Positive electrode composition for all-solid-state battery and all-solid-state battery using the same

Abstract

To provide a positive electrode composition for an all-solid-state battery and an all-solid-state battery using the same which can improve the conductivity of the all-solid-state battery and achieve a theoretical specific capacity while using sulfur as an electrode.SOLUTION: There are provided a positive electrode composition for the all-solid-state battery which includes a complex of (1) S-C-PXn in which S is elemental sulfur, C is at least one conductive carbon, PXn is phosphorus halide, X is selected from Cl, Br, or I in the formula, n is an integer selected from 3 to 5, and at least one additive, a convenient method for preparing the positive electrode composition for the all-solid-state battery, and an all-solid-state battery with discharge capacity in the range of 1700 to 2200 mAh / g at a discharge rate of 1 / 30C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates generally to the field of batteries, and more particularly to all-solid-state batteries. The present disclosure particularly relates to positive electrode compositions in all-solid-state batteries. [Background technology]

[0002] Lithium-ion batteries are the battery of choice for hybrid and electric vehicles due to their high energy density and long life. Among the lithium-ion batteries, lithium-sulfur batteries, which have high specific energy, low cost, and flexibility, are attracting considerable attention as a promising power source for future flexible and wearable electronic devices. Sulfur has a theoretical specific capacity of 1672 mAhg -1 The high solubility of sulfur makes it a highly attractive candidate cathode material. Sulfur also has the advantages of being abundant, inexpensive, and environmentally friendly. This makes lithium-sulfur batteries a key player in next-generation energy storage systems. However, a variety of challenges have limited their large-scale commercial deployment so far.

[0003] Among the major issues limiting the use of sulfur as a cathode is its insulating properties, which reduces the electrochemical utilization of sulfur and limits its power output. This necessitates the use of various conductive additives that enable intimate contact between cathode particles. Significant efforts have been devoted to improving the lithium-sulfur system, and various types of conductive carbon materials and conductive polymers have been used to enhance the electronic conductivity of the cathode composite. To date, a number of interesting approaches have been successfully explored to develop sulfur cathodes with high specific capacity and good cycling performance.

[0004] However, the sulfur content in the sulfur composite or the sulfur loading mass on the electrode compromises the electrochemical performance improvement of sulfur cathode materials, which significantly reduces the overall energy density of lithium / sulfur batteries. Increasing the sulfur content usually leads to a significant decrease in the conductivity of the sulfur composite, while the optimal sulfur loading in the porous structure composite is determined by a balance between the desire to achieve increased capacity and the allowable volume change to ensure the stability of the cathode.

[0005] Patent Document 1 discloses metal sulfide and metal halide composites containing carbon additives to enhance electronic conductivity. Patent Document 2 discloses metal polysulfide composites containing carbon black as an additive. In addition to carbon-based additives, scientists have also used solid electrolytes to enhance ionic conductivity. Patent Document 3 discloses the use of metal sulfides and non-metal sulfides containing Li-based solid electrolytes for all-solid-state battery applications. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 201663877 [Patent Document 2] U.S. Patent No. 6,200,704 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-006674 Summary of the Invention [Problem to be solved by the invention]

[0007] Efforts are ongoing to identify suitable electrode modifications for practical application in all-solid-state batteries that can improve the conductivity and achieve theoretical specific capacity while using sulfur as an electrode. [Means for solving the problem]

[0008] In one embodiment of the present disclosure, there is provided a) a conjugate of formula I, Formula I SC-PX n wherein S is elemental sulfur; C is at least one conductive carbon; and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5; and b) at least one additive. A positive electrode composition for an all-solid-state battery is provided, comprising:

[0009] In another embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one conductive carbon to obtain a first mixture; b) grinding a phosphorus halide with the first mixture to obtain a second mixture; and c) contacting the second mixture with at least one additive to obtain a positive electrode composition for an all-solid-state battery.

[0010] In yet another embodiment of the present disclosure, there is provided a) a conjugate of formula I, Formula I SC-PX n wherein S is elemental sulfur; C is at least one conductive carbon; and PX n is a phosphorus halide, where X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5, and at least one additive; b) a negative electrode; and c) at least one solid electrolyte.

