example, by mass fraction, 1 to 10% of a binder, 0 to 10% of a conductive material, 1 to 30% of a sulfide SE, and the remainder being an active material. In addition to the active material, the remainder may include, for example, inevitable impurities, additives, etc.

[0024] (Sulfide solid electrolyte) The sulfide SE can form an ion conduction path in the electrode layer. The sulfide SE is a particle group (powder state). The sulfide SE is dispersed in the electrode layer. The sulfide SE may have a D50 of, for example, 0.05 to 5 μm. "D50" indicates the particle size at which the cumulative frequency from the smaller particle size side reaches 50% in the volume-based particle size distribution. The D50 of the sulfide SE may be, for example, 0.1 to 1.5 μm, 0.1 to 1 μm, 0.1 to 0.7 μm, 0.1 to 0.5 μm, 0.1 to 0.3 μm, or 0.1 to 0.15 μm. The sulfide SE may have a particle size of, for example, 4 to 40 μm. 2 The "BET specific surface area" can be measured by a gas adsorption method (BET single-point method). The BET specific surface area of ​​the sulfide SE is, for example, 8 to 32 m 2 / g, 10-32m 2 / g, 14-32m 2 / g, 18-32m 2 / g, 23-32m 2 / g, or 29-32m 2 / g.

[0025] The sulfide SE may be, for example, a glass ceramic type or an argyrodite type. The sulfide SE includes Li, S, and P. The sulfide SE may further include, for example, Cl, Br, I, O, etc. The sulfide SE may include multiple framework structural units. The sulfide SE may be, for example, PS4 3- Unit and P2Sx The sulfide SE contains PO x The ratio of each unit may be measured using an XPS device. A measurement sample (part of the electrode layer) is recovered from inside the battery. A P2p spectrum and an S2p spectrum are obtained. The ratio of each unit may be determined by peak separation. The settings of the XPS device are, for example, as follows. The device is an example, and an equivalent device to the one below may also be used. The preferred settings may vary depending on the device.

[0026] XPS equipment: Product name "VersaProbe III", manufactured by ULVAC-PHI, Inc. X-ray source: monо-AlKα (hν=1486.6eV) Photoelectron take-off angle: 45° X-ray beam diameter: 100 μm Analysis location: Center of sample, rectangular area (500μ×300μm)

[0027] C1 is PS4 3- Indicates the ratio of units present. C2 is P2S x The ratio of the units is shown. C3 is PO x This indicates the ratio of units present. It may be "C1+C2+C3=1." For example, "C1+C2+C3" may not be 1 due to the presence of components that cannot be classified into the three units. "C1+C2+C3" may be, for example, 0.90 to 1.10, or 0.95 to 1.08.

[0028] PS4 3- The unit is a highly ion-conductive phase. Since "C1 / (C1+C2+C3)" is greater than 0.5, PO x The occurrence of units (low ionic conductivity phases) can be suppressed. 3- The higher the ratio of the units present, the more reduced the resistance is expected. "C1 / (C1+C2+C3)" may be, for example, 0.6 to 1, 0.7 to 1, 0.8 to 1, or 0.9 to 1. "C1 / (C1+C2+C3)" may be, for example, 0.67 to 0.72.

[0029] P2S x The unit "x" is a number equal to or greater than 1. "C2 / (C1+C2+C3)" may be, for example, less than 0.3. "C2 / (C1+C2+C3)" may be, for example, 0 to 0.25, 0.1 to 0.25, or 0.19 to 0.24.

[0030] P2S x The unit availability ratio is PS4 3- It is small compared to the abundance ratio of the units. "C2 / C1" may be, for example, less than 0.4. "C2 / C1" may be, for example, 0.34 or less, or 0.30 or less. "C2 / C1" may be, for example, 0.01 or more, 0.1 or more, 0.2 or more, or 0.29 or more.

