Solid ion conductor, solid electrolyte and electrochemical device including the same, and method of preparing the solid ion conductor

Abstract

A solid ion conductor, a solid electrolyte and an electrochemical device comprising the same, and a method for manufacturing the solid ion conductor are disclosed. The solid ion conductor may include a compound represented by the following chemical formula 1: LiaMbM'cXdOe In the above chemical formula 1, M, M', X, a, b, c, d, and e are each as described in the specification.

Description

Technology Field

[0001] The invention relates to a solid ion conductor, a solid electrolyte and an electrochemical device including the same, and a method for manufacturing the solid ion conductor. Background Technology

[0002] Electrochemical devices, such as all-solid-state secondary batteries, employ materials with high energy density, such as lithium metal, for the negative electrode to achieve high energy density, and use solid-state ion conductors as the electrolyte for safe operation.

[0003] Oxide-based and sulfide-based solid ion conductors are widely studied as solid ion conductors depending on the type of anion. However, while oxide-based solid ion conductors exhibit high chemical stability, their performance is inferior to that of sulfide-based solid ion conductors in terms of ion conductivity and moldability. Sulfide-based solid ion conductors possess high ion conductivity and excellent moldability, but they generate toxic gases upon reaction with water.

[0004] Therefore, there is a need for a solid ion conductor that enables excellent ion conductivity, excellent cycle stability with a lithium-containing metal electrode during cell assembly, and reversible expression of the designed anode capacity, a solid electrolyte and electrochemical device including the same, and a method for manufacturing the solid ion conductor. The problem to be solved

[0005] One aspect is to provide a solid-state ion conductor that enables excellent ion conductivity, excellent cycle stability with a lithium-containing metal electrode during cell assembly, and reversible realization of the designed anode capacity.

[0006] Another aspect is to provide a solid electrolyte comprising the above-mentioned solid ion conductor.

[0007] Another aspect is to provide an electrochemical device comprising the above-mentioned solid ion conductor.

[0008] Another aspect is to provide a method for manufacturing the above-mentioned solid ion conductor. means of solving the problem

[0009] Depending on one aspect,

[0010] A solid ionic conductor comprising a compound represented by the following chemical formula 1 is provided:

[0011] <Chemical Formula 1>

[0012] Li a M b M' c X d O e

[0013] In the above chemical formula 1,

[0014] M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0015] M' is one or more metals selected from Na, K, Cs, Cu, or A having an oxidation number of +1, and

[0016] X is one or more elements selected from among halogen elements, and

[0017] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1.

[0018] Depending on other aspects of work,

[0019] A solid electrolyte comprising the solid ion conductor described above is provided.

[0020] Depending on other aspects of work,

[0021] It includes an anode layer, a cathode layer, and a solid electrolyte layer,

[0022] An electrochemical device comprising the aforementioned solid electrolyte is provided.

[0023] Depending on other aspects of work,

[0024] An electrochemical device comprising an anode layer, a cathode layer, and a solid electrolyte layer, and comprising the solid electrolyte described above is provided.

[0025] Depending on other aspects of work,

[0026] Step of preparing a precursor for forming a solid ion conductor;

[0027] A step of providing a precursor mixture for forming a solid ion conductor by performing mechanical milling on the precursor for forming a solid ion conductor; and

[0028] A method for manufacturing a solid ion conductor is provided, comprising the step of molding the above-described precursor mixture for forming a solid ion conductor to produce a solid ion conductor comprising a compound represented by the following chemical formula 1:

[0029] <Chemical Formula 1>

[0030] Li a M b M' c X d O e

[0031] In the above chemical formula 1,

[0032] M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0033] M' is one or more metals selected from Na, K, Cs, Cu, or Ag with an oxidation number of +1, and

[0034] X is one or more elements selected from among halogen elements, and

[0035] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1. Effects of the invention

[0036] A solid ion conductor according to one aspect is a halide-based solid ion conductor having a metal with an oxidation number of +3 or +4 as the central element and a portion of the halide element substituted with oxygen. Alternatively, the above compound is a halide-based solid ion conductor having a metal with an oxidation number of +3 or +4 as the central element, a portion of the halide element substituted with oxygen, and a Li site substituted with a metal with an oxidation number of +1.

[0037] The above-described solid ion conductor can be used as a solid electrolyte that possesses excellent ion conductivity and suppresses a chain reaction in which the central metal is reduced upon contact with a lithium-containing metal electrode due to the introduction of oxygen. When the above-described solid ion conductor is applied to an electrochemical device, the device enables excellent cycle stability with a lithium-containing metal electrode and reversible realization of the designed anode capacity.

[0038] The above solid ion conductor may be included in the solid electrolyte layer, anode layer, cathode layer, anode layer protective film, or cathode layer protective film of an electrochemical device, for example, an all-solid-state secondary battery or a metal-air battery. Brief explanation of the drawing

[0039] Figure 1a is a schematic diagram showing that when a halide-based solid ion conductor, which is compared as a solid electrolyte, comes into contact with a metal electrode containing lithium, an electron-conducting decomposition product is produced through a chain reduction reaction. FIG. 1b is a schematic diagram showing that when a halide-based solid ion conductor according to one embodiment as a solid electrolyte comes into contact with a metal electrode containing lithium, a metal oxide that inhibits the reduction reaction is formed. FIG. 2a is a schematic diagram showing the crystal structure of a solid ion conductor compound according to one embodiment. FIG. 2b is a schematic diagram showing a unit in the crystal structure of a solid ion conductor compound according to one embodiment. FIGS. 3 to 5 are cross-sectional views of an all-solid-state secondary battery according to one embodiment. Figure 6 shows the cyclovoltammetry results of a lithium symmetric cell having a Li / solid ion conductor / Li structure prepared using solid ion conductor pellets prepared according to Examples 1 to 4 and Comparative Examples 1 to 4 as the solid electrolyte. Figure 7 shows the cyclovoltammetry results of a cell having a Li / Li6PS5Cl solid ion conductor / manufactured solid ion conductor / SUS structure, prepared using solid ion conductor pellets prepared according to Example 1 and Comparative Examples 1 to 3 as the solid electrolyte. Figure 8 shows the voltage profile of the all-solid-state secondary battery manufactured according to Example 1. Specific details for implementing the invention

[0040] Hereinafter, a solid ion conductor according to one embodiment of the present invention, a solid electrolyte and an electrochemical device including the same, and a method for manufacturing the solid ion conductor will be described in detail with reference to the attached drawings. The following is presented as an example and is not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0041] In this specification, expressions such as "at least one," "one or more," or "one or more" preceding components are to supplement the list of all components and do not mean that they are to supplement the individual components described above. In this specification, the term "combination" includes mixtures, alloys, reaction products, etc., unless specifically stated otherwise.

[0042] In this specification, the term "includes" means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0043] In this specification, terms such as "first," "second," etc., are used to distinguish one element from another without indicating order, quantity, or importance. Unless otherwise indicated in this specification or clearly contradicted by the context, they should be interpreted to include both singular and plural forms. "Or" means "and / or" unless otherwise specified.

[0044] Throughout this specification, terms such as “one embodiment,” “an embodiment,” etc., mean that specific elements described in relation to an embodiment are included in at least one embodiment described herein and may or may not be present in other embodiments. Furthermore, it should be understood that the described elements may be combined in any appropriate manner in various embodiments.