[0011] These and other features, aspects, and advantages of the present subject matter will become better understood with reference to the following description and appended claims. This Summary is provided to introduce a selection of concepts in a simplified form. It is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0012] The detailed description is set forth with reference to the accompanying drawings, in which the leftmost digit(s) of a reference number identifies the figure in which the reference number first appears, and the same numbers are used throughout the drawings to reference like features and components. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows a transmission electron microscope (TEM) image of positive electrode composition 1 according to one embodiment of the present disclosure. [Figure 2] FIG. 2 shows a transmission electron microscope (TEM) image of positive electrode composition 2, according to one embodiment of the present disclosure. [Figure 3] FIG. 3 illustrates the fabrication of an all-solid-state battery cell according to one embodiment of the present disclosure. [Figure 4] FIG. 4 shows the ionic resistance of a positive electrode composition according to one embodiment of the present disclosure. [Figure 5] FIG. 5 shows the charge transfer resistance of a positive electrode composition according to one embodiment of the present disclosure. [Figure 6] FIG. 6 shows a Nyquist plot of electrochemical impedance spectra (at 100% SOC and 0% SOC) of a positive electrode composition according to one embodiment of the present disclosure. [Figure 7] FIG. 7 shows the first cycle of constant current charging and discharging at a rate of 1 / 30C according to one embodiment of the present disclosure. [Figure 8] FIG. 8 shows the rate performance of a positive electrode composition according to one embodiment of the present disclosure. [Figure 9] FIG. 9 shows a broader range of rate capabilities for a positive electrode composition according to one embodiment of the present disclosure. [Figure 10] FIG. 10 shows the capacity-voltage curves for the third cycle of a positive electrode composition at a discharge rate of 1 / 30C, according to one embodiment of the present disclosure. [Figure 11] FIG. 11 shows the capacity-voltage curves of a positive electrode composition at a discharge rate of 1 / 10 C, according to one embodiment of the present disclosure. [Figure 12] FIG. 12 shows the capacity-voltage curves of a positive electrode composition at a discharge rate of 1 / 3 C, according to one embodiment of the present disclosure. [Figure 13] FIG. 13 shows the DC internal resistance of a battery having a positive electrode composition according to one embodiment of the present disclosure. [Figure 14] FIG. 14 shows the DC internal resistance of a battery at various discharge rates, according to one embodiment of the present disclosure. [Figure 15] FIG. 15 shows the DC internal resistance of batteries having various positive electrode compositions, according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] Those skilled in the art will recognize that the present disclosure is subject to variations and modifications other than those specifically described. It should be understood that the present disclosure encompasses all such variations and modifications. The present disclosure also encompasses all of the steps, features, compositions, and compounds referred to or shown herein, individually or collectively, and any and all combinations of one or more of any of such steps or features.

[0015] Definition: For convenience, before further description of the present disclosure, specific terms and examples used herein are summarized here.These definitions should be read in light of the remaining part of the present disclosure and understood as those skilled in the art would.Terms used herein have the meanings that are recognized and well-known to those skilled in the art, but for convenience and completeness, specific terms and their meanings are described below.

[0016] The articles "a", "an" and "the" are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

[0017] The terms "comprise" and "comprising" are used in an inclusive, open-ended sense and mean that additional elements may be included. The term is not intended to be construed as "consists of only."

[0018] Throughout this specification, unless the context requires otherwise, the words "comprise" and variations such as "comprises" and "comprising" will be understood to mean the inclusion of stated elements or steps or groups of elements or steps, but not the exclusion of other elements or steps.

[0019] The term "including" is used to mean "including but not limited to," and "including" and "including but not limited to" are used interchangeably.

[0020] The term "solid electrolyte" refers to a solid that exhibits high ionic conductivity through the movement of cations and anions. For example, in this disclosure, solid electrolyte refers to an electrolyte used in an all-solid-state battery cell / battery. The solid electrolyte in an all-solid-state battery cell / battery allows for the movement of ions without the need for a liquid or a flexible membrane separating the electrodes.

[0021] The term "activator" refers to a catalyst capable of enhancing the reaction rate. In this disclosure, the term activator refers to a phosphorous halide that mediates the conduction of Li ions by catalyzing the reaction rate of the conversion of lithium polysulfides to lithium sulfide.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this disclosure belongs.Methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, and suitable methods and materials are described below.All publications mentioned herein are incorporated herein by reference.

[0023] Ratios, concentrations, amounts, and other numerical data may be presented in range format herein. It should be understood that such range formats are used for convenience and brevity only, and should be interpreted flexibly to include each individual numerical value or subrange, as if all individual numerical values ​​or subranges within the range were expressly stated, rather than just the numerical values ​​stated as the endpoints of the range. For example, a weight range of about 50% to about 75% should be understood to include not only the stated endpoints of about 50% to about 75%, but also subranges such as 50% to 70%, 55% to 65%, etc., and individual amounts within the specified range, including fractions such as 50.5%, 58.2%, and 74.5%, for example.

[0024] The specific embodiments described herein are intended for the purpose of example only, and the present disclosure is not limited in scope by those specific embodiments. Products, compositions, and methods that are functionally equivalent to those described herein are clearly within the scope of the present disclosure.

[0025] To address the challenges discussed in the Background section, conductive carbon materials and activator components must be incorporated into sulfur-based positive electrodes to enhance their electronic and ionic conductivity. A key issue associated with the electrochemical process of Li / S battery operation is the easy dissolution of lithium polysulfides in most organic electrolytes when elemental sulfur reacts with lithium ions to form LiS. These intermediate products may participate in a "sulfur shuttle mechanism," whereby dissolved polysulfides migrate to the Li anode and form an electrochemically inactive layer composed of lithium polysulfides on the surface of the Li anode. These issues result in reduced active material utilization, shorter cycle life, and reduced system efficiency, as well as adversely affecting anode operation. To avoid these issues, an activator component is needed that can either prevent the formation of lithium polysulfides or convert them to eliminate the formation of the electrochemically inactive layer. The activator has strong adsorption and activation sites for polar polysulfides, which can catalyze the redox reaction of polysulfides to lithium sulfide. The activator also enhances Li-ion conduction in a manner that enhances Li-ion conduction. This disclosure discloses a sulfur-based composite for use in a cathode of an all-solid-state battery, which contains a carbon additive and a phosphorus halide activator component. The activator component serves a dual role in catalyzing the conversion of polysulfides to lithium sulfide, thereby preventing the formation of an electrochemically inactive layer and mediating Li-ion conduction. The cathode composite of this disclosure can achieve exceptional electrochemical performance with improved electronic and ionic conductivity.

[0026] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; and b) at least one additive.

