All-solid-state battery, solid electrolyte, and manufacturing method therefor

Abstract

Provided in the present embodiments are an all-solid-state battery, a solid electrolyte therefor, and a method for preparing the solid electrolyte, wherein the battery comprises: a positive electrode comprising a positive electrode active material; a negative electrode comprising a negative electrode active material; and a solid electrolyte disposed between the positive electrode and the negative electrode and comprising Cl-doped Li6-xPS5-xCl1+x (where x is a real number satisfying 0 < x < 0.8).

Description

All-solid-state battery and solid electrolyte, method of manufacturing the same

[0001] The present invention relates to an all-solid-state battery, a solid electrolyte, and a method for manufacturing the same.

[0002] Lithium-ion batteries have a wide range of applications. Among them, the highest capacity applications are in automobiles and energy storage devices. Conventional lithium-ion batteries using organic liquid electrolytes pose a risk of fire due to electrolyte leakage if the battery is damaged by electrode reactions. To address these issues with liquid electrolytes, all-solid-state batteries utilizing solid electrolytes with superior stability are attracting attention.

[0003] Sulfide-based solid electrolytes exhibit excellent inter-particle contact characteristics through room-temperature pressurization alone, without the need for a sintering process, due to their softer nature compared to oxide-based materials (low elasticity / plasticity modulus). Consequently, they offer the advantage of lower contact resistance and higher ionic conductivity compared to oxide-based materials. However, they have a disadvantage in terms of stability due to lower chemical stability compared to oxide-based materials.

[0004] Therefore, there is a need to develop solid electrolytes that can maintain stability while maintaining high ionic conductivity.

[0005] The present embodiments provide an all-solid-state battery and a solid electrolyte that maximize ionic conductivity in a solid electrolyte while maintaining stability, and a method for manufacturing the same.

[0006] In one aspect, an all-solid-state battery according to one embodiment comprises a positive electrode including a positive active material, a negative electrode including a negative active material, and Li disposed between the positive and negative electrodes and doped with Cl. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함하는 고체 전해질을 포함한다.

[0007] In another aspect, a solid electrolyte according to another embodiment comprises Cl-doped Li between a positive electrode containing a positive active material of an all-solid-state battery and a negative electrode containing a negative active material. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함한다.

[0008] In another aspect, a method for manufacturing a solid electrolyte according to another embodiment comprises: 0.5 P2S5 + (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x According to, Cl-doped Li between the anode containing the positive electrode active material and the cathode containing the negative electrode active material of an all-solid-state battery. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)을 포함하는 혼합물을 제조하는 단계 및 이 혼합물을 열처리하는 단계를 포함한다.

[0009] The all-solid-state battery and solid electrolyte according to the embodiments and the method for manufacturing the same can maximize ionic conductivity in the solid electrolyte while simultaneously maintaining stability.

[0010] FIG. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment.

[0011] Figure 2 illustrates the azirodite crystal structure of the solid electrolyte of Figure 1.

[0012] Figure 3 shows the results of a stability analysis according to the number of antisite defects in the solid electrolyte of Figure 1.

[0013] Figure 4 shows the ionic conductivity according to the ratio of Cl ions occupying the S sites in the solid electrolyte of Figure 1.

[0014] Figure 5 is a flowchart of a molecular dynamics analysis method using machine learned potential (MLP).

[0015] Figure 6 shows the molar ratio of raw materials for the synthesis of the solid electrolyte of Figure 1.

[0016] FIG. 7 is a flowchart of a method for manufacturing a solid electrolyte according to another embodiment.

[0017] Hereinafter, some embodiments of the present disclosure will be described in detail with reference to the exemplary drawings. In assigning reference numerals to the components of each drawing, the same components may have the same reference numeral as much as possible, even if they are shown in different drawings. Furthermore, in describing the embodiments, if it is determined that a detailed description of related known components or functions may obscure the essence of the technical concept, such detailed description may be omitted. Where terms such as "comprising," "having," or "consisting of" are used in this specification, other parts may be added unless "only" is used. Where a component is expressed in the singular, it may include a plural unless otherwise specified.

[0018] Additionally, terms such as first, second, A, B, (a), (b), etc., may be used to describe the components of the present disclosure. These terms are used merely to distinguish the components from other components, and the nature, order, sequence, or number of the components are not limited by such terms.

[0019] In describing the positional relationship of components, where it is stated that two or more components are "connected," "combined," or "joined," it should be understood that while the two or more components may be directly "connected," "combined," or "joined," they may also be "connected," "combined," or "joined" with other components "intervened." Here, the other components may be included in one or more of the two or more components that are "connected," "combined," or "joined" with one another.