[0045] Unless otherwise defined, technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, in the event that terms in this specification contradict or conflict with terms in the incorporated reference, terms from this specification shall prevail over conflicting terms in the incorporated reference. Although specific embodiments and embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently anticipated or cannot be anticipated may arise to the applicant or those skilled in the art. Accordingly, the appended claims and subject to amendment are intended to include all such alternatives, variations, improvements, and substantial equivalents.

[0046] Solid ion conductors are used as solid electrolytes. However, solid electrolytes cannot possess high ionic conductivity compared to liquid electrolytes. Therefore, when solid electrolytes are applied to electrochemical devices, these devices exhibit poor charge and discharge characteristics at room temperature.

[0047] Among solid ion conductors, sulfide-based and oxide-based solid ion conductors are being widely studied. Sulfide-based solid ion conductors exhibit excellent ion conductivity, but their chemical and electrochemical stability are degraded due to factors such as gas generation. Oxide-based solid ion conductors have excellent chemical stability but poor moldability and low ion conductivity, resulting in poor charge-discharge characteristics when applied to electrochemical devices. Therefore, to compensate for these shortcomings, a process for crystallizing oxide-based solid ion conductors at high temperatures exceeding 1000°C is required.

[0048] Recently, halide-based solid electrolytes are being studied as solid ion conductors. Halide-based solid electrolytes can be molded by applying pressure alone and do not generate gas. Li3InCl6 is an example of a halide-based solid electrolyte. Alternatively, Li3YCl6 is widely used. However, halide-based solid electrolytes such as Li3InCl6 or Li3YCl6 may still have unsatisfactory ionic conductivity. Furthermore, when these halide-based solid electrolytes come into contact with a lithium-containing metal electrode during cell assembly, the central metal may be reduced, potentially leading to increased resistance or the generation of decomposition products that cause a short circuit.

[0049] To address these issues, the inventors of the present invention propose a solid ion conductor, a solid electrolyte and an electrochemical device including the same, and a method for manufacturing the solid ion conductor.

[0050] Hereinafter, a solid ion conductor, a solid electrolyte and an electrochemical device including the same, and a method for manufacturing the solid ion conductor are described in detail.

[0052] Solid ion conductors

[0053] A solid ion conductor according to one embodiment may include a compound represented by the following chemical formula 1:

[0054] <Chemical Formula 1>

[0055] Li a M bM' c X d O e

[0056] In the above chemical formula 1,

[0057] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0058] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0059] X may be one or more elements selected from among halogen elements, and

[0060] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1.

[0061] The compound represented by the above chemical formula 1 may include a compound represented by the following chemical formula 2:

[0062] <Chemical Formula 2>

[0063] Li a M b M' c Cl d1 Br d2 F d3 I d4 O e

[0064] In the above chemical formula 2,

[0065] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0066] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0067] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0< d1 < 6.5, 0< d2< 6.5, 0 ≤ d3 < 6.5, 0 ≤ d4 < 6.5, 0 < e < 1.

[0068] The above compound is a halide-based solid ion conductor having a metal with an oxidation state of +3 or +4 as the central element and a portion of the halide elements substituted with oxygen. Alternatively, the above compound is a halide-based solid ion conductor having a metal with an oxidation state of +3 or +4 as the central element, with a portion of the halide elements substituted with oxygen and the Li site substituted with a metal with an oxidation state of +1. The above solid ion conductor can be used as a solid electrolyte that possesses excellent ion conductivity and suppresses a chain reaction in which the central metal is reduced upon contact with a lithium-containing metal electrode due to the introduction of oxygen. When the above solid ion conductor is applied to an electrochemical device, the electrochemical device enables excellent cycle stability with a lithium-containing metal electrode and reversible realization of the designed anode capacity.

[0069] The reasons why the above compound enables superior cycle stability with a lithium-containing metal electrode and reversible expression of the designed anode capacity during cell assembly compared to halide-based solid ion conductors such as Li3InCl6 or Li3YCl6 are explained in more detail below; however, this is intended to aid in understanding the present invention and the scope of the present invention is not limited to the scope of the following description.

[0070] FIG. 1a is a schematic diagram showing that when a halide-based solid ion conductor, which is compared as a solid electrolyte, comes into contact with a metal electrode containing lithium, an electron-conducting decomposition product is generated by a chain reduction reaction. FIG. 1b is a schematic diagram showing that when a halide-based solid ion conductor according to one embodiment comes into contact with a metal electrode containing lithium as a solid electrolyte, a metal oxide that inhibits the reduction reaction is generated.

[0071] As shown in FIG. 1a, when a halide-based solid ion-conducting solid electrolyte (200) comes into contact with a metal electrode (100) containing lithium, a chain reduction reaction occurs according to the following reaction equation 1 to produce an electron-conducting decomposition product (M, 300):

[0072] <Reaction Equation 1>

[0073] Li3MCl6 + 3Li → M + 6LiCl

[0074] Among the foods,

[0075] M is a metal with an oxidation number of +3.

[0076] The above electronically conductive decomposition product (M) may cause a short circuit when in contact with a metal electrode (1) containing lithium as an electronic conductor. Additionally, the LiCl generated by the reduction reaction may increase resistance as an insulator. When such a halide-based solid ion-conducting solid electrolyte (200) is applied to a cell using a metal electrode containing lithium, not only is stable cycle operation difficult, but the reversible expression of the designed anode capacity is also difficult.

[0077] As shown in FIG. 1b, when a halide-based solid ion conductor (400) according to one embodiment comes into contact with a metal electrode containing lithium, almost no electron-conducting decomposition product (M, 300) is generated, and a metal oxide M2O (500) that inhibits the reduction reaction is generated by the following reaction scheme 2:

[0078] <Reaction Equation 2>

[0079] 2Li3MCl6+ 3Li2O → 12LiCl + M2O3

[0080] Among the foods,

[0081] M is a metal with an oxidation number of +3.

[0082] The reduction reaction from the metal oxide M2O (500) to the central element M is a non-spontaneous reaction according to the following reaction equation 3:

[0083] <Reaction Equation 3>

[0084] M2O3 + 6Li → 2M + 3Li2O

[0085] Among the foods,

[0086] M is a metal with an oxidation number of +3.

[0087] For example, in the case where the above M is Lu △H = 99 kJ mol -1 am.

[0088] Therefore, when a halide-based solid ion conductor solid electrolyte (400) according to one implementation is applied to a cell using a lithium-containing metal electrode, excellent cycle stability with the lithium-containing metal electrode and reversible expression of the designed anode capacity are enabled.

[0089] The above compound may include a compound represented by the following chemical formula 3:

[0090] <Chemical Formula 3>

[0091] Li a M b M' c X d O e

[0092] In the above chemical formula 3,

[0093] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0094] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0095] X may be one or more elements selected from Cl or Br, and

[0096] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1, and 0 < e / b < 0.5.

[0097] When the molar ratio of O / M of the above compound is greater than 0 and less than 0.5, it can be used as a solid electrolyte while maintaining excellent ionic conductivity.

[0098] The above compound may include a compound represented by the following chemical formula 4:

[0099] <Chemical Formula 4>

[0100] Li a M b M' c X d O e

[0101] In the above chemical formula 4,

[0102] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0103] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0104] X may be one or more elements selected from Cl or Br, and

[0105] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1, and 2≤ a / b ≤ 6.