[0027] In one embodiment of the present disclosure, a compound of formula I SC-PX n wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is Br and n is an integer selected from 3 to 5, and at least one additive. In another embodiment of the present disclosure, there is provided a positive electrode composition for an all-solid-state battery disclosed herein, wherein X is Cl and n is an integer selected from 3 to 5. In yet another embodiment of the present disclosure, there is provided a positive electrode composition for a battery disclosed herein, wherein X is I and n is an integer selected from 3 to 5.

[0028] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; and at least one additive, wherein the weight percentage of the composite of Formula I is in the range of 50% to 75% relative to the weight of the positive electrode composition.

[0029] In one embodiment of the present disclosure, there is provided a positive electrode composition for an all-solid-state battery disclosed herein, wherein the composite of Formula I has a weight percentage in the range of 50% to 75% relative to the positive electrode composition. In another embodiment of the present disclosure, the composite of Formula I has a weight percentage in the range of 55% to 70% relative to the positive electrode composition. In yet another embodiment of the present disclosure, the composite of Formula I has a weight percentage in the range of 58% to 65% relative to the positive electrode composition.

[0030] In one embodiment of the present disclosure, a) a compound of formula I SC-PX nwherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; and b) at least one additive, wherein S of the complex of Formula I has a weight percentage in the range of 35% to 45% relative to the composite; C of the complex of Formula I has a weight percentage in the range of 10% to 25% relative to the composite; PX of the complex of Formula I n has a weight percentage in the range of 1% to 5% of the composite.

[0031] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; and b) at least one additive, wherein S of the composite of Formula I has a weight percentage in the range of 35% to 45% relative to the positive electrode composition; C of the composite of Formula I has a weight percentage in the range of 10% to 25% relative to the positive electrode composition; and PX of the composite of Formula I n has a weight percentage in the range of 1% to 5% of the positive electrode composition.

[0032] In one embodiment of the present disclosure, there is provided a battery positive electrode composition disclosed herein, wherein S of the composite of Formula I has a weight percentage in the range of 38% to 45% relative to the composite; C of the composite of Formula I has a weight percentage in the range of 11% to 22% relative to the composite; and PX of the composite of Formula I n In another embodiment of the present disclosure, S of the composite of Formula I has a weight percentage in the range of 40% to 44% of the composite; C of the composite of Formula I has a weight percentage in the range of 13% to 20% of the composite; and PX of the composite of Formula I nhas a weight percentage in the range of 1% to 5% relative to the composite. In yet another embodiment of the present disclosure, S of the composite of Formula I has a weight percentage in the range of 42% relative to the composite; C of the composite of Formula I has a weight percentage in the range of 13% to 17% relative to the composite; and PX of the composite of Formula I n has a weight percentage in the range of 1% to 5% relative to the complex. Preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to less than 5% of the complex. More preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to 4% of the complex. More preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to 3% relative to the complex. Particularly preferred is PX of the complex of formula I n has a weight percentage in the range of 1% to 2% of the complex. Most preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to less than 2% of the composite.

[0033] In one embodiment of the present disclosure, there is provided a positive electrode composition for a battery disclosed herein, wherein S of the composite of Formula I has a weight percentage in the range of 38% to 45% relative to the positive electrode composition; C of the composite of Formula I has a weight percentage in the range of 11% to 22% relative to the positive electrode composition; and PX of the composite of Formula I n In another embodiment of the present disclosure, S of the composite of Formula I has a weight percentage in the range of 40% to 44% of the positive electrode composition; C of the composite of Formula I has a weight percentage in the range of 13% to 20% of the positive electrode composition; and PX of the composite of Formula I n has a weight percentage in the range of 1% to 5% relative to the positive electrode composition. In yet another embodiment of the present disclosure, S of the composite of Formula I has a weight percentage in the range of 42% relative to the positive electrode composition; C of the composite of Formula I has a weight percentage in the range of 13% to 17% relative to the positive electrode composition; and PX of the composite of Formula I n has a weight percentage in the range of 1% to 5% relative to the positive electrode composition. Preferably, PX of the complex of formula I nhas a weight percentage in the range of 1% or more and less than 5% relative to the positive electrode composition. More preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to 4% of the positive electrode composition. n has a weight percentage in the range of 1% to 3% relative to the positive electrode composition. Particularly preferably, PX of the complex of formula I n has a weight percentage in the range of 1% to 2% of the positive electrode composition. Most preferably, PX of the complex of formula I n has a weight percentage in the range of 1% or more and less than 2% of the positive electrode composition.

[0034] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; and b) at least one additive, wherein the at least one conductive carbon is selected from the group consisting of Ketjen black, acetylene black, Vulcan XC-72, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, and combinations thereof.

[0035] In one embodiment of the present disclosure, there is provided a battery positive electrode composition disclosed herein, wherein the at least one conductive carbon is selected from the group consisting of Ketjen black, acetylene black, Vulcan XC-72, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, and combinations thereof. In another embodiment of the present disclosure, there is provided a battery positive electrode composition disclosed herein, wherein the at least one conductive carbon is selected from the group consisting of Ketjen black, acetylene black, and combinations thereof. In yet another embodiment of the present disclosure, the at least one conductive carbon is Ketjen black.

[0036] In one embodiment of the present disclosure, a compound of formula I SC-PX n and at least one additive, wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, n is an integer selected from 3 to 5, and at least one additive is selected from Li3PS4, Li 10 GeP2S 12 and combinations thereof.

[0037] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n and at least one solid electrolyte, wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5, and at least one solid electrolyte; and b) at least one additive, wherein the at least one additive has a weight percentage in the range of 25% to 50% relative to the weight of the positive electrode composition.