[0031] PO x The unit "x" is an arbitrary number. "C3 / (C1+C2+C3)" may be, for example, less than 0.2. "C3 / (C1+C2+C3)" may be, for example, 0.15 or less, 0.12 or less, 0.1 or less, 0.09 or less, or 0.07 or less. PO x The abundance ratio of the unit may be, for example, zero.

[0032] The abundance ratio of each unit can correspond to the mole fraction. The sulfide SE has a mole fraction of, for example, 0 to 15% PO x Units and P2S of 0.1 to 24% x Unit and remaining PS4 3- It may also include a unit.

[0033] The sulfide SE can be synthesized by any method. For example, the sulfide SE can be synthesized by a gas phase method, a solid phase method, or a liquid phase method. The sulfide SE can be synthesized from, for example, Li2S and P2S5. In the electrode layer, PS4 3- The sulfide SE can be synthesized and the electrode layer can be formed so that the abundance ratio of the unit exceeds 50%. 3-In order to increase the abundance ratio of the unit, it is conceivable to reduce the mechanical energy applied to the sulfide SE during the formation process of the electrode layer. In particular, in the pulverization treatment of the sulfide SE, a large amount of mechanical energy may be applied to the sulfide SE. For example, by avoiding the pulverization treatment (mechanical particle size adjustment), PS4 3- It is expected that the abundance ratio of the unit will increase.

[0034] (Active material) The active material causes an electrode reaction. The active material may be, for example, a particle group. The active material may have a D50 of, for example, 1 to 30 μm. The active material may contain hollow particles or solid particles. "Hollow particles" refer to particles in which the cross-sectional area of the central cavity is 30% or more of the cross-sectional area of the entire particle in a cross-sectional image of the particle (e.g., an electron microscope image, etc.). "Solid particles" refer to particles in which the cross-sectional area of the central cavity is less than 30% of the cross-sectional area of the entire particle in a cross-sectional image of the particle. <00​​​​​​​​​​​​​The conductive material can form an electron conduction path in the electrode layer, and may include, for example, at least one selected from the group consisting of acetylene black (AB), vapor-grown carbon fiber (VGCF), carbon nanotube (CNT), and graphene flake (GF).

[0037] (binder) The binder can bind the solid materials together, and may include, for example, at least one selected from the group consisting of styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).

[0038] <Bipolar structure> FIG. 2 is a second conceptual diagram of an all-solid-state battery according to this embodiment. The second battery 200 includes a second power generating element 250. The second power generating element 250 has a bipolar structure. A "bipolar structure" refers to a structure in which a positive electrode layer is disposed on one side of a current collector and a negative electrode layer is disposed on the other side. In contrast, a "unipolar structure" refers to a structure in which an electrode layer of only one polarity is disposed on one current collector (FIG. 1).

[0039] In the bipolar structure, the third current collector 231 includes a first main surface 231a and a second main surface 231b. The second main surface 231b is the surface opposite to the first main surface 231a. The first electrode layer 210 is disposed on the first main surface 231a. The second electrode layer 220 is disposed on the second main surface 231b. The second electrode layer 220 has a polarity different from that of the first electrode layer 210. The separator layer 230 separates the first electrode layer 210 and the second electrode layer 220. The third current collector 231 may include, for example, an Al-Ni clad material or a single-sided Ni-plated Al foil. In the second power generating element 250, the first current collector 211 may be disposed at one end in the stacking direction, and the second current collector 221 may be disposed at the other end.

[0040] The adoption of a bipolar structure is expected to reduce resistance. On the other hand, in a bipolar structure, the electrode layer is more likely to have a high potential than in a unipolar structure. In a bipolar structure, oxidation degradation of sulfide SE is likely to progress. In the electrode layer included in the bipolar structure, PS4 3- A high ratio of units is expected to reduce the rate of increase in resistance. [Example]

