Solid electrolyte and preparing method thereof

Abstract

A method of preparing a solid electrolyte includes preparing a mixed powder with a sulfur powder, a phosphorus powder and a lithium powder. The sulfur in the sulfur powder, the phosphorus in the phosphorus powder, and the lithium in the lithium powder are each in an elemental form. The mixed powder is milled to obtain an amorphous powder. The method includes heat-treating the amorphous powder to form a crystallized solid electrolyte.

Claims

1. A method of preparing a solid electrolyte, the method comprising: preparing a mixed powder comprising a sulfur powder, a phosphorus powder, a lithium powder, and a nickel powder, wherein the sulfur in the sulfur powder, the phosphorus in the phosphorus powder, the lithium in the lithium powder, and the nickel in the nickel powder are each in an elemental form; milling the mixed powder to obtain an amorphous powder; and heat-treating the amorphous powder to form a crystallized solid electrolyte, wherein the sulfur powder, the phosphorus powder, the lithium powder, and the nickel powder are mixed according to a composition of Li.sub.aP.sub.bS.sub.cNi.sub.d (12a18, 0.8b6.4, 13.2c26, 1.2d9.6).

2. The method of claim 1, wherein the mixed powder consists of the sulfur powder, the phosphorus powder, and the lithium powder.

3. The method of claim 1, wherein the amorphous powder is obtained by milling the mixed powder under conditions of 300 RPM to 1000 RPM and 4 hrs to 40 hrs by using a planetary mill.

4. A method of preparing a solid electrolyte, the method comprising: preparing a mixed powder comprising a sulfur powder, a phosphorus powder, a lithium powder, and a nickel powder, wherein the sulfur in the sulfur powder, the phosphorus in the phosphorus powder, the lithium in the lithium powder, and the nickel in the nickel powder are each in an elemental form; milling the mixed powder to obtain an amorphous powder, wherein the milling comprises: forming a slurry by mixing a 1 wt % to 50 wt % of the mixed powder with 50 wt % to 99 wt % of a solvent and then wet milling the slurry to obtain the amorphous powder; and heat-treating the amorphous powder to form a crystallized solid electrolyte, wherein heat-treating the amorphous powder comprises heat-treating the wet milled slurry, wherein the sulfur powder, the phosphorus powder, the lithium powder, and the nickel powder are mixed according to a composition of Li.sub.aP.sub.bS.sub.cNi.sub.d (12a18, 0.8b6.4, 13.2c26, 1.2d=9.6).

5. The method of claim 4, wherein the solvent is at least one selected from a group consisting of: at least one hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, and methyl cyclohexane; at least one BTX-based solvent of benzene, toluene, xylene, and ethylbenzene; at least one ether-based solvent of diethyl ether, tetrahydrofuran, and 1,4-dioxane; at least one ester-based solvent of ethyl propionate, and propyl propionate; or a mixture thereof.

6. The method of claim 1, wherein the milling comprises dry milling.

7. The method of claim 1, wherein the heat-treating comprises heat-treating the amorphous powder at 200 C. to 500 C. and 1 min to 100 hrs.

8. The method of claim 1, wherein the preparing, the milling, and the heat-treating are performed in a dry room.

9. A method of preparing a solid electrolyte, the method comprising: preparing a mixed powder comprising a sulfur powder, a phosphorus powder, a lithium powder, and a nickel powder, wherein the sulfur in the sulfur powder, the phosphorus in the phosphorus powder, the lithium in the lithium powder, and the nickel in the nickel powder are each in an elemental form; adding the mixed powder in to a solvent; wet milling the mixed powder in the solvent, wherein the wet milling amorphizes the mixed powder in the solvent; and heat-treating the amorphized mixed powder in the solvent, wherein the heat-treating removes the solvent and crystallizes the amorphized mixed powder to form the solid electrolyte, wherein the sulfur powder, the phosphorus powder, the lithium powder, and the nickel powder are mixed according to a composition of LiaPbScNid (12a18, 0.8b6.4, 13.2c26, 1.2d9.6).

10. The method of claim 9, wherein the mixed powder consists of the sulfur powder, the phosphorus powder, and the lithium powder.

11. The method of claim 9, wherein the wet milling comprises milling the mixed powder under conditions of 300 RPM to 1000 RPM and 4 hrs to 40 hrs by using a planetary mill.

12. The method of claim 9, wherein adding the mixed powder in to the solvent comprises: mixing a 1 wt % to 50 wt % of the mixed powder with 50 wt % to 99 wt % of the solvent.