[0038] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n and b) at least one additive, wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5, the composite of Formula I has a weight percentage in the range of 50% to 75% relative to the positive electrode composition, and the at least one additive has a weight percentage in the range of 25% to 50% relative to the positive electrode composition.

[0039] In one embodiment of the present disclosure, a) a compound of formula I SC-PXn and b) Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5, the composite of Formula I has a weight percentage in the range of 50% to 75% relative to the positive electrode composition, and the at least one additive has a weight percentage in the range of 25% to 50% relative to the positive electrode composition.

[0040] In one embodiment of the present disclosure, a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX, ... n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 75% of the positive electrode composition, and the at least one additive having a weight percentage in the range of 25% to 50% of the positive electrode composition.

[0041] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12and at least one additive selected from the group consisting of: and combinations thereof; wherein S is elemental sulfur having a weight percentage in the range of 35% to 45% relative to the composite; C is at least one conductive carbon selected from the group consisting of Ketjen Black, acetylene black, Vulcan XC-72, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, and combinations thereof, having a weight percentage in the range of 10% to 25% relative to the composite; PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5, wherein the composite of Formula I has a weight percentage in the range of 50% to 75% of the positive electrode composition, and the at least one additive has a weight percentage in the range of 25% to 50% of the positive electrode composition.

[0042] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage ranging from 13% to 17% relative to the composite; and PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is Br; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and b) a composite of Formula I, wherein X is Br; 10 GeP2S 12 and at least one additive selected from the group consisting of:

[0043] In one embodiment of the present disclosure, a compound of formula I SC-PX nwherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage of 13% to 17% relative to the composite; and PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is Cl; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and b) a composite of Formula I, wherein X is Cl; 10 GeP2S 12 and at least one additive selected from the group consisting of:

[0044] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage of 13% to 17% relative to the composite; and PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is I; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and b) a composite of Formula I, wherein X is I; 10 GeP2S 12 and at least one additive selected from the group consisting of:

[0045] In one embodiment of the present disclosure, a compound of formula I SC-PX n wherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage of 13% to 17% relative to the composite; PX nis a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is Br; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and the all-solid-state battery positive electrode further comprises at least one additive which is Li3PS4 having a weight percentage in the range of 38% to 42% of the positive electrode composition.

[0046] In one embodiment of the present disclosure, a compound of formula I SC-PX n wherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage of 13% to 17% relative to the composite; and PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is Cl; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and b) at least one additive which is Li3PS4 having a weight percentage in the range of 38% to 42% of the positive electrode composition.

[0047] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n wherein S is elemental sulfur having a weight percentage of 42% relative to the composite; C is at least one conductive carbon which is Ketjen black having a weight percentage ranging from 13% to 17% relative to the composite; and PX n is a phosphorus halide having a weight percentage in the range of 1% to 5% of the composite, where X is I; and n is an integer selected from 3 to 5, the composite of Formula I having a weight percentage in the range of 50% to 65% of the positive electrode composition; and b) at least one additive which is Li3PS4 having a weight percentage in the range of 38% to 42% of the positive electrode composition.

[0048] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) grinding a phosphorus halide with the first mixture to obtain a second mixture; and c) contacting the second mixture with at least one additive to obtain a positive electrode composition for an all-solid-state battery.

[0049] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) grinding a phosphorus halide together with the first mixture at a temperature in the range of 180°C to 190°C for a time in the range of 8 to 10 hours to obtain a second mixture; and c) contacting the second mixture with at least one additive to obtain a positive electrode composition for an all-solid-state battery.

[0050] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) milling a phosphorus halide together with the first mixture by hand milling, ball milling, vibratory milling, high-energy milling, or a combination thereof to obtain a second mixture; and c) contacting the second mixture with at least one additive to obtain a positive electrode composition for an all-solid-state battery.

[0051] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) grinding a phosphorus halide together with the first mixture to obtain a second mixture; and c) contacting the second mixture with at least one additive for a period of 7 to 9 hours to obtain a positive electrode composition for an all-solid-state battery.

[0052] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) milling a phosphorus halide together with the first mixture for a time period ranging from 8 to 10 hours at a temperature ranging from 180°C to 190°C by hand milling, ball milling, vibratory milling, high-energy milling, or a combination thereof to obtain a second mixture; and c) contacting the second mixture with at least one additive for a time period ranging from 7 to 9 hours to obtain a positive electrode composition for an all-solid-state battery.

[0053] In one embodiment of the present disclosure, there is provided a method for preparing a positive electrode composition for an all-solid-state battery, the method comprising: a) contacting sulfur powder with at least one type of conductive carbon to obtain a first mixture; b) grinding a phosphorus halide together with the first mixture by hand milling at a temperature of 180°C for a period of 9 hours to obtain a second mixture; and c) contacting the second mixture with at least one additive for a period of 8 hours at a speed in the range of 250 to 300 rpm to obtain a positive electrode composition for an all-solid-state battery.

[0054] In one embodiment of the present disclosure, a compound of formula I SC-PX n and at least one solid electrolyte, wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5, and at least one solid electrolyte, the method for preparing a positive electrode composition for an all-solid-state battery comprising: a) contacting sulfur powder with at least one conductive carbon to obtain a first mixture; b) grinding the phosphorus halide with the first mixture to obtain a second mixture; and c) contacting the second mixture with at least one additive to obtain the positive electrode composition for an all-solid-state battery.

