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

Abstract

The present invention relates to a solid material obtained by melt-quenching a mixture of lithium sulfide, boron sulfide and boron oxide, thereby forming 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 is evidenced by a large ΔT x , particularly a ΔT exceeding 100 °C x as confirmed by.

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, thereby forming 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, particularly as an electrolyte, in an electrochemical cell such as an all-solid-state battery.

Background Art

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

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

[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 is Li 2 S-SiS 2 、Li 2 S-P 2 S 5 、or Li 2 S-B 2 S 3It is a sulfide-based amorphous solid (which may be equivalently referred to as a glassy solid). In the glassy solid electrolyte material, due to the absence of a crystal path, isotropic conduction with substantially no grain boundary resistance can be obtained. Since there are no grain boundaries in the glassy electrolyte material, the formation of dendritic crystals can also be prevented. This is because the glassy amorphous electrolyte material can be obtained as a high-density and defect-free film by a melt-quenching method.

[0005] A major issue in the manufacture of glassy solid electrolytes is to avoid crystal regions in the solid material. The thermal stability ΔT of the glass x can be characterized as the stability against crystallization, and is the temperature difference between the onset temperature of crystallization (T x ) and the glass transition temperature (T g ), that is, ΔT x = T x - T g . ΔT x being large generally involves an improvement in glass-forming ability and an increase in glass stability during post-treatment.

[0006] In initial studies on Li 2 S-B 2 S 3 compositions having molar ratios of 70:30 and 60:40, ΔT x values of about 70 °C and about 110 °C were reported respectively (Zhang et al, Solid State Ionics 1990, 38, 217 - 224).

[0007] U.S. Patent No. 5500291 contemplates a sulfide-based lithium ion conductive solid electrolyte of the Li 2 S-SiS 2 -Li 4 SiO 4 type.

[0008] International Publication No. 2020 / 254314 (A1) discloses a Li 2 S-B 2 S obtained from a mixture further comprising an oxide of P, Si, Ge, As or Sb in combination with lithium halide.3 A sulfide-based lithium ion conductive solid electrolyte of the type is contemplated. The obtained glassy solid is said to have a favorable lithium ion conductivity, as well as electrochemical stability in direct contact with lithium metal, and chemical stability against air and moisture. The ΔT of these solids x is in the range of 5 to 36 °C (Table 3 of International Publication No. 2020 / 254314 (A1)).

[0009] International Publication No. 2016 / 089899 (A1) contemplates a number of glass systems (many of which are speculative or unsubstantiated). Paragraphs 186 and 188 of International Publication No. 2016 / 089899 (A1) suggest adding oxygen to improve ΔT x . In paragraph 190 of International Publication No. 2016 / 089899 (A1), Li 2 S / Li 2 0-B 2 S 3 -SiS 2 -based systems are speculated to have a ΔT x exceeding 100 °C.

[0010] A drawback regarding most sulfide-based lithium ion conductive solid electrolytes known in the art is that they have either a low ionic conductivity or a high ΔT x . Therefore, there is a great need to provide a sulfide-based lithium ion conductive solid electrolyte having both characteristics at present.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0012]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0013] An object of the present invention is to provide a sulfide-based lithium ion conductive solid electrolyte having a large ΔT x , particularly a ΔT exceeding 100°C x . Another object of the present invention is to provide a sulfide-based lithium ion conductive solid electrolyte having a high ionic conductivity. Another object of the present invention is to provide a sulfide-based lithium ion conductive solid electrolyte having a low electrical conductivity.

Means for Solving the Problems

[0014] The present inventors have found that one or more objects of the present invention can be achieved by providing a sulfide-based lithium ion conductive solid electrolyte obtained by melt-quenching a combination of Li 2 S;B 2 S 3 and B 2 O 3 in a clearly defined ratio. It has been found that it can be achieved by providing a sulfide-based lithium ion conductive solid electrolyte obtained by melt-quenching a combination of B 2 S 3 ;B 2 O 3 and LiX (wherein X represents Cl, Br, I or a combination thereof). As shown in the attached examples, the obtained glassy solid actually exhibits high thermal stability ΔT x , high ionic conductivity and / or low electrical conductivity in Li-S-based glasses.

