Aliovalently substituted argyrodite-type solid electrolytes

Abstract

It is disclosed a solid electrolyte having a composition according to formula (1), Li48 - n1c1-m1d1-b1An1(c1)Mm1(d1)O24-b1Xb1 (1), wherein 1 ≤ n1 ≤ 3, c is the oxidation state of A, being one of +1, +2, +3, +4, +5, +6, or +7, 1 ≤ m1 ≤ 3, d is the oxidation state of M, being one of +1, +2, +3, +4, +5, +6, or +7, 0 ≤ b ≤ 8, A and M is at least one element selected from the selected from the list of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi, and X is F, Cl, Br, I or combinations thereof.

Description

ALIOVALENTLY SUBSTITUTED ARGYRODITE-TYPE SOLID ELECTROLYTES TECHNICAL FIELD

[0001] This present disclosure relates to a solid electrolyte, a method for manufacturing said solid electrolyte and a battery comprising said solid electrolyte.BACKGROUND

[0002] As the development of small and lightweight electronic products, electronic devices, communication devices and the like has advanced rapidly and a need for electric vehicles has widely emerged with respect to environmental issues, there is a demand for improvement of performance of secondary batteries used as power sources for these products. Among these, a lithium secondary battery has emerged as a high-performance battery due to a high energy density and a high reference electrode potential.

[0003] However, electrolytes conventionally used in lithium secondary batteries are liquid electrolytes such as organic solvents. Accordingly, safety problems such as leakage of electrolytes and risk of fire may continuously occur. Recently, solid-state batteries with solid electrolytes instead of liquid electrolytes are being developed to improve the safety function of the lithium secondary battery and have attracted much attention. For example, solid electrolytes are typically safer than liquid electrolytes due to non-combustible or flame-retardant properties.

[0004] Solid electrolytes may include oxide-based solid electrolytes, polymer-based electrolytes and sulfide-based electrolytes. Oxide-based solid electrolytes have generally been used due to their higher stability and compatibility with electrodes when compared to sulfide-based electrolytes, which is critical to the long-term performance of batteries.

[0005] WO23170418 Al describes the synthesis of solid electrolytes having the general formula LiaMYi4X, wherein a is from 5 to 8, such as Li6.75Po.25Sio.375Geo.37505CI and LiySiOsCI.SUMMARY

[0006] It is an object of the present disclosure to provide an aliovalently substituted argyrodite-type solid electrolyte according to formula (1)Li48-n lcl-mld 1-blAnl (Cl) Mml(d 1 )O24-blXbl (1),wherein nl is the number of atoms of A, cl is the value of the oxidation state of A, ml is the number of atoms of M, dl is the value of the oxidation state of M and bl is the number of atoms of X, and wherein:• 1 < nl < 3, preferably nl = 1, 2 or 3;• cl is the oxidation state of A, being one of +1, +2, +3, +4, +5, +6, or +7;• 1 < ml < 3, preferably ml = 1, 2 or 3;• dl is the oxidation state of M, being one of +1, +2, +3, +4, +5, +6, or +7;• 0 < bl < 8;• A and M is at least one element selected from the selected from the list of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi; and• X is F, Cl, Br, I or combinations thereof.

[0007] The solid electrolytes disclosed herein are aliovalently substituted argyrodite-type compositions and are suitable for solid-state electrolytes due to their ability to achieve high ionic conductivity, advantageously up to 2 mS.cnr1.

[0008] Without wishing to be bound to any theory, the present inventors believe that aliovalent substitution of P with the combination of two metals from Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi leads to an change of the unit cell, in addition to further advantageous effects, such as the inclusion of additional lithium cations within the structure. Additionally, halide substitutions (i.e. X elements in the formulas) may result in increased site disorder. Therefore, by changing the structure, the lithium content and the ion interactions increase, which is expected to enhance ionic conductivity. Moreover, these observations are supported by computational modelling, which focused on predicting the rate of lithium diffusion into the argyrodite structure and stability based on two indicators, Ehuii (energy above hull) and Emig(migration energy barrier). The Ehuii identifies the stability of certain argyrodite compounds, while the Emig is an ionic conductivity predictor.

[0009] It is a further object of the present disclosure to provide a method for manufacturing said solid electrolyte.

[0010] It is a further object of the present disclosure to provide a battery comprising said solid electrolyte.

[0011] In the following detailed description, various embodiments are described in detail to enable practice of the present technology. Although the present technology is described with reference to these specific preferred embodiments, it will be understood that the present technology is not limited to the disclosed embodiments, which is defined by the following claims, as interpreted according to the principles of patent law, including the doctrine of equivalents. To the contrary, the present disclosure includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description and accompanying drawings. Unless otherwise indicated, it is not meant that the alternatives, modifications, and equivalents described herein are understood as separate, non-combinable, embodiments. That is, provided it is technically feasible, the different parts of the present disclosure may be combined with one another.

