Sulfide-based lithium-ion conductive solid electrolyte and method for producing the same

Abstract

The objective of the present invention is to increase ΔT x , especially ΔT above 100℃ x The objective is to provide a sulfide-based lithium-ion conductive solid electrolyte having [specific properties]. [Solution] The present invention relates to a solid material obtained by melting and quenching a mixture of lithium sulfide, boron sulfide, and boron oxide to form a glassy solid suitable for use as a lithium ion conductive electrolyte. These sulfide-based lithium ion conductive solid electrolytes exhibit high thermal stability, which means a large ΔT x , especially ΔT above 100℃ x This is supported by [the following].

Description

[Technical Field]

[0001] The present invention relates to a solid material obtained by melting and quenching a mixture of lithium sulfide, boron sulfide, and boron oxide to form a glassy solid suitable for use as a lithium-ion conductive electrolyte. The present invention further relates to a method for preparing the solid material, an electrochemical cell such as an all-solid-state battery containing the solid material, and the use of the solid material in an electrochemical cell such as an all-solid-state battery, particularly as an electrolyte. [Background technology]

[0002] The three main functional components of a lithium-ion battery are the anode, cathode, and electrolyte. While many variations exist, the anode of a conventional lithium-ion battery is typically made from carbon, the cathode from a transition metal oxide (particularly cobalt, nickel, and / or manganese oxides), and the electrolyte is typically a non-aqueous solvent containing a lithium salt. For example, a mixture of organic carbonates and lithium hexafluorophosphate is a well-known liquid electrolyte for lithium-ion batteries.

[0003] A major drawback of liquid electrolytes is that their composition, particularly the solvent, is flammable, posing a significant safety risk during normal operation, especially in the event of an accident. Another drawback, inherent to the liquid nature of electrolytes, is the increased risk of leakage and, in the event of spills or leaks, the risk of environmental contamination.

[0004] In recent years, efforts have been made to develop solid electrolytes that enable the provision of solid lithium-ion batteries. Such solid batteries significantly reduce EHS (environment, health, and safety) risks. A new class of lithium-ion conductive solid electrolytes are sulfide-based amorphous solids (interchangeably referred to as glassy solids) such as Li2S-SiS2, Li2S-P2S5, or Li2S-B2S3. In glassy solid electrolyte materials, the absence of crystalline pathways results in isotropic conductivity with virtually no grain boundary resistance. The absence of grain boundaries in the glassy electrolyte material also prevents the formation of dendritic crystals. This is because glassy amorphous electrolyte materials can be obtained as high-density, defect-free films by melt-quenching methods.

[0005] A major challenge in the production of glassy solid electrolytes is avoiding crystalline regions in the solid material. The thermal stability of glass ΔT x This can be characterized as stability against crystallization, and the crystallization onset temperature (T x ) and glass transition temperature (T g The temperature difference with ΔT x =T x -T g Determined by ΔT x A larger value generally leads to improved glass formation ability and increased glass stability during post-processing.

[0006] Early studies on Li2S-B2S3 compositions with molar ratios of 70:30 and 60:40 showed that ΔT was approximately 70°C and approximately 110°C, respectively. x The values ​​were reported (Zhang et al, Solid State Ionics 1990, 38, 217-224).

[0007] U.S. Patent No. 5,500,291 concerns a Li2S-SiS2-Li4SiO4 type sulfide-based lithium-ion conductive solid electrolyte.

[0008] WO 2020 / 254314 A1 contemplates a Li₂S-B₂S₃ type sulfide-based lithium ion conductive solid electrolyte obtained from a mixture further comprising an oxide of P, Si, Ge, As or Sb in combination with lithium halide. The resulting glassy solid is said to have favorable lithium ion conductivity, electrochemical stability in direct contact with lithium metal, and chemical stability against air and moisture. ΔT of these solids x is in the range of 5 to 36°C (see Table 3 of WO 2020 / 254314 A1).

[0009] WO 2016 / 089899 A1 contemplates numerous glass systems, many of which are speculative or unsupported. Paragraphs 186 and 188 of WO 2016 / 089899 A1 disclose ΔT x suggests adding oxygen to improve. Paragraph 190 of WO 2016 / 089899 A1 speculates that a Li₂S / Li₂O-B₂S₃-SiS₂ based system may have a ΔT x exceeding 100°C.

[0010] A drawback with most sulfide-based lithium ion conductive solid electrolytes known in the art is that they have either low ionic conductivity or high ΔT x Accordingly, there is currently a great need to provide a sulfide-based lithium ion conductive solid electrolyte that combines both properties. [PRIOR ART DOCUMENT] [PATENT DOCUMENT]

[0011] [Patent Document 1] U.S. Patent No. 5500291 [Patent Document 2] WO 2020 / 254314 [Patent Document 3] WO 2016 / 089899 [NON-PATENT DOCUMENT]

[0012] [Non-Patent Document 1] Zhang et al,Solid State Ionics 1990,38,217-224 [Overview of the project] [Problems that the invention aims to solve]

[0013] The objective of the present invention is to increase ΔT x , especially ΔT above 100℃ x The present invention aims to provide a sulfide-based lithium-ion conductive solid electrolyte having [a certain characteristic]. Another object of the present invention is to provide a sulfide-based lithium-ion conductive solid electrolyte having high ionic conductivity. Another object of the present invention is to provide a sulfide-based lithium-ion conductive solid electrolyte having low electrical conductivity. [Means for solving the problem]

[0014] The inventors have found that one or more of the present invention can be achieved by providing a sulfide-based lithium-ion conductive solid electrolyte obtained by melting and quenching a combination of Li2S;B2S3 and B2O3 in clearly defined ratios. They have also found that this can be achieved by providing a sulfide-based lithium-ion conductive solid electrolyte obtained by melting and quenching a combination of B2S3;B2O3 and LiX (wherein X represents Cl, Br, I, or a combination thereof). As shown in the attached examples, the resulting glassy solid exhibits high thermal stability ΔT in Li-S based glasses. x In practice, it is observed that these materials exhibit high ionic conductivity and / or low electrical conductivity.

[0015] Embodiment 1 Therefore, in the first aspect of the present invention, General formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d(I) (In the formula, X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, or a combination thereof. a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. A solid material is provided having a composition in which d is in the range of 0.001 to 0.14.

[0016] Preferably, general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (In the formula, X represents Cl, Br, I, or a combination thereof. a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. A solid material is provided having a composition in which d is in the range of 0.001 to 0.14.

[0017] Embodiment 2 In another aspect of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A and B, The molar ratio of A to B in the mixture before rapid cooling is in the range of 60:40 to 99:1. Component A is of general formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85. y is within the range of 15 to 45. z is in the range of 0 to 15. This is due to the fact that x+y+z=100. Component B is LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, or a combination thereof, preferably X represents Cl, Br, I, or a combination thereof).

[0018] Embodiment 3 In another aspect of the present invention, a method for preparing a solid material, (i) The following precursors: ●Li2S, ●B2S3 and / or both boron and sulfur, ●Optionally, B2O3, and ●A step of providing LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4 or a combination thereof, preferably X represents Cl, Br, I or a combination thereof), (ii) A step of preparing a mixture containing the precursor provided in step (i), ●The molar ratio of elements Li, S, B, O, and X in the mixture is given by general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (In the formula, a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. (where d is within the range of 0.001 to 0.14) or ●In the mixture, the molar ratio of the precursor is given by General Formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85. y is within the range of 15 to 45. z is in the range of 0 to 15. The process is consistent with x+y+z=100. (iii) A step of heat-treating the mixture prepared in step (ii) to obtain a molten product, A method is provided which includes (iv) a step of rapidly cooling the molten material obtained in step (iii) to obtain a solid material.