[0015] Embodiment 1 Therefore, in the first aspect of the present invention, the general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (wherein X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 or a combination thereof, and a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14) provides a solid material having a composition.

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

[0017] Embodiment 2 In another aspect of the present invention, a solid material obtainable by melt - quenching a mixture of A and B is provided, the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 99:1, component A has the general formula (II) xLi 2 S - yB 2 S 3 - zB 2 O 3 (II) (wherein x is in the range of 55 to 85, y is in the range of 15 to 45, z is in the range of 0 to 15, and x + y + z = 100) Component B is LiX (wherein X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 or a combination thereof, and 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, comprising: (i) the following precursors: ● Li 2 S, ● B 2 S 3 and / or both boron and sulfur, ● optionally, B 2 O 3 , and ● LiX (wherein X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 or a combination thereof, and preferably, X represents Cl, Br, I or a combination thereof) are provided; (ii) preparing a mixture comprising the precursors provided in step (i), wherein ● in the mixture, the molar ratios of the elements Li, S, B, O and X are in the general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (wherein a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is within the range of 0.001 to 0.14), or ● In the mixture, the molar ratio of the precursors is represented by the general formula (II) xLi 2 S - yB 2 S 3 - zB 2 O 3 (II) (wherein x is within the range of 55 to 85, y is within the range of 15 to 45, z is within the range of 0 to 15, x + y + z = 100), and a step that conforms to this, (iii) A step of heat - treating the mixture prepared in step (ii) to obtain a melt, (iv) A step of rapidly cooling the melt obtained in step (iii) to obtain a solid material. A method including these steps is provided.

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

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

[0021] Embodiment 6 In another aspect of the present invention, the use of the solid material described herein (i.e., the solid material of Embodiment 1 or 2) or the 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 at least one electrochemical cell comprising the solid material described herein (i.e., the solid material of Embodiment 1 or 2), for example, a battery comprising two or more electrochemical cells described in Embodiment 5, more specifically a lithium ion battery or a lithium metal battery.

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

[0024] Embodiment 9 A further aspect of the present disclosure is the use of an electrochemical cell comprising the solid material of the present invention (i.e., the electrochemical cell described in Embodiment 5) in an automobile, a bicycle operated by an electric motor, a robot, an aircraft (e.g., an unmanned aircraft including a drone), a ship, or a stationary energy storage device.

[0025] Embodiment 10 In another aspect of the present invention, the use of a lithium salt of the formula LiX (wherein X represents F, Cl, Br, I, N x to improve the thermal stability ΔT of a glassy solid, in particular the thermal stability ΔT of a sulfide-based lithium ion conductive solid electrolyte x is provided. 3 SCN, CN, OCN, BF 4 BH 4 or a combination thereof, preferably X represents Cl, Br, I or a combination thereof).

DETAILED DESCRIPTION OF THE INVENTION

[0026] In the following detailed description, in order to implement the present invention, preferred embodiments are described in detail. The present invention is described with reference to these specific preferred embodiments, but it should be understood that the present invention is not limited to these preferred embodiments. In contrast, however, the present invention includes numerous alternatives, modifications, and equivalents, as will become apparent in view of the following forms for carrying out the invention.

[0027] As referred to herein, the glass transition temperature (T g ) refers to the onset temperature of the glass transition determined by differential scanning calorimetry (DSC). This is preferably determined by constructing tangents to the DSC curve baselines 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 occurs in the drop of the DSC baseline before the exothermic crystallization peak. The DSC is preferably recorded using a temperature profile of 100 °C to 350 °C at a rate of 10 °C / min and is preferably recorded for a sample of 5 to 10 mg in a sealed aluminum pan. A suitable DSC apparatus is the DSC3500 Sirius.

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

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

[0030] As used herein, the electrical conductivity refers to the electrical conductivity measured at 25 °C. The electrical conductivity is preferably determined using an ion-blocking electrode on a hot-pressed sample densified at 350 MPa and 125 °C for 5 minutes, and then the electrical conductivity is measured at 25 °C under an operating pressure of 125 MPa. Preferably, the electrical conductivity is measured by stepwise potentiostatic 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) (wherein, X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 , or a combination thereof, a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14) provides a solid material having a composition.