[0106] For example, in the above chemical formula 4, 2 ≤ a / b ≤ 4.

[0107] When the molar ratio of Li / M of the above compound is 2 or more and 6 or less, it can be used as a solid electrolyte while maintaining excellent ionic conductivity due to the large number of Li cations distributed within the crystal structure of the above compound.

[0108] For example, the above compound may include a compound represented by the following chemical formula 5 or chemical formula 6:

[0109] <Chemical Formula 5>

[0110] Li p M q X r-w O w

[0111] In the above chemical formula 5,

[0112] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, and

[0113] X may be one or more elements selected from Cl or Br, and

[0114] 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 0 < w / q < 0.5.

[0115] <Chemical Formula 6>

[0116] Li p M q M' z X r-w O w

[0117] In the above chemical formula 6,

[0118] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, and

[0119] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0120] X may be one or more elements selected from Cl or Br, and

[0121] 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 2 < p / q ≤ 6, 0 < w / q < 0.5. For example, in the above chemical formula 6, 2 < p / q ≤ 4.

[0122] For example, the above compound is Li 3.6 Lu 0.9 Cl 5.7 O 0.3 , Li 3.6 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Ho 0.9 Cl 5.7 O 0.3 , Li 3.6 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Nd 0.9 Cl 5.7 O 0.3 , Li 3.6 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Sm 0.9 Cl 5.7 O 0.3 , Li 3.6 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Eu 0.9 Cl 5.7 O 0.3 , Li 3.6 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Gd 0.9 Cl 5.7 O 0.3 , Li 3.6 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Tb 0.9 Cl 5.7 O 0.3 , Li 3.6 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Dy 0.9 Cl 5.7 O 0.3 , Li 3.6 Dy 0.9 Cl 1.7 Br4O0.3 , Li 3.6 Tm 0.9 Cl 5.7 O 0.3 , Li 3.6 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Yb 0.9 Cl 5.7 O 0.3 , Li 3.6 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Ga 0.9 Cl 5.7 O 0.3 , Li 3.6 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 In 0.9 Cl 5.7 O 0.3 , Li 3.6 In 0.9 Cl 1.7 Br4O 0.3 ;

[0123] Li 3.57 Na 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Gd 0.9 Cl 1.7 Br4O0.3 , Li 3.57 Na 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;

[0124] Li 3.57 K 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;

[0125] Li 3.57 Cs 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Tb 0.9 Cl1.7 Br4O 0.3 , There 3.57 Cs 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;

[0126] There 3.57 Cu 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 I have 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Tb 0.9 Cl 1.7 Br4O 0.3, Li 3.57 Cu 0.03 House 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cu 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cu 0.03 Ub 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cu 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cu 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;

[0127] Li 3.57 Ag 0.03 Many 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Their 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Lee 3.57 Ag 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Lee 3.57 Ag 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Lee 3.57 Ag 0.03 Him 0.9 Cl 1.7 Br4O 0.3 , Lee 3.57 Ag 0.03 In 0.9 Cl 1.7 Br4O 0.3 ; or

[0128] Li 3.2 LuCl6O 0.1 , Lee 3.2 HoCl6O 0.1 , Lee 3.2 NdCl6O 0.1 , Lee 3.2 SmCl6O 0.1 , Lee 3.2 EuCl6O 0.1 , Lee 3.2 GdCl6O 0.1 , Lee 3.2 TbCl6O 0.1 , Lee 3.2 DyCl6O 0.1 , Lee 3.2 ErCl6O 0.1 , Lee 3.2 TmCl6O 0.1 , Lee 3.2 YbCl6O 0.1 , Lee 3.2 GaCl6O 0.1 , Lee 3.2 InCl6O 0.1 , Lee 3.2 CeCl6O 0.1 , Lee 3.2 PrCl6O 0.1

[0129] to include

[0130] FIG. 2a is a schematic diagram showing the crystal structure of a solid ion conductor compound according to one embodiment. FIG. 2b is a schematic diagram showing a unit in the crystal structure of a solid ion conductor compound according to one embodiment.

[0131] As shown in FIGS. 2a and 2b, a solid ion conductor compound according to one embodiment has a distorted rock-salt type crystal structure. The compound is an MX6 (X = one or more halogen elements) octahedron centered around an M metal having an oxidation state of +3 or +4 within the crystal structure, with X anions located at the edges, and oxygen anions located in some of the X anion sites. The octahedrons are positioned in an edge-sharing manner. Li around the octahedrons + It is a layered crystal structure in which a metal and a metal in which some are substituted with a non-lithium metal (M') having an oxidation state of +1 are located. + The metal is Cl - LiCl can have ionic bonds depending on the distance from. Li + Li on the site + Li is substituted with a metal (M') cation with an ionic radius greater than that of Li + Since a space for ions to move freely can be secured, the compound may have lithium ion transport channels in three-dimensional regions in the x-axis, y-axis, and z-axis directions other than the region where the MX6 (X = one or more halogen elements) octahedra are located within the crystal structure. The compound may have three-dimensionally connected lithium ion transport channels within the crystal structure. As a result, it is believed that the lithium ion conductivity is excellent.

[0132] The above solid ion conductor is 1.0 x 10⁻⁶ at 25℃ -5 mS·cm -1It can have an ionic conductivity greater than or equal to 1.2 x 10⁻⁶ at 25°C. For example, the solid ionic conductor has 1.2 x 10⁻⁶ at 25°C -5 mS·cm -1 or more than 1.4 x 10 -5 mS·cm -1 or more than 1.6 x 10 -5 mS·cm -1 or more than 1.8 x 10 -5 mS·cm -1 or more than 2.0 x 10 -5 mS·cm -1 It can have an ionic conductivity greater than that.

[0134] Solid Electrolytes and Electrochemical Devices

[0135] A solid electrolyte according to another embodiment may include the solid ion conductor described above. The solid electrolyte may be electrochemically stable in a voltage window of 0.6 V to 4.3 V (vs. Li).

[0136] An electrochemical device according to another embodiment includes an anode layer, a cathode layer, and a solid electrolyte layer, and may include the solid electrolyte described above.

[0137] The above solid electrolyte may be included in the solid electrolyte layer, the anode layer, the cathode layer, the anode layer protective film, the cathode layer protective film, or a combination thereof.

[0138] The above anode layer may include an anode active material selected from lithium transition metal oxide, lithium transition metal phosphate, sulfide, or a combination thereof, and the above solid electrolyte.

[0139] For example, the above-mentioned cathode active material may be formed using lithium cobalt oxide (hereinafter referred to as LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (hereinafter referred to as NCA), lithium nickel cobalt manganese oxide (hereinafter referred to as NCM), lithium manganate, lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, etc. Each of these cathode active materials may be used individually or in combination of two or more types. For example, the cathode active material is LiNi x Co y Al z O2(NCA) or LiNi x Co y Mn z Examples include lithium salts of ternary transition metal oxides such as O2(NCM) (where 0 < x < 1, 0 < y < 1, 0 < z < 1, x + y + z = 1).

[0140] A coating layer may be formed on the cathode active material. Any coating layer that is used as a coating layer for the cathode active material of an all-solid-state secondary battery may be used. Examples of coating layers include, for instance, Li2O-ZrO2.