[0019] Embodiment 4 In another aspect of the present invention, a solid composition is provided which comprises a first solid material which is a solid material described herein (i.e., the solid material of Embodiment 1 or 2), and further comprises at least a second solid material which has a composition different from that of the first solid material.

[0020] Embodiment 5 In another aspect of the present invention, an electrochemical cell comprising a solid material described herein (i.e., the solid material of Embodiment 1 or 2) is provided.

[0021] Embodiment 6 In another aspect of the present invention, the use of a solid material described herein (i.e., the solid material of Embodiment 1 or 2) or a solid composition described herein (i.e., the solid composition of Embodiment 4) as a solid electrolyte for an electrochemical cell is provided.

[0022] Embodiment 7 Another aspect of the present invention relates to a battery, more specifically a lithium-ion battery or a lithium-metal battery, comprising at least one electrochemical cell containing a solid material described herein (i.e., the solid material of Embodiment 1 or 2), for example, two or more electrochemical cells as described in Embodiment 5.

[0023] Embodiment 8 A further aspect of the present invention is a method for fabricating or operating stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOSes, communication equipment, remote car locks, and energy storage devices for power plants, by using at least one electrochemical cell comprising at least one battery or solid material described herein (i.e., the electrochemical cell described in Example 5).

[0024] Embodiment 9 Further aspects of this disclosure include the use of an electrochemical cell comprising the solid material of the present invention (i.e., the electrochemical cell described in Embodiment 5) in automobiles, electric motor-driven bicycles, robots, aircraft (e.g., unmanned aerial vehicles including drones), ships, or fixed energy storage devices.

[0025] Embodiment 10 In another aspect of the present invention, the thermal stability ΔT of a glassy solid x To improve the thermal stability ΔT of sulfide-based lithium-ion conductive solid electrolytes, in particular. x To improve this, the use of a lithium salt of the formula LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4 or a combination thereof, preferably X represents Cl, Br, I or a combination thereof) is provided. [Modes for carrying out the invention]

[0026] The following detailed description provides a detailed description of preferred embodiments for realizing the implementation of the present invention. While the present invention is described with reference to these specific preferred embodiments, it will be understood that the present invention is not limited to these preferred embodiments. However, in contrast, the present invention includes a number of substitutes, variations, and equivalents, as will become apparent when considering the modes for carrying out the invention described below.

[0027] Where referred to herein, the glass transition temperature (T g) refers to the onset temperature of the glass transition as determined by differential scanning calorimetry (DSC). This is preferably determined by constructing tangents to the baseline of the DSC curve before and after the glass transition and determining the extrapolated onset temperature by the intersection of these tangents, which essentially corresponds to the temperature at which the highest gradient in the descent of the DSC baseline occurs before the exothermic crystallization peak. The DSC is preferably recorded at a rate of 10°C / min using a temperature profile from 100°C to 350°C, and preferably for a sample of 5 to 10 mg in a sealed aluminum pan. A suitable DSC instrument is the DSC3500 Sirius.

[0028] The thermal stability (ΔT) referred to herein x ) is the crystallization onset temperature (T) determined by DSC. x ) and the glass transition temperature (T) determined by DSC g This is the difference from ). In other words, ΔT x =T x -T g As explained in the previous paragraph, the glass transition temperature (T) is used where referred to herein. g ) refers to the onset temperature of the glass transition, as determined by differential scanning calorimetry (DSC).

[0029] The ionic conductivity referred to herein is that measured at 25°C by electrochemical impedance spectroscopy (EIS). Ionic conductivity was preferably measured using an ion-blocking electrode on a hot-pressed sample, densified at 350 MPa and 125°C for 5 minutes, and then measured at 25°C under an operating pressure of 125 MPa. Preferably, an excitation voltage of 10 mV was applied in the frequency range of 7 MHz to 1 Hz, and the data were interpreted by equivalent circuit analysis. A suitable conductivity analyzer is a potentiostat with a frequency analyzer, such as those available from Biologic.

[0030] The electrical conductivity referred to herein refers to the electrical conductivity measured at 25°C. The electrical conductivity was preferably determined using an ion-blocking electrode on a hot-pressed sample, densified at 350 MPa and 125°C for 5 minutes, and then measured at 25°C under an operating pressure of 125 MPa. Preferably, the electrical conductivity was measured by stepwise constant-potential polarization at 0.2, 0.4, and 0.6 V for 20 minutes. A suitable conductivity analyzer is a potentiostat equipped with a frequency analyzer, such as those available from Biologic.

[0031] Embodiment 1 In a first aspect of the present invention, general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (In the formula, X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, or a combination thereof. a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. A solid material is provided having a composition in which d is in the range of 0.001 to 0.14.

[0032] While we do not wish to be bound by any theory, the inventors state that the solid material according to formula (I) is a product obtained by melting and quenching a mixture of Li2S, B2S3;B2O3 and LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, or a combination thereof) in clearly defined proportions, as described herein in the context of other aspects and examples of the invention.

[0033] General formula (I) (In the formula, X represents Cl, Br, I, or a combination thereof. a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. A solid material having a composition in which d is in the range of 0.001 to 0.14 is preferably provided.

[0034] General formula (I) (wherein, a is within the range of 0.06 to 0.1. b is within the range of 0 to 0.03. c is within the range of 0.12 to 0.20. d is within the range of 0.001 to 0.14. More preferably, in the formula, a is within the range of 0.06 to 0.1. b is within the range of 0.002 to 0.02. c is within the range of 0.14 to 0.19. A solid material having a composition in which d is in the range of 0.001 to 0.14 is preferably provided.

[0035] Generally, d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04. In some embodiments, d is in the range of 0.01 to 0.14, preferably in the range of 0.02 to 0.14, and more preferably in the range of 0.025 to 0.14. In some embodiments, d is in the range of 0.02 to 0.08, preferably in the range of 0.025 to 0.08, and more preferably in the range of 0.03 to 0.07.

[0036] Therefore, in some embodiments of the present invention, the general formula (I) (wherein, a is within the range of 0.06 to 0.1. b is within the range of 0 to 0.03. c is within the range of 0.12 to 0.20. d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04. More preferably, in the formula, a is within the range of 0.06 to 0.1. b is within the range of 0.002 to 0.02. c is within the range of 0.14 to 0.19. A solid material is provided having a composition in which d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04.

[0037] According to a very preferred embodiment of the present invention, General formula (I) (In the formula, a is in the range of 0.06 to 0.8, preferably in the range of 0.07 to 0.09) b is in the range of 0.002 to 0.02, preferably in the range of 0.010 to 0.015. c is in the range of 0.11 to 0.21, preferably in the range of 0.14 to 0.18. A solid material is provided having a composition in which d is in the range of 0.001 to 0.13, preferably in the range of 0.02 to 0.06.

[0038] Therefore, in some embodiments of the present invention, the general formula (I) (wherein, a is within the range of 0.07 to 0.09. b is within the range of 0.010 to 0.015. c is within the range of 0.14 to 0.18. A solid material is provided having a composition in which d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04.