[0032] While not wishing to be bound by any theory, the inventors believe that the solid material according to formula (I), as described herein in the context of other aspects and embodiments of the invention, has a well-defined ratio of Li 2 S, B 2 S 3 ; B 2 O 3 and LiX (wherein X is F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 , or a combination thereof) obtained by melt-quenching a mixture thereof.

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

[0034] General formula (I) (wherein a is in the range of 0.06 to 0.1, b is in the range of 0 to 0.03, c is in the range of 0.12 to 0.20, d is in the range of 0.001 to 0.14, more preferably, wherein a is in 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, d is in the range of 0.001 to 0.14) is preferably provided with a solid material having a composition.

[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, general formula (I) (wherein, a is in the range of 0.06 to 0.1, b is in the range of 0 to 0.03, c is in 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 in 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, 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) provides a solid material having a composition.

[0037] According to a highly preferred embodiment of the present invention, general formula (I) (wherein 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 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, is provided.

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

[0039] In a highly preferred embodiment of the present invention, the solid material is of the 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 of the formula (I)a, (I)b, (I)c or (I)d (wherein, a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14).

Chemical formula

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

[0041] In a specific preferred embodiment, the solid material of the present invention is of the formula (I)' Li 2c+d B 2a+2b S 3a+c O 3b Y 1 e Y 2 f (I)' (wherein Y 1 and Y 2 are, independently, selected from the group consisting of F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 and Y 1 ≠ Y 2 and (wherein a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26), or e is in the range of 0.001 to 0.14, f is in the range of 0.001 to 0.14).

[0042] In a preferred embodiment, Y 1 and Y 2 are, independently, selected from the group consisting of Cl, Br and I.

[0043] Preferably, the solid material is of formula (I)' (wherein a is in 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), or e is in the range of 0.001 to 0.14, f is in the range of 0.001 to 0.14).

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

[0045] In a highly preferred embodiment, the solid material is according to formula (I)'a, (I)'b or (I)'c.

Chemical formula

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

[0047] In a particular highly 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 5 i (I)'' (wherein Y 3 、Y 4 and Y 5が are independently selected from the group consisting of F, Cl, Br, I, N 3 、SCN, CN, OCN, BF 4 、BH 4 and Y 3 ≠Y 4 ≠Y 5 and also (wherein, a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26) or g is in the range of 0.001 to 0.14, h is in the range of 0.001 to 0.14, i is in the range of 0.001 to 0.14).

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

[0049] Preferably, the solid material has the formula (I)’’ (wherein, a is in 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), or g is in the range of 0.001 to 0.14, h is in the range of 0.001 to 0.14, i is in the range of 0.001 to 0.14).

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

[0051] In a highly preferred embodiment, the solid material has the formula (I)’’a.

Chemical formula

[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 of the embodiments 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. Further, in each of the embodiments of the present composition according to general formula (I)' or formula (I)'', 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] A solid material having a composition according to general formula (I), when prepared, for example, by melt - quenching, may typically have a minor impurity phase consisting of a precursor or an intermediate formed from the precursor, which is mainly used for preparing the solid material. Further, a solid material having a composition according to general formula (I)' or formula (I)'', when prepared, for example, by melt - quenching, may typically have a minor impurity phase consisting of a precursor or an intermediate formed from the precursor, which is mainly used for preparing the solid material.

[0055] Embodiment 2 In another aspect of the present invention, there is provided a solid material obtainable by melt - quenching a mixture of A and B, wherein the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 99:1, Component A has the general formula (II) xLi 2 S - yB 2 S 3 - zB 2 O 3 (II) (wherein, 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, 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, is due to x + y + z = 100, Component B is LiX (where X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 or a combination thereof).

[0056] In a preferred embodiment of the present invention, the solid material can be obtained by melt - quenching a mixture of A and B, and the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 99:1, Component A is represented by the general formula (II) xLi 2 S - yB 2 S 3 - zB 2 O 3 (II) (where 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, 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, and x + y + z = 100), and component B is LiX (where X represents Cl, Br, I or a combination thereof).

[0057] In a preferred embodiment of the present invention, there is provided a solid material that can be obtained by melt - 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, 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, 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 wherein x + y + z = 100.