[0020] In describing the temporal flow relationship regarding components, methods of operation, or methods of production, for example, when the temporal or sequential relationship is described using "after," "following," "next," or "before," it may include cases where the relationship is not continuous unless "immediately" or "directly" is used.

[0021] Meanwhile, where numerical values ​​or corresponding information regarding a component (e.g., levels, etc.) are mentioned, even without separate explicit notation, the numerical values ​​or corresponding information may be interpreted as including a range of error that may occur due to various factors (e.g., process factors, internal or external shocks, noise, etc.).

[0022] A person skilled in the art will understand that the terms "learning" or "learning" appearing throughout the detailed description and claims of the present invention refer to performing machine learning through procedural computing, and are not intended to refer to mental activities such as human educational activities.

[0023] A solid-state battery is described below with reference to the drawings, and embodiments are described in detail.

[0024] FIG. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment.

[0025] Referring to FIG. 1, the all-solid-state battery (100) comprises a positive electrode (110) containing a positive active material, a negative electrode (120) containing a negative active material, and a solid electrolyte (130) located between them. The all-solid-state battery (100) may be a secondary battery or an energy storage system containing the solid electrolyte (130), but is not limited thereto. In this specification, a lithium secondary battery utilizing lithium ions is described as an example, but is not limited thereto.

[0026] A solid electrolyte (130) is disposed between the cathode (110) and the anode (110) and the cathode (120), and is Li doped with Cl. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함한다.

[0027] The positive electrode (110) includes a positive electrode active material layer (not shown) containing a positive electrode active material. The positive electrode active material layer may include a conductive agent and a binder together with the positive electrode active material. The positive electrode active material may include a metal or a transition metal oxide, a transition metal phosphate, etc. When the positive electrode active material is a metal, for example, the all-solid-state battery may be a lithium-sulfur all-solid-state battery that uses lithium in the positive electrode and sulfur in the negative electrode. The transition metal oxide may be, for example, a sodium transition metal oxide, a nickel transition metal oxide, a Baltic transition metal oxide, an iron transition metal oxide, a copper transition metal oxide (CuO), a yttrium transition metal oxide, etc.

[0028] Currently, the most widely used nickel transition metal oxides may be lithium cobalt oxide (LCO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NCM), magnesium rustium oxide (Mg-RuO2), etc.

[0029] Transition metal phosphates can be lithium iron phosphate (LFP), lithium manganese phosphate (LiMnPO4), lithium nickel phosphate (LiNiPO4), etc.

[0030] The binder serves to firmly bond the positive active material particles to each other and also to firmly attach the positive active material to the current collector. The conductive material is used to impart conductivity to the electrode, and in the battery being constructed, any electronically conductive material that does not cause chemical changes can be used.

[0031] The positive electrode is manufactured by preparing an active material composition by mixing an active material, a conductive material, and a binder in a solvent, and applying this composition to a current collector. The solvent may include N-methylpyrrolidone, but is not limited thereto.

[0032] The negative electrode (120) includes a negative electrode active material layer, and the negative electrode active material layer includes a negative electrode active material.

[0033] The cathode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.

[0034] Carbon materials capable of reversibly intercalating / deintercalating lithium ions can be used, and any carbon-based negative electrode active material commonly used in lithium-ion all-solid-state batteries can be used. Representative examples include crystalline carbon, amorphous carbon, or a combination thereof.

[0035] As an alloy of lithium metal, an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn can be used.

[0036] Materials capable of doping and dedoping lithium include Si, SiOx (0 < x < 2), Si-Y alloy (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, and is not Si), Sn, SnO2, Sn-Y (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, and is not Sn).

[0037] Examples of transition metal oxides include vanadium oxide and lithium vanadium oxide.

[0038] The cathode active material layer also includes a binder and may optionally further include a conductive material.

[0039] As a binder, polyvinyl alcohol, carboxymethylcellulose / styrene-butadiene rubber, hydroxypropylene cellulose, diacetylene cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene or polypropylene, etc. may be used, but are not limited thereto.

[0040] As for the conductive material, there are no specific limitations as long as it is conductive without causing chemical changes in the battery. Specifically, graphite such as natural graphite or synthetic graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride, aluminum, or nickel powder; conductive whiskey such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives may be used.

[0041] The negative electrode (120) is manufactured by mixing an active material, a conductive material, and a binder in a solvent to produce an active material composition, and then applying this composition to a negative electrode current collector. The solvent may include N-methylpyrrolidone, but is not limited thereto.