[0039] In a very preferred embodiment of the present invention, the solid material is given by formula (I) (wherein X represents a combination of Cl, Br and / or I). In other words, the solid material according to the present invention is given by formula (I)a, (I)b, (I)c or (I)d (wherein a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. This is because d is within the range of 0.001 to 0.14. [ka]

[0040] As will be understood by those skilled in the art, all embodiments relating to formula (I) are equally applicable to formulas (I)a, (I)b, (I)c and (I)d.

[0041] In certain preferred embodiments, the solid material of the present invention is of formula (I)' Li 2c+d B 2a+2b S 3a+c O 3b Y 1 e Y 2 f (I)' (In the formula, Y 1 and Y 2 However, independently selected from the group consisting of F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, and Y 1 ≠Y 2 is, and (In the formula, a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26) or e is within the range of 0.001 to 0.14. This is because f is within the range of 0.001 to 0.14.

[0042] In a preferred embodiment, Y1 and Y 2 This is independently selected from the group consisting of Cl, Br, and I.

[0043] Preferably, the solid material is formula (I)' (wherein, a is within the range of 0.06 to 0.1. b is within the range of 0.002 to 0.02. (c is within the range of 0.14 to 0.19) or e is within the range of 0.001 to 0.14. This is because f is within the range of 0.001 to 0.14.

[0044] Preferably, the solid material is formula (I)' (wherein, e is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04. This is because f is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04.

[0045] In a very preferred embodiment, the solid material is based on formula (I)'a, (I)'b, or (I)'c. [ka]

[0046] As will be understood by those skilled in the art, all embodiments relating to formula (I)' are equally applicable to formulas (I)'a, (I)'b, and (I)'c.

[0047] In a particular very preferred embodiment, the solid material of the present invention is (I)'' (wherein, Li 2c+d B 2a+2b S 3a+c O 3b Y 3 g Y 4 h Y 5i (I)'' (In the formula, Y 3 , Y 4 and Y 5が Independently selected from the group consisting of F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, and Y 3 ≠Y 4 ≠Y 5 And also (In the formula, a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26) or g is within the range of 0.001 to 0.14. h is within the range of 0.001 to 0.14. This is because i is within the range of 0.001 to 0.14.

[0048] In a preferred embodiment, Y 3 , Y 4 and Y 5 This is independently selected from the group consisting of Cl, Br, and I.

[0049] Preferably, the solid material is formula (I)'' (wherein, a is within the range of 0.06 to 0.1. b is within the range of 0.002 to 0.02. (c is within the range of 0.14 to 0.19) or g is within the range of 0.001 to 0.14. h is within the range of 0.001 to 0.14. This is because i is within the range of 0.001 to 0.14.

[0050] Preferably, the solid material is formula (I)'' (wherein, g is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04. h is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04. This is because i is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.04.

[0051] In a very preferred embodiment, the solid material is given by formula (I)''a. [ka]

[0052] As will be understood by those skilled in the art, all embodiments relating to formula (I)'' are equally applicable to formula (I)''a.

[0053] In each embodiment of the composition according to general formula (I) described herein, the molar ratio is calculated such that the sum of 5a + 5b + 3c + 2d is in the range of 0.9 to 1.1, preferably in the range of 0.99 to 1.01, and most preferably about 1. Furthermore, in each embodiment of the composition according to general formula (I)' or formula (I)'' described herein, the molar ratio is calculated such that the sum of 5a + 5b + 3c + 2d is in the range of 0.9 to 1.1, preferably in the range of 0.99 to 1.01, and most preferably about 1.

[0054] Solid materials having a composition according to general formula (I), when prepared, for example by melting and quenching, may typically be accompanied by a small amount of impurity phase consisting mainly of precursors or intermediates formed from precursors, which are primarily used to prepare solid materials. Furthermore, solid materials having a composition according to general formula (I)' or formula (I)'', when prepared, for example by melting and quenching, may typically be accompanied by a small amount of impurity phase consisting mainly of precursors or intermediates formed from precursors, which are primarily used to prepare solid materials.

[0055] Embodiment 2 In another aspect of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A and B, The molar ratio of A to B in the mixture before rapid cooling is in the range of 60:40 to 99:1. Component A is of general formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85, preferably in the range of 55 to 75, more preferably in the range of 60 to 70. y is in the range of 15 to 45, preferably in the range of 20 to 40, and more preferably in the range of 25 to 35. z is in the range of 0 to 15, preferably in the range of 0 to 10, and more preferably in the range of 0 to 6. This is due to the fact that x+y+z=100. Component B is LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4, or a combination thereof).

[0056] In a preferred embodiment of the present invention, the solid material can be obtained by melting and quenching a mixture of A and B. The molar ratio of A to B in the mixture before rapid cooling is in the range of 60:40 to 99:1. Component A is of general formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85, preferably in the range of 55 to 75, more preferably in the range of 60 to 70. y is in the range of 15 to 45, preferably in the range of 20 to 40, and more preferably in the range of 25 to 35. z is in the range of 0 to 15, preferably in the range of 0 to 10, and more preferably in the range of 0 to 6. This is due to the fact that x+y+z=100. Component B is LiX (wherein X represents Cl, Br, I, or a combination thereof).

[0057] In a preferred embodiment of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A and B, where, x is in the range of 62 to 68, preferably in the range of 63 to 67, and more preferably in the range of 64 to 66. y is in the range of 27 to 33, preferably in the range of 28 to 32, and more preferably in the range of 29 to 31. z is in the range of 1 to 8, preferably in the range of 3 to 7, more preferably in the range of 4 to 6. A solid material where x + y + z = 100.

[0058] A very preferred embodiment of the present invention provides a solid material that can be obtained by melting and quenching a mixture of A and B, where, x is approximately 65, y is approximately 30, z is approximately 5.

[0059] Generally, the molar ratio of A to B in the mixture before quenching is preferably in the range of 75:25 to 98:2, more preferably 80:20 to 96:4, and more preferably 85:15 to 96:4. In some embodiments, the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 96:4, more preferably 70:30 to 96:4, and more preferably 75:25 to 96:4. In some embodiments, the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 94:6, more preferably 70:30 to 93:7, and more preferably 75:25 to 92:8.

[0060] Therefore, in some embodiments of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A and B, where, x is in the range of 62 to 68, preferably in the range of 63 to 67, and more preferably in the range of 64 to 66. y is in the range of 27 to 33, preferably in the range of 28 to 32, and more preferably in the range of 29 to 31. z is in the range of 1 to 8, preferably in the range of 3 to 7, more preferably in the range of 4 to 6. x+y+z=100, The molar ratio of A to B in the mixture before rapid cooling is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 96:4, and more preferably in the range of 85:15 to 96:4.

[0061] In some embodiments of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A and B, where, x is approximately 65, y is approximately 30, z is approximately 5, x+y+z=100, The molar ratio of A to B in the mixture before rapid cooling is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 96:4, and more preferably in the range of 85:15 to 96:4.