[0141] In addition, if the cathode active material is formed from a lithium salt of a ternary transition metal oxide such as NCA or NCM and includes nickel (Ni), the capacity density of the electrochemical device can be increased, thereby reducing metal leaching from the cathode active material in the charged state. This can improve the long-term reliability and cycle characteristics of the electrochemical device in the charged state.

[0142] Examples of the shapes of the above-mentioned positive active material include particle shapes such as oval or spherical. Furthermore, the particle size of the positive active material is not limited, and it can be used as long as it is within a range applicable to the positive active material of an electrochemical device, for example, an all-solid-state secondary battery. The content of the positive active material in the positive layer is also not limited, and it can be used as long as it is within a range applicable to the positive of an all-solid-state secondary battery.

[0143] The above cathode layer may include lithium metal or lithium alloy.

[0144] For example, the lithium alloy may be an alloy comprising one or more selected from lithium and indium (In), silicon (Si), gallium (Ga), tin (Sn), aluminum (Al), titanium (Ti), zirconium (Zr), niobium (Nb), germanium (Ge), antimony (Sb), bismuth (Bi), gold (Au), platinum (Pt), palladium (Pd), magnesium (Mg), palladium (Pd), silver (Ag), and zinc (Zn). However, it is not limited thereto, and any metal or metalloid capable of forming an alloy with lithium available in the art may be used.

[0145] The reduction potential of the lithium metal of the above solid electrolyte may be 0 V or less.

[0146] The reduction current of the above solid electrolyte relative to lithium metal at 0 V is 0.1 mA / cm 2 It may be less than.

[0147] The above solid electrolyte enables excellent cycle stability with a lithium-containing metal electrode and reversible expression of the designed anode capacity.

[0148] The above solid electrolyte layer may include the above solid electrolyte, a sulfide-based solid electrolyte, or a solid electrolyte selected from a combination thereof.

[0149] The above sulfide-based solid electrolyte may include a solid electrolyte represented by the following chemical formula 7:

[0150] <Chemical Formula 7>

[0151] Li + 12-n-z A n+ X 2- 6-z Y' - z

[0152] In the above chemical formula 3,

[0153] A can be P, As, Ge, Ga, Sb, Si, Sn, Al, In, Tl, V, Nb, or Ta, and

[0154] X can be S, Se, or Te, and

[0155] Y' can be Cl, Br, I, F, CN, OCN, SCN, or N3, and

[0156] 1 < n < 5, 0 < z < 2.

[0157] The above sulfide-based solid ion conductor is Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an azirodite-type compound containing one or more selected from (0≤x≤2). For example, the sulfide-based solid ion conductor may be an azirodite-type compound containing one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0158] If necessary, the above sulfide-based solid ion conductor is Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m, n are positive numbers, Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, or Li2S-SiS2-Li p MO q (p, q are positive numbers, M is one of P, Si, Ge, B, Al, Ga, In, etc.) may be included. For example, the sulfide-based solid ion conductor may include Li2S-P2S5. If the sulfide-based solid ion conductor is Li2S-P2S5, the molar ratio of Li2S and P2S5 may be, for example, in the range of Li2S:P2S5 = 50:50 to 90:10.

[0159] The above oxide-based solid ion conductor is Garnet-based ceramics Li 3+x La3M2O 12 (M = Te, Nb, or Zr, x is an integer from 1 to 10), lithium phosphorus oxynitride (Li x PO y N z )(0< x <1, 0< y <1, 0< z <1)(LiPON: Lithium Phosphorus Oxynitride), Li x P y O z N k (2.7≤ x ≤3.3, 0.8≤ y ≤1.2, 3.5≤ z ≤3.9, 0.1≤ k ≤0.5), Li w PO x N y S z(0< w <1, 0< x <1, 0< y <1, 0< z <1), Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0< x <2, 0 < y <3), BaTiO3, Pb(Zr,Ti)O3(PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT)(0≤ x <1, 0≤ y <1), Pb(Mg3Nb 2 / 3 )O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, SiC, Lithium Phosphate (Li3PO4), Lithium Titanium Phosphate (Li x Ti y (PO4)3, 0< x <2, 0< y <3), lithium aluminum titanium phosphate (Li x Al y Ti z (PO4)3, 0< x <2, 0< y <1, 0< z <3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (0≤ x ≤1, 0≤ y ≤1), lithium lanthanum titanate (Li x La y TiO3, 0 < x < 2, 0 < y < 3), lithium germanium thiophosphate (Li x Ge y P z S w , 0< x <4, 0< y <1, 0< z <1, 0< w <5), lithium nitride glass (Li x N y , 0< x <4, 0< y <2), SiS2(Li x Si y S z, 0< x <3, 0< y <2, 0< z <4), P2S5 series glass (Li x P y S z , 0< x <3, 0< y <3, 0< z <7), Li2O, LiF, LiOH, Li2CO3, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2-based ceramics, Garnet-based ceramics Li 3+x La3M2O 12 (M = Te, Nb, or Zr, where x is an integer from 1 to 10), or a combination thereof may be used. For example, the oxide-based solid ion conductor may use a garnet-based oxide-based solid electrolyte that exhibits excellent reduction stability when in contact with a lithium anode. Garnet-based ceramics Li 3+x La3M2O 12 (M = Te, Nb, or Zr), for example LLZO(Li 6.5 La3Zr 1.5 Ta 0.5 O 12 ) can be used.

[0160] The above solid electrolyte may further include a binder. For example, the binder included in the above solid electrolyte may be styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or a combination thereof. However, it is not limited thereto, and any binder used in the relevant technical field is acceptable.

[0161] If necessary, the solid electrolyte may further comprise an organic solid electrolyte. Examples of the organic solid electrolyte may include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly-adhesion lysines, polyester sulfides, polyvinyl alcohols, polyvinylidene fluoride, or polymers containing ionic dissociators. If necessary, the solid electrolyte may further comprise an amorphous solid electrolyte. The solid electrolyte may comprise a mixed solid electrolyte comprising a mixture of a crystalline solid electrolyte and an amorphous solid electrolyte. If necessary, the solid electrolyte may further comprise a lithium salt or / and an ionic liquid.

[0162] If necessary, the solid electrolyte may further include an ion-conducting inorganic material.

[0163] Ion-conducting inorganic materials include one or more selected from glass or amorphous metal ion conductors, ceramic active metal ion conductors, and glass ceramic active metal ion conductors, but are not necessarily limited to these, and any material used as an ion-conducting inorganic material in the relevant technical field is acceptable. The ion-conducting inorganic materials are, for example, in the form of ion-conducting inorganic particles or sheets thereof.

[0164] Ionic conductive inorganic materials include, for example, BaTiO3, Pb(Zr,Ti)O3(PZT), and Pb 1-x La x Zr 1-y Ti y O3(PLZT)(0≤x<1, 0≤y<1), Pb(Mg3Nb 2 / 3 )O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, SiC, Lithium Phosphate (Li3PO4), Lithium Titanium Phosphate (Li x Ti y(PO4)3, 0 <x<2, 0<y<3), 리튬알루미늄티타늄포스페이트 (Li x Al y Ti z (PO4)3, 0 <x<2, 0<y<1, 0<z<3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (0≤x≤1, 0≤y≤1), lithium lanthanum titanate(Li x La y TiO3, 0 <x<2, 0<y<3), 리튬게르마늄티오포스페이트(Li x Ge y P z S w , 0 <x<4, 0<y<1, 0<z<1, 0<w<5), 리튬나이트라이드(Li x N y , 0 <x<4, 0<y<2), SiS2(Li x Si y S z , 0 <x<3,0<y<2, 0<z<4) 계열 글래스, P2S5(Li x P y S z , 0 <x<3, 0<y<3, 0<z<7) 계열 글래스, L i2 O, LiF, LiOH, Li2CO3, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2-based ceramics, Garnet-based ceramics (Li 3+x La3M2O 12 It is one or more selected from (M = Te, Nb, Zr)) or a combination thereof.