[0012] The term "comprising", as used herein and in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It needs to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" should not be limited to compositions consisting only of components A and B. It means that with respect to the present disclosure, the only relevant components of the composition are A and B. Accordingly, the terms "comprising" and "including" encompass the more restrictive terms "consisting essentially of" and "consisting of".

[0013] The term "solid-state battery" as used herein refers to a cell or a battery that includes only solid or substantially solid-state components, such as solid electrodes (e.g. anode and cathode) and a solid electrolyte.

[0014] The term "argyrodite-type crystal structure" as used herein refers to a crystal structure having a crystal structure or system similar to naturally existing Ag8GeSe and Li7PS6 Argyrodites. The argyrodite-type crystal structure may have cubic symmetry and may be described in the F-43m space group.

[0015] In some embodiments the argyrodite-type crystal structure can also be determined empirically, for example by X-ray diffraction, by observing diffraction peaks around at 20=15.5±1°, 18±1°, 26±1°, 30.5±l° and 32 ±1° using CuKo X-ray wavelength. X-Ray diffraction (XRD) as referred to herein, refers to XRD experiments that may be performed using, for example, Bruker D8 diffractometersor the like equipped with either Cu (Kol-Ko2) radiation in an 0-0 configuration. Preferably, an air-tight (X-ray transparent) dome window of the sample holder is used. Preferably, the patterns are collected between 20 = 10-50° with a step size of 0.02°.

[0016] The term "solid electrolyte" or "solid-state electrolyte" as used herein refers to an electrolyte is substantially free of any liquid. The term "substantially free of liquid" means that the solid electrolyte comprises less than 10 wt.% of a liquid by total weight of the solid electrolyte, preferably less than 7.5 wt.%, more preferably less than 5 wt.%, even more preferably less than 2.5 wt.%, most preferably less than 1 wt.%, based on the total weight of the solid electrolyte. In an embodiment, the solid electrolyte comprises less than 1000 ppm of a liquid by total weight of the solid electrolyte, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm, most preferably less than 10 ppm by total weight of the solid electrolyte.

[0017] Various embodiments are disclosed in the claims and the description of the present disclosure. The embodiments and examples recited in the claims and description are freely combinable with one another, unless otherwise expressly stated. Throughout the disclosure, where numerical ranges are given, the ranges include endpoint values unless otherwise expressly stated.

[0018] Modifications of the disclosure will occur to those skilled in the art and to those who make or use the disclosed technology. Therefore, it is understood that the embodiments described herein are merely for illustrative purposes and not intended to limit the scope of the disclosure, which is defined by the following claims, as interpreted according to the principles of patent law, including the doctrine of equivalents.DETAILED DESCRIPTIONSolid Electrolyte

[0019] In one aspect, the present disclosure relates to a solid electrolyte having a composition according to formula (1)Li48-n lcl-mld 1-blAnl (Cl) Mml(d 1 )O24-blXbl (1), wherein nl is the number of atoms of A, cl is the value of the oxidation state of A, ml is the number of atoms of M, dl is the value of the oxidation state of M and bl is the number of atoms of X, and wherein:• 1 < nl < 3, preferably nl = 1, 2 or 3;• cl is the oxidation state of A, being one of +1, +2, +3, +4, +5, +6, or +7;• 1 < ml < 3, preferably ml = 1, 2 or 3;• dl is the oxidation state of M, being one of +1, +2, +3, +4, +5, +6, or +7;• 0 < bl < 8;• A and M is at least one element selected from the selected from the list of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi; and• X is F, Cl, Br, I or combinations thereof.

[0020] In an embodiment, the solid electrolyte has an argyrodite-type crystal structure.

[0021] As appreciated by the skilled person, the solid electrolyte material may contain some impurities and / or additives and that are not taken into account in the disclosed formulas of the solid-electrolyte compounds. In an embodiment the solid electrolyte is according to the disclosed technology having a purity of at least 90 wt%, preferably at least 95 wt%, more preferably at least 99 wt%.

[0022] In an embodiment, the solid electrolyte has a conductivity between 0.1 and 12 mS / cm, preferably between 0.5 and 10 mS / cm, more preferably between 1 and 8 mS / cm.

[0023] In an embodiment, the solid electrolyte has a composition according to formula (2)Li48-n2c2-m2d2-b2An2(c2)Mm2(d2)O24-b2Xb2 (2),wherein:• 2 < n2 < 3, preferably n2 = 2 or 3;• c2 is the oxidation state of A, being one of +2, +3 or +4;• 1 < ml < 2, preferably m2 = 1 or 2;• d2 is the oxidation state of M, being one of +2 or +3;• 0 < b2 < 8;• A is at least one element selected from the group consisting of Zn, Ti, Ge, Be, B, Al, and Ag;• M is at least one element selected from the group consisting of Be, Ag, Ga, Bi, Tb, Fe, B, and Tb; and• X is F, Cl, Br, I or combinations thereof.