[0041] <Manufacturing of all-solid-state batteries> No. 1 (Synthesis of sulfide SE) Li2S and P2S5 were weighed to prepare raw material powder. The mixing ratio of Li2S and P2S5 in the raw material powder was "Li2S / P2S5 = 75 / 25 (molar ratio)." The raw material powder and tetrahydrofuran (THF) were placed in a glass container. The mixing ratio of the raw material and THF was "raw material powder / THF = 1 / 20 (mass ratio)." The raw material powder and THF were stirred at 25°C for 72 hours. After stirring, a precipitate (powder) was collected. The precipitate is a precursor of sulfide SE. The precursor was dried at 25°C under an argon atmosphere to form a dried product. The dried product was calcined at 100°C for 1 hour under atmospheric pressure (open system) to form a calcined product. The calcined product was vacuum-sealed in a quartz tube. The quartz tube was baked in a muffle furnace at 140°C for 12 hours to obtain sulfide SE, which will hereinafter also be referred to as "LPS."

[0042] (Formation of positive electrode layer) As a kneading device, a "FILMICS (registered trademark)" manufactured by Primix Corporation was prepared. 80 parts by mass of a positive electrode active material (LiNi 1 / 3 Co 1 / 3 Mn 1 / 3O2), 9.51 parts by mass of sulfide SE (LPS), and 2 parts by mass of conductive material (VGCF) were added. Then, a binder dispersion (SBR dispersion, concentration 5%) and 32.21 parts by mass of dispersion medium (tetralin) were added to the mixing container. The solid content was 69% (mass fraction). The mixture was kneaded to form a positive electrode slurry. During kneading, the peripheral speed of the Filmix was adjusted within the range of 5 to 30 m / s. The positive electrode slurry was applied to both sides of a positive electrode current collector (Ni foil) using a blade-type applicator to form a positive electrode layer. The positive electrode layer was dried at 100°C for 30 minutes.

[0043] (Formation of negative electrode layer) A high-speed shearing PC wheel was set in the FILMICS. 18.6 parts by mass of negative electrode active material (Si), 8.69 parts by mass of sulfide SE (LPS), 2.4 parts by mass of conductive material (VGCF), binder dispersion (SBR dispersion, concentration 5%), and dispersion medium (diisobutyl ketone) were mixed in the FILMICS to form negative electrode slurry. The solid content of the negative electrode slurry was 43% (mass fraction). During mixing, the peripheral speed of the FILMICS was adjusted within the range of 5 to 30 m / s. The negative electrode slurry was applied to one side of the substrate (Al foil) using a blade-type applicator to form a negative electrode layer. The positive electrode layer was dried at 100°C for 30 minutes. The negative electrode layer was densified using a roll press.

[0044] (Formation of separator layer) A binder solution was formed by dissolving acrylate butadiene rubber (ABR) in heptane. The concentration of ABR in the binder solution was 5% (mass fraction). A separator slurry was formed by mixing 40 parts by mass of sulfide SE (LPS), 8 parts by mass of the binder solution, 25.62 parts by mass of heptane, and 8 parts by mass of dibutyl ether using an ultrasonic homogenizer. The separator slurry was applied to the surface of the substrate (Al foil) to form a separator layer. The separator layer was dried at 100°C for 30 minutes.

[0045] (assembly) The separator layer was pressure-transferred onto the positive electrode layer using a 20 kN press. The positive electrode layer and separator layer were densified together using roll press processing. The roll linear pressure was 4 ton / cm, and the roll gap was 100 μm. The negative electrode layer (already densified) was pressure-transferred onto the separator layer to form a power generating element. A lead tab was attached to the power generating element. A pouch made of Al laminate film was prepared as the exterior body. The power generating element was sealed in the exterior body. A restraining member was attached to the outside of the exterior body so that a pressure of 20 MPa would be applied to the power generating element. A test battery was manufactured using the above steps.

[0046] No.2-7 Test batteries were prepared in the same manner as No. 1, except that sulfide SE was synthesized so that the D50 of sulfide SE was the value shown in Table 1 below.

[0047] No.8-14 Test batteries were produced in the same manner as Nos. 1 to 7, except that after synthesis of the sulfide SE, a crushing treatment was carried out to adjust the D50 of the sulfide SE.