[0165] The above-mentioned solid electrolyte may be in the form of a powder or a molded article. The solid electrolyte in the form of a molded article may be, for example, in the form of pellets, sheets, thin films, etc., but is not necessarily limited to these and may have various forms depending on the application.

[0166] The thickness of the solid electrolyte layer may be 10 micrometers (μm) to 1 millimeter (mm). The solid electrolyte layer may be a single layer or a multilayer structure of two or more layers.

[0167] For example, the solid electrolyte may comprise a solid ion conductor comprising a compound represented by Chemical Formula 1 alone in the solid electrolyte layer. Alternatively, the solid electrolyte layer may comprise an oxide-based solid ion conductor or a sulfide-based solid ion conductor as a separate layer in addition to the solid ion conductor.

[0168] For example, the solid electrolyte may comprise, alone, a solid ion conductor comprising a compound represented by Formula 1 in the anode layer or / and cathode layer. Alternatively, in addition to the solid ion conductor, the anode layer or / and cathode layer may comprise a sulfide-based solid ion conductor, an oxide-based solid ion conductor solid electrolyte, or / and an ionic liquid-containing electrolyte in a separate single-layer or multi-layer structure. For example, the electrochemical element may comprise, in the order of an anode layer, an ionic liquid-containing electrolyte, an oxide-based solid ion conductor solid electrolyte (or a sulfide-based solid ion conductor solid electrolyte), a solid ion conductor solid electrolyte containing a compound represented by Formula 1, an oxide-based solid ion conductor solid electrolyte (or a sulfide-based solid ion conductor solid electrolyte), and a cathode layer.

[0169] The above electrochemical device may be an all-solid-state secondary battery or a metal-air battery. However, it is not limited thereto, and any electrochemical device usable in the relevant technical field is acceptable.

[0170] For example, the above electrochemical device may be an all-solid-state secondary battery.

[0171] FIGS. 3 to 5 are cross-sectional views of an all-solid-state secondary battery according to one embodiment.

[0172] Referring to FIGS. 3 to 5, the all-solid-state secondary battery (1) comprises a positive electrode layer (10) including a positive electrode current collector (11) and a positive electrode active material layer (12); a negative electrode layer (20); and a solid electrolyte layer (30) disposed between the positive electrode layer (10) and the negative electrode layer (20). The negative electrode layer (20) comprises a negative electrode current collector (21) and a negative electrode active material layer (22) disposed on the negative electrode current collector (21), wherein the negative electrode active material layer (22) comprises lithium metal or a negative electrode active material that forms an alloy with lithium. One or more of the positive electrode layer (10); the negative electrode layer (20); and the solid electrolyte layer (30) of the all-solid-state secondary battery (1) comprise a solid ion conductor comprising a compound represented by the above chemical formula 1.

[0173] For the positive current collector (11), for example, a plate or foil made of indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof may be used. The positive current collector (11) may be omitted.

[0174] The positive active material layer (12) may include the positive active material and / or a solid electrolyte described above. The solid electrolyte included in the positive layer (10) may be the same as or different from the solid electrolyte included in the solid electrolyte layer (30).

[0175] The anode layer (10) may further include an ion-conducting inorganic material. The types of ion-conducting inorganic materials are the same as those described above, so further explanation is omitted.

[0176] The anode layer (10) may appropriately incorporate additives such as, for example, a conductive agent, a binder, a filler, a dispersant, and an ion-conducting aid, in addition to the anode active material or / and solid electrolyte described above.

[0177] Examples of conductive agents that can be incorporated into the anode layer (10) include graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or metal powder. Examples of binders that can be incorporated into the anode layer (10) include styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, and polyethylene. Known materials generally used in electrodes of all-solid-state secondary batteries can be used as coating agents, dispersants, and ion-conducting aids that can be incorporated into the anode layer (10).

[0178] The negative electrode layer (20) may include a negative electrode current collector (21) and a negative electrode active material layer (22).

[0179] Materials constituting the negative electrode current collector (21) may include copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), or nickel (Ni). The negative electrode current collector (21) may be composed of one type of metal, or an alloy of two or more types of metals or a coating material. The negative electrode current collector (21) may be formed, for example, in a plate shape or a thin shape.

[0180] The negative electrode active material layer (22) may include the lithium metal or lithium alloy described above. If necessary, the negative electrode active material layer (22) may include a carbon-based negative electrode active material, or a negative electrode active material in combination with the lithium metal or lithium alloy and the carbon-based negative electrode active material. Examples of lithium alloys are the same as those described above.

[0181] Carbon-based cathode active materials may include graphite, carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, carbon nanotubes, or carbon nanofibers.

[0182] The negative electrode active material layer (22) may also appropriately incorporate additives such as a conductive agent, binder, filler, dispersant, and ion conductivity aid.

[0183] If necessary, the cathode active material layer (22) may be a non-cathode coating layer. For example, the non-cathode coating layer may have a structure containing a metal such as silicon and carbon, and a conductive binder disposed around the metal and carbon. The thickness of the non-cathode coating layer may be 1 μm to 20 μm.

[0184] The solid electrolyte layer (30) can be manufactured by depositing using known film deposition methods, such as aerosol deposition, cold spray, or sputtering. Alternatively, the solid electrolyte layer (30) can be manufactured by pressurizing a single solid electrolyte particle. Alternatively, the solid electrolyte layer (30) can be manufactured by mixing the solid electrolyte, solvent, and binder, applying the mixture, drying, and pressurizing.

[0185] As shown in FIG. 4, a thin film (24) may be formed on the surface of a negative electrode current collector (21). The thin film (24) may contain elements capable of forming an alloy with lithium. Elements capable of forming an alloy with lithium may include, for example, gold, silver, zinc, tin, indium, silicon, aluminum, and bismuth. The thin film (24) may be composed of one of these metals or may be composed of several types of alloys. By having the thin film (24), the precipitation pattern of the metal layer (23) shown in FIG. 5 may be further flattened, and the characteristics of the all-solid-state secondary battery (1) may be further improved.

[0186] The thickness of the thin film (24) may be 1 nm to 500 nm, but is not limited thereto. When the thickness of the thin film (24) is within the above range, the function of the thin film (24) is sufficiently performed, and the amount of lithium precipitated in the negative electrode layer is appropriate, so the characteristics of the all-solid-state secondary battery (1) are excellent. The thin film (24) can be formed on the negative electrode current collector (21) by, for example, vacuum deposition, sputtering, plating, etc.