[0024] In an embodiment, X (i.e. a halide in the disclosed solid electrolytes) is F, Cl, Br or I, preferably X is F, Cl or Br, more preferably is F or Cl, even more preferably F.

[0025] In an embodiment,• A is Zn;• n2 is 3;• c2 is +2;• M is Be;• m2 is 1;• d2 is +2;• X is F; and• 0 < b2 < 4, preferably a=4.

[0026] In an embodiment,• A is Ti or Ge;• n2 is 2;• c2 is +4;• M is Be;• m2 is 2;• d2 is +2; and• 0 < b2 < 4, preferably a=0.

[0027] In an embodiment,• A is Be;• n2 is 3;• c2 is +2;• M is Ag;• m2 is 1;• d2 is +2;• X is F; and• 0 < b2 < 4, preferably a=4.

[0028] In an embodiment,• A is B, Al or Ag;• n2 is 3;• c2 is +3;• M is Bi, Tb, Ga, Fe or B;• m2 is 1;• d2 is +1; and• 0 < b2 < 4, preferably a=0.

[0029] In an embodiment, the solid electrolyte has the formula (2a)-(2k):

[0030] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (36-38): (2-3): (1-2): (20-24): (0-8), preferably (36):(2):(2):(24):(0), (36):(3):(l):(20):(4) or (36):(3):(l):(24):(0).

[0031] In an embodiment, the solid electrolyte has a composition according to formula (3)Li48-n3c3-m3d3-b3An3(c3)Mm3(d3)O24-b3Xb3 (3),wherein:• 2 < n3 < 3, preferably n=3 or 2;• c3 is the oxidation state of A, being one of +2;• 1 < n3 < 2, preferably n = l or 2;• d3 is the oxidation state of M, being one of +2;• 0 < b3 < 6;• A is at least one element selected from the group consisting of Be or Pb;• M is at least one element selected from the group consisting of Zn or Yb; and• X is F, Cl, Br, I or combinations thereof.

[0032] In an embodiment,• A is Be;• n3 is 3;• c3 is +2;• M is Zn;• m3 is 1;• d3 is +2;• X is F; and. b3 = 6.

[0033] In an embodiment,• A is Pb;• n3 is 2;• c3 is +2;• M is Yb;• m3 is 2;• d3 is +3;• X is F; and. b3 = 2.

[0034] In an embodiment, the solid electrolyte has the formula (3a)-(3b):

[0035] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (34-36):(2-3):(l-2):(18-24):(0-6), preferably (34):(3):(1):(18):(6) or (34):(2):(2):(22):(2).

[0036] In an embodiment, the solid electrolyte has a composition according to formula (4)U48 -n4c4-m4d4- b4An4(c4)Mm4(d4)O24-b4Xb4 (4), wherein:• 2 < n4 < 3, preferably n4 = 2 or 3;• c4 is the oxidation state of A, being one of +2, +3, +4, or +5;• 1 < m4 < 2, preferably m4 = 1 or 2;• d4 is the oxidation state of M, being one of +2, +3, +4, +5, or +6;• 0 < b4 < 4;• A is at least one element selected from the group consisting of Al, Be, V, Ti, Si, Sb, Mo, Ge, Cr, Bi, and B;• M is at least one element selected from the group consisting of B, Te, C, Se, Bi, Ti, Si, Se, Sb, Mo, Cr, Al, and Ga; and • X is F, Cl, Br, I or combinations thereof.

[0037] In an embodiment,• A is ;• n4 is 2;• c4 is +5;• M is B;• m4 is 2;• d4 is +3; and• 0 < b4 < 4, preferably b4=0.

[0038] In an embodiment,• A is Ti or Si;• n4 is 2 or 3;• c4 is +4;• M is Te or Se;• m4 is 1 or 2;• d4 is +4; and• 0 < b4 < 4, preferably b4=0.

[0039] In an embodiment,• A is Sb or P;• n4 is 2;• c4 is +5;• M is Bi or Al;• m4 is 2;• d4 is +3; and• 0 < b4 < 4, preferably b4=0.

[0040] In an embodiment,• A is Ge;• n4 is 3;• c4 is +4;• M is Ti, Si or Se;• m4 is 1;• d4 is +4; and• 0 < b4 < 4, preferably b4=0.

[0041] In an embodiment,• A is Bi;• n4 is 2;• c4 is +3;• M is Sb;• m4 is 2;• d4 is +5; and• 0 < b4 < 4, preferably b4=0.

[0042] In an embodiment,• A is Be;• n4 is 2;• c4 is +2;• M is Mo or Cr;• m4 is 2;• d4 is +6; and• 0 < b4 < 4, preferably b4=0.

[0043] In an embodiment,• A is B or Al;• n4 is 3;• c4 is +3;• M is Al or Ga;• m4 is 1;• d4 is +3;• X is F or Cl; and• 0 < b4 < 4, preferably b4=4.

