Recycling process for solid halide electrolytes

Abstract

The present invention relates to formula (I)M 3-z (Me k+ ) f X 3-z+k*f The present invention relates to a recycling process for materials containing a halide solid electrolyte (HSE), the process comprising, in order: (a) adding an ammonium salt of at least one X' to a solution containing the HSE, where X and X' are halogens, and in particular independently selected from Cl, Br, I and any combination thereof; (b) filtering and evaporating the solution obtained in step (a) to obtain a dry powder; (c) heating the dry powder obtained in step (b); and (d) obtaining recycled HSE of formula (I). The present invention further relates to a cathode complex and electrolyte containing recycled HSE obtained from the recycling process according to the present invention, and to an all-solid-state battery containing such a cathode complex and / or electrolyte.

Description

[Technical Field]

[0001] This invention belongs to the field of all-solid-state batteries (ASSBs), and more particularly to the recycling and reuse of their components. Specifically, this invention relates to the recycling and reuse of halide solid electrolyte materials. [Background technology]

[0002] ASSBs are attracting particular attention as an alternative to conventional Li-ion batteries because they have relatively few safety concerns and relatively high capacity.

[0003] To obtain an ASSB, a solid electrolyte is used in place of the liquid electrolyte used in lithium-ion batteries. Typically, an ASSB uses lithium metal anode and energy NMC cathode particles as cathode active materials, and these particles are incorporated into the solid electrolyte to form the cathode composite of the ASSB.

[0004] Such solid electrolytes are selected from, for example, lithium thiophosphate (β-Li3PS4, also called LPS), argyrodites (Li6PS5Cl), such as those described by H.J. Deiseroth et al. in "Li6PS5X: A type of lithium-rich crystalline solid with very high Li+ mobility" (Angew. Chem. Int. Ed., 47 (2008), pp. 755-758), and halides, such as Li3InCl6, such as those described below: "Air-stable Li3InCl6 electrolyte with high voltage compatibility for all-solid-state batteries" by X. Li et al. (Energy Environ. Sci., 2019, 12, pp. 2665-267); and "Zur Kristallstruktur von Li3InCl6." by Schmidt, MO et al. (Zeitschrift fur Anorg.und Allg. 1999, 625(4), 539-540; and "Physical and Chemical Handbook of Rare Earths" by G. Meyer et al. (V.28, Chapter 177, 2000 Elsevier Sci.).

[0005] Halide solid electrolytes have attracted particular attention because they exhibit good ionic conductivity (over 2 mS / cm), high electrochemical stability against oxidation on the cathode side, and better compressibility (deformability) than other solid electrolytes.

[0006] However, concerns regarding environmental impact and resource depletion have arisen from the production and disposal of batteries.

Summary of the Invention

Problems to be Solved by the Invention

[0007] One of the major problems associated with halide solid electrolytes in ASSBs is their degradation (ionic conductivity, structural integrity) over multiple charge-discharge cycles. This degradation can significantly limit the overall performance and lifespan of ASSBs, which causes increased costs associated with their disposal and environmental problems. Therefore, means for recycling and reusing halide solid electrolytes are needed.

Means for Solving the Problems

[0008] The inventors have surprisingly discovered that the above-mentioned halide solid electrolyte can be recovered by adding a halide ammonium salt to a solution containing the corresponding halide solid electrolyte.

[0009] Thus, in a first aspect, the present invention relates to a recycling process for a material containing a halide solid electrolyte of formula (I), M 3-z (Me k+ ) f X 3-z+k*f (I) where -3 ≤ z < 3, 2 ≤ k < 6, 0 < f ≤ 1; - M contains an alkali metal element; - Me includes divalent, trivalent, tetravalent, pentavalent, or hexavalent metallic elements, or any combination thereof, and in particular, Me is: i. Alkaline earth metals, such as Ba, Mg, Ca, Sr, etc. ii. Rare earth elements, such as Y, Sc, Ce, Gd, Er, La, Yb and combinations thereof, iii. 3d transition metals, such as Zn, Cu, V, etc. iv. Elements selected from Zr, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, Te, In, Bi, Al, Ga, and v. Any combination of those, Selected from, and, - X is a halogen, specifically selected from Cl, Br, I and any combination thereof. The above process, in order, is as follows: a. Add at least one ammonium salt of X' to a solution containing the halogen solid electrolyte of formula (I). Here, X' is a halogen, and is particularly selected from Cl, Br, I and any combination thereof. b. Filter and evaporate the solution obtained in step (a) to obtain a dry powder. c. Heat the dried powder obtained in step (b), d. Obtain a recycled halide solid electrolyte of formula (I), Includes.