[0188] Method for manufacturing a solid ion conductor

[0189] A method for manufacturing a solid ion conductor according to one embodiment may include: a step of preparing a precursor for forming a solid ion conductor; a step of performing mechanical milling on the precursor for forming a solid ion conductor to provide a precursor mixture for forming a solid ion conductor; and a step of molding the precursor mixture for forming a solid ion conductor to manufacture a solid ion conductor comprising a compound represented by the following chemical formula 1:

[0190] <Chemical Formula 1>

[0191] <Chemical Formula 1>

[0192] Li a M b M' c X d O e

[0193] In the above chemical formula 1,

[0194] M may be one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf having an oxidation number of +3 or +4, and

[0195] M' may be one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, and

[0196] X may be one or more elements selected from among halogen elements, and

[0197] 0 < a < 4, 0.5 < b < 1.5, 0≤ c < 1.5, 0 < d < 6.5, 0 < e < 1.

[0198] The above method for manufacturing a solid ion conductor enables the easy production of a solid ion conductor at low temperatures that has excellent ion conductivity, electrochemical stability over a wide potential window when applied as a solid electrolyte in an electrochemical device, excellent cycle stability with a metal electrode containing lithium, and reversible expression of the designed anode capacity.

[0199] When preparing the above-mentioned precursor mixture for forming a solid ion conductor, a lithium precursor, an M precursor, an M' precursor, and a halogen element precursor may be mixed. The M precursor is a precursor of a metal element with an oxidation number of +3 or +4, and the M' precursor may be a precursor of a metal element with an oxidation number of +1.

[0200] The lithium precursor, the M precursor, and the M' precursor may each include a chloride, halide, oxide, nitride, oxynitride, nitrate, hydroxide, and carbonate of lithium. For example, the lithium precursor may be a lithium chloride. For example, the M precursor may include a chloride, oxide, nitride, oxynitride, nitrate, hydroxide, and carbonate of one element selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, In, Ce, Pr, Ti, Zr, or Hf. For example, the M' precursor may be a chloride of one element selected from Na, K, Cs, Cu, or Ag.

[0201] The above compound can be used to prepare a mixture by contacting the starting material in an appropriate amount, for example, a stoichiometric amount. Mechanical milling is performed on the mixture.

[0202] The mechanical milling described above may utilize a ball mill, airjet mill, bead mill, roll mill, planetary mill, hand milling, high energy ball mill, planetary ball mill, stirred ball mill, vibrating mill, mechanofusion milling, shaker milling, planetary milling and atritor milling, disk milling, shape milling, nauta milling, nobilta milling, high speed mix, or a combination thereof. For example, the mechanical milling may be planetary milling and may be performed at room temperature. The method may further include a forming step after performing the mechanical milling.

[0203] After the above mechanical milling, a resting step may be further included. For example, the resting step may be performed at room temperature for 1 to 10 minutes.

[0205] Examples and comparative examples of the present invention are described below. However, the following examples are merely one example of the present invention, and the present invention is not limited to the following examples.

[0207] [Example]

[0209] (Solid ion conductor)

[0210] Example 1: Li 3.6 Lu 0.9 Cl 5.7 O 0.3 Manufacturing of solid ion conductors

[0211] LuCl3, LiCl, and Li2O were introduced into a reactor in a stoichiometric ratio of 0.9:3:0.3 and mixed to prepare a precursor mixture for forming a solid ion conductor. The precursor mixture was fed into a planetary mill (Pulverisette 7 premium line) equipped with 10 mm diameter zirconia (YSZ) balls and subjected to a cycle of mixing at 500 rpm for 15 minutes followed by a 5-minute rest for a total of 24 hours to obtain the precursor mixture. The precursor mixture was placed into a 1-inch diameter pelletizer, and a weight of 5 tons was applied using uniaxial pressure for 2 minutes to form Li in the shape of a circular disc. 3.6 Lu 0.9 Cl 5.7 O 0.3 Solid ion conductor pellets were manufactured.

[0212] Example 2: Li 3.6 Lu 0.9 Cl 1.7 Br 4 O 0.3 Manufacturing of solid ion conductors

[0213] LuBr in the reactor 3, Except for adjusting the stoichiometric ratios of LiCl, LiBr, and Li2O to 0.9:1.7:1.3:0.3, Li was prepared in the same manner as in Example 1. 3.6 Lu 0.9 Cl 1.7 Br4O 0.3 Solid ion conductor pellets were manufactured.

[0214] Example 3: Li 3.6 Ho 0.9 Cl 1.7 Br 4 O 0.3 Manufacturing of solid ion conductors

[0215] Except for adjusting HoCl3, LiCl, LiBr, and Li2O in the reactor to a stoichiometric ratio of 0.9:1.7:1.3:0.3, Li was prepared in the same manner as in Example 1. 3.6 Ho 0.9 Cl 1.7 Br4O 0.3 Solid ion conductor pellets were manufactured.

[0216] Example 4: Li 3.57 Na 0.03 Ho 0.9 Cl 1.7 Br 4 O 0.3 Manufacturing of solid ion conductors

[0217] Except for adjusting HoBr3, LiCl, NaCl, LiBr, and Li2O in the reactor to a stoichiometric ratio of 0.9:1.67:0.03:1.3:0.3, Li was prepared in the same manner as in Example 1. 3.57 Na 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 Solid ion conductor pellets were manufactured.

[0218] Example 5: Li 3.2 InCl 6 O 0.1 Manufacturing of solid ion conductors

[0219] Except for adjusting InCl3, LiCl, and Li2O in the reactor to a stoichiometric ratio of 1:3:0.1, Li was prepared in the same manner as in Example 1. 3.2 InCl6O 0.1 Solid ion conductor pellets were manufactured.

[0220] Comparative Example 1: Li 3 LuCl 6 Manufacturing of solid ion conductors

[0221] Li3LuCl6 solid ion conductor pellets were prepared in the same manner as in Example 1, except that LuCl3 and LiCl were adjusted to a stoichiometric ratio of 1:3 in the reactor.

[0222] Comparative Example 2: Li 3 HoCl 6 Manufacturing of solid ion conductors

[0223] Li3HoCl6 solid ion conductor pellets were prepared in the same manner as in Example 1, except that HoCl3 and LiCl were mixed in a stoichiometric ratio of 1:3 in the reactor.

[0224] Comparative Example 3: Li 3 InCl 6 Manufacturing of solid ion conductors

[0225] Li3InCl6 solid ion conductor pellets were prepared in the same manner as in Example 1, except that InCl3 and LiCl were mixed in a stoichiometric ratio of 1:3 in the reactor.

[0226] Comparative Example 4: Li 3 YCl 6 Manufacturing of solid ion conductors

[0227] Li3YCl6 solid ion conductor pellets were prepared in the same manner as in Example 1, except that YCl3 and LiCl were mixed in a stoichiometric ratio of 1:3 in the reactor.

[0229] (All-solid-state secondary battery)

[0230] Example 6: Preparation of an all-solid-state secondary battery

[0231] (Manufacturing of the cathode layer)

[0232] A cathode layer was prepared by placing a foil with a thickness of 20 μm deposited on one side of a Cu current collector with a thickness of 10 μm on the bottom surface of a tubular cell case with an inner diameter of 13 mm.

[0233] (Solid electrolyte layer)

[0234] Li prepared according to Example 1 3.6 Lu 0.9 Cl 5.7 O 0.3 Solid ion conductor powder was prepared by filling pellets into a 13 mm tubular cell case.