[0058] According to a highly preferred embodiment of the present invention, there is provided a solid material obtainable by melt-quenching a mixture of A and B, wherein x is about 65, y is about 30, z is about 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 in the range of 80:20 to 96:4, still more preferably in the range of 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, preferably in the range of 70:30 to 96:4, more preferably in the range of 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, preferably in the range of 70:30 to 93:7, more preferably in the range of 75:25 to 92:8.

[0060] Thus, in some embodiments of the present invention, there is provided a solid material obtainable by melt-quenching a mixture of A and B, wherein x is in the range of 62 to 68, preferably in the range of 63 to 67, 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, 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, and the molar ratio of A to B in the mixture before quenching is in the range of 75:25 to 98:2, preferably in the range of 80:20 to 96:4, more preferably in the range of 85:15 to 96:4.

[0061] In some embodiments of the present invention, a solid material can be obtained by melt-quenching a mixture of A and B, where x is about 65, y is about 30, z is about 5, x + y + z = 100, the molar ratio of A to B in the mixture before quenching 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 can be obtained by melt-quenching a mixture of A, B, and C, the molar ratio of A, B, and C in the mixture before quenching is in the range of 40:30:30 to 98:1:1, Component A has the general formula (II) xLi 2 S - yB 2 S 3 -zB 2 O 3 (II) (where 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, and more preferably in the range of 0 to 6, 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 (where Y 7 represents Br, Cl, I, or a combination thereof, preferably Y 7represents Br, Cl or I, and Y 6 ≠Y 7 is).

[0063] In a preferred embodiment of the present invention, a solid material can be provided by melt - quenching a mixture of A, B and C, wherein x is in the range of 62 to 68, preferably in the range of 63 to 67, 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, 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] According to a highly preferred embodiment of the present invention, a solid material can be provided by melt - quenching a mixture of A, B and C, wherein x is about 65, y is about 30, z is about 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 in the range of 56:22:22 to 90:5:5, and even more preferably in the range of 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, preferably in the range of 70:15:15 to 90:5:5, and more preferably in the range of 76:12:12 to 82:9:9. In some highly 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, preferably in the range of 60:20:20 to 90:5:5, and more preferably in the range of 70:15:15 to 80:10:10.

[0066] Although not wishing to be bound by any theory, generally, and thus in some preferred embodiments of the present invention, the solid material obtainable by melt-quenching the mixture of A and B described herein is considered to be the solid material having the composition according to the general formula (I) described herein (i.e., the solid material of Embodiment 1).

[0067] The solid materials according to various aspects of the present invention described herein, i.e., the solid material having the composition according to the general formula (I) described herein (i.e., the solid material of Embodiment 1) and the solid material obtainable by melt-quenching the 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 attached examples, these materials have better performance with respect to the thermal stability ΔT x than the material in which 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 better performance with respect to the thermal stability ΔT x than the material in which 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 as described elsewhere in this specification. In some embodiments, the solid material is in the form of a monolithic glass such as a melt-cast monolithic glass. The glassy solid preferably essentially does not contain a crystalline phase. This may mean that in some embodiments the amount of crystalline phase determined by X-ray diffraction is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume of the solid material. A phase is considered crystalline if its reflection intensity exceeds the background by more than 10%.

[0072] The solid material of the present invention has been found to have 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, preferably at least 0.3 mS / cm at 25°C. As shown in the attached examples, the 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. Thus, in some embodiments of the present invention, there is provided a solid material having an ionic conductivity of at least 0.1 mS / cm, preferably at least 1.1 mS / cm, more preferably at least 1.2 mS / cm at 25°C. In certain embodiments 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, and most preferably X represents Br, and - at 25°C, has an ionic conductivity of at least 1 mS / cm, 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] The solid material of the present invention has both high ionic conductivity and surprisingly low electrical conductivity, and thus has been found to be a very attractive solid battery electrolyte material. According to a preferred embodiment of the present invention, at 25 °C, 1 × 10 -4 less than mS / cm, preferably less than 6 × 10 -5 A solid material having an electrical conductivity of mS / cm is provided. As shown in the attached examples, the 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 less than 1 × 10 -9 mS / cm or less than 1 × 10 -10 mS / cm. Therefore, in some embodiments of the present invention, a solid material having an electrical conductivity of less than 1 × 10 -5 mS / cm at 25 °C, preferably less than 1 × 10 -6 mS / cm is provided. In a specific embodiment of the present invention, - X represents Br, I or a combination thereof, and - The solid material has an electrical conductivity of less than 1 × 10 -9 mS / cm at 25 °C, preferably less than 1 × 10 -10 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 attached 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, 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, more preferably at least 1.2 mS / cm at 25 °C, and - The solid material has an electronic conductivity of less than 1×10 -9 mS / cm, or less than 1×10 -10 mS / cm at 25 °C.