[0055] In one embodiment of the present disclosure, a compound of formula I SC-PX nand at least one additive, wherein S is elemental sulfur; C is at least one conductive carbon; PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5, and at least one additive, the method comprising: a) contacting sulfur powder with at least one conductive carbon selected from the group consisting of Ketjen black, acetylene black, Vulcan XC-72, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, and combinations thereof to obtain a first mixture; b) grinding the phosphorus halide together with the first mixture to obtain a second mixture; c) grinding the second mixture with Li3PS4, Li 10 GeP2S 12 and contacting the composition with at least one additive selected from the group consisting of:

[0056] In one embodiment of the present disclosure, a compound of formula I SC-PX n and at least one additive, wherein S is elemental sulfur, C is at least one conductive carbon, and PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5, and at least one additive, the method for preparing a positive electrode composition for an all-solid-state battery comprising: a) contacting sulfur powder having a weight percentage in the range of 35% to 45% relative to the composite with at least one conductive carbon having a weight percentage in the range of 10% to 25% relative to the composite to obtain a first mixture; b) grinding a phosphorus halide having a weight percentage in the range of 1% to 5% relative to the composite with the first mixture to obtain a second mixture; and c) contacting the second mixture having a weight percentage in the range of 50% to 75% with at least one additive having a weight percentage in the range of 25% to 50% to obtain the positive electrode composition for an all-solid-state battery.

[0057] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, where X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5; a) a positive electrode composition; and c) at least one solid electrolyte.

[0058] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, where X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; a) a positive electrode composition; and b) a negative electrode selected from the group consisting of lithium, lithium-indium, lithium-aluminum, lithium-tin, and combinations thereof.

[0059] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX nis a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; b) a positive electrode composition, and a negative electrode selected from the group consisting of lithium, lithium-indium, lithium-aluminum, lithium-tin, and combinations thereof; c) a negative electrode composition, wherein Li3PS4, Li 10 GeP2S 12 and at least one solid electrolyte selected from the group consisting of:

[0060] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; a) a positive electrode; and c) at least one solid electrolyte, wherein the discharge capacity is in the range of 1700 to 2200 mAh / g at a discharge rate of 1 / 30C.

[0061] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; a) a positive electrode composition; and c) at least one solid electrolyte, wherein the positive electrode composition has a solubility of 10 e -8 S / cm~10e -9 All-solid-state batteries are provided that have electronic conductivities in the range of S / cm.

[0062] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, where X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; a) a negative electrode; and c) at least one solid electrolyte, wherein the positive electrode composition has a diffusion resistance in the range of 300 Ω to 430 Ω.

[0063] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX n is a phosphorus halide, where X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; a) a negative electrode; and c) at least one solid electrolyte, wherein the positive electrode composition has a reaction resistance in the range of 220 Ω to 370 Ω.

[0064] In one embodiment of the present disclosure, a) a compound of formula I SC-PX n The complex of Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: PX nis a phosphorus halide, wherein X is selected from Cl, Br, or I, and n is an integer selected from 3 to 5; b) a positive electrode composition, and a negative electrode selected from the group consisting of lithium, lithium-indium, lithium-aluminum, lithium-tin, and combinations thereof; c) a negative electrode composition, wherein Li3PS4, Li 10 GeP2S 12 and at least one solid electrolyte selected from the group consisting of: -8 S / cm~10e -9 An all-solid-state battery is provided that has an electronic conductivity in the range of 0.1 S / cm, a diffusion resistance in the range of 300 Ω to 430 Ω, and a reaction resistance in the range of 220 Ω to 370 Ω.

[0065] In one embodiment of the present disclosure, there is provided an all-solid-state battery as disclosed herein for use in an electric vehicle.

[0066] Although the present subject matter has been described in considerable detail with reference to certain preferred embodiments thereof, other embodiments are possible. [Example]

[0067] The present disclosure will be described below using examples, but these examples are intended to illustrate the implementation of the present disclosure and are not intended to be limited and understood as implying any limitations on the scope of the present disclosure.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present disclosure belongs.Methods and materials similar or equivalent to those described herein can be used in the practical application of the disclosed methods and compositions, and exemplary methods, devices, and materials are described below.It should be understood that the present disclosure is not limited to the specific methods and experimental conditions described, such as those that can be applied to such methods and conditions.

[0068] As mentioned in the Background section, there is a need for a positive electrode composition containing an activator component capable of inhibiting electrochemically inactive layers. The present disclosure provides a positive electrode composite comprising sulfur, conductive carbon, and a phosphorus halide activator component. The present disclosure provides a positive electrode composite having the formula I SC-PX n wherein S is elemental sulfur, C is conductive carbon, and PX n a complex of formula I, wherein X is selected from Cl, Br, or I, and n is an integer ranging from 3 to 5, and Li3PS4, Li 10 GeP2S 12 and at least one additive selected from the group consisting of: a cathode composition for an all-solid-state battery; and a cathode composition for an all-solid-state battery comprising: a cathode material selected from the group consisting of: a cathode material having a high conductivity and a low ionic strength; a cathode material having a low ionic strength and a low ionic strength; and a cathode material having a high conductivity ...

[0069] [Example 1] Preparation of the Positive Electrode Composition of the Present Disclosure The positive electrode composition of the present disclosure has the formula SC-PX n wherein PX n The starting materials included a composite in which the starting material was a phosphorus halide, and an additive, Li3PS4 (LPS). In the actual preparation method, the precursors, sulfur powder and Ketjen black, were first mixed to obtain a first mixture. The phosphorus halide was added to the first mixture in various weight ratios. The mixture containing all three components was hand-ground and heated at 185°C for 9 hours to obtain a second mixture. The second mixture was then mixed with the additive and ground at 280 rpm for approximately 8 hours. Thus, the positive electrode compositions of the present disclosure were obtained. Various positive electrode compositions of the present disclosure prepared from the starting components, along with the weight ratios of the starting components, are listed in Table 1 below.