[0062] In another aspect of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A, B, and C. The molar ratios of A, B, and C in the mixture before rapid cooling are in the range of 40:30:30 to 98:1:1. Component A is of general formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85, preferably in the range of 55 to 75, more preferably in the range of 60 to 70. y is in the range of 15 to 45, preferably in the range of 20 to 40, and more preferably in the range of 25 to 35. z is in the range of 0 to 15, preferably in the range of 0 to 10, and more preferably in the range of 0 to 6. This is due to the fact that x+y+z=100. Component B is LiY 6 (Y 6 represents Br, Cl, I, or a combination thereof, preferably Y 6 (represents Br, Cl, or I), Component C is LiY 7 (In the formula, Y 7 represents Br, Cl, I, or a combination thereof, preferably Y 7 represents Br, Cl, or I, and Y 6 ≠Y 7 It is.

[0063] In a preferred embodiment of the present invention, a solid material is provided that can be obtained by melting and quenching a mixture of A, B, and C, where, x is in the range of 62 to 68, preferably in the range of 63 to 67, and more preferably in the range of 64 to 66. y is in the range of 27 to 33, preferably in the range of 28 to 32, and more preferably in the range of 29 to 31. z is in the range of 1 to 8, preferably in the range of 3 to 7, more preferably in the range of 4 to 6. x + y + z = 100.

[0064] A very preferred embodiment of the present invention provides a solid material that can be obtained by melting and quenching a mixture of A, B, and C, where, x is approximately 65, y is approximately 30, z is approximately 5.

[0065] Generally, the molar ratio of A, B, and C in the mixture before quenching is preferably in the range of 50:25:25 to 98:1:1, more preferably 56:22:22 to 90:5:5, and more preferably 64:15:21 to 80:10:10. In some embodiments, the molar ratio of A, B, and C in the mixture before quenching is in the range of 60:20:20 to 95:3:2, more preferably 70:15:15 to 90:5:5, and more preferably 76:12:12 to 82:9:9. In some very preferred embodiments, the molar ratio of A, B, and C in the mixture before quenching is in the range of 50:25:25 to 96:2:2, more preferably 60:20:20 to 90:5:5, and more preferably 70:15:15 to 80:10:10.

[0066] While we do not wish to be bound by any theory, generally, and therefore in some preferred embodiments of the present invention, the solid material that can be obtained by melting and quenching the mixture of A and B described herein is considered to be a solid material having a composition according to general formula (I) described herein (i.e., the solid material of Embodiment 1).

[0067] Solid materials according to various embodiments of the present invention described herein, namely solid materials having a composition according to general formula (I) described herein (i.e., the solid material of Embodiment 1) and solid materials that can be obtained by melting and quenching a mixture of A and B described herein (i.e., the solid material of Embodiment 2), are collectively referred to as "solid materials" (i.e., the solid materials of Embodiment 1 or 2).

[0068] According to a preferred embodiment of the present invention, a solid material is provided in which X represents Br, I, or a combination thereof. As shown in the appended examples, these materials have a thermal stability ΔT x Regarding this, it performs better than materials where X represents Cl.

[0069] According to a preferred embodiment of the present invention, a solid material is provided in which at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, and most preferably X represents Br. As shown in the attached examples, the material in which X represents Br has a thermal stability ΔT x Regarding this, it performs better than materials where X represents Cl.

[0070] According to a preferred embodiment of the present invention, a solid material is provided in which X represents Br, I, or a combination thereof, and at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br.

[0071] The solid material of the present invention is typically a glassy solid and can be obtained by melting and quenching a mixture of precursors described elsewhere in this specification. In some embodiments, the solid material is in the form of a monolithic glass, such as molten-cast monolithic glass. The glassy solid is preferably essentially free of a crystalline phase. This may mean that, in some embodiments, the amount of crystalline phase determined by X-ray diffraction is less than 5 volume%, preferably less than 2 volume%, and more preferably less than 1 volume% of the solid material. A phase is considered crystalline if its reflectance intensity is more than 10% above the background.

[0072] It has been found that the solid material of the present invention has surprisingly high ionic conductivity. According to a preferred embodiment of the present invention, there is provided a solid material having an ionic conductivity of at least 0.1 mS / cm at 25°C, preferably at least 0.3 mS / cm. As shown in the appended examples, the present inventors have surprisingly found that when at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, and most preferably X represents Br, the ionic conductivity at 25°C can be as high as 1.2 mS / cm. Therefore, in some embodiments of the present invention, there is provided a solid material having an ionic conductivity of at least 0.1 mS / cm at 25°C, preferably at least 1.1 mS / cm, more preferably at least 1.2 mS / cm. In a specific embodiment of the present invention, the solid material of the present invention is - at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br, and - has an ionic conductivity of at least 1 mS / cm at 25°C, preferably at least 1.1 mS / cm, more preferably at least 1.2 mS / cm.

[0073] For example, in some embodiments of the solid material of the present invention, at least 80 mol% of X represents Br, and the ionic conductivity of the solid material at 25°C is at least 1.1 mS / cm, or X represents Br, and the ionic conductivity of the solid material at 25°C is at least 1.2 mS / cm, for example at least 1.21 mS / cm, or at least 1.25 mS / cm.

[0074] It has been found that the solid material of the present invention combines high ionic conductivity and surprisingly low electrical conductivity, which makes it a very attractive solid battery electrolyte material. According to a preferred embodiment of the present invention, at 25°C it is 1×10 -4 less than mS / cm, preferably 6×10 -5A solid material having an electrical conductivity of less than mS / cm is provided. As shown in the appended examples, the present inventors have surprisingly found that when X represents Br, I or a combination thereof, the electrical conductivity at 25°C is very low, for example 1×10 -9 less than mS / cm or 1×10 -10 it can be less than mS / cm. Therefore, in some embodiments of the present invention, 1×10 at 25°C -5 less than mS / cm, preferably 1×10 -6 a solid material having an electrical conductivity of less than mS / cm is provided. In a particular embodiment of the present invention, -X represents Br, I or a combination thereof, and -the solid material has, at 25°C, 1×10 -9 less than mS / cm, preferably 1×10 -10 has an electrical conductivity of less than mS / cm.

[0075] In some particularly preferred embodiments of the present invention, a material combining high ionic conductivity and low electronic conductivity is provided. As shown in the appended examples, this is possible when X represents Br. For example, in some embodiments of the solid material of the present invention, -at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br, -the solid material has an ionic conductivity of at least 1 mS / cm at 25°C, preferably at least 1.1 mS / cm, more preferably at least 1.2 mS / cm, and -the solid material has, at 25°C, 1×10 -9 less than mS / cm, or 1×10 -10 has an electronic conductivity of less than mS / cm.

[0076] For example, in some embodiments, at least 50 mol% of X represents Br, preferably at least 80 mol% of X represents Br, most preferably X represents Br. The solid material has an ionic conductivity of at least 1.2 mS / cm at 25°C, and the solid material has 1×10 at 25°C -10It has an electronic conductivity of less than mS / cm.

[0077] As shown in the attached examples, the glassy solid of the present invention has high thermal stability ΔT compared to Li-S based glass. x It was found that the following is observed. According to a preferred embodiment of the present invention, the thermal stability ΔT is greater than 100°C, preferably greater than 110°C, and more preferably greater than 115°C. x A solid material having the following is provided. In some embodiments, in particular, when X represents Br, I, or a combination thereof, the thermal stability ΔT x The temperature exceeds 120°C, preferably exceeds 125°C, and more preferably exceeds 130°C.