[0235] (Manufacturing of the anode layer)

[0236] LiNi as a positive electrode active material 0.8 Co 0.15 Mn 0.05 O2 (NCM), an argyrodite-type Li6PS5Cl solid ion conductor pellet (Mitusi, S33) as a solid electrolyte, and carbon nanofiber (CNF) as a conductive agent were mixed in a mass ratio of 60:35:5. An anode layer was prepared by filling 15 mg of the above mixture into a solid electrolyte layer inside a 13 mm tubular cell case.

[0237] (Manufacturing of all-solid-state secondary batteries)

[0238] A torque cell type all-solid-state secondary battery was manufactured by placing a SUS electrode with a diameter of 13 mm, which serves as a current collector, on the above-mentioned cathode layer / solid electrolyte layer / anode layer and applying a weight of 4 ton for 2 minutes.

[0240] Examples 7 to 10: Preparation of all-solid-state secondary batteries

[0241] An all-solid-state secondary battery was manufactured in the same manner as in Example 6, except that the solid ion conductor pellets prepared according to Examples 2 to 5 were used in the solid electrolyte layer.

[0242] Comparative Examples 5 to 8: Manufacturing of all-solid-state secondary batteries

[0243] An all-solid-state secondary battery was manufactured in the same manner as Example 6, except that solid ion conductor pellets prepared according to Comparative Examples 1 to 4 were used in the solid electrolyte layer.

[0245] Evaluation Example 1: Cyclovoltammetry

[0246] (1) Cycle stability evaluation

[0247] 300 mg of solid ion conductor pellets prepared according to Examples 1 to 5 and Comparative Examples 1 to 4 were compacted to a diameter of 13 mm. Then, Li electrodes with a diameter of 8 mm were attached to both sides of each solid ion conductor pellet by applying CIP (cold isostatic pressing) at 250 MPa for 3 minutes to prepare a lithium symmetric cell with a Li / solid ion conductor / Li structure. For the lithium symmetric cell, 0.1 mA / cm² at -1.0 V to 1.0 V 2 Cycle stability was evaluated by performing cyclovoltammetry analysis while changing the current direction every hour at a current density. Some or all of the results are shown in Fig. 6 and Table 1 below.

[0248] Cycle stability (times) Example 1 255 Example 2 489 Example 3 295 Example 4 300 Example 5 122 Comparative Example 1 72 Comparative Example 2 1 Comparative Example 3 1 Comparative Example 4 6

[0249] Referring to FIG. 6 and Table 1, the lithium symmetric cell using the solid ion conductor pellets prepared according to Examples 1 to 5 as the solid electrolyte operated stably for more than 122 cycles. In comparison, the lithium symmetric cell using the solid ion conductor pellets prepared according to Comparative Example 1 as the solid electrolyte operated for up to 72 cycles, and the lithium symmetric cell using the solid ion conductor pellets prepared according to Comparative Examples 2 to 4 as the solid electrolyte had difficulty operating for cycles.

[0250] (2) Evaluation of reduction potential and 0V reduction current

[0251] A cathode layer was prepared by placing a foil with a thickness of 20 μm, on one side of a 10 μm thick Cu current collector, on the bottom surface of a tubular cell case with an inner diameter of 13 mm. A cell was manufactured by sequentially filling 150 mg of an argyrodite-type Li6PS5Cl solid ion conductor pellet, 300 mg of solid ion conductor pellets prepared according to Examples 1 to 5 and Comparative Examples 1 to 4, and SUS, and then compacting it to 4t. Cyclovoltametry analysis was performed on a cell in which the SUS electrode was the working electrode and the lithium electrode was the counter electrode by sweeping from -1.0 V to 4.0 V at a sweep rate of 0.1 mV / s. The threshold of the reduction current was set as the reduction potential of the solid electrolyte. The 0 V reduction current was obtained from the above cyclovoltametry analysis. Some or all of the results are shown in Fig. 7 and Table 2 below.

[0252] Reduction potential (V) 0V reduction current (mA / cm²) 2 ) Example 1 -0.02 0.004 Example 2 -0.02 0.003 Example 3 -0.02 0.010 Example 4 -0.02 0.002 Example 5 -0.01 0.098 Comparative Example 1 0.44 0.28 Comparative Example 2 0.44 0.25 Comparative Example 3 1.7 0.62 Comparative Example 4 0.44 1.01

[0253] Referring to FIG. 7 and Table 2, the cell using the solid ion conductor pellets prepared according to Examples 1 to 5 as the solid electrolyte had a reduction potential of 0 V or less with respect to the lithium metal electrode, and a 0 V reduction current of 0.1 mA / cm² 2 It was less than or equal to. In comparison, the cell using the solid ion conductor pellets prepared according to Comparative Examples 1 to 4 as the solid electrolyte had a reduction potential of 0.44 V or higher for the lithium metal electrode and a 0 V reduction current of 0.25 mA / cm² 2 That was all.

[0254] From this, it can be confirmed that the cell using the solid ion conductor pellets prepared according to Examples 1 to 5 as a solid electrolyte has significantly improved stability for the lithium metal electrode compared to the cell using the solid ion conductor pellets prepared according to Comparative Examples 1 to 4 as a solid electrolyte.

[0256] Evaluation Example 2: Charge / Discharge Profile

[0257] The all-solid-state secondary battery prepared according to Example 1 at 25°C and a voltage range of 2.5 to 4.2 V at 1C = 1.9 mA / cm² 2 Charge and discharge were performed at a current rate of 0.025-1C. The battery was charged with a constant current of 0.05C until the battery voltage reached 4.2 V, and then discharged with a constant current of 0.025C until the battery voltage reached 2.5 V (1st cycle).

[0258] Then, the battery was charged with a constant current of 0.1C until the battery voltage reached 4.2 V, and then discharged with a constant current of 0.03C until the battery voltage reached 2.5 V (2nd cycle).

[0259] Then, the battery was charged with a constant current of 0.1C until the battery voltage reached 4.2 V, and then discharged with a constant current of 0.5C until the battery voltage reached 2.5 V (3rd cycle).

[0260] Then, the battery was charged with a constant current of 0.03C until the battery voltage reached 4.2 V, and then discharged with a constant current of 1C until the battery voltage reached 2.5 V (4th cycle).

[0262] After performing each charge and discharge, the voltage profile is shown in Fig. 8.

[0263] Referring to Fig. 8, it can be confirmed that the all-solid-state secondary battery prepared according to Example 1 reversibly exhibits a positive capacity of about 200 mAh / g. Explanation of the symbols

[0264] 1, 1a: All-solid-state secondary battery 10: Cathode layer 11: Positive current collector 12: Positive active material layer 20: Cathode layer 21: Cathode current collector 22: Cathode active material layer 23: Metal layer 24: Thin film 30: Solid electrolyte layer

Claims

Claim 1 A solid ionic conductor comprising the following compound represented by the following chemical formula 5 or chemical formula 6: <Chemical Formula 5>Li p M q X r-w O w In the above Chemical Formula 5, M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, X is one or more elements selected from Cl or Br, 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 0 < w / q < 0.

5. <Chemical Formula 6> Li p M q M' z X r-w O w In the above chemical formula 6, M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, M' is one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, X is one or more elements selected from Cl or Br, 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 2 < p / q ≤ 6, 0 < w / q < 0.