[0070] [Table 1]

[0071] Table 1 shows various positive electrode compositions obtained using various phosphorus halides at different weight ratios. For example, positive electrode composition 1 was obtained from a mixture containing 42% sulfur powder, 18% Ketjen black, and 40% LPS. Positive electrode composition 1 was prepared by the method described above, resulting in a composition of formula S-LPS-C.

[0072] Similarly, positive electrode compositions 2, 3, 4, 5, and 6, corresponding to formulas SC-PBr5-LPS(1), SC-PBr5-LPS(2), SC-PBr5-LPS(5), SC-PCl5-LPS(1), and SC-PI3-LPS(1), respectively, were prepared using the relative weights and methods described above in Table 1. The resulting positive electrode compositions were subjected to further testing of their electrochemical performance.

[0073] Transmission electron microscopy investigation of the positive electrode composition The cathode composition SC-PBr5-LPS (1) prepared by the method described herein was examined under a transmission electron microscope (TEM). TEM images of the composition were obtained for characterization and component identification. Figure 1 shows the TEM image of cathode composition 1, S-LPS-C, which clearly shows the presence of only carbon. Meanwhile, the TEM image of cathode composition 2 (Figure 2) also showed the presence of phosphorus bromide. These images indicated the inclusion of phosphorus halides within the cathode composition.

[0074] [Example 2] Fabrication of the disclosed all-solid-state battery cell The method for preparing the positive electrode composition of the present disclosure was carried out for use in an all-solid-state battery, which is an assembly of all-solid-state battery cells. To analyze the positive electrode composition, an all-solid-state battery cell was fabricated. In one example of the present disclosure described herein, the all-solid-state battery cell contained the positive electrode composition of Example 1, a lithium-indium alloy negative electrode, and LGPS (Li 10 GeP2S 12 ) was composed of

[0075] The fabrication procedure for the all-solid-state battery cell is described below. 80 mg of the solid electrolyte LGPS was pressed at a pressure of 400 MPa for approximately 3 minutes to obtain a solid electrolyte pellet. Approximately 7.5 mg of the positive electrode composition from Example 1 was pressed onto one side of the solid electrolyte pellet at a pressure of 200 MPa for 3 minutes to prepare a positive electrode-solid electrolyte pellet. A 50 μm-thick lithium foil and a 200 μm-thick indium foil with a Li / In molar ratio of 0.79 were placed on the other side of the solid electrolyte pellet, resulting in the solid electrolyte being bonded to both the anode and cathode. Figure 3 shows the fabrication of an all-solid-state battery cell of the present disclosure, including the disclosed positive electrode, anode, and solid electrolyte. The fabricated all-solid-state battery cell, including the disclosed positive electrode composition, was then subjected to electrochemical testing.

[0076] [Example 3] Electrochemical impedance spectroscopy To investigate the electrode resistance of the positive electrode compositions of the present disclosure, electrochemical impedance spectroscopy of all-solid-state battery cells was performed. The all-solid-state battery cells of the present disclosure from Example 2 were subjected to electrochemical impedance studies in the frequency range of 100 MHz to 10 Hz at 100% state of charge (SOC) with an amplitude of 10 mV. Figure 4 shows the ionic resistance curves of all-solid-state battery cells containing positive electrode compositions 1 and 2 (i.e., SC-LPS and SC-PBr5-LPS) as the positive electrode.

[0077] Figure 5 shows the charge transfer resistance of all-solid-state battery cells fabricated using compositions 1 and 2 (i.e., SC-LPS and SC-PBr5-LPS) in the cathode. Figures 4 and 5 clearly demonstrate that the cathode compositions of the present disclosure exhibit lower ionic resistance and lower charge transfer resistance. The cathode compositions of the present disclosure were calculated to have diffusion resistances in the range of 300 Ω to 430 Ω and reaction resistances in the range of 220 Ω to 370 Ω.

[0078] FIG. 6 shows the Nyquist plots of the electrochemical impedance spectra of positive electrode compositions 1 and 2 of the present disclosure (at 100% SOC and 0% SOC). From the Nyquist plots, it can be observed that the all-solid-state battery cell with positive electrode composition 1 (SC-LPS) had a higher resistance value, while from the Nyquist plots, it can be observed that the all-solid-state battery cell with positive electrode composition 2 (SC-PBr5-LPS) had a lower resistance value. There was no significant change in the semicircular curve of positive electrode composition 2 at 100% SOC and 0% SOC, which revealed the stability of the interface between the positive electrode and the electrolyte. Furthermore, the lower resistance value is due to the 10e -8 S / cm~10e -9 This showed a higher electronic conductivity of the positive electrode, in the range of S / cm.

[0079] [Example 4] Constant current charge / discharge cycle of the all-solid-state battery of the present disclosure The all-solid-state battery cells prepared in Example 2 were subjected to constant-current charge-discharge cycling at various rates and various charge-discharge cycles. Figure 7 shows the first cycle of constant-current charge-discharge at a rate of 1 / 30 C for all-solid-state battery cells having positive electrode compositions 1, 2, 3, and 4. The charge-discharge capacities of the all-solid-state battery cells were obtained in the voltage range of 0.5 to 2.5 V. Table 2 shows the capacity values ​​for each positive electrode composition in mAh / g. These values ​​clearly demonstrate that the positive electrode compositions containing phosphorus halide had higher capacities compared to the positive electrode compositions not containing phosphorus halide.