[0044] In an embodiment, the solid electrolyte has the formula (4a)-(4p):

[0045] In an embodiment, wherein the ratios of Li:A:M:0:X are between (32-34):(2-3):(l-2):(20-24):(0-4), preferably (32):(2):(2):(24):(0),(32) :(3) : (1) : (24) : (0) or (32):(3):(l):(20):(4).

[0046] In an embodiment, the solid electrolyte has a composition according to formula (5)Li48-n5c5-m5d5-b5An5(c5)Mm5(d5)O24-b5Xb5 (5),wherein:• 1 < n5 < 2, preferably n5 = 2;• c5 is the oxidation state of A, being one of +4 or +5;• 1 < m5 < 2, preferably m5=2;• d5 is the oxidation state of M, being one of +3 or +4;• 0 < b5 < 2;• A is at least one element selected from the group consisting of Si, C, and Bi;• B is at least one element selected from the group consisting of Ge, Si, and Ag; and• X is F, Cl, Br, I or combinations thereof.

[0047] In an embodiment,• A is Si;• n5 is 2;• c5 is +4;• M is Ge;• m5 is 2;• d5 is +4;• X is F; and• 0 < b5 < 2, preferably b5 = 2.

[0048] In an embodiment,• A is Bi;• n5 is 2;• c5 is +5;• M is Ag;• m5 is 2;• d5 is +3;• X is F, and• 0 < b5 < 2, preferably b5 = 2.

[0049] In an embodiment, the solid electrolyte has the formula (5a)-(5b):

[0050] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (30-32): (2-3): (1-2): (20-24): (0-2), preferably (30) : (2) : (2) : (22) : (2) .

[0051] In an embodiment, the solid electrolyte has a composition according to formula (6)Li48-n6c6-m6d6-b6Ane(c6)Bm6(d6)O24-b6Xb6 (6), wherein:• 2 < n6 < 3, preferably n6 = 2 or 3;• c6 is the oxidation state of A, being one of +3, +4, +5, or +6; • 1 < m6 < 2, preferably m6 = 1 or 2;• d6 is the oxidation state of M, being one of +2, +3, +4, +5, or +6;• 0 < b6 < 8;• A is at least one element selected from the group consisting of V, Si, Se, P, N, Ga, Cr, and As;• M is at least one element selected from the group consisting of As, C, Mo, N, V, Dy, Be, Si, and Ge; and• X is F, Cl, Br, I or combinations thereof.

[0052] In an embodiment,• A is ;• n6 is 2 or 3;• c6 is +5;• M is As;• m6 is 1 or 2;• d6 is +5; and• 0 < b6 < 8, preferably b6=0.

[0053] In an embodiment,• A is P;• n6 is 3;• c6 is +5;• M is N or As;• m6 is 1;• d6 is +5; and• 0 < b6 < 8, preferably b6=0.

[0054] In an embodiment,• A is N;• n6 is 3;• c6 is +5;• M is V or As;• M6 is 1;• d6 is +5; and• 0 < b6 < 8, preferably b6=0.

[0055] In an embodiment,• A is Ga;• n6 is 2;• c6 is +3;• M is Dy;• m6 is 2;• d6 is +3;• X is Cl; and• 0 < b6 < 8, preferably b6=8.

[0056] In an embodiment,• A is Cr;• n6 is 2 or 3;• c6 is +6;• M is Be, Si or Ge;• m6 is 1 or 2;• d6 is +1 or +2; and• 0 < b6 < 8, preferably b6=0.

[0057] In an embodiment,• A is As;• n6 is 3;• c6 is +5;• M is N;• m6 is 1;• d6 is +5; and• 0 < b6 < 8, preferably b6=0.

[0058] In an embodiment, the solid electrolyte has the formula (6a)-(6k):

[0059] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (28-30): (2-3): (1-2): (20-24): (0-8), preferably (28):(3):(l):(24):(0), (28):(2):(2):(24):(0) or (28):(2):(2):(24):(8).

[0060] In an embodiment, the solid electrolyte has a composition according to formula (7)Li48-n7c7-m7d7-b7An7(c7)Bm7(d7)O24-b7Xb7 (7)wherein:• 2 < n7 < 3, preferably n7 = 2 or 3;• c7 is the oxidation state of A, being one of +4, +5, or +6;• 1 < m7 < 2, preferably m7 = 1 or 2;• d7 is the oxidation state of M, being one of +4, 5, or +6;• 0 < b7 < 2;• A is at least one element selected from the group consisting of V, Mo, C, and As;• M is at least one element selected from the group consisting of As, N, C, Si, and V; and• X is F, Cl, Br, I or combinations thereof.

[0061] In an embodiment,• A is ;• n7 is 2 or 3;• c7 is +5;• M is As or N;• m7 is 1 or 2;• d7 is +1 or +2; and• 0 < b7 < 2, preferably b7 = 2.