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

[0077] As shown in the attached examples, the glassy solid of the present invention has been found to exhibit a high thermal stability ΔT x with respect to Li-S-based glass. According to a preferred embodiment of the present invention, a solid material having a thermal stability ΔT x exceeding 100 °C, preferably exceeding 110 °C, more preferably exceeding 115 °C is provided. In some embodiments, particularly when X represents Br, I or a combination thereof, the thermal stability ΔT x exceeds 120 °C, preferably exceeds 125 °C, more preferably exceeds 130 °C.

[0078] In certain very preferred embodiments, a solid material of the present invention is provided, wherein - 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 a thermal stability ΔT x exceeding 100 °C, preferably exceeding 110 °C, more preferably exceeding 115 °C, - Preferably, the solid material has an electronic conductivity of less than 1×10 -5 mS / cm, preferably less than 1×10 -6 mS / cm at 25 °C.

[0079] In certain highly preferred embodiments, a solid material of the present invention is provided, where - at least 50 mol% of -X represents Br, preferably at least 80 mol% of X represents Br, and 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, - the solid material has a thermal stability ΔT above 120 °C, preferably above 125 °C, more preferably above 130 °C x and - preferably, the solid material has an electronic conductivity of less than 1×10 -9 mS / cm at 25 °C, preferably less than 1×10 -10 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 at 25 °C, more preferably at least 1.2 mS / cm, and the solid material also has a thermal stability ΔT above 115 °C, preferably above 125 °C x and

[0081] Without wishing to be bound by any theory, generally, and thus in some preferred embodiments of the present invention, the solid material obtainable by melt-quenching the mixture of A, B, and C described herein is considered to be a solid material having the composition according to general formula (I)' described herein.

[0082] The solid materials according to various aspects of the present invention described herein, namely, the solid materials having the composition according to general formula (I)' described herein and the solid materials obtainable by melt-quenching the 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, in general formula (I)' (where Y 1 represents Br, Y2 a solid material represented by (wherein Y represents Cl) is provided, wherein Y 1 at least 50 mol% of represents Br, preferably Y 1 at least 80 mol% of represents Br, more preferably Y 1 represents Br, and Y 2 at least 50 mol% of represents Cl, preferably Y 2 at least 80 mol% of represents Cl, more preferably Y 2 represents Cl.

[0084] The solid material of the present invention has been found to have surprisingly high ionic conductivity. According to a preferred embodiment of the present invention, a solid material represented by formula (I)' is provided, and this material 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 attached examples, the inventors have surprisingly found that Y 1 at least 50 mol% of represents Br, preferably Y 1 at least 80 mol% of represents Br, more preferably Y 1 represents Br, and Y 2 at least 50 mol% of represents Cl, preferably Y 2 at least 80 mol% of represents Cl, more preferably Y 2 represents Cl, it has been found that the ionic conductivity at 25°C can be as high as 0.67 mS / cm.

[0085] Therefore, 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, 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 Y 1 at least 50 mol% of represents Br, preferably Y 1At least 80 mol% of which represents Br, more preferably Y 1 represents Br, and Y 2 at least 50 mol% of which represents Cl, preferably Y 2 at least 80 mol% of which represents Cl, more preferably Y 2 represents Cl, and at 25 °C, has an ionic conductivity of at least 0.40 mS / cm, preferably at least 0.50 mS / cm, 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 which represents Cl, preferably Y 1 at least 80 mol% of which represents Cl, more preferably Y 1 represents Cl, and at least 50 mol% of Y2 represents I, preferably at least 80 mol% of Y2 represents I, 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 which represents Cl, preferably Y 1 at least 80 mol% of which represents Cl, more preferably Y 1 represents Cl, and Y 2 at least 50 mol% of which represents I, preferably Y 2 at least 80 mol% of which represents I, more preferably Y 2 when represents I, it has been 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 is provided that has an ionic conductivity of at least 0.40 mS / cm, preferably at least 0.50 mS / cm, more preferably at least 0.62 mS / cm at 25 °C.