13. The method of claim 9, wherein the solvent is a solvent selected from a group consisting of: a hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, or methyl cyclohexane; a BTX-based solvent of benzene, toluene, xylene, or ethylbenzene; an ether-based solvent of diethyl ether, tetrahydrofuran, or 1,4-dioxane; and an ester-based solvent of ethyl propionate, or propyl propionate.

14. The method of claim 9, wherein the heat-treating comprises heat-treating at 200 C. to 500 C. and 1 min to 100 hrs.

15. The method of claim 9, wherein the preparing, the adding, the wet milling, and the heat-treating are performed in a dry room.

16. The method of claim 4, wherein the mixed powder consists of the sulfur powder, the phosphorus powder, and the lithium powder.

17. The method of claim 4, wherein the amorphous powder is obtained by milling the mixed powder under conditions of 300 RPM to 1000 RPM and 4 hrs to 40 hrs by using a planetary mill.

18. The method of claim 4, wherein the heat-treating comprises heat-treating the amorphous powder at 200 C. to 500 C. and 1 min to 100 hrs.

19. The method of claim 4, wherein the preparing, the milling, and the heat-treating are performed in a dry room.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated in the accompanying drawings which are given herein below by way of illustration only, and thus are not limitative of the present invention, and wherein:

(2) FIG. 1 schematically illustrates a method of preparing a solid electrolyte according to the present invention;

(3) FIG. 2 is a scanning electron microscope (SEM) measurement result for a solid electrolyte in Examples 1 to 3. FIG. 2A is a result for Example 1, FIG. 2B is a result for Example 2, and FIG. 2C is a result for Example 3;

(4) FIG. 3 is an X-ray diffraction spectroscopy (XRD) result for the solid electrolyte in Examples 1 to 3;

(5) FIG. 4 is an SEM measurement result for a solid electrolyte in Example 4;

(6) FIG. 5 is an SEM measurement result for a solid electrolyte in Example 5;

(7) FIG. 6 is a result of measuring a current when predetermined voltage is applied to the solid electrolyte in Examples 1 and 4;

(8) FIG. 7 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte is applied in Example 1;

(9) FIG. 8 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte is applied in Example 4; and

(10) FIG. 9 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte is applied in Example 5.

(11) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.

(12) In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(13) Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.

(14) Hereinafter, the present invention will be described in detail through exemplary embodiments. The exemplary embodiments of the present invention may be modified in various forms as long as the gist of the invention is not changed. However, the scope of the present invention is not limited to the following exemplary embodiments.

(15) When it is determined that the description for the known configurations and functions may obscure the gist of the present invention, the description for the known configurations and functions will be omitted. In this specification, the term comprise means that other constituent elements may be further included unless otherwise listed.

(16) A solid electrolyte derived from a single element according to the present invention may include a sulfur (S) element derived from a simple substance sulfur powder, a phosphorus (P) element derived from a simple substance phosphorus powder and a lithium (Li) element derived from a simple substance lithium powder.

(17) As illustrated in FIG. 1, the solid electrolyte derived from the single element may be prepared by (1) preparing a mixed powder containing a simple substance sulfur powder, a simple substance phosphorus powder and simple substance lithium powder (S1), (2) milling and amorphizing the mixed powder (S2), and (3) heat-treating and crystallizing the amorphized mixed powder (S3).

(18) In this specification, the simple substance means a single element material constituted by a single element to have a unique chemical property. Accordingly, the simple substance sulfur powder means a powder state of the simple substance sulfur which is constituted by only the sulfur (S) element to have a unique chemical property, the simple substance phosphorus powder means a powder state of the simple substance phosphorus which is constituted by only the phosphorus (P) element to have a unique chemical property, and the simple substance lithium powder means a powder state of the simple substance lithium which is constituted by only the lithium (Li) element to have a unique chemical property.

(19) In the related art, in order to manufacture the sulfide-based solid electrolyte such as Li.sub.3PS.sub.4, a starting material in which Li.sub.2S and P.sub.2S.sub.5 are mixed at a mole % ratio of 75:25 was used. In the related art, in the case of using a compound type starting material, material cost is very high. In the case of the starting material (75Li.sub.2S-25P.sub.2S.sub.5), the material cost reaches about 5 million won/kg (approximately USD$4500/Kg). Further, since Li.sub.2S is vulnerable to moisture and P.sub.2S.sub.5 is a compound that has a high risk of explosion in air, the materials need to be handled in a separate glove box.