[0010] According to a second aspect, the present invention relates to a cathode composite, which is designed for use in an all-solid-state battery and comprises a recycled halide solid electrolytic of formula (I) obtained from a recycling process according to the present invention.

[0011] According to a third aspect, the present invention relates to an electrolyte, which is designed for use in an all-solid-state battery and includes a recycled halogen solid electrolyte of formula (I) obtained from a recycling process according to the present invention.

[0012] According to a fourth aspect, the present invention relates to an all-solid-state battery comprising a cathode composite and / or an electrolyte according to the present invention. [Effects of the Invention]

[0013] The recycling process according to the present invention offers numerous advantages. Firstly, it promotes the efficient use of resources by recovering valuable materials from discarded batteries, thereby reducing the demand for new raw materials. This enables a relatively sustainable and environmentally friendly approach to battery manufacturing and disposal.

[0014] Furthermore, the recycling process according to the present invention makes it possible to maintain the electrochemical properties of the original halide solid electrolyte.

[0015] Furthermore, the recycling process according to the present invention can be carried out with respect to battery components containing a halide solid electrolyte, such as the cathode and / or electrolyte, without the need to mechanically separate the halide solid electrolyte from these components.

[0016] Finally, the recycling process according to the present invention is relatively more energy-efficient than known battery recycling processes. In fact, the above process typically requires at least one additional heating step intended to disassemble and / or separate the battery components, but as will be described later herein, the process according to the present invention can be carried out on the complete components of the battery. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 shows a comparison of the XRD diffraction patterns of recycled Li3YCl5Br (bottom row) and the original Li3YCl5Br (top row) according to Example 1.

[0018] [Figure 2]Figure 2 shows the resistivity measurements of recycled Li3YCl5Br (Figure 2b) according to Example 1 compared to the original Li3YCl5Br (Figure 2a). These measurements are used to obtain the conductivity of the material according to methods well known to those skilled in the art.

[0019] [Figure 3] Figure 3 shows a comparison of the XRD diffraction patterns of recycled Li3YCl5Br (bottom panel) and the original Li3YCl5Br (top panel) according to Example 2.

[0020] [Figure 4] Figure 4 shows the resistivity measurements of recycled Li3YCl5Br (Figure 4b) compared to the original Li3YCl5Br (Figure 4a) according to Example 2. These measurements are used to obtain the conductivity of the material according to methods well known to those skilled in the art. [Modes for carrying out the invention]

[0021] Halide solid electrolytes can be represented by the following chemical formula (I): M 3-z (Me k+ ) f X 3-z+k*f Here, -3 ≤ z < 3, k is the valence of Me, and 2 ≤ k < 6, 0 <f≦1であり; - M contains alkali metal elements; - Me includes metals other than alkali metals, - X is a halogen.

[0022] f is not zero.

[0023] In certain embodiments, Me may comprise multiple metallic elements, and k may be the average value of the sum of the valencies of each metallic element. For example, if Me comprises equimolar amounts of trivalent and tetravalent elements, then k = (3 + 4) / 2 = 3.5. In particular, k may be 2, 3, 4, or 5.

[0024] It is understood that atomic vacancies can exist within the unit cell of the halide solid electrolyte. In this case, the atomic vacancy can be represented as M 3-z (Me k+ ) f●y X 3-z+k*f where ● represents an atomic vacancy within the unit cell and y is the number of vacancy atomic positions. In certain embodiments, y can be f*(k - 1).

[0025] In certain embodiments, M can include Li, Na, K, Rb, Cs, or any combination thereof. For example, M can include at least one of Li and Na, or a combination thereof. In yet another aspect, M can consist of at least one alkali metal element. For example, M can consist essentially of at least one alkali metal element selected from the group consisting of Li, Na, K, Rb, and Cs. In another example, M can consist of Li. In yet another example, M can consist of a combination of Li and at least one of Na, K, Rb, and Cs. In yet another example, M can consist of Na and at least one of Cs and Rb. In another example, M can consist of at least one of Na and Cs.

[0026] In a preferred embodiment, M is selected from Li and Na, and particularly, M is Li.