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

[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 which represents Br, preferably 1 at least 80 mol% of which represents Br, more preferably 1 represents Br, and Y 2 at least 50 mol% of which represents I, preferably 2 at least 80 mol% of which represents I, more preferably 2 represents I.

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

[0093] The solid material of the present invention has both high ionic conductivity and surprisingly low electrical conductivity, and thus has been found to be a very attractive solid electrolyte material for solid batteries. According to a preferred embodiment of the present invention, there is provided a solid material represented by formula (I)’, which has an electrical conductivity of less than 1×10 -4 mS / cm, preferably less than 1×10 -5 mS / cm. As shown in the attached examples, the inventors have surprisingly found that at least 50 mol% of Y 1 represents Br, preferably at least 80 mol% of Y 1 represents Br, more preferably Y 1 represents Br, and at least 50 mol% of Y 2 represents Cl, preferably at least 80 mol% of Y 2 represents Cl, more preferably Y 2 represents Cl, in which case the electrical conductivity at 25 °C can be very low, such as less than 1×10 -5 mS / cm or less than 8×10 -6 mS / cm.

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

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

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

[0097] According to a preferred embodiment of the present invention, less than 1×10 -4 mS / cm, preferably less than 1×10 -5A 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 represents Br, preferably Y 1 at least 80 mol% of represents Br, more preferably Y 1 represents Br, and Y 2 at least 50 mol% of represents I, preferably Y 2 at least 80 mol% of represents I, more preferably Y 2 represents I, and the electrical conductivity at 25 °C can be very low, such as less than 1×10 -5 mS / cm.

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

[0099] As described throughout the present application, the solid material 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 for the material to be provided in the form of a particulate solid such as a powder. This can, for example, facilitate blending with a cathode material. The solid can be obtained directly in the form of a particulate solid (such as a powder), or can be pulverized (by milling, micronization, etc.) to form a particulate solid (such as a powder). In other applications, the solid material may preferably be provided in the form of a thin sheet or film, preferably a sheet or film having a thickness of less than 500 microns, preferably less than 100 microns.

[0100] The inventors contemplate adding small amounts of other materials during synthesis such that the general formula (I) of the obtained solid material is no longer considered, or the general formula (II) is no longer considered, where the changes do not substantially affect the basic and novel properties (s) of the solid material of the present invention. Such variations are considered to be 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 ● Li 2 S, ● B 2 S 3 and / or both boron and sulfur, ● optionally, B 2 O 3 , and ● LiX (wherein X represents F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , BH 4 or a combination thereof) are provided, (ii) a step of preparing a mixture comprising the precursors provided in step (i), ● in the mixture, the molar ratios of the elements Li, S, B, O and X are of the general formula (I) Li2c+d B 2a+2b S 3a+c O 3b X d (I) (wherein, a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14) and coincides with, or ● In the mixture, the molar ratio of the precursors is represented by the general formula (II) xLi 2 S - yB 2 S 3 - zB 2 O 3 (II) (wherein, x is in the range of 55 to 85, y is in the range of 15 to 45, z is in the range of 0 to 15, x + y + z = 100), and a step of preparing; (iii) A step of heat-treating the mixture prepared in step (ii) to obtain a melt; (iv) A step of rapidly cooling the melt obtained in step (iii) to obtain a solid material. A method including these steps is provided.

[0102] In a preferred embodiment, a method for preparing a solid material, (i) The following precursors: ● Li 2 S, ● B 2 S 3 and / or both boron and sulfur, ● Optionally, B 2 O 3 and ● LiX (wherein X represents Cl, Br, I, or a combination thereof) are provided; (ii) A step of preparing a mixture containing the precursors provided in step (i), ● In the mixture, the molar ratios of the elements Li, S, B, O, and X are in accordance with the general formula (I) Li 2c+d B 2a+2b S 3a+c O 3b X d (I) (wherein a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14) or or ● In the mixture, the molar ratio of the precursors is in accordance with the general formula (II) xLi 2 S-yB 2 S 3 -zB 2 O 3 (II) (wherein x is in the range of 55 to 85, y is in the range of 15 to 45, z is in the range of 0 to 15, x + y + z = 100), a step of preparing, (iii) a step of heat-treating the mixture prepared in step (ii) to obtain a melt, (iv) a step of rapidly cooling the melt obtained in step (iii) to obtain a solid material, and a method including these steps is provided.