[0042] As previously mentioned, the solid electrolyte (130) is Li doped with Cl. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함한다.

[0043] The solid electrolyte (130) may additionally include other sulfide-based electrolytes, oxide-based electrolytes, polymer electrolytes, etc., but is not limited thereto.

[0044] Li 6-x PS 5-x Cl 1+xAs shown in FIG. 2, it may include a crystal phase having an argyrodite-based crystal structure.

[0045] Cl can be doped into S sites that form anti-site defects. An anti-site defect can refer to one of the defects (abnormal changes within the material structure) occurring within a material. Cl can occupy the positions where S atoms are supposed to be in crystal phases with an argyrodite-based crystal structure.

[0046] The crystal structure of the sulfide-based solid electrolyte Li6PS5Cl, which has an azirodite crystal structure as illustrated in Fig. 2, contains voids within itself and exhibits high Li ion conductivity compared to other solid electrolytes.

[0047] S 2- and Cl - Due to their similar ionic radii, ions can create antisite defects that swap positions with one another, and these antisite defects can significantly affect the ionic conductivity of the solid electrolyte Li6PS5Cl. Such a solid electrolyte can be prepared through a relatively simple process of milling solid-state P2S5, LiCl, and Li2S and heating them under constant pressure. Therefore, the solid electrolyte being synthesized can be doped with Cl by increasing the molar ratio of the dopant Cl through controlling the molar ratio of the starting materials.

[0048] S of various compositions 2- / Cl - As a result of analyzing stability according to the number of antisite defects that exchange positions with each other (Cl doping concentration, etc.), the results shown in Figure 3 were obtained.

[0049] The structure formation energy for the amount of excess Cl (x) was calculated. Through convex hull analysis, the energetically preferred doping concentration and composition could be identified.

[0050] Specifically, (1) it was confirmed that at high temperatures (600K or higher), a Cl doping concentration of x > 0.8 is energetically preferred compared to a lower doping concentration. In high-temperature processes, Cl can theoretically be doped up to x > 0.8.

[0051] (2) It was observed that at low temperatures, the structure formation energy gradually increased at high Cl doping concentrations. For example, the structure formation energy at x~0.8 was higher than the structure formation energy at x~0.7, suggesting that Cl could be precipitated.

[0052] Based on the contents of items (1) and (2) mentioned above, even when doping is performed using an excess amount of Cl in a high-temperature process, Cl may gradually precipitate or decompose into other phases due to the characteristics of the battery operating at room temperature. In studies measuring ionic conductivity at actual room temperature, when an excess amount of Cl is used, not all of the Cl is doped in, but is mixed in the form of LiCl, etc., which can lower the ionic conductivity. Based on these results, approximately 0 <x<0.8인 Li 6-x PS 5-x Cl 1+x This may be a composition that ensures stability and maximizes ion conductivity.

[0053] As previously mentioned, the solid electrolyte (130) is Li doped with Cl. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함한다. 다시 말해 X가 0.8 이상인 이온전도도가 떨어지는 것을 도 3을 통해 확인할 수 있다.

[0054] Figure 4 shows the ionic conductivity according to the proportion of Cl ions occupying the S site.

[0055] Referring to Figure 4, the excess Cl added is doped into the S site, which can form antisite defects. It can be seen that the ionic conductivity increases as the Cl doping concentration increases.

[0056] Solid electrolyte Li 6-x PS 5-x Cl 1+x It was confirmed that the intrinsic ionic conductivity increases linearly as the x value increases. In the case of a composition with a sufficiently high doping concentration while ensuring stability, it was confirmed that the proportion of antisites was approximately 60–80%.

[0057] When summarizing the results described above, the proportion of anti-sites doped with Cl at S sites may be 60–80%, but is not limited thereto.

[0058] Generally, in Li6PS5Cl solid electrolytes, ionic conductivity improves as the Cl doping concentration increases; however, when the concentration exceeds a certain level, the stability of the electrolyte decreases, preventing it from functioning as an electrolyte and causing decomposition into other substances. Consequently, there was a problem where the ionic conductivity decreased below the expected value.

[0059] In addition, to determine the structure, stability, and ionic conductivity of a solid electrolyte (130), the existing molecular dynamics method using first principles requires a lot of time and resources. To compensate for this, a molecular dynamics analysis method (200) using a machine learned potential (MLP) was used as shown in FIG. 5.

[0060] Various atomic arrangements and structures in the solid electrolyte Li6PS5Cl were simulated through first-principles calculations, and the structure and energy of the solid electrolyte (130) at that time were calculated (S210).