[0062] In an embodiment,• A is As;• n2 is 3;• c2 is +5;• M is V;• m2 is 1;• d2 is +5; and• 0 < b2 < 6, preferably 0 < b2 < 2, more preferably b2=2.

[0063] In an embodiment, the solid electrolyte has the formula (7a)-(7c):

[0064] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (26-28): (2-3):(l-2): (20-24): (0-2), preferably (26):(3):(1):(22):(2) or (26):(2):(2):(22):(2).

[0065] In an embodiment, the solid electrolyte has a composition according to formula (8)Li48-n8c8-M8d8-b8An8(c8)Mm8(d8)O24-b8Xb8 (8) wherein:• 2 < n8 < 3, preferably n8 = 2;• c8 is the oxidation state of A, being one of +4, +6, or +7;• 1 < m8 < 2, preferably m8 = 2;• d8 is the oxidation state of M, being one of +2 or +4;• 0 < b8 < 8;• A is at least one element selected from the group consisting of W, Se, Ru, Mo, Mn, Ge and Cr;• M is at least one element selected from the group consisting of C and Hf; and• X is F, Cl, Br, I or combinations thereof.

[0066] In an embodiment,• A is Ge;• n8 is 2;• c8 is +4;• M is Hf;• m8 is 2;• d8 is +4; and• 0 < b8 < 8, preferably b2=8.

[0067] In an embodiment, the solid electrolyte has the formula (8a):

[0068] In an embodiment, wherein the molar ratios of Li:A:M:O:X are between (26-28): (2-3): (1-2): (16-24): (0-8), preferably (24) : (2) : (2) : (16) : (8).Method for manufacturing

[0069] In a second aspect, the disclosure relates to a method for manufacturing a solid electrolyte comprising the following steps:a) providing a set of precursors comprising Li, 0, A, M and X; andb) mixing of the set of precursors to obtain a solid electrolyte mixture; and c) heat-treating of the solid electrolyte mixture to obtain a solid electrolyte, wherein Y is selected from the group consisting of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi, wherein X is selected from the group consisting of F, Cl, Br, and I and combinations thereof, preferably F, Cl or Br, more preferably F or Cl.

[0070] In an embodiment, in the method, the set of precursors comprises U2O, one or more of the group consisting of BeO, B2O3, AS2O3, AI2O3, AU2O3, Bi2O3, SiC , Sb20s, Sb2O3, Ag2O, HO2O3, LU2O3, PbO2, HfO2, SeO2, Ge02, Ga2O3, Cr2O3, CrO2, ZnO, ZrO2, TiO2, V2O5, V2O3, VO2, MOO2, Nb2O5, ReO3, RuO2, RuO4, Tb2O3, Dy2O3, WO3, WO2, FeO, and Fe2C>3, and one or more of the group consisting of Li F, Lil, LiBr, and LiCI.

[0071] In an embodiment of the method, the solid electrolyte is the solid electrolyte according to the first aspect of the disclosure, preferably the solid electrolyte according to formula (1) and / or according to formula (2)-(8).

[0072] As appreciated by the skilled person, all embodiments related to the solid electrolyte according to first aspect of the disclosure apply mutatis mutandis to the method for manufacturing the solid electrolyte according to the disclosure. For example, the various embodiments relating to formula (1) and / or according to formula (2-8), purity level and conductivity level as explained hereinabove in the context of the solid electrolyte are equally applicable to the method for manufacturing the solid electrolyte according to the second aspect.

[0073] In an embodiment of the method, the mixing of the solid electrolyte precursor of step b) may comprise mixing, grinding, stirring, ball-milling, or a combination thereof.

[0074] In an embodiment of the method, the mixing of the set of precursors of step b) is at a mixing speed of at least 100 rpm, preferably a mixing speed of at least 300 rpm, most preferably a mixing speed of at least 400 rpm. In an embodiment, the mixing of the set of precursors of step b) is at a mixing speed of at most 1000 rpm, preferably a mixing speed of at most 900 rpm, most preferably a mixing speed of at most 800 rpm. In an embodiment, the mixing of the set of precursors of step b) is at a mixing speed of 100-1000 rpm, preferably a mixing speed of 300-900 rpm, most preferably a mixing speed of 400-800 rpm.

[0075] In an embodiment of the method, wherein the mixing of the set of precursors of step b) is carried out by using a mixing means such as a ball mill such as an electric ball mill, a vibration ball mill, a planetary ball mill, a vibration mixer mill or a SPEX mill; a bead mill; a homogenizer; a screw mixer; a horizontal mixer; a ploughshare mixer; a jar mill; a drum mill or a roller bench. In an embodiment, the mixing of the set of precursors of step b) is carried out by adding one or more ceramic or zirconia balls to the set of precursors. As appreciated by the skilled person, the quantity and size of the ceramic or zirconia balls is varied in relation to the total solid quantity of the set of precursors. As appreciated by the skilled person, the ceramic or zirconia balls may be removed before the heat-treating step c).