5. Claim 2 In claim 1, the compound is Li 3.6 Lu 0.9 Cl 5.7 O 0.3 , Li 3.6 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Ho 0.9 Cl 5.7 O 0.3 , Li 3.6 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Nd 0.9 Cl 5.7 O 0.3 , Li 3.6 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Sm 0.9 Cl 5.7 O 0.3 , Li 3.6 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Eu 0.9 Cl 5.7 O 0.3 , Li 3.6 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Gd 0.9 Cl 5.7 O 0.3 , Li 3.6 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Tb 0.9 Cl 5.7 O 0.3 , Li 3.6 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Dy 0.9 Cl 5.7 O 0.3 , Li 3.6 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Tm 0.9 Cl 5.7 O 0.3 , Li 3.6 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Yb 0.9 Cl 5.7 O 0.3 , Li 3.6 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 Ga 0.9 Cl 5.7 O 0.3 , Li 3.6 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.6 In 0.9 Cl 5.7 O 0.3 , Li 3.6 In 0.9 Cl 1.7 Br4O 0.3 ;Li 3.57 Na 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Na 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;Li 3.57 K 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 K 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;Li 3.57 Cs 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Ho 0.9 Cl 1.7 Br4O 0.3 , L 3.57 Cs 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Cs 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cs 0.03 In 0.9 Cl 1.7 Br4O 0.3 ;There 3.57 Cu 0.03 Lu 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 I have 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , There 3.57 Cu 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 The 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 The 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 The 0.03 You 0.9 Cl 1.7 Br4O 0.3 ; The 3.57 Ag 0.03 Ridiculous 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Your 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Nd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Sm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Eu 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Gd 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Tb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Dy 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Tm 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Yb 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 Ga 0.9 Cl 1.7 Br4O 0.3 , Li 3.57 Ag 0.03 In 0.9 Cl 1.7 Br4O 0.3 ; or Li 3.2 LuCl6O 0.1 , Li 3.2 HoCl6O 0.1 , Li 3.2 NdCl6O 0.1 , Li 3.2 SmCl6O 0.1 , Li 3.2 EuCl6O 0.1 , Li 3.2 GdCl6O 0.1 , Li 3.2 TbCl6O 0.1 , Li 3.2 DyCl6O 0.1 , Li 3.2 ErCl6O 0.1 , Li 3.2 TmCl6O 0.1 , Li 3.2 YbCl6O 0.1 , Li 3.2 GaCl6O 0.1 , Li 3.2 InCl6O 0.1 , Li 3.2 CeCl6O 0.1 , Li 3.2 PrCl6O 0.1 A solid ion conductor containing Claim 3 In claim 1, the compound is a solid ion conductor having a distorted rock-salt type structure. Claim 4 A solid ion conductor according to claim 1, wherein the compound is a crystal structure in which X anions are located at the edges centered around an M metal having an oxidation number of +3, and MX6 (X = one or more of halogen elements) octahedra are located in an edge-sharing manner, and oxygen anions are located in some of the X anion sites. Claim 5 A solid ion conductor having a crystal structure in which the compound has lithium ion transport channels in three-dimensional regions in the x-axis, y-axis, and z-axis directions other than the region where the MX6 (X = one or more of the halogen elements) octahedron is located within the crystal structure. Claim 6 In claim 4, the solid ion conductor having lithium ion transport channels connected in three dimensions within the crystal structure of the compound. Claim 7 In claim 1, the solid ion conductor is 1.0 x 10 at 25°C -5 mS·cm -1 A solid ion conductor having an ion conductivity greater than or equal to the above. Claim 8 A solid electrolyte comprising a solid ion conductor according to any one of claims 1 to 7. Claim 9 In claim 8, the solid electrolyte is an electrochemically stable solid electrolyte in a voltage window of 0.6 V to 4.3 V (vs. Li). Claim 10 An electrochemical device comprising an anode layer, a cathode layer, and a solid electrolyte layer, and a solid electrolyte according to claim 8. Claim 11 In claim 10, the electrochemical device comprising the solid electrolyte in the anode layer, the cathode layer, the solid electrolyte layer, the anode layer protective film, the cathode layer protective film, or a combination thereof. Claim 12 An electrochemical device comprising, in claim 10, a positive electrode layer selected from a positive electrode active material comprising a lithium transition metal oxide, a lithium transition metal phosphate, a sulfide, or a combination thereof, and a solid electrolyte. Claim 13 In claim 10, the electrochemical device wherein the cathode layer comprises lithium metal or lithium alloy. Claim 14 In claim 10, an electrochemical device in which the reduction potential of the solid electrolyte for lithium metal is 0 V or less. Claim 15 In item 10, the 0 V reduction current of the solid electrolyte relative to lithium metal is 0.1 mA / cm 2 Electrochemical device with less than 100 Claim 16 In claim 10, the electrochemical device comprising a solid electrolyte layer comprising a solid electrolyte, a sulfide-based solid electrolyte, or a combination thereof. Claim 17 In claim 16, the electrochemical device comprising a solid electrolyte represented by the following chemical formula 7, wherein the sulfide-based solid electrolyte is: <Chemical Formula 7>Li + 12-n-z A n+ X 2- 6-z Y' - z In the above chemical formula 7, A is P, As, Ge, Ga, Sb, Si, Sn, Al, In, Tl, V, Nb, or Ta, X is S, Se, or Te, Y' is Cl, Br, I, F, CN, OCN, SCN, or N3, and 1 < n < 5, 0 < z < 2. Claim 18 In claim 10, an electrochemical device having a thickness of 10 micrometers (㎛) to 1 millimeter (㎜) of the solid electrolyte layer. Claim 19 In item 10, the electrochemical device is an all-solid-state secondary battery or a metal-air battery. Claim 20 A method for manufacturing a solid ion conductor comprising: a step of preparing a precursor for forming a solid ion conductor; a step of performing mechanical milling on the precursor for forming a solid ion conductor to provide a precursor mixture for forming a solid ion conductor; and a step of molding the precursor mixture for forming a solid ion conductor to manufacture a solid ion conductor comprising a compound represented by the following chemical formula 5 or chemical formula 6: <Chemical Formula 5> Li p M q X r-w O w In the above Chemical Formula 5, M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, X is one or more elements selected from Cl or Br, 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 0 < w / q < 0.

5. <Chemical Formula 6> Li p M q M' z X r-w O w In the above chemical formula 6, M is one or more metals selected from Lu, Ho, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Ga, or In having an oxidation number of +3, M' is one or more metals selected from Na, K, Cs, Cu, or Ag having an oxidation number of +1, X is one or more elements selected from Cl or Br, 0 < p < 4, 0.5 < q < 1.5, 0 < r < 6.5, 0 < w < 1, and 2 < p / q ≤ 6, 0 < w / q < 0.

5. Claim 21 A method for manufacturing a solid ion conductor according to claim 20, wherein the mechanical milling is a ball mill, airjet mill, bead mill, roll mill, planetary mill, hand milling, high energy ball mill, planetary mill ball mill, stirred ball mill, vibrating mill, mechanofusion milling, shaker milling, planetary milling, atritor milling, disk milling, shape milling, nauta milling, nobilta milling, high speed mix, or a combination thereof. Claim 22 In claim 20, the above mechanical milling is planetary milling and is a method for manufacturing a solid ion conductor performed at room temperature. Claim 23 A method for manufacturing a solid ion conductor according to claim 20, further comprising a step of leaving it after the above mechanical milling. Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete

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