[0061] For example, first-principle calculations are used to calculate the electronic structure describing the ions constituting a solid electrolyte and the interactions between them. This includes electronic states, electron distributions, and energy band structures. First-principle calculations are also used to calculate the energy levels and reaction entropy of the solid electrolyte to predict the thermodynamic properties of chemical reactions.

[0062] Consequently, the energy for various structures was used as a training set for machine learning. The structure and energy of solid electrolytes were learned through machine learning to generate a machine learning potential (MLP) for molecular dynamics calculations (S220).

[0063] It is possible to generate machine learning potentials for molecular dynamics by learning the structure and energy of solid electrolytes. This approach is useful for predicting and explaining material properties by combining molecular dynamics simulations and machine learning modeling.

[0064] Machine learning potentials use machine learning models (e.g., neural networks, support vector machines, random forests, etc.) to model the properties and interactions of molecules or materials. These machine learning potentials include numerical values ​​for the types of atoms, bond lengths, and angles.

[0065] Through molecular dynamics calculations using machine learning potentials, molecular dynamics calculations were performed under various conditions, such as changing the temperature or composition, and energy and ionic conductivity were quantitatively analyzed (S230). In particular, it was possible to calculate defects at very low concentrations that are practically impossible to calculate using first-principles calculations, such as doping and antisite defects, or to calculate ion diffusion on a nanosecond scale.

[0066] Conditions for achieving desired properties, such as maximizing ionic conductivity or stability that does not cause decomposition reactions, were explored (S240). In this way, it is possible to suggest process conditions that can achieve desired properties, such as the ratio of the synthesis starter material or the process temperature.

[0067] The molar ratio of raw materials for the synthesis of the aforementioned solid electrolyte (130) was determined as shown in Table 1 and Figure 6.

[0068] x-mol ratio LiClLi2SP2S500.250.6250.1250.10.2750.60.1250.20.30.5750.1250.30.3250.550.1250.40.350.5250.1250.50.3750.50.1250.60.40.4750.1250.70.4250.450.1250.80.450.4250.125

[0069] Referring to Table 1 and FIG. 6, the solid electrolyte (130) is Li doped with Cl as described above. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함한다. X는 0<x<0.8인 실수인 것으로 설명하였으나, X는 0.3<x<0.8, 0.5<x≤0.7일 수 있다. 예를 들어, X=0.7인 경우, Li 6-x PS 5-x Cl 1+x The above Li 5.3 PS 4.3 Cl 1.7 It can be expressed as.

[0070] As mentioned above, the chemical and thermal stability of the electrolyte decreased as the doping concentration increased. This decrease in stability can cause problems during long-term battery operation, and in particular, when the doping concentration increased, a phenomenon was observed in which it decomposed into another phase with low ionic conductivity.

[0071] As a result of evaluating the ion conductivity and stability of the aforementioned solid electrolyte (130) at various doping concentrations and compositions, an optimal doping concentration was determined at a Cl doping composition of x to 0.7 (Li6-xPS5-xCl1+x) to maximize the ion conductivity of the solid electrolyte while simultaneously maintaining stability.

[0072] When synthesizing the solid electrolyte Li6PS5Cl by adjusting the molar ratio without using an excess amount of Cl, the following reaction scheme 1 is followed.

[0073] [Reaction Equation 1]

[0074] 0.5 P2S5+ LiCl + 2.5 Li2S -> Li6PS5Cl

[0075] By using an excess of Cl to cause Cl ions to occupy the position of S ions and to create defects in Li ions, the aforementioned Li 6-x PS 5-x Cl 1+x It can be synthesized by the following reaction scheme 2, but is not limited thereto.

[0076] [Reaction Equation 2]

[0077] 0.5 P2S5+ (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x

[0078] Battery cells can be manufactured from the aforementioned solid-state battery (100). Subsequently, these battery cells can be bundled to form modules, and these modules can be combined to finally produce a battery pack, or these cells can be directly integrated into one large unit to produce a battery pack. Alternatively, the aforementioned solid-state battery (100) can be packaged directly into a battery bag as a battery cell.

[0079] FIG. 7 is a flowchart of a method for manufacturing a solid electrolyte according to another embodiment.

[0080] Referring to FIG. 7, a method (300) for manufacturing a solid electrolyte according to another embodiment comprises 0.5 P2S5 + (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x According to, Cl-doped Li between the anode containing the positive electrode active material and the cathode containing the negative electrode active material of an all-solid-state battery. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)을 포함하는 혼합물을 제조하는 단계(S310) 및 상기 혼합물을 열처리하는 단계(S320)를 포함한다.