(20) Embodiments of the present invention are contrived to solve the above problems and constraints and have a technical feature that the solid electrolyte is prepared from the starting material mixed by measuring the simple substance sulfur powder, the simple substance phosphorus powder, and the simple substance lithium powder according to the composition of the desired solid electrolyte.

(21) In various embodiments of the present invention, since the simple substance sulfur powder, the simple substance phosphorus powder, the simple substance lithium powder, and the like are used as the starting material, the material cost is about 150,000 won/kg (approximately USD$135/Kg) and thus the solid electrolyte may be prepared at significantly low cost compared to the case of using the compound type powder. That is, embodiments of the present invention have a technical significance in that it is verified that when the solid electrolyte is prepared by amorphizing and crystallizing the mixed powder, the solid electrolyte having excellent lithium ion conductivity, discharging capacity when applied to the battery, and the like can be obtained at low cost.

(22) Embodiments of the present invention have advantages of preparing the solid electrolyte safely and easily without requiring a separate device such as a glove box because a compound type starting material which is harmful to the human body, vulnerable to moisture, or has the risk of explosion is not used.

(23) In particular, step (1) is a step of preparing the mixed powder containing the simple substance sulfur powder, the simple substance phosphorus powder, and the simple substance lithium powder.

(24) The simple substance lithium powder may be replaced with a single material containing a lithium metal. The single material may correspond to any material which may be mixed and amorphized with the simple substance sulfur powder, the simple substance phosphorus powder, and the like by milling and the like, not the compound type, and for example, lithium foil and the like.

(25) According to an exemplary embodiment of the present invention, step (1) may be a step of preparing a mixed powder by measuring and mixing the simple substance sulfur powder, the simple substance phosphorus powder, and the simple substance lithium powder according to a composition of Li.sub.2xP.sub.2yS.sub.x+5y (0.65x0.85, 0.15y0.35) which is a desired solid electrolyte.

(26) Step (2) may be a step of milling and amorphizing the mixed powder. Particularly, the amorphizing may be milling the mixed powder under conditions of 300 RPM to 1,000 RPM and 4 hrs to 40 hrs by using a planetary mill.

(27) The amorphizing may be performed by wet milling or dry milling and preferably performed by wet milling for uniform formation of the crystal when the crystallization is performed through heat-treating.

(28) The wet milling may be wet milling by mixing 1 wt % to 50 wt % of the mixed powder and 50 wt % to 99 wt % of the solvent, preferably 4 wt % to 20 wt % of the mixed powder and 80 wt % to 96 wt % of the solvent, and more preferably 5 wt % to 15 wt % of the mixed powder and 75 wt % to 95 wt % of the solvent. When the mixed powder is less than 1 wt %, the yield is too low and thus it may not be suitable for mass production, and when the mixed powder is more than 50 wt %, it may be difficult to obtain a uniformly amorphized material like dry milling.

(29) The solvent may be any one selected from a group consisting of at least one hydrocarbon-based solvent of pentane, hexane, 2-ethyl hexane, heptane, octane, cyclohexane, and methyl cyclohexane; at least one BTX-based solvent of benzene, toluene, xylene, and ethylbenzene; at least one ether-based solvent of diethyl ether, tetrahydrofuran and 1,4-dioxane; and at least one ester-based solvent of ethyl propionate and propyl propionate, or a mixed solvent thereof. However, in embodiments of the present invention, the solvent is not limited thereto and it is understood that the solvent includes all solvents which are mainly used for wet milling through a planetary mill.

(30) Step (3) may be a step of heat-treating and crystallizing the amorphized mixed powder through milling. In detail, the crystallization may be heat-treating the mixed powder under conditions of 200 C. to 500 C. and 1 min to 100 hrs.

(31) In the case of amorphizing the mixed powder through wet milling in step (2), a drying step before performing step (3) may be further performed. The dry step is to remove the remaining solvent in the milled mixed powder and may be vacuum drying, heat drying, or vacuum and heat drying under conditions of room temperature to 200 C. and 1 min to 10 hrs.

(32) The preparing method of the solid electrolyte derived from the single element according to the present invention does not need to be performed in the glove box because the mixed powder is used as the starting material. Accordingly, steps (1) to (3) may be performed in a dry room.

(33) According to another exemplary embodiment of the present invention, in step (1), the simple substance nickel powder is further mixed with the mixed powder to obtain a solid electrolyte further containing a nickel (Ni) element derived from the simple substance nickel powder.