[0048] <Evaluation> CCCV charging and discharging (upper limit charge voltage 4.55V, lower limit discharge voltage 2.5V) was performed. The design capacity of the cell was 0.3Ah. The time rate for CC charging and CC discharging was 0.1C. At a time rate of 1C, the design capacity is discharged in 1 hour. 100 charge / discharge cycles were performed. The resistance increase rate was calculated by dividing the resistance after 100 cycles by the initial resistance. In this evaluation, the resistance after 3 cycles was considered the "initial resistance." The resistance increase rates in Table 1 below are shown as percentages.

[0049] The test battery was disassembled, and the positive electrode layer was recovered from the inside of the test battery. The abundance ratio of each unit in the LPS of the positive electrode layer was measured using an XPS device.

[0050] [Table 1]

[0051] <Result> In Nos. 1 to 7, no mechanical particle size adjustment was performed after the synthesis of sulfide SE. 3- The ratio of units present is large. In Nos. 1 to 7, "C1 / (C1+C2+C3)" exceeds 0.5. In Nos. 1 to 7, the resistance increase rate is lower than in Nos. 8 to 14.

[0052] In Nos. 8 to 14, mechanical particle size adjustment was carried out after synthesis of sulfide SE. 3- The ratio of the units is decreasing. In No. 8 to 14, "C1 / (C1+C2+C3)" is 0.5 or less. In No. 8 to 14, the ratio of the units is decreasing compared to No. 1 to 7. x The proportion of units is increasing. In No.8-14, compared to No.1-7, the proportion of P2S x The number of units is also increasing.

[0053] Figure 3 shows the abundance ratio of the skeletal structure units in Nos. 1 and 8. The vertical axis of the graph shows percentages such as "C1 / (C1+C2+C3)". In the sulfide SE powder before use (before the formation of the positive electrode layer), both Nos. 1 and 8 contained PS4 3- The ratio of the unit exceeds 50%. In the sulfide SE powder before use, there is little difference between No. 1 and No. 8. However, in the sulfide SE in the positive electrode layer recovered from the test battery, there is a large difference between No. 1 and No. 8. That is, the PS4 in No. 1 3- The unit presence rate is over 50%. 3- The ratio of units is less than 50%. x The amount of units generated is PO No.8 x As mentioned above, sulfide SE in No. 1 has not been subjected to mechanical particle size adjustment, while sulfide SE in No. 8 has been subjected to mechanical particle size adjustment. [Explanation of symbols]

[0054] 100 first battery, 110, 210 first electrode layer, 111, 211 first current collector, 120, 220 second electrode layer, 121, 221 second current collector, 130, 230 separator layer, 150 first power generating element, 200 second battery, 231 third current collector, 231a first main surface, 231b second main surface, 250 second power generating element.

Claims

[Claim 1] A charged and discharged all-solid-state battery, a positive electrode layer that is a coating layer, the positive electrode layer includes an active material, a sulfide solid electrolyte, and a binder, In the positive electrode layer, the sulfide solid electrolyte satisfies the formulas (1) to (4) after 100 CCCV charge-discharge cycles (upper limit charge voltage 4.55 V, lower limit discharge voltage 2.5 V): 0.67≦C 1 / (C 1 +C 2 +C 3 ) (1) 0.1≦C 2 / (C 1 +C 2 +C 3 )≦0.24 (2) 0.07≦C 3 / (C 1 +C 2 +C 3 )≦0.15 (3) 0.2≦C 2 / C 1 ≦0.34 (4) Fulfilling the relationship, In the formulas (1) to (4), C 1 , C 2 and C 3 represents the abundance ratio of the framework structure units contained in the sulfide solid electrolyte, C 1 P.S. 4 3- Indicates the ratio of units present, C 2 Is, P 2 S x Indicates the ratio of units present, C 3 , PO x Shows the ratio of units present, All-solid-state battery.

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