[0076] In an embodiment of the method, wherein the mixing of the set of precursors of step b) is at least 1 hour, preferably at least 5 hours, most preferably at least 10 hours. In an embodiment, in the method, wherein the mixing of the set of precursors of step b) is at most 70 hours, preferably at most 50 hours, mostpreferably at most 30 hours. In an embodiment, the mixing of the set of precursors in step b) is between 1 hour and 70 hours, preferably between 5 hours and 50 hours, most preferably between 10 hours and 30 hours.

[0077] In an embodiment of the method, the mixing of the solid electrolyte precursor mixture of step b) occurs at a temperature of at least 5°C, preferably at least 10°C, more preferably at least 15°C. In an embodiment, the mixing of the solid electrolyte precursor mixture of step b) occurs at a temperature of less than 50°C, preferably less than 40°C, more preferably less than 30°C. In an embodiment, the mixing of the solid electrolyte precursor mixture of step b) occurs at a temperature between 5 and 50 °C, preferably a temperature between 10 and 40°C, more preferably a temperature between 15 and 30°C.

[0078] In an embodiment, the method comprises the following mixing in step b):• with a mixing time between 1 hour and 70 hours, preferably between 5 hours and 50 hours, most preferably between 10 hours and 30 hours; and / or• at a mixing speed of 100-1000 rpm, preferably a mixing speed of 300-900 rpm, most preferably a mixing speed of 400-800 rpm.

[0079] In an embodiment of the method, the heat-treating of the solid electrolyte mixture of step c) occurs at a temperature of at least 100°C, preferably at least 150°C, more preferably at least 200°C, even more preferably at least 250°C, most preferably at least 300°C. In an embodiment, the heat-treating of the solid electrolyte mixture of step c) occurs at a temperature of less than 1000°C, preferably less than 900°C, more preferably less than 750°C, even more preferably less than 600°C, most preferably less than 500°C. In an embodiment, the heat-treating of the solid electrolyte mixture of step c) occurs at a temperature between 100 and 1000°C, preferably between 200 and 750°C, most preferably between 250 and 450°C.

[0080] In an embodiment of the method, the heat-treating of the solid electrolyte mixture of step c) is at least 1 min, preferably at least 0.5 hour, more preferably at least 1 hour, even more preferably at least 1.5 hours, most preferably at least 2 hours. In an embodiment, the heat-treating of the solid electrolyte mixture of step c) is less than 24 hours, preferably less than 12 hours, more preferably less than 10 hours, even more preferably less than 8 hours, even more preferably less than 6 hours. In an embodiment, the heat-treating of the solid electrolyte mixture of step c) is between 0.5 hour and 24 hours, preferably between 1 hours and 12 hours, more preferably between 2 hours and 6 hours.

[0081] In an embodiment, the method comprises the following heat-treatment of the solid electrolyte mixture of step c):• occurs at a temperature between 100 and 1000 °C, preferably between 200 and 750 °C, most preferably between 250 and 450 °C; and / or• is between 0.5 hour and 24 hours, preferably between 1 hours and 12 hours, most preferably between 2 hours and 6 hours.Product-by-process

[0082] In a third aspect, the disclosure relates to the solid electrolyte obtainable by the method according to the second aspect of the disclosure.

[0083] As appreciated by the skilled person, all embodiments directed to the solid electrolyte according to the first aspect of the disclosure and / or the method according to the second aspect of the disclosure apply mutatis mutandis to solid electrolyte obtainable by the method according to the disclosure. For example, the various embodiments relating to formula (1) and / or according to formula (2-8), purity level and conductivity level as explained hereinabove in the context of the solid electrolyte are equally applicable to the solid electrolyte obtainable by the method for manufacturing the solid electrolyte.Batery

[0084] In a fourth aspect, the disclosure relates to a battery comprising a solid electrolyte according to any of the preceding aspects.

[0085] The battery may comprise a negative electrode, a positive electrode and a solid electrolyte layer, wherein at least one of the positive electrode, the negative electrode and the solid electrolyte layer comprises the solid electrolyte according to the disclosure. The solid electrolyte of the present disclosure may be used as a solid electrolyte layer of a solid lithium-ion battery or a solid lithium primary cell, or as a solid electrolyte that is mixed with an electrode mixture for a positive electrode or a negative electrode.

[0086] In an embodiment, the battery is a solid-state battery, preferably a lithium solid-state battery.Use

[0087] In a fifth aspect, the disclosure relates to a use of the solid electrolyte according to any of the preceding aspects 1-3 in a battery, preferably a solid-state-battery, most preferably a lithium solid-state-battery.