(34) Particularly, steps (2) and (3) are performed by using the mixed powder, as the starting material, mixed by measuring the simple substance sulfur powder, the simple substance phosphorus powder, the simple substance lithium powder and the simple substance nickel powder in step (1) according to a composition of Li.sub.aP.sub.bS.sub.cNi.sub.d (12a18, 0.8b6.4, 13.2c26, 1.2d9.6) as a desired solid electrolyte, respectively, to prepare the solid electrolyte containing the nickel element.

(35) According to yet another exemplary embodiment of the present invention, the simple substance nickel powder and a lithium chloride (LiCl) powder are further mixed in the mixed powder in step (1) to obtain the solid electrolyte containing a nickel (Ni) element derived from the simple substance nickel powder and a chlorine (Cl) element derived from the lithium chloride powder.

(36) Particularly, steps (2) and (3) are performed by using the mixed powder, as the starting material, mixed by measuring the simple substance sulfur powder, the simple substance phosphorus powder, the simple substance lithium powder, the simple substance nickel powder and the lithium chloride powder in step (1) according to a composition of Li.sub.aP.sub.bS.sub.cNi.sub.dCl.sub.e (12a22, 0.8b6.4, 13.2c26, 1.2d9.6, 1e4) as a desired solid electrolyte, respectively, to prepare the solid electrolyte containing the nickel element and the chloride element.

(37) As such, the present invention has an advantage in that the composition of the solid electrolyte is easily changed, removed, and added by using the simple substance phosphorus material, not the compound type material as the starting material. Accordingly, the present invention can also provide induction in the development of solid electrolytes having various compositions.

(38) Hereinafter, the present invention will be described in more detail through detailed Examples and Test Examples. However, these Examples and Test Examples are to exemplify the present invention and the scope of the present invention is not limited thereto.

EXAMPLES

(39) The following examples illustrate the invention and are not intended to limit the same.

Example 1

(40) In order to prepare a solid electrolyte represented by Li.sub.3PS.sub.4(75Li.sub.2S-25P.sub.2S.sub.5), the following steps were performed. A simple substance sulfur powder (Sigma Aldrich Corporation, sulfur), a simple substance phosphorus powder (Sigma Aldrich Corporation, phosphorous), and a simple substance lithium powder (FMC Corporation, lithium powder) were used as a starting material. 7.12 g of the simple substance sulfur powder, 1.72 g of the simple substance phosphorus powder, and 1.16 g of the simple substance lithium powder were measured and mixed to have the same composition ratio (mole ratio) as 75Li.sub.2S-25P.sub.2S.sub.5 to prepare a mixed powder. 82.5 g of xylene was mixed with the mixed powder and then put into a planetary ball mill container together with 575 g of zirconia balls. The mixed powder was milled and amorphized at about 360 RPM. Thereafter, the obtained mixed powder was vacuum-dried for 2 hrs at about 160 C. to remove the remaining xylene. Next, the mixed powder was heat-treated for 2 hrs at 230 C. and crystallized to obtain the solid electrolyte.

Example 2

(41) Except for using lithium foil (HONJO METAL Corporation, purity 99.9%) instead of the simple substance lithium powder as a starting material, a solid electrolyte was prepared by the same material and method as Example 1.

Example 3

(42) In order to prepare a solid electrolyte represented by Li.sub.3PS.sub.4(75Li.sub.2S-25P.sub.2S.sub.5), the following steps were performed. A simple substance sulfur powder (Sigma Aldrich Corporation, sulfur), a simple substance phosphorus powder (Sigma Aldrich Corporation, phosphorous), and lithium foil (HONJO METAL Corporation, purity 99.9%) were used as a starting material. 7.12 g of the simple substance sulfur powder, 1.72 g of the simple substance phosphorus powder, and 1.16 g of the lithium foil were measured and mixed to have the same composition ratio (mole ratio) as 75Li.sub.2S-25P.sub.2S.sub.5 to prepare a mixed powder. The mixed powder was put into a planetary ball mill container together with 300 g of zirconia balls. The mixed powder was milled and amorphized at about 360 RPM. Next, the mixed powder was heat-treated for 2 hrs at 230 C. and crystallized to obtain the solid electrolyte.

(43) FIG. 2 is a scanning electron microscope (SEM) measurement result for a solid electrolyte in Examples 1 to 3. FIG. 2A is a result for Example 1, FIG. 2B is a result for Example 2, and FIG. 2C is a result for Example 3.