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

[0104] The fact that both boron and sulfur are provided in step (i) should be interpreted to mean that elemental boron and elemental sulfur are provided. Elemental boron and elemental sulfur may be provided in an amorphous form or a crystalline form, and the specific allotropes used do not particularly limit the present invention.

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

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

[0107] The heat treatment may be performed 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 the reaction with the glass components. Such a sealed vessel is made of 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 under an inert gas atmosphere, preferably 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 atmosphere, more preferably less than 0.01 atmosphere. Typically, therefore preferably, step (iii) is carried out at a pressure of less than 10 -4 atmospheres, preferably less than 10 -5 atmospheres, preferably under an inert gas atmosphere, preferably an inert atmosphere containing one or more noble gases (such as argon). The use of nitrogen as an inert atmosphere should generally be avoided considering the potential reaction with the glass precursor.

[0109] The melt-quenching 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) comprises (iv)a quenching the melt obtained in step (iii) to obtain a solid material; (iv)b pulverizing the solid material of step (iv)a to obtain a granular solid such as 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, is - dissolving or suspending the granular solid of 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, or - further comprising a step of reheating the granular solid of step (iv)b to a temperature sufficient to allow stretching of the film or sheet, and forming the film or sheet by stretching the film or sheet.

[0111] In an alternative embodiment, step (iv) comprises a step of quenching the melt of step (iii) while maintaining a temperature high enough to allow stretching of the thin film or sheet, and a step of 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 the desired size.

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

[0114] Embodiment 4 In another aspect of the present invention, there is provided a solid composition comprising a first solid material which is a solid material described herein (i.e., 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 be present in the form of discrete particles optionally blended in combination with a binder material and one or more additional 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 a 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, anode or separator of an electrochemical cell, especially as a separator or cathode. In some embodiments, the second solid material is a cathode material such as a nickel-cobalt or nickel-manganese-cobalt cathode material.

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

[0116] Embodiment 6 In another aspect of the present invention, there is provided 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, there is provided the use of a solid material described herein as a solid electrolyte for an electrochemical cell.

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

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

[0120] Embodiment 9 A further aspect of the present disclosure is the use of an electrochemical cell comprising the solid material of the present invention (i.e., the electrochemical cell according to embodiment 5) in an automobile, a bicycle operated by an electric motor, a robot, an aircraft (e.g., an unmanned aerial vehicle, including a drone), a ship, or a stationary energy storage. The present invention further provides a device comprising at least one electrochemical cell according to embodiment 5. Preferred are mobile devices such as vehicles, e.g., automobiles, bicycles, aircraft, or water vehicles, e.g., boats or ships. Other examples of mobile devices are portable, e.g., computers, especially laptops, phones, or power tools, e.g., from the construction sector, especially drills, battery-powered screwdrivers or battery-powered tackers.

[0121] EMBODIMENT 10 In another aspect of the invention, the thermal stability ΔT x To improve the thermal stability ΔT of lithium-ion conducting solid electrolytes, especially sulfide-based ones x To improve the above, the compound of formula LiX (wherein X is F, Cl, Br, I, N 3 , SCN, CN, OCN, BF 4 , B.H. 4 or a combination thereof, preferably X represents Cl, Br, I or a combination thereof. In some embodiments, the use provides a method for the preparation of a glassy solid according to general formula (II) as described in embodiment 2, which is characterized in that the thermal stability ΔT x The preferred embodiments of general formula (II), in particular x, y and z, described herein in the context of embodiment 2 are equally applicable to the use of embodiment 10.