[0078] In a particular very preferred embodiment, the solid material of the present invention is provided, where, - The solid material has an ionic conductivity of at least 0.1 mS / cm, preferably at least 0.3 mS / cm, at 25°C. - The solid material has thermal stability ΔT above 100°C, preferably above 110°C, and more preferably above 115°C. x It has, - Preferably, the solid material has 1 × 10 at 25°C. -5 Less than mS / cm, preferably 1 × 10⁻⁶ -6 It has an electronic conductivity of less than mS / cm.

[0079] In a particular very preferred embodiment, the solid material of the present invention is provided, where, -X represents at least 50 mol% Br, preferably at least 80 mol% Br, and most preferably X represents Br. - The solid material has an ionic conductivity of at least 1 mS / cm, preferably at least 1.1 mS / cm, and more preferably at least 1.2 mS / cm at 25°C. - The thermal stability ΔT of the solid material is above 120°C, preferably above 125°C, and more preferably above 130°C. x It has, - Preferably, the solid material has a temperature of 1 × 10 at 25°C. -9Less than mS / cm, preferably 1 × 10⁻⁶ -10 It has an electronic conductivity of less than mS / cm.

[0080] For example, in some embodiments, X represents I or Br, preferably Br. The solid material has an ionic conductivity of at least 1.1 mS / cm, more preferably at least 1.2 mS / cm, at 25°C, and the solid material has a thermal stability ΔT above 115°C, preferably above 125°C. x It holds.

[0081] While we do not wish to be bound by any theory, generally speaking, and therefore in some preferred embodiments of the present invention, the solid material that can be obtained by melting and quenching the mixture of A, B, and C described herein is considered to be a solid material having a composition according to the general formula (I)' described herein.

[0082] Solid materials according to various embodiments of the present invention described herein, namely solid materials having a composition according to general formula (I)' described herein and solid materials that can be obtained by melting and quenching a mixture of A, B, and C described herein, are collectively referred to as "solid materials".

[0083] According to a preferred embodiment of the present invention, the general formula (I)' (wherein Y 1 represents Br, Y 2 A solid material is provided by (where represents Cl), In the formula, Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents Cl, preferably Y 2 At least 80 mol% of it represents Cl, and more preferably Y 2 represents Cl.

[0084] The solid material of the present invention has been found to have a surprisingly high ionic conductivity. According to a preferred embodiment of the present invention, a solid material according to formula (I)' is provided, which has an ionic conductivity of at least 0.1 mS / cm, preferably at least 0.2 mS / cm, at 25°C. As shown in the appended examples, the inventors have surprisingly found that, Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents Cl, preferably Y 2 At least 80 mol% of it represents Cl, and more preferably Y 2 If represents Cl, We found that the ionic conductivity at 25°C can be as high as 0.67 mS / cm.

[0085] Accordingly, in some embodiments of the present invention, a solid material having an ionic conductivity of at least 0.3 mS / cm, preferably at least 0.40 mS / cm, and more preferably at least 0.49 mS / cm at 25°C is provided.

[0086] In a particular embodiment of the present invention, the solid material of the present invention is Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents Cl, preferably Y 2 At least 80 mol% of it represents Cl, and more preferably Y 2 represents Cl, and At 25°C, it has an ionic conductivity of at least 0.40 mS / cm, preferably at least 0.50 mS / cm, and more preferably at least 0.54 mS / cm.

[0087] According to a preferred embodiment of the present invention, a solid material according to formula (I)' is provided, Y 1 At least 50 mol% of it represents Cl, preferably Y 1 At least 80 mol% of it represents Cl, and more preferably Y 1 represents Cl, and At least 50 mol% of Y2 represents I, preferably at least 80 mol% of Y2 represents I, and more preferably Y2 represents I.

[0088] As shown in the attached examples, the inventors have surprisingly found that Y 1 At least 50 mol% of it represents Cl, preferably Y 1 At least 80 mol% of it represents Cl, and more preferably Y 1 represents Cl, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 If represents I, We found that the ionic conductivity at 25°C can be as high as 0.67 mS / cm.

[0089] Accordingly, in some embodiments of the present invention, a solid material having an ionic conductivity of at least 0.40 mS / cm, preferably at least 0.50 mS / cm, and more preferably at least 0.62 mS / cm at 25°C is provided.

[0090] In a particular embodiment of the present invention, the solid material of the present invention is Y 1 At least 50 mol% of it represents Cl, preferably Y 1 At least 80 mol% of it represents Cl, and more preferably Y 1 represents Cl, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 This represents I, and At 25°C, it has an ionic conductivity of at least 0.50 mS / cm, preferably at least 0.60 mS / cm, and more preferably at least 0.62 mS / cm.

[0091] According to a preferred embodiment of the present invention, a solid material according to formula (I)' is provided, Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 This represents I.

[0092] As shown in the attached examples, the inventors have surprisingly found that Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 If represents I, We found that the ionic conductivity at 25°C can be as high as 0.76 mS / cm. Therefore, in some embodiments of the present invention, a solid material having an ionic conductivity of at least 0.40 mS / cm, preferably at least 0.50 mS / cm, and more preferably at least 0.54 mS / cm at 25°C is provided.

[0093] The solid material of the present invention possesses both high ionic conductivity and remarkably low electrical conductivity, which has been found to make it a very attractive solid battery electrolyte material. According to a preferred embodiment of the present invention, a solid material according to formula (I)' is provided, which exhibits 1 × 10⁻¹⁶ conductivity at 25°C. -4Less than mS / cm, preferably 1 × 10⁻⁶ -5 It has an electrical conductivity of less than mS / cm. As shown in the attached examples, the inventors have surprisingly found that Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents Cl, preferably Y 2 At least 80 mol% of it represents Cl, and more preferably Y 2 If represents Cl, The electrical conductivity at 25°C is 1 × 10⁻⁶. -5 Less than mS / cm or 8 × 10 -6 We found that the levels can be extremely low, such as less than mS / cm.

[0094] In a particular embodiment of the present invention, Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents Cl, preferably Y 2 At least 80 mol% of it represents Cl, and more preferably Y 2 represents Cl, and The solid material is 1.0 × 10 at 25°C. -5 It has an electrical conductivity of less than mS / cm.

[0095] According to a preferred embodiment of the present invention, a solid material according to formula (I)' is provided, which is 1 × 10 at 25°C. -4 Less than mS / cm, preferably 1 × 10⁻⁶ -5 It has an electrical conductivity of less than mS / cm. As shown in the attached examples, the inventors have surprisingly found that Y 1 At least 50 mol% of it represents Cl, preferably Y 1At least 80 mol% of it represents Cl, and more preferably Y 1 represents Cl, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 If represents I, The electrical conductivity at 25°C is 1 × 10⁻⁶. -5 We found that the levels can be extremely low, such as less than mS / cm.

[0096] In a particular embodiment of the present invention, Y 1 At least 50 mol% of it represents Cl, preferably Y 1 At least 80 mol% of it represents Cl, and more preferably Y 1 represents Cl, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 This represents I, and The solid material is 1.0 × 10 at 25°C. -5 It has an electrical conductivity of less than mS / cm.

[0097] According to a preferred embodiment of the present invention, 1 × 10 at 25°C -4 Less than mS / cm, preferably 1 × 10⁻⁶ -5 A solid material having an electrical conductivity of less than mS / cm is provided. As shown in the attached examples, the inventors have surprisingly found that Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 represents Br, and Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 If represents I, The electrical conductivity at 25°C is 1 × 10⁻⁶. -5We found that the levels can be extremely low, such as less than mS / cm.