(44) It can be seen that the crystal of the solid electrolyte in Example 1 (the simple substance lithium powder and wet milling) is uniformly formed and it can be verified that in Example 2 (lithium foil and wet milling) and Example 3 (lithium foil and dry milling), the formation of crystals is slightly uneven.

(45) This can be seen from an X-ray diffraction spectroscopy (XRD) result for the solid electrolyte in Examples 1 to 3 in FIG. 3. It can be verified that the solid electrolyte in Example 1 has substantially the same peak as Li.sub.3PS.sub.4 which is a similar phase as THIO-LISICON III, whereas in the solid electrolytes in Examples 2 and 3, the peaks are clearly separated and not measured and thus the growth and the uniformity of the crystals slightly deteriorate.

(46) Accordingly, in the preparation of the solid electrolyte according to the present invention, like Example 1, the mixed powder may be prepared by using a simple substance lithium powder as a starting material and amorphized by wet milling and then crystallized.

Example 4

(47) In order to prepare a solid electrolyte represented by Li.sub.16P.sub.4S.sub.20Ni.sub.3(8Li.sub.2S-2P.sub.2S.sub.5-1Ni.sub.3S.sub.2), the following steps were performed. As a starting material, a simple substance sulfur powder, a simple substance phosphorus powder, a simple substance lithium powder and a simple substance nickel powder were used. 6.09 g of the simple substance sulfur powder, 1.18 g of the simple substance phosphorus powder, 1.06 g of the simple substance lithium powder, and 1.67 g of the simple substance nickel powder were measured and mixed to have the same composition ratio (mole ratio) as 8Li.sub.2S-2P.sub.2S.sub.5-1Ni.sub.3S.sub.2 to prepare a mixed powder. 82.5 g of xylene was mixed with the mixed powder and then put into a planetary ball mill container together with 575 g of zirconia balls. The mixed powder was milled and amorphized at about 360 RPM. Thereafter, the obtained mixed powder was vacuum-dried for 2 hrs at about 160 C. to remove the remaining xylene. Next, the mixed powder was heat-treated for 2 hrs at 260 C. and crystallized to obtain the solid electrolyte.

Example 5

(48) In order to prepare a solid electrolyte represented by Li.sub.20P.sub.4S.sub.20Ni.sub.3Cl.sub.4(8Li.sub.2S-2P.sub.2S.sub.5-1Ni.sub.3S.sub.2-4LiCl), the following steps were performed. As a starting material, a simple substance sulfur powder, a simple substance phosphorus powder, a simple substance lithium powder, a simple substance nickel powder and a lithium chloride powder were used. 5.25 g of the simple substance sulfur powder, 1.01 g of the simple substance phosphorus powder, 0.91 g of the simple substance lithium powder, 1.44 g of the simple substance nickel powder, and 1.39 g of the lithium chloride powder were measured and mixed to have the same composition ratio (mole ratio) as 8Li.sub.2S-2P.sub.2S.sub.5-1Ni.sub.3S.sub.2-4LiCl to prepare a mixed powder. 82.5 g of xylene was mixed with the mixed powder and then put into a planetary ball mill container together with 575 g of zirconia balls. The mixed powder was milled and amorphized at about 360 RPM. Thereafter, the obtained mixed powder was vacuum-dried for 2 hrs at about 160 C. to remove the remaining xylene. Next, the mixed powder was heat-treated for 2 hrs at 260 C. and crystallized to obtain the solid electrolyte.

(49) FIG. 4 is an SEM measurement result for a solid electrolyte in Example 4 and FIG. 5 is an SEM measurement result for a solid electrolyte in Example 5. In Examples 4 and 5, like Example 1, it can be seen that the simple substance lithium powder is used as the starting material and amorphized by wet milling and then crystallized, and thus the crystals are uniformly formed.

(50) Hereinafter, for convenience of description, the solid electrolytes in Examples 1, 4, and 5 are referred to as LSPS, LNPS and LNPS-Cl, respectively, and called according to a kind of element included in each solid electrolyte.

TEST EXAMPLES

Test Example 1

(51) Lithium-ionic conductivities of solid electrolytes in Example 1 (LSPS), Example 4 (LNPS) and Example 5 LNPS-Cl) were measured. LSPS, LNPS and LNPS-Cl were compressively molded to form a molding body for measurement (with a diameter of 13 mm and a thickness of 0.6 mm). An AC potential of 10 mV was applied to the molding body and then an impedance value was measured by performing a frequency sweeping of 110.sup.6 to 100 Hz to see lithium-ion conductivity.