[0088] In a sixth aspect, the present disclosure relates to a use of the battery according to the fourth aspect in either one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or in a hybrid electric vehicle, preferably in a vehicle or in a hybrid electric vehicle.

[0089] The disclosed technology is further illustrated in the following examples.EXAMPLESDescriotion of testing methodsComputational protocol

[0090] The used computational model focuses on predicting the thermodynamic stability and the rate of lithium diffusion into the argyrodite structure based on Ehuii (energy above hull) and Emig(migration energy barrier), respectively.

[0091] The Ehuii is a key indicator for identifying the relative stability of a phase as compared to the other phases present in the multicomponent phase diagram of the combining elements. For example, to identify the phase stability of an argyrodite compound, one would need to calculate the energies of all known phases in the compound chemical space to construct the phase diagram. The method of constructing a convex hull of a multicomponent phase diagram at 0 K is a standard computational method. The energy of each phase is then calculated with respect to the energy of the convex hull, which is taken as 0, and referred to as "Ehuii". Thus, the higher the value of Ehuii, the higher it is above the convex hull of the most stable phases and the lower is it's thermodynamic stability. This parameter is used to rank the most stable compounds and indicate the most likely to be synthesizable.

[0092] During charging and discharging, the lithium ions jump from one stable site to another by overcoming an energy barrier to traverse the potential energy landscape. The height of these energy barriers is estimated by the bond valence method, which relates the length of the bond (RA-X calculated from the geometry) to its strength (SA-X), where A and X are the lithium ion and its neighboring atoms, respectively. The relationship is given by the following formula:SA-X =exp[(Ro-RA-x / b)],where Ro and b are empirical bond valence (BO) parameters. This relationship allows one to locate the accessible positions for mobile lithium ions in the local structure of electrolyte as positions where the sum of these bond valence V(A) = lx sA-x is closest to Videat, the ideal valence (oxidation state) of a lithium ion. The lowest energy pathway is the one where the valence sum deviation \V(A)-Videai(A)\ is minimum and the corresponding energy barrier is the minimum migration energy barrier for lithium ions to diffuse in the electrolyte. The lower the migration energy barrier (Emig), the higher the lithium-ion diffusivity and, therefore the higher ionic conductivity of the electrolyte. Thus, Emigis an ionic conductivity indicator for ranking promising candidates. The migration energies have been evaluated with the code BOND_STR, distributed within the FullProf package of the CrysFML library.Examples

[0093] Table 1 shows the Ehuii and Emig for EX1-EX44 according to formula (1).Tablel-partl : Ehuii and Emigfor EX1-EX30.Tablel-part2: Ehuii and Emig for EX31-EX44.

Claims

CLAIMS1. A solid electrolyte having a composition according to formula (1):Li48-nlcl-mldl-blAnl(Cl )Mml(d l)O24-blXbl ( 1 ), wherein:• 1 < nl < 3, preferably nl = 1, 2 or 3;• cl is the oxidation state of A, being one of +1, +2, +3, +4, +5, +6, or +7;• 1 < ml < 3, preferably ml = 1, 2 or 3;• dl is the oxidation state of M, being one of +1, +2, +3, +4, +5, +6, or +7;• 0 < bl < 8;• A and M is at least one element selected from the selected from the list of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi; and• X is F, Cl, Br, I or combinations thereof.

2. The solid electrolyte according to claim 1, having a composition according to formula (2):Li48-n2c2-m2d2-b2An2(c2)Mm2(d2)O24-b2Xb2 (2), wherein:• 2 < n2 < 3, preferably n2 = 2 or 3;• c2 is the oxidation state of A, being one of +2, +3 or +4;• 1 < m2 < 2, preferably m2 = 1 or 2;• d2 is the oxidation state of M, being one of +2 or +3;• 0 < b2 < 8;• A is at least one element selected from the group consisting of Zn, Ti, Ge, Be, B, Al, and Ag;• M is at least one element selected from the group consisting of Be, Ag, Ga, Bi, Tb, Fe, B, and Tb; and• X is F, Cl, Br, I or combinations thereof.

3. The solid electrolyte according to claim 1 or 2, having a composition according to any of formula (2a)-(2k):

4. The solid electrolyte according to claim 1, having a composition according to formula (3):Li48-n3c3-m3d3-b3An3(c3)Mm3(d3)O24-b3Xb3 (3), wherein:• 2 < n3 < 3, preferably n=3 or 2;• c3 is the oxidation state of A, being one of +2;• 1 < n3 < 2, preferably n = l or 2;• d3 is the oxidation state of M, being one of +2 or +3;• 0 < b3 < 6;• A is at least one element selected from the group consisting of Be or Pb;• M is at least one element selected from the group consisting of Zn or Yb; and • X is F, Cl, Br, I or combinations thereof.