[0080] [Table 2]

[0081] Figure 8 shows the performance of the positive electrode compositions at various charge / discharge rates when the rate was changed from 0.01 to 0.1 and the corresponding output characteristics were measured. From Figure 8, it can be seen that the rate performance of the positive electrode tended to be SC-PBr5-LPS(2) > SC-PBr5-LPS(1) > S-LPS-C > SC-PBr5-LPS(5). A clear increase in rate performance was demonstrated for the positive electrode composition of the present disclosure.

[0082] Figure 9 shows the rate performance of positive electrode compositions 1, 2, and 3 over a wider range of charge / discharge rates, varying from 0.01 to 0.3. It was found that the performance of the positive electrodes across a wider rate range maintained the following trend: SC-PBr5-LPS(2) > SC-PBr5-LPS(1) > S-LPS-C. The positive electrode composition SC-PBr5-LPS(2) retained 90% of its discharge capacity at a rate of 1 / 10C, ​​while only 44% of its discharge capacity was retained at a rate of 1 / 3C.

[0083] Figure 10 shows the capacity-voltage curves of the third cycle at a charge-discharge rate of 1 / 30C for positive electrode compositions 1, 2, 3, and 4. Table 3 shows the corresponding capacity measurements at a charge-discharge rate of 1 / 30C.

[0084] [Table 3]

[0085] From Table 3, it is clear that the positive electrode composition of the present disclosure has higher capacity when compared to the SC-LPS positive electrode alone.

[0086] Figure 11 shows the capacity-voltage curves of positive electrode compositions 1, 2, 3, and 4 at a charge rate of 1 / 30 C and a discharge rate of 1 / 10 C. Table 4 shows the corresponding capacity measurements at a discharge rate of 1 / 10 C.

[0087] [Table 4]

[0088] Table 4 shows that the positive electrode compositions of the present disclosure have improved capacity when compared to the positive electrode alone.

[0089] 12 shows the capacity-voltage curves for positive electrode compositions 1, 2, 3, and 4 at a charge rate of 1 / 30 C and a discharge rate of 1 / 3 C. Table 5 shows the corresponding capacity measurements at a discharge rate of 1 / 3 C, which demonstrated the improved capacity values ​​of the positive electrodes of the present disclosure.

[0090] [Table 5]

[0091] From the capacity measurements described herein, the PX n It can be noted that as the amount of PX increases from 0 to 5%, the capacity also tends to increase. n In the case of the positive electrode composition 2, the capacity is increased compared to the positive electrode composition 1, and PX n The PX content increased as the weight percentage of PX increased. n The capacity decreased in the positive electrode composition 4 with 5% of PX n It was demonstrated that when the amount of PX exceeded 5%, the positive electrode composite did not produce the desired characteristics of the positive electrode. Therefore, the positive electrode composite was prepared by adding PX in the range of 1 to 5% of the positive electrode composition. n This volume reduction is due to the optimum weight percentage of PX n was thought to be primarily the result of the replacement of conductive carbon in the positive electrode composite by the respective weight percentages, resulting in a corresponding decrease in conductive carbon in the positive electrode composite.

[0092] [Example 5] Positive electrode resistance DC internal resistance method The direct current internal resistance (DCIR) of a battery is the resistance to current flowing through the battery, and changes in DCIR have a significant impact on the battery's discharge performance. Generally, the more improved the battery, the lower the internal resistance. Therefore, the DCIR method can be used as an important indicator for evaluating the quality of a battery. The DCIR measurement method involves injecting a high current into the negative and positive electrodes of the battery for a short period of time, and then recording the changes in the battery's voltage and charge / discharge current.

[0093] In this disclosure, DCIR tests were conducted on cathode compositions 1 and 2 with Al as the anode. Figure 13 shows the DCIR curves for cathode compositions 1 and 2, which are graphs of current versus time flowing through an all-solid-state battery cell containing the corresponding cathode. The measured electrical resistance of the cathode SC-PBr5-LPS was 3.06 x 10 6 Ω, and the measured electrical resistance of SC-LPS was 6.09 × 10 7 This demonstrated the decrease in electrical resistance and the increase in electrical conductivity of positive electrode composition 2 of the present disclosure.

[0094] Figure 14 shows the reaction resistance of positive electrode compositions 1 and 2 for 30 seconds at various charge rates of 0.03C, 0.05C, 0.1C, and 0.3C, respectively, and the values ​​are summarized in Table 6. The initial state was maintained at 50% SOC and allowed to stand for 1 hour. Discharge at various rates was then performed for the remaining 4 hours. From Figure 14, it can be seen that positive electrode composition 2 of the present disclosure had a lower reaction resistance compared to positive electrode composition 1 alone. Therefore, the DCIR method demonstrated that the positive electrode of the present disclosure has improved conductivity and quality.

[0095] [Table 6]

[0096] Similar DCIR tests were performed on cathode compositions 5 and 6, SC-PCl5-LPS, and SC-PI3-LPS, and compared with cathode compositions 1 and 2. FIG. 15 shows the electron-reaction resistances of cathode compositions 1, 2, 5, and 6 for 30 seconds at 50% SOC and a 0.1 C discharge rate, and Table 7 shows the reaction resistance values ​​of the aforementioned cathode compositions. For convenience, the all-solid-state battery cells fabricated for this test had the cathode composition of the present disclosure and a lithium-indium anode. The stand-alone cathode had a higher resistance when compared to cathode compositions 4 and 5. Therefore, these results demonstrated that the cathode of the present disclosure had a lower reaction resistance and improved the electrochemical quality of the corresponding batteries.