[0098] In a particular embodiment of the present invention, Y 1 At least 50 mol% of it represents Br, preferably Y 1 At least 80 mol% of it represents Br, and more preferably Y 1 This represents Br, Y 2 At least 50 mol% of it represents I, preferably Y 2 At least 80 mol% of it represents I, and more preferably Y 2 This represents I, and The solid material is 1.0 × 10 at 25°C. -4 It has an electrical conductivity of less than mS / cm.

[0099] As described throughout this application, the solid materials of the present invention can be obtained by melting and quenching a mixture of precursors to obtain a glassy solid. In some applications, it may be preferable that the material be provided in the form of a granular solid, such as a powder. This may facilitate blending with a cathode material, for example. The solid can be obtained directly in the form of a granular solid (such as a powder) or it can be ground (by milling, pulverizing, etc.) to become a granular solid (such as a powder). In other applications, the solid material may be preferred to be provided in the form of a thin sheet or film, preferably with a thickness of less than 500 microns, preferably less than 100 microns.

[0100] The inventors intend to add small amounts of other materials during synthesis such that general formula (I) or general formula (II) of the resulting solid material is no longer considered, but the changes do not substantially affect the basic and novel properties (or multiple properties) of the solid material of the present invention. Such forms of changes are considered to fall within the scope of general formula (I) or (II) for the purposes of the present invention.

[0101] Embodiment 3 In another aspect of the present invention, a method for preparing a solid material, (i) The following precursors ●Li2S, ●B2S3 and / or both boron and sulfur, ●Optionally, B2O3, and ●A process to provide LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4 or a combination thereof), (ii) A step of preparing a mixture containing the precursor provided in step (i), ●The molar ratio of elements Li, S, B, O, and X in the mixture is given by general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (In the formula, a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. (d is within the range of 0.001 to 0.14) or or ●In the mixture, the molar ratio of the precursor is given by General Formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85. y is within the range of 15 to 45. z is in the range of 0 to 15. The preparation process is such that it matches x+y+z=100. (iii) A step of heat-treating the mixture prepared in step (ii) to obtain a molten product, A method is provided which includes (iv) a step of rapidly cooling the molten material obtained in step (iii) to obtain a solid material.

[0102] In a preferred embodiment, a method for preparing a solid material, (i) The following precursors: ●Li2S, ●B2S3 and / or both boron and sulfur, ●Optionally, B2O3, and ●A process of providing LiX (wherein X represents Cl, Br, I, or a combination thereof), (ii) A step of preparing a mixture containing the precursor provided in step (i), ●The molar ratio of elements Li, S, B, O, and X in the mixture is given by general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (In the formula, a is within the range of 0.03 to 0.1. b is within the range of 0 to 0.04. c is within the range of 0.12 to 0.26. (d is within the range of 0.001 to 0.14) or or ●In the mixture, the molar ratio of the precursor is given by General Formula (II) xLi2S-yB2S3-zB2O3(II) (In the formula, x is in the range of 55 to 85. y is within the range of 15 to 45. z is in the range of 0 to 15. The preparation process is such that it matches x+y+z=100. (iii) A step of heat-treating the mixture prepared in step (ii) to obtain a molten product, A method is provided which includes (iv) a step of rapidly cooling the molten material obtained in step (iii) to obtain a solid material.

[0103] This method is generally referred to as the melt-quench method of the present invention. This process is cost-effective and easily scalable. In the context of Embodiment 1, preferred embodiments of general formula (I), particularly a, b, c, and d, described herein are equally applicable to methods for preparing solid materials. Similarly, in the context of Embodiment 2, preferred embodiments of general formula (II), particularly x, y, and z, described herein are equally applicable to the melt-quench method of the present invention. In addition, preferred embodiments of solid materials of the present invention (i.e., Embodiment 1 or 2) are generally equally applicable to the melt-quench method of Embodiment 3 (with respect to, for example, the identity, conductivity, thermal stability, etc., of X).

[0104] The provision of both boron and sulfur in step (i) should be interpreted as meaning that elemental boron and elemental sulfur are provided. Elemental boron and elemental sulfur may be provided in amorphous or crystalline form, and the specific allotropes used do not particularly limit the invention.

[0105] The preparation of the mixture in step (ii) may be carried out by any suitable means, preferably by mechanical milling (e.g., ball milling).

[0106] Step (iii) includes heating the mixture prepared in step (ii) to obtain a melt, i.e., heat-treating it at a temperature higher than the melting point of the mixture prepared in step (ii). Preferably, step (iii) includes heat-treating the mixture prepared in step (ii) at a temperature of at least 400°C, preferably at least 600°C, and more preferably at least 800°C. The mixture is preferably held at this temperature for at least 15 minutes, preferably at least 30 minutes, and more preferably at least 2 hours.

[0107] The heat treatment may be carried out in a sealed vessel. The sealed vessel may be a sealed quartz tube or any other type of vessel that can withstand the heat treatment temperature and is not affected by reactions with the glass components, and such a sealed vessel may be made from a material selected from magnesium oxide, boron nitride, copper, tungsten, silicon nitride, aluminum nitride, carbon, and combinations thereof. The heat treatment in step (iii) may be a single-stage or multi-stage heat treatment.

[0108] Step (iii) is preferably carried out in an inert gas atmosphere, preferably in an inert atmosphere containing one or more noble gases (such as argon), and / or at a pressure of less than 1 atmosphere, preferably less than 0.1 atmospheres, and more preferably less than 0.01 atmospheres. Typically, and therefore preferably, step (iii) is carried out at 10 -4 Less than atmospheric pressure, preferably 10 -5 The process is carried out at a pressure below atmospheric pressure, preferably in an inert gas atmosphere, and more preferably in an inert atmosphere containing one or more noble gases (such as argon). The use of nitrogen as the inert atmosphere should generally be avoided due to the potential for reaction with the glass precursor.

[0109] The melting-quick cooling method of the present invention is very preferably for preparing a solid material according to Embodiment 1 or Embodiment 2 described herein.

[0110] In some embodiments of the melt-quenching method of the present invention, step (iv) is: (iv)a A step of rapidly cooling the molten material obtained in step (iii) to obtain a solid material, (iv)b A step of crushing the solid material from step (iv)a to obtain a granular solid such as a powder, (iv)c Optionally, a thin film or sheet, preferably a film or sheet having a thickness of less than 500 microns, preferably less than 100 microns, - A step of dissolving or suspending the granular solid from step (iv)b in a liquid phase to obtain a solution or suspension, and then depositing from the solution or suspension to obtain a thin film or sheet, a step of further comprising the step of forming by reheating the granular solid of step (iv)b to a temperature sufficient to enable stretching of the film or sheet and stretching the film or sheet;

[0111] In an alternative embodiment, step (iv) comprises quenching the melt of step (iii) while maintaining a temperature sufficiently high to enable stretching of the thin film or sheet, and stretching the film or sheet, preferably stretching a film or sheet having a thickness of less than 500 microns, preferably less than 100 microns.

[0112] The method is preferably operated in the form of a continuous process to produce a continuous glass film or sheet that is cut to a desired size.