[0027] In certain embodiments, Me can include an alkaline earth metal element; a rare earth element; a 3d transition metal; an element selected from Zr, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, Te, In, Bi, Al, Ga; and any combination thereof. For example, Me can include an alkaline earth metal, such as Ba, Mg, Ca, and Sr, or any combination thereof. In another example, Me can include a rare earth element, particularly, Me can consist of at least one rare earth element. The rare earth element can be selected from Y, Sc, Ce, Gd, Er, La, Yb, and combinations thereof. As a further example, Me can include a 3d transition metal, particularly, a 3d transition metal selected from Zn, Cu, V, and any combination thereof. In yet another example, Me can include an element selected from Zr, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, Te, In, Bi, Al, Ga, and any combination thereof.

[0028] In a preferred embodiment, Me is selected from Y, In, and any combination thereof.

[0029] In a particularly preferred embodiment, Me is selected from Y, In, and any combination thereof, k is 3, and f is 1.

[0030] In certain embodiments, X can include a halogen, particularly, a halogen selected from Cl, Br, I, and any combination thereof. As an example, X can include at least one of Cl and Br. Preferably, X can consist of Cl, Br, or any combination thereof.

[0031] In certain embodiments, X is Cl 6-y Br y and represents that 0 < y < 6, particularly 1 ≤ y ≤ 5, preferably 1 ≤ y ≤ 3.

[0032] In certain embodiments, the halide solid electrolyte is Li 3-z Me k+ X 3-z+kIt can be expressed as follows: If z is not 0, the composite metal halide can be non-stoichiometric. If z is 0, the composite metal halide can be stoichiometric. For example, -0.95 ≤ z ≤ 0.95. Another example is that Me includes Y, Gd, Yb, In, Sc, Zn, Mg, Ca, Ba, Sn or combinations thereof, and X is Cl, Br or combinations thereof.

[0033] In a preferred embodiment, z is 0.

[0034] In certain embodiments, the solid halide electrolyte may be represented as Li3MeBr6. In other specific embodiments, the solid halide electrolyte may be represented as Li3MeCl6. In these embodiments, Me may consist of at least one of the aforementioned metal elements and have a valence of 3. Me may contain at least one of the aforementioned metal elements, the average valence of this at least one metal element is 3.

[0035] In another specific embodiment, the solid halide electrolyte may consist of Li, Y, and at least one of Cl and Br. For example, the solid halide electrolyte may consist of Li, Y, and Cl. In yet another example, the solid halide electrolyte may consist of Li, Y, and Br. In yet another example, the solid halide electrolyte may consist of Li, Y, Cl, and Br. In a particular example, the solid halide electrolyte may consist of Li 3x Y 1-x Cl3 or Li 3x Y 1-x It can be represented as Br3, where 0 <x≦0.5である。

[0036] In another specific embodiment, the solid halide electrolyte may consist of Li, Gd, and at least one of Cl and Br. For example, the solid halide electrolyte may consist of Li, Gd, and Cl. In yet another example, the solid halide electrolyte may consist of Li, Gd, and Br. In yet another example, the solid halide electrolyte may consist of Li, Gd, Cl, and Br. In a particular example, the solid halide electrolyte is Li3x Gd 1-x Cl3 or Li 3x Gd 1-x It can be expressed as Br3, where 0.01 ≤ x < 1.

[0037] In another specific embodiment, the solid halide electrolyte may consist of Li, In, and at least one of Cl and Br. For example, the solid halide electrolyte may consist of Li, In, and Cl. In yet another example, the solid halide electrolyte may consist of Li, In, and Br. In yet another example, the solid halide electrolyte may consist of Li, In, Cl, and Br. In a particular example, the solid halide electrolyte is Li 3x In 1-x Cl3 or Li 3x In 1-x It can be expressed as Br3, where 0 ≤ x < 0.5.

[0038] In another specific embodiment, the solid halide electrolyte may consist of Li, In, Y, and at least one of Cl and Br. For example, the solid halide electrolyte may consist of Li, In, Y, and Cl. In yet another example, the solid halide electrolyte may consist of Li, In, Y, and Br. In yet another example, the solid halide electrolyte may consist of Li, In, Cl, and Br. In a particular example, the solid halide electrolyte is Li3Y 1-x InxCl6, Li3Y 1-x In x Br6, or Li3Y 1-x In x Cl 6-y Br y This can be expressed as, where 0 <x<0.5かつ1.0<y<3.0である。