[0097] [Table 7]

[0098] From all of the above examples, positive electrode compositions 2, 3, 4, 5, and 6 exhibited lower resistance and higher conductivity. Positive electrode composition 1, which did not contain a phosphorus halide, exhibited higher resistance and lower conductivity. Positive electrode compositions 2 to 6, which contained a phosphorus halide as an activator component, were found to be electrochemically improved over the positive electrode alone without the phosphorus halide.

[0099] Although the present subject matter has been described in considerable detail with reference to particular examples and embodiments thereof, other embodiments are possible.

[0100] Advantages of the present disclosure The present disclosure provides compounds of formula I SC-PX nThe present disclosure provides a positive electrode composition comprising elemental sulfur, conductive carbon, and a phosphorus halide, wherein X is a halogen selected from Cl, Br, or I, and n is an integer between 3 and 5, and at least one additive. The positive electrode composition for an all-solid-state battery disclosed herein has an activator component that can prevent or reduce the formation of an electrochemically inactive layer at the interface between the electrolyte and electrode. The phosphorus halide acts as an activator that catalyzes the conversion of polysulfides to lithium sulfide at the interface and mediates Li-ion conduction. The positive electrode composition of the present disclosure has a 10e -8 S / cm~10e -9 The positive electrode composition has an electronic conductivity in the range of 0.1 S / cm. The positive electrode composition exhibits a lower reaction resistance in the range of 220 Ω to 370 Ω. The positive electrode composition of the present disclosure has a diffusion resistance in the range of 300 Ω to 430 Ω. An all-solid-state battery including the positive electrode composition has a discharge capacity in the range of 1700 to 2200 mAh / g at a discharge rate of 1 / 30C.

[0101] This application is based on Indian Patent Application No. 202041032190, filed on July 27, 2020, the disclosure of which is incorporated by reference in its entirety.

Claims

1. a) a conjugate of formula I, Formula I S---PX ｎ wherein S is elemental sulfur; C is at least one conductive carbon; PX ｎ is a phosphorus halide, wherein X is selected from Cl, Br, or I; and n is an integer selected from 3 to 5; b) at least one additive; and Including, The positive electrode composition for an all-solid-state battery, wherein the at least one additive is selected from the group consisting of Li 3 PS 4 , Li 10 GeP 2 S 12 , and combinations thereof.

2. 2. The positive electrode composition for an all-solid-state battery according to claim 1, wherein the composite of Formula I has a weight percentage in the range of 50% to 75% relative to the positive electrode composition, and the at least one additive has a weight percentage in the range of 25% to 50% relative to the positive electrode composition.

3. S of said conjugate of formula I has a weight percentage in the range of 35% to 45% of the conjugate; C of said conjugate of formula I has a weight percentage in the range of 10% to 25% of the conjugate; PX of said conjugate of formula I ｎ The positive electrode composition for an all-solid-state battery according to claim 1 or 2, wherein the weight percentage of the composite is in the range of 1% to 5%.

4. 4. The positive electrode composition for an all-solid-state battery according to claim 1, wherein the at least one conductive carbon is selected from the group consisting of acetylene black, multi-walled carbon nanotubes, single-walled carbon nanotubes, graphene, and combinations thereof.

5. a) contacting sulfur powder with the at least one conductive carbon to obtain a first mixture; b) grinding a phosphorus halide with the first mixture to obtain a second mixture; c) contacting the second mixture with at least one additive to obtain the all-solid-state battery positive electrode composition; The method for preparing the positive electrode composition for an all-solid-state battery according to any one of claims 1 to 4, comprising:

6. 6. The method of claim 5, wherein the step of grinding the phosphorus halide with the first mixture is carried out at a temperature in the range of 180°C to 190°C for a period of 8 to 10 hours.

7. 7. The method of claim 5 or 6, wherein the step of milling a phosphorus halide with the first mixture is carried out by hand milling, ball milling, vibratory milling, high energy milling, and combinations thereof.

8. 8. The method of any one of claims 5 to 7, wherein the step of contacting the second mixture with the at least one additive is carried out for a period of from 7 to 9 hours.

9. i. the positive electrode composition according to any one of claims 1 to 4; ii. a negative electrode; iii. at least one solid electrolyte; Including solid-state batteries.

10. 10. The all-solid-state battery of claim 9, wherein the negative electrode is selected from the group consisting of lithium, lithium-indium, lithium-aluminum, lithium-tin, and combinations thereof.

11. The at least one solid electrolyte is Li ３ P.S. ４ , Li １０ GeP ２ S １２ 11. The all-solid-state battery according to claim 9 or 10, wherein the compound is selected from the group consisting of:

12. In the first cycle of constant current charge / discharge at a rate of 1 / 30 C, the discharge capacity obtained in the voltage range of 0.5 to 2.5 V is 1700 to 2200 mAh / g, and the electronic conductivity of the positive electrode composition is 10 e －８ S / cm to 10e －９ The all-solid-state battery according to any one of claims 9 to 11, wherein the conductivity is in the range of S / cm.

13. The all-solid-state battery according to any one of claims 9 to 12, wherein the positive electrode composition has a diffusion resistance in the range of 300Ω to 430Ω and a reaction resistance in the range of 220Ω to 370Ω.

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