[0122] The present invention is further illustrated by the following non-limiting examples. EXAMPLES

[0123] 1. Preparation of Materials For each example, 15 g of final material was prepared using the following starting products: Amorphous B 2 S 3 (99% by weight), Li2 S (99.9 wt%), B 2 O 3 (99.95 wt%), and LiX (LiI (99 wt%), LiBr (99 wt%), LiCl (99 wt%)). In an argon-filled glove box, appropriate amounts of starting materials were weighed, mixed, and introduced into a carbon-coated silica ampoule. The tube was sealed and introduced into a vertical rocking furnace. The melt was homogenized at an internal temperature of 950 °C for 30 minutes and then quenched in water at room temperature. The ampoule was then opened in the argon-filled glove box. An orange or brown glassy material with good transparency was obtained.

[0124] In some examples, B 2 S 3 An alternative synthesis was carried out successfully in which the amounts of boron and sulfur provided by B

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

[0126] The glass transition temperature (T g ) was determined by constructing tangents to the DSC curve baseline 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 occurs in the drop of the DSC baseline before the exothermic crystallization peak. The T g start temperature thus obtained was taken as T g .

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

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

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

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

[0131] Samples of the glassy materials were weighed in a glove box under an Ar atmosphere to avoid reaction with water or O 2 and added to a microwave vessel container. An acid combination was added, the vessel container was closed, and it was digested in a microwave until it became transparent. The substrate elements (Li & B) were analyzed using a high-precision ICP-OES method.

[0132] S is determined via elemental analysis after sample preparation in an Ar-filled glove box. Sample preparation consists of inserting approximately 100 mg of the sample into a sealed capsule, and then adding the sealed capsule and additives to a ceramic crucible. Subsequently, the filled crucible is O 2In an atmosphere, it is heated in an induction furnace. The existing S is released from the sample and converted into SO 2 gas, and the SO 2 is detected by a specific IR detector. The detected SO 2 signal is finally converted into the S concentration by using a calibration curve and taking into account the accurate sample mass.

[0133] The composition of the glass was found to correspond to the overall formula predicted based on the molar ratios of the precursors subjected to melt-quenching within the expected margins 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) (wherein X is F, Cl, Br, I, N ３ , SCN, CN, OCN, BF ４ , BH ４ , or a combination thereof, represents a is in the range of 0.03 to 0.1, b is in the range of 0 to 0.04, c is in the range of 0.12 to 0.26, d is in the range of 0.001 to 0.14) and having a composition, a solid material.

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

3. wherein a is in 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, d is in the range of 0.001 to 0.14, the solid material according to claims 1 and 2.

4. wherein d is in the range of 0.005 to 0.08, preferably in the range of 0.01 to 0.06, more preferably in the range of 0.01 to 0.04, the solid material according to any one of claims 1 to 3.

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

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

7. A solid material obtainable by melting and quenching a mixture of A and B, preferably the solid material according to any one of claims 1 to 6, wherein the molar ratio of A to B in the mixture before quenching is in the range of 60:40 to 99:1, Component A is of general formula (II) xLi ２ S - yB ２ S ３ - zB ２ O ３ (II) (wherein 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, 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, x + y + z = 100) Component B is LiX (wherein X represents F, Cl, Br, I, N ３ , SCN, CN, OCN, BF ４ , BH ４ or a combination thereof), a solid material.

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, 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, 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, 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 that exceeds 100° C., preferably exceeds 110° C., more preferably exceeds 115° C. ｘ and where ΔT ｘ = T ｘ − T ｇ and in the formula, T ｘ is the crystallization onset temperature determined by DSC, and T ｇ is the glass transition temperature determined by DSC. The solid material according to any one of claims 1 to 12.

14. A method for preparing a solid material, preferably the solid material according to any one of claims 1 to 13, comprising: (i) the following precursors: ● Li ２ S, ● B ２ S ３ and / or both boron and sulfur, ● Optionally, B ２ O ３ and ● LiX (wherein X represents F, Cl, Br, I, N ３ , SCN, CN, OCN, BF ４ , BH ４ or a combination thereof), and (ii) a step of preparing a mixture comprising the precursors provided in step (i), wherein: ● the molar ratio of the elements Li, S, B, O, and X in the mixture corresponds to the general formula (I) according to claims 1 to 6, or ● the molar ratio of the precursors in the mixture corresponds to the general formula (II) according to 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 melt; (iv) a step of rapidly cooling the melt 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 according to any one of claims 1 to 13.

17. The electrochemical cell according to claim 16, wherein the separator comprises the 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.

Images