[0039] Solid halide electrolytes include Li3InCl6, Li3InBr6, Li3YCl6, Li3YBr6, and Li 2.7 Y 0.7 Zr 0.3 Cl6, Li 2.8 Y 0.8 Sn 0.2 Cl6, Li 3.2 Y0.8 Zn 0.2 Cl6, Li 3.2 Y 0.8 Mg 0.2 Cl6, Li3Y1 / 3Zr1 / 3Mg1 / 3Cl6, Li3Y1 / 3Sn1 / 3Mg1 / 3Cl6, Li3Y1 / 3Zr1 / 3Zn1 / 3Cl6, Li 2.95 Na 0.05 YGr6, Li 2.95 K 0.05 YGr6, Li 2.95 Cs 0.05 YBr6, Li3Y 0.7 Gd 0.3 Br6, Li3Y 0.8 Yb 0.2 Br6, Li3Y 0.9 La 0.1 Br6, Li 2.9 Y 0.9 Ce 0.1 Br6, Li3In 0.5 Y 0.5 It can be selected from Cl6, Li3Y(Cl,Br)6, or Li3(Y,In)1(Cl,Br)6.

[0040] The process according to the present invention comprises step (a), which is to add an ammonium salt of at least one X' to a solution containing a halide solid electrolyte of formula (I), where X' is a halogen, in particular selected from Cl, Br, I and any combination thereof.

[0041] In other words, the process according to the present invention may include adding at least one salt selected from: NH4Cl, NH4Br, NH4I, and any combination thereof.

[0042] In a preferred embodiment of the present invention, if the recycled halide solid electrolyte contains different halide ions, at least one ammonium salt added during step (a) contains these halide ions.

[0043] In a more preferred embodiment, X and X' are identical.

[0044] Preferably, the one or more ammonium salts added in step (a) of the process of the present invention are NH4Cl and NH4Br.

[0045] During step (a) of the present invention, one or more ammonium salts may be added to the halide solid electrolyte in a molar ratio of at least 4, preferably at least 5, and more preferably at least 6.

[0046] This means that the amount of one or more ammonium salts in the solution obtained after step (a) is at least four times, preferably at least five times, and more preferably at least six times, the amount of recycled halide solid electrolyte.

[0047] After step (a), the pH of the resulting solution can be controlled. By setting the pH to less than 9, particularly an acidic pH, preferably 6 or less, the solubility of one or more ammonium salts can be ensured.

[0048] The process according to the present invention further includes step (b), which involves filtering and evaporating the solution obtained in step (a) to obtain a dry powder.

[0049] Step (b) above may be carried out by any filtration means well known to those skilled in the art.

[0050] The above-mentioned dried powder is, for example, in the form of beads.

[0051] The evaporation component of step (b) may be carried out by any evaporation means well known to those skilled in the art.

[0052] The above-mentioned dried powder may consist of a complex formed by a halogen solid electrolyte and one or more ammonium salts.

[0053] The process according to the present invention further includes step (c), which is to heat the dried powder obtained in step (b).

[0054] Preferably, the above heating is carried out under a nitrogen atmosphere.

[0055] The above heating is intended to decompose the complex obtained in step (b) in particular by generating gaseous NH3 and HX'.

[0056] Therefore, step (c) above is preferably carried out at a temperature in the range of 250°C to 650°C, particularly 260°C to 600°C, and preferably 275°C to 550°C.

[0057] The above temperatures are considered for the case where step (c) proceeds under atmospheric pressure. Those skilled in the art can easily adapt step (c) to be carried out at a relatively low pressure, thereby obtaining the decomposition of the complex and the release of gaseous NH3 and HX' with a relatively low heating temperature.

[0058] Once the above species (NH3 and HX') are no longer released, the residue is a recycled halide solid electrolyte of formula (I), as demonstrated in the following examples.

[0059] Therefore, the recycling process according to the present invention includes step (d) of obtaining a recycled halide solid electrolyte of formula (I).

[0060] The recycling process according to the present invention is applied to materials containing a halogen solid electrolyte of formula (I).

[0061] The above materials are materials for batteries, particularly for all-solid-state batteries, and are selected from cathode composites, solid electrolytes, and mixtures thereof.

[0062] In fact, the present invention is particularly advantageous in that, unlike conventional recycling processes in the battery field, and especially in the field of all-solid-state batteries, it does not require a step of decomposing the starting material into, for example, elemental materials.

[0063] A cathode complex refers to a complex containing a cathode active material and a halogen solid electrolyte of formula (I).

[0064] The cathode active material is a material that can store and release metal ions, particularly alkali metal ions, such as Li ions and Na ions.