[0113] The quenching step in step (iv) is preferably carried out by direct contact of the melt obtained in step (iii), or by bringing into contact with water, ice, optionally cooled gas (such as air), optionally cooled metal plate (by roller quenching or the like), and / or chemically inert molds while the vessel is closed or open (preferably while closed).

[0114] Embodiment 4 In another aspect of the present invention, there is provided a solid composition comprising a first solid material which is the solid material described herein (that is, the solid material of Embodiment 1 or 2), and further comprising at least a second solid material having a composition different from that of the first solid material. The first solid material may be present in the form of discrete particles embedded in a matrix of the second solid material. Alternatively, the first solid material and the second solid material may optionally be present in the form of discrete particles blended in combination with a binder material and one or more further materials, and the blend is preferably compressed. Alternatively, the first solid material and the second solid material may be present in the form of different layers of a multilayer thin sheet or film, preferably a multilayer thin sheet or film having a total thickness of less than 500 microns, preferably less than 200 microns. Such a solid composition comprising a first solid material which is the solid material described herein and further comprising at least a second solid material having a composition different from that of the first solid material is particularly useful as a cathode, an anode or a separator of an electrochemical cell, especially as a separator or a cathode. In some embodiments, the second solid material is a cathode material such as a nickel-cobalt or a nickel-manganese-cobalt cathode material.

[0115] Embodiment 5 In another aspect of the present invention, there is provided an electrochemical cell comprising the solid material described herein (that is, the solid material of Embodiment 1 or 2). In particular, there is provided an electrochemical cell wherein the cathode, anode and / or separator comprise the solid material as defined herein. In some embodiments, there is provided an electrochemical cell wherein the cathode, anode and / or separator comprise the solid material as defined herein in the form of a solid composition that comprises a first solid material which is the solid material described herein and further comprises at least a second solid material having a composition different from that of the first solid material. Such a solid composition is described in connection with another aspect of the present invention. In a particularly preferred embodiment of the present invention, there is provided an electrochemical cell wherein the separator comprises the solid material as defined herein, optionally in the form of the solid composition described herein. In some embodiments, the separator consists of the solid material described herein.

[0116] Embodiment 6 Another aspect of the present invention provides the use of a solid material described herein (i.e., the solid material of Embodiment 1 or 2) or a solid composition described herein (i.e., the solid composition of Embodiment 4) as a solid electrolyte for an electrochemical cell. Preferably, the use of a solid material described herein as a solid electrolyte for an electrochemical cell is provided.

[0117] In the context of the various embodiments of the present invention described herein, suitable electrochemically active cathode materials and suitable electrochemically active anode materials are known in the art. For example, the anode may include graphite carbon, metallic lithium, or a metal alloy containing lithium as the anode active material. For example, the cathode may include nickel-cobalt or nickel-manganese-cobalt cathode materials. The electrochemical cells described herein preferably have charge transport by Li + This is a lithium-ion-containing cell that operates using ions. The electrochemical cell may have a disc-shaped or prismatic shape. The electrochemical cell may include a housing that may be made of steel or aluminum. Multiple electrochemical cells can be combined to form an all-solid-state battery having both solid electrodes and a solid electrolyte.

[0118] Embodiment 7 Another aspect of the present invention relates to a battery, more specifically a lithium-ion battery or a lithium metal battery, comprising at least one electrochemical cell containing the solid material described herein (i.e., the solid material of Embodiment 1 or 2), for example, two or more electrochemical cells as described in Embodiment 5. A particular embodiment relates to a solid battery, preferably a lithium solid battery comprising at least one electrochemical cell containing the solid material described herein (i.e., the solid material of Embodiment 1 or 2), for example, two or more electrochemical cells as described in Embodiment 5. The electrochemical cells as described in Embodiment 5 can be combined with each other, for example, in series or parallel. Series connection is preferred. Each of the electrochemical cells described herein can be used to manufacture or operate stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOSes, communication devices, or remote car locks, and energy storage devices for power plants.

[0119] Embodiment 8 A further aspect of the present invention is a method for manufacturing or operating stationary applications such as cars, computers, personal digital assistants, mobile phones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOSes, communication equipment, remote car locks, and energy storage devices for power plants, by using at least one electrochemical cell comprising at least one battery or solid material as described herein (i.e., the electrochemical cell described in Example 5).

[0120] Embodiment 9 Further aspects of the present disclosure relate to the use of electrochemical cells comprising the solid material of the present invention (i.e., the electrochemical cell described in Embodiment 5) in automobiles, electric motor-driven bicycles, robots, aircraft (e.g., unmanned aerial vehicles including drones), ships, or fixed energy storage devices. The present invention further provides a device comprising at least one electrochemical cell described in Embodiment 5. Mobility devices such as vehicles, e.g., automobiles, bicycles, aircraft, or water vehicles, e.g., boats or ships are preferred. Other examples of mobility devices are portable devices such as computers, particularly laptops, telephones, or power tools from the construction sector, e.g., particularly drills, battery-powered screwdrivers, or battery-powered tackers.

[0121] Embodiment 10 In another aspect of the present invention, the thermal stability ΔT of a glassy solid x To improve the thermal stability ΔT of sulfide-based lithium-ion conductive solid electrolytes, in particular. x To improve the thermal stability ΔT of a glassy solid according to the general formula (II) described in Embodiment 2, the use of a lithium salt of formula LiX (wherein X represents F, Cl, Br, I, N3, SCN, CN, OCN, BF4, BH4 or a combination thereof, preferably X represents Cl, Br, I or a combination thereof) is provided. In some embodiments, the use is provided for the thermal stability ΔT of a glassy solid according to the general formula (II) described in Embodiment 2. x Provided to improve the above. In the context of Embodiment 2, preferred embodiments of general formula (II), in particular x, y, and z, described herein are equally applicable to the use of Embodiment 10.

[0122] The present invention is further illustrated by the following, non-limiting embodiments. [Examples]

[0123] 1. Preparation of materials For each example, 15 g of the final material was prepared using the following starting products: amorphous B2S3 (99 wt%), Li2S (99.9 wt%), B2O3 (99.95 wt%), and LiX (LiI (99 wt%), LiBr (99 wt%), LiCl (99 wt%)). Appropriate amounts of the starting materials were weighed and mixed in an argon-filled glove box and introduced into carbon-coated silica ampoules. The ampoules were sealed and introduced into a vertical oscillating furnace. The molten material was homogenized at an internal temperature of 950°C for 30 minutes, and then rapidly cooled in water at room temperature. The ampoules were then opened in an argon-filled glove box. An orange or brown glassy material with good transparency was obtained.

[0124] In some examples, alternative synthesis methods were successfully implemented in which the amounts of boron and sulfur provided by B2S3 were provided in the form of amorphous element B (99 wt%) and element S (99.999 wt%).

[0125] 2. Thermal stability ΔT x decision Thermal analysis was performed using a differential scanning calorimetry (DSC) 3500 Sirius. 5-10 mg of glassy material samples were placed in a sealed aluminum pan and analyzed using a temperature profile from 100°C to 350°C at a rate of 10°C / min. For all samples, the glass transition temperature (T) was determined. g ) and the start of crystallization (T x ) was determined. Next, thermal stability was estimated from the simple difference between these values ​​(ΔT x =T x -T g ).