5. The solid electrolyte according to claim 1 or 4, having a composition according to formula (3a)-(3b):

6. The solid electrolyte according to claim 1, having a composition according to formula (4):Li48 -n4c4-m4d4- b4An4(c )Mm4(d )O24-b4Xb4 (4), wherein:• 2 < n4 < 3, preferably n4 = 2 or 3;• c4 is the oxidation state of A, being one of +2, +3, +4, or +5;• 1 < m4 < 2, preferably m4 = 1 or 2;• d4 is the oxidation state of M, being one of +2, +3, +4, +5, or +6;• 0 < b4 < 4;• A is at least one element selected from the group consisting of Al, Be, V, Ti, Si, Sb, Mo, Ge, Cr, Bi, and B;• M is at least one element selected from the group consisting of B, Te, C, Se, Bi, Ti, Si, Se, Sb, Mo, Cr, Al, and Ga; and• X is F, Cl, Br, I or combinations thereof.

7. The solid electrolyte according to claim 1 or 6, having a composition according to any of formula (4a)-(4p):

8. The solid electrolyte according to claim 1, having a composition according to formula (5):Li48-n5c5-m5d5-b5A n5(c5)Mm5(d5)O24-bsXb5 (5),wherein:• 1 < n5 < 2, preferably n5 = 2;• c5 is the oxidation state of A, being one of +4 or +5;• 1 < m5 < 2, preferably m5=2;• d5 is the oxidation state of M, being one of +3 or +4;• 0 < b5 < 2;• A is at least one element selected from the group consisting of Si, C, and Bi; • B is at least one element selected from the group consisting of Ge, Si, and Ag;and• X is F, Cl, Br, I or combinations thereof.

9. The solid electrolyte according to claim 1 or 8, having a composition according to any of formula (5a)-(5b):

10. The solid electrolyte according to claim 1, having a composition according to formula (6):Li48-n6c6-m6d6-b6An6(c6)Me(d6)O24-b6Xb6 (6),wherein:• 2 < n6 < 3, preferably n6 = 2 or 3;• c6 is the oxidation state of A, being one of +3, +4, +5, or +6;• 1 < m6 < 2, preferably m6 = 1 or 2;• d6 is the oxidation state of M, being one of +2, +3, +4, +5, or +6;• 0 < b6 < 8;• A is at least one element selected from the group consisting of V, Si, Se, P, N, Ga, Cr, and As;• M is at least one element selected from the group consisting of As, , Mo, N, V, Dy, Be, Si and2 Ge; and• X is F, Cl, Br, I or combinations thereof.

11. The solid electrolyte according to claim 1 or 10, having a composition according to any of formula (6a)-(6k):

12. The solid electrolyte according to claim 1, having a composition according to formula (7):Li48-n7c7-m7d7-b7An7(c7)Bm7(d7)O24-b7Xb7 (7), wherein:• 2 < n7 < 3, preferably n7 = 2 or 3;• c7 is the oxidation state of A, being one of +4, +5, or +6;• 1 < m7 < 2, preferably m7 = 1 or 2;• d7 is the oxidation state of M, being one of +4, 5, or +6;• 0 < b7 < 2;• A is at least one element selected from the group consisting of V, Mo, C, and As;• M is at least one element selected from the group consisting of As, N, C, Si, and V; and• X is F, Cl, Br, I or combinations thereof.

13. The solid electrolyte according to claim 1 or 12, having a composition according to any of formula (7a)-(7c):

14. The solid electrolyte according to claim 1, having a composition according to formula (8):Li48-n8c8-M8d8-b8An8(c8)Mm8(d8)O24-b8Xb8 (8), wherein:• 2 < n8 < 3, preferably n8 = 2;• c8 is the oxidation state of A, being one of +4, +6, or +7;• 1 < m8 < 2, preferably m8 = 2;• d8 is the oxidation state of M, being one of +2 or +4;• 0 < b8 < 8;• A is at least one element selected from the group consisting of W, Se, Ru, Mo, Mn, Ge and Cr;• M is at least one element selected from the group consisting of C and Hf; and • X is F, Cl, Br, I or combinations thereof.

15. The solid electrolyte according to claim 1 or 14, having a composition according to any of formula (8a):

16. A method for manufacturing a solid electrolyte, preferably the solid electrolyte according to any of claims 1-15, comprising the following steps:a) providing a set of precursors comprising Li, 0, Y and X;b) mixing of the set of precursors to obtain a solid electrolyte mixture; and c) heat-treating of the solid electrolyte mixture to obtain a solid electrolyte, wherein Y is selected from the group consisting of Be, B, C, N, Al, Si, P, Ti, V, Cr, Fe, Zn, Ga, Ge, As, Se, Zr, Mo, Ru, Ag, Sb, Te, Tb, Dy, Hf, W, Au, and Bi, and wherein X is selected from the group consisting of F, Cl, Br, and I and combinations thereof.

17. A battery comprising a solid electrolyte layer comprising a solid electrolyte according to any of claims 1-15 or a solid electrolyte obtained from the method according to claim 16.

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