[0081] As explained with reference to FIG. 2, Li 6-x PS 5-x Cl 1+x It may include a crystal phase having an argyrodite-based crystal structure.

[0082] As described with reference to FIGS. 3 and 4, Cl can be doped into S sites that form anti-site defects. The proportion of anti-sites doped with Cl into S sites can be 60 to 80 percent.

[0083] As explained with reference to FIG. 6, Li 6-x PS 5-x Cl 1+x The above Li 5.3 PS 4.3 Cl 1.7 It could be.

[0084] The all-solid-state battery (100) and solid electrolyte (130) and the method of manufacturing the same (300) according to the embodiments can maximize ion conductivity in the solid electrolyte while simultaneously maintaining stability.

[0085] Although the all-solid-state battery, solid electrolyte, and method of manufacturing the same according to the embodiments have been described with reference to the drawings above, the present invention is not limited thereto.

[0086] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0087] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

[0088] The foregoing description is merely an illustrative explanation of the technical concept of the present disclosure, and those skilled in the art to which the present disclosure pertains may make various modifications and variations within the scope of the essential characteristics of the technical concept. Furthermore, since these embodiments are intended to explain, not limit, the scope of the technical concept is not limited by these embodiments. The scope of protection of the present disclosure shall be interpreted by the claims below, and all technical concepts within an equivalent scope shall be interpreted as being included within the scope of rights of the present disclosure.

Claims

1. A cathode comprising a positive electrode active material; A cathode comprising a cathode active material; and Li placed between the anode and cathode and doped with Cl 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함하는 고체 전해질을 포함하는 전고체 전지.

2. In Paragraph 1, The above Li 6-x PS 5-x Cl 1+x is an all-solid-state battery comprising a crystalline phase having an argyrodite-based crystal structure.

3. In Paragraph 1, The above Cl is doped into an S site forming an anti-site defect in an all-solid-state battery.

4. In Paragraph 3, All-solid-state battery in which the ratio of anti-sites doped with Cl at S sites is 60 to 80%.

5. In Paragraph 1, The above Li 6-x PS 5-x Cl 1+x is an all-solid-state battery synthesized by the following reaction equation: 0.5 P2S5+ (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x 6. In Paragraph 1, The above Li 6-x PS 5-x Cl 1+x The above Li 5.3 PS 4.3 Cl 1.7 Phosphorus all-solid-state battery.

7. Cl-doped Li between a positive electrode containing a positive electrode active material and a negative electrode containing a negative electrode active material of an all-solid-state battery 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)를 포함하는 고체 전해질.

8. In Paragraph 7, The above Li 6-x PS 5-x Cl 1+x is a solid electrolyte containing a crystalline phase having an argyrodite-based crystal structure.

9. In Paragraph 7, The above Cl is a solid electrolyte doped into S sites forming anti-site defects.

10. In Paragraph 9, A solid electrolyte in which the ratio of anti-sites doped with Cl at S sites is 60 to 80%.

11. In Paragraph 7, The above Li 6-x PS 5-x Cl 1+x is a solid electrolyte synthesized by the following reaction equation: 0.5 P2S5+ (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x 12. In Paragraph 7, The above Li 6-x PS 5-x Cl 1+x The above Li 5.3 PS 4.3 Cl 1.7 Phosphorus solid electrolyte. 0.5 P2S5+ (1+x)LiCl + (2.5-x)Li2S -> Li 6-x PS 5-x Cl 1+x According to, Cl-doped Li between the anode containing the positive electrode active material and the cathode containing the negative electrode active material of an all-solid-state battery. 6-x PS 5-x Cl 1+x (X is 0 <x<0.8인 실수)을 포함하는 혼합물을 제조하는 단계; 및 A method for manufacturing a solid electrolyte comprising the step of heat-treating the above mixture.

14. In Paragraph 13, The above Li 6-x PS 5-x Cl 1+x A method for manufacturing a solid electrolyte comprising a crystalline phase having an argyrodite-based crystal structure.

15. In Paragraph 13, A method for manufacturing a solid electrolyte in which the above Cl is doped into an S site forming an anti-site defect.

16. In Paragraph 15, A method for manufacturing a solid electrolyte in which the ratio of anti-sites doped with Cl at S sites is 60 to 80%.

17. In Paragraph 1, The above Li 6-x PS 5-x Cl 1+x The above Li 5.3 PS 4.3 Cl 1.7 Method for manufacturing a solid electrolyte.

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