[0126] Glass transition temperature (T g ) is determined by constructing tangents to the DSC curve baselines before and after the glass transition, and determining the extrapolation start temperature by the intersection of these tangents, which essentially corresponds to the temperature at which the highest gradient in the descent of the DSC baseline occurs before the exothermic crystallization peak. The T thus obtained g T starting temperature g That's what I decided.

[0127] 3. Measurement of Conductivity Ionic conductivity was measured by electrochemical impedance spectroscopy (EIS) at room temperature (25°C) on hot-pressed samples in a pellet cell equipped with ion-blocking electrodes. The samples were densified at 350 MPa and 125°C for 5 minutes. Ionic conductivity was measured under an operating pressure of 125 MPa. For EIS, an excitation voltage of 10 mV was applied over a frequency range from 7 MHz to 1 Hz. Data were interpreted by equivalent circuit analysis.

[0128] Electrical conductivity was measured at room temperature (25°C) on hot-pressed samples in a pellet cell equipped with ion-blocking electrodes. The samples were densified at 350 MPa and 125°C for 5 minutes. Electrical conductivity was measured under an operating pressure of 125 MPa. Electrical conductivity was measured by stepped constant potential polarization at 0.2, 0.4 and 0.6 V for 20 minutes each.

[0129] Both measurements were performed using a potentiostat equipped with a frequency analyzer (Biologic).

[0130] 4. Determination of the Identity of the Obtained Glass Inductively coupled plasma optical emission spectroscopy (ICP-OES) was applied to the example glassy materials prepared as described above.

[0131] Samples of the glassy material are weighed in a glove box under an Ar atmosphere and added to a microwave vessel to avoid reaction with water or O₂. A combination of acids is added, the vessel is closed, and digestion is performed in a microwave until the solution becomes clear. Matrix elements (Li & B) are analyzed using a high-precision ICP-OES method.

[0132] S is determined by elemental analysis after sample preparation in an Ar-filled glove box. Sample preparation consists of placing approximately 100 mg of sample into a sealed capsule, and then adding the sealed capsule and additive to a ceramic crucible. Subsequently, the filled crucible is heated in an induction furnace under an O2 atmosphere. The present S is released from the sample, converted to SO2 gas, and detected by an SO2-specific IR detector. The detected SO2 signal is finally converted to the S concentration by using a calibration curve and taking into account the exact sample mass.

[0133] The composition of the glass was found to correspond to the overall formula predicted based on the molar ratio of the precursor subjected to melting and quenching, within the expected margin of experimental error and variation.

[0134] 5.Results

[0135] [Table 1]

[0136] [Table 2]

[0137] [Table 3A]

[0138] [Table 3B]

Claims

1. General formula (I) Li ２ｃ＋ｄ B ２ａ＋２ｂ S ３ａ＋ｃ O ３ｂ X ｄ (I) (In the formula, X is F, Cl, Br, I, N ３ , SCN, CN, OCN, BF ４ BH ４ , or a combination thereof, a is within the range of 0.03 to 0.

1. b is in the range of 0 to 0.04, c is within the range of 0.12 to 0.

26. A solid material having a composition in which d is in the range of 0.001 to 0.

14.

2. The solid material according to claim 1, wherein X represents Cl, Br, I, or a combination thereof.

3. During the ceremony, a is within the range of 0.06 to 0.

1. b is in the range of 0.002 to 0.02, c is in the range of 0.14 to 0.

19. The solid material according to claims 1 and 2, wherein d is in the range of 0.001 to 0.

14.

4. During the ceremony, The solid material according to any one of claims 1 to 3, wherein d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, and more preferably in the range of 0.01 to 0.

04.

5. The solid material is the solid material according to any one of claims 1 to 4, wherein the solid material is a solid material according to formula (I)a, (I)b, (I)c, or (I)d. 【Chemistry 1】

6. A solid material according to any one of claims 1 to 5, wherein 5a + 5b + 3c + 2d = 1.

7. A solid material that can be obtained by melting and rapidly cooling a mixture of A and B, preferably the solid material according to any one of claims 1 to 6, The molar ratio of A to B in the mixture before rapid cooling is within the range of 60:40 to 99:

1. Component A is general formula (II) xLi ２ S-yB ２ S ３ -zB ２ O ３ (II) (In the formula, x is in the range of 55 to 85, preferably in the range of 55 to 75, and more preferably in the range of 60 to 70. y is in the range of 15 to 45, preferably in the range of 20 to 40, and more preferably in the range of 25 to 35. z is in the range of 0 to 15, preferably in the range of 0 to 10, more preferably in the range of 0 to 6. This is due to the fact that x + y + z = 100. Component B is LiX (wherein X is F, Cl, Br, I, N) ３ , SCN, CN, OCN, BF ４ BH ４ A solid material (or a combination thereof).

8. The solid material according to claim 7, wherein X represents Cl, Br, I, or a combination thereof.

9. x is in the range of 62 to 68, preferably in the range of 63 to 67, and more preferably in the range of 64 to 66. y is in the range of 27 to 33, preferably in the range of 28 to 32, and more preferably in the range of 29 to 31. z is in the range of 1 to 8, preferably in the range of 3 to 7, and more preferably in the range of 4 to 6. The solid material according to claim 7 or 8, wherein x + y + z = 100.

10. The solid material according to any one of claims 7 to 9, wherein the molar ratio of A to B in the mixture before rapid cooling is in the range of 70:30 to 96:

4.

11. The solid material according to any one of claims 1 to 10, wherein X represents Br, I, or a combination thereof.

12. The solid material according to any one of claims 1 to 11, wherein the material is a glassy solid.

13. The material has an ionic conductivity of at least 0.1 mS / cm, preferably at least 0.3 mS / cm, at 25°C, and a thermal stability ΔT greater than 100°C, preferably greater than 110°C, more preferably greater than 115°C. ｘ It has, where ΔT ｘ = T ｘ -T ｇ And in the formula, T ｘ However, this is the crystallization start temperature determined by DSC, and T ｇ The solid material according to any one of claims 1 to 12, wherein the glass transition temperature is determined by DSC.

14. A method for preparing a solid material, preferably the solid material described in any one of claims 1 to 13, (i) The following precursors: ●Li ２ S、 ●B ２ S ３ And / or both boron and sulfur, ●Optional, B ２ O ３ , and ●LiX (wherein X is F, Cl, Br, I, N) ３ , SCN, CN, OCN, BF ４ BH ４ A process of providing (or a combination thereof), (ii) A step of preparing a mixture containing the precursor provided in step (i), ● The molar ratio of the elements Li, S, B, O, and X in the mixture matches the general formula (I) described in claims 1 to 6, or ●A preparation step in which, in the mixture, the molar ratio of the precursor matches the general formula (II) described in claims 7 to 10, and the molar ratio of A to B in the mixture is as described in claims 7 to 10, (iii) A step of heat-treating the mixture prepared in step (ii) to obtain a molten product, A method comprising the step of (iv) rapidly cooling the molten material obtained in step (iii) to obtain the solid material, preferably the solid material according to any one of claims 1 to 13.

15. The method according to claim 14, wherein X represents Cl, Br, I, or a combination thereof.

16. An electrochemical cell comprising the solid material described in any one of claims 1 to 13.

17. The electrochemical cell according to claim 16, wherein the separator comprises a solid material according to any one of claims 1 to 13.

18. Use of the solid material according to any one of claims 1 to 13 as a solid electrolyte for an electrochemical cell.

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