[0065] As cathode active materials, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, transition metal oxynitrides, and lithium-containing transition metal oxides may be used, whether doped or undoped, coated or uncoated. In particular, the cathode active material may be a transition metal oxide, such as lithium cobalt oxide, lithium nickel cobalt aluminum oxide, or lithium nickel manganese cobalt oxide (NMC). A transition metal oxide suitable for use as a cathode active material is, for example, LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622), LiNi 0.8 Mn 0.1 Co 0.1 The cathode active material may be O2(NMC811), Li(NiCoAl)O2, and LiCoO2. Preferably, the cathode active material is of the formula LiNi 0.6 Mn 0.2 Co 0.2 O2 (NMC622) is a transition metal oxide.

[0066] Cathode complexes may include the following: - 55-75% by weight, particularly 60-70% by weight, preferably 66.7% by weight, cathode active material, - 20-40% by weight, particularly 25-30% by weight, preferably 28.6% by weight, of a halogen solid electrolyte of formula (I), and optionally, - An electronically conductive carbon compound in an amount of 1 to 10% by weight, particularly 2 to 7% by weight, preferably 4.8% by weight.

[0067] Electronically conductive compounds can be selected from natural or artificial graphite, graphene, carbon nanotubes, acetylene black, Ketjenblack, activated carbon, fluorinated carbon, metal powders, conductive whiskers, conductive metal oxides, conductive polymers, metal fibers, or carbon fibers.

[0068] Furthermore, the recycled halide solid electrolyte obtained from the process according to the present invention may be used to create new components for all-solid-state batteries, and may also be used to assemble a complete all-solid-state battery.

[0069] In fact, as demonstrated herein, the process according to the present invention enables recycled halide solid electrolytes to retain electrochemical properties compared to the original material.

[0070] Accordingly, the present invention also relates to a cathode composite designed for use in an all-solid-state battery, which comprises a recycled halide solid electrolyte of formula (I) obtained from a recycling process according to the present invention.

[0071] The cathode composite according to the present invention may correspond to the definition of cathode composite herein, with a notable exception being that the halide solid electrolyte is at least partially made of a recycled halide solid electrolyte obtained from the recycling process according to the present invention.

[0072] The present invention further relates to a solid electrolyte designed for use in all-solid-state batteries, which includes a recycled halide solid electrolyte of formula (I) obtained from a recycling process according to the present invention.

[0073] Finally, the present invention also relates to an all-solid-state battery comprising a cathode composite and / or an electrolyte according to the present invention. [Examples]

[0074] Example 1: Recycling of Halide Solid Electrolytes

[0075] Li3YCl5Br1 (110.07 g) was dissolved in 240 g of pure water. The pH of the resulting solution was controlled to approximately 2 or 3.

[0076] Next, ammonium bromide (33.42 g) and ammonium chloride (91.27 g) were added to the solution. The solution was then filtered and dried in a rotary evaporator until all the water in the solution had evaporated.

[0077] For example, drying in a rotary evaporator is performed at 135°C and a pressure of 27 millibars (mbar).

[0078] Approximately 227 g of Li3YCl5Br1-NH4Cl / NH4Br complex powder was obtained. This complex was heated at 540°C under a nitrogen atmosphere. Approximately 106 g of Li3YCl5Br1 ingot was recovered.

[0079] In this way, Li3YCl5Br1 was recycled with a yield of 96%.

[0080] Subsequently, the ingots were crushed using a mechanical crusher (Retsch RM 400) and further characterization was performed.

[0081] Figure 1 shows that the XRD pattern of recycled Li3YCl5Br1 has the same peak positions and relative intensities as the original material, confirming the recovery of the exact same compound.

[0082] Conductivity measurements were performed on both recycled Li3YCl5Br1 and the original Li3YCl5Br1 (see Figures 2b and 2a, respectively). The original Li3YCl5Br1 showed a conductivity of 2.09 μS / cm (±0.09), while the recycled Li3YCl5Br1 was measured at 2.05 μS / cm (±0.05).

[0083] Therefore, the recycling process according to the present invention enables the halide solid electrolyte to retain its electrochemical properties.

[0084] Example 2: Recycling of cathode complex

[0085] A cathode composite was prepared containing 110.7 g of Li3YCl5Br1, 1.11 g of NMC811 cathode active material, and 1.01 g of carbon fiber. The composite was dissolved in 1500 g of pure water to obtain a solution.