(52) As a result, the lithium-ionic conductivities of 1.010.sup.4 S/cm of the LSPS in Example 1, 1.410.sup.4 S/cm of the LNPS in Example 4, and 1.410.sup.3 S/cm of the LNPS-Cl in Example 5 were shown.

Test Example 2

(53) The lithium ion transport number of the solid electrolytes according to Example 1 (LSPS) and Example 4 (LNPS) was measured. LSPS and LNPS were compressively molded to form a molding body for measurement (with a diameter of 13 mm and a thickness of 0.6 mm). Then, a current was measured by applying 1 V. The result is illustrated in FIG. 6.

(54) Resistance values R of the LSPS and the LNPS were calculated through FIG. 6 and the Ohm's law (V=IR). Electronic conductivity (1/Rt/A) was calculated from the resistance value R, a cross-sectional area A of the molding body for measurement, and a thickness t of the molding body for measurement. The electronic conductivity of the LSPS was calculated as 1.9410.sup.9 S/cm, and the electronic conductivity of the LNPS was calculated as 1.8810.sup.9 S/cm. Next, the lithium ion transport number (.sub.i/.sub.e+.sub.i), .sub.i is conductivity of lithium ions and .sub.e is conductivity of electrons) was calculated from the electronic conductivity.

(55) As a result, the lithium ion transport number of the LSPS was calculated as 0.9999981 and the lithium ion transport number of the LNPS was calculated as 0.9999963 to be very close to 1.

(56) Referring to the results of Test Examples 1 and 2, it can be seen that the solid electrolyte prepared according to the present invention contributes to improvement of the characteristic of the all solid-state battery because the lithium-ionic conductivity is 10.sup.4 S/cm or more and the lithium ion transport number is approximately 1.

Test Example 3

(57) An all solid-state battery was manufactured by applying solid electrolytes in Example 1 (LSPS), Example (LNPS) and Example 5 (LNPS-Cl) to solid electrolyte layers and a discharge capacity was measured. The all solid-state battery was constituted by a positive electrode, a negative electrode, and a solid electrolyte layer interposed between the positive electrode and the negative electrode. The solid electrolyte layer was formed with a thickness of 500 m by compressively molding the LSPS, the LNPS, and the LNPS-Cl, and as the positive electrode, a powder containing an active material (Nb-coated NCM622), a solid electrolyte (a solid electrolyte used in the solid electrolyte layer), and a conductive material (Super C) was formed on the solid electrolyte layer with an active material loading amount of 5.8 mg/cm.sup.2 and a thickness of 30 m, and as the negative electrode, indium foil with a thickness of 100 m was used.

(58) With respect to the all solid-state battery, a discharge capacity was measured by performing charging and discharging under a constant current (CC) condition in a range of 2 V to 3.58 V at rate limiting of 0.02 C rate.

(59) FIG. 7 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte (LSPS) of Example 1 is applied. It can be seen that when the LSPS is applied to the solid electrolyte layer, a discharge capacity of about 140 mAh/g may be implemented.

(60) FIG. 8 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte (LNPS) of Example 4 is applied. It can be seen that when the LNPS is applied to the solid electrolyte layer, a discharge capacity of about 110.3 mAh/g may be implemented.

(61) FIG. 9 is a result of measuring a discharge capacity of an all solid-state battery to which the solid electrolyte (LNPS-Cl) of Example 5 is applied. It can be seen that when the LNPS-Cl is applied to the solid electrolyte layer, a discharge capacity of about 111.7 mAh/g may be implemented.

(62) According to the solid electrolyte derived from the single element and the preparing method thereof according to the present invention through Test Examples 1 to 3, it can be seen that the solid electrolyte capable of implementing equivalent or higher lithium-ionic conductivity and a discharge capacity can be obtained at much lower material costs than the related art.

(63) Accordingly, embodiments of the present disclosure describe a solid electrolyte derived from single element powders and not based on compound powders.

(64) The present invention proposes a new paradigm for the solid electrolyte and the preparing method thereof beyond the old framework in the related art. Therefore, it will be apparent to those skilled in the art that clues capable of overcoming the limitations of mass production and a large area of the all solid-state battery can be obtained from the present invention.

(65) The invention has been described in detail with reference to preferred embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.