[0086] Next, ammonium bromide (33.27 g) and ammonium chloride (91.42 g) were added to the solution. The pH of the solution was controlled to approximately 6. The solution was then filtered and dried in a rotary evaporator.

[0087] 228.5 g of Li3YCl5Br1-NH4Cl / NH4Br complex powder was obtained. This complex was heated at 540°C under a nitrogen atmosphere. 106.8 g of Li3YCl5Br1 ingot was recovered.

[0088] In this way, Li3YCl5Br1 was recycled with a yield of 97%.

[0089] Subsequently, the ingots were crushed using a mechanical crusher (Retsch RM 400) and then further characterization was performed.

[0090] Figure 3 shows that the XRD pattern of recycled Li3YCl5Br1 has the same peak positions and relative intensities as the original material, confirming the recovery of the exact same compound.

[0091] Conductivity measurements were performed on both recycled Li3YCl5Br1 and the original Li3YCl5Br1 (see Figures 4b and 4a, respectively). The original Li3YCl5Br1 showed a conductivity of 2.09 μS / cm (±0.09), while the recycled Li3YCl5Br1 was measured at 1.89 μS / cm (±0.08).

[0092] Therefore, the recycling process according to the present invention enables the halide solid electrolyte to retain its electrochemical properties.

Claims

1. A recycling process for materials containing a halogen solid electrolyte of formula (I), M ３－ｚ (Me ｋ＋ ) ｆ X ３－ｚ＋ｋ＊ｆ (I) Here, -3 ≤ z < 3, 2 ≤ k < 6, 0 < f ≤ 1; - M contains alkali metal elements; - Me includes divalent, trivalent, tetravalent, pentavalent, or hexavalent metallic elements, or any combination thereof, and in particular, Me is: i. Alkaline earth metals, such as Ba, Mg, Ca, Sr, etc. ii. Rare earth elements, such as Y, Sc, Ce, Gd, Er, La, Yb and combinations thereof, iii. 3d transition metals, such as Zn, Cu, V, etc. iv. Elements selected from Zr, Ti, Sn, Th, Ge, Ta, Nb, Mo, W, Sb, Te, In, Bi, Al, Ga, and, v. Any combination of them, Selected from, and, - X is a halogen, and is particularly selected from Cl, Br, I and any combination thereof. The above process, in order, is as follows: (a) Adding at least one ammonium salt of X' to the solution containing the halogen solid electrolyte of formula (I), Here, X' is selected from halogens, particularly Cl, Br, I, and any combination thereof. (b) Filter and evaporate the solution obtained in step (a) to obtain a dry powder. (c) Heating the dried powder obtained in step (b), (d) To obtain a recycled halogen solid electrolyte of formula (I), A recycling process that includes this.

2. The recycling process according to claim 1, wherein M is selected from Li and Na, and in particular M is Li.

3. The recycling process according to claim 1 or 2, wherein z is 0.

4. The recycling process according to any one of claims 1 to 3, wherein Me is selected from Y, In and any combination thereof, k is 3, and f is 1.

5. X is Cl ６－ｙ Br ｙ The recycling process according to any one of claims 1 to 4, wherein 0 < y < 6, particularly 1 ≤ y ≤ 5, preferably 1 ≤ y ≤ 3.

6. The recycling process according to any one of claims 1 to 5, wherein X and X' are the same.

7. In process (a), NH ４ Cl and NH ４ A recycling process according to any one of claims 1 to 6, wherein Br is added.

8. The recycling process according to any one of claims 1 to 7, comprising adding one or more of the ammonium salts to the halide solid electrolyte in a molar ratio of at least 4, preferably at least 5, more preferably at least 6.

9. The recycling process according to any one of claims 1 to 8, wherein the heating step (c) is performed in a temperature range of 250°C to 650°C, particularly 260°C to 600°C, preferably 275°C to 550°C.

10. The recycling process according to any one of claims 1 to 9, wherein the material is a battery material, particularly a solid-state battery material, and is selected from anode composites, solid electrolytes, and mixtures thereof.

11. A cathode composite, designed for use in an all-solid-state battery, comprising a recycled halide solid electrolyte of formula (I) obtained from a recycling process according to any one of claims 1 to 10.

12. A solid electrolyte, designed for use in an all-solid-state battery, comprising a recycled halide solid electrolyte of formula (I) obtained from a recycling process according to any one of claims 1 to 10.

13. A solid-state battery comprising the cathode composite described in claim 11 and / or the electrolyte described in claim 12.

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