# Patent

## Title
Lithium argyrodite

## Abstract

The invention relates to lithium argyrodite of the general formula (I): Li+(12-n-x)Bn+X2−6-xY−x (I), where Bn+ is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, and Ta; X2− is selected from the group consisting of S, Se, and Te; Y− is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, and N3; 0≦x≦2, and a method for the production thereof, and the use thereof as a lithium-ion electrolyte in primary and secondary electrochemical energy storage.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Stage of International Application No. PCT/EP2008/063412, filed on Oct. 7, 2008, which claims the benefit of German Application Serial No. 10 2007 048 289.4, filed on Oct. 8, 2007, the contents of both of the foregoing applications are hereby incorporated by reference in their entirety.
The present invention relates to a novel class of lithium-rich solid-state compounds, a process for their preparation and their use as solid electrolytes in primary and secondary electrochemical energy stores.
Argyrodites have long been known and are derived from argyrodite Ag8GeS6, which was described for the first time in 1886 by C. Winkler and the analysis of which led to the discovery of germanium. The argyrodite family consists of more than 100 crystalline solids and includes, for example, those solid-state compounds in which the silver is replaced by copper, the germanium by gallium or phosphorus and the sulfur by selenium. Thus, Nitsche, Kuhs, Krebs, Evain, Boucher, Pfitzner and Nilges describe, inter alia, compounds such as Cu9GaS6, Ag7PSe6 and Cu8GaS5Cl, the solid-state structures of which are derived from argyrodite.
Li argyrodites were unknown for a long time, with the exception of the insufficiently characterized compound Li7PS6 (J. F. Brice, C. R. Seances in Acad. Sci. 1976, C283, 581). Recent investigations, for example by Eckert, Zhang and Kennedy in Chem. of Mat. 1990, 2, 273-279, relate to thermomechanical optimization experiments for the Li2S—P2S5 system and show as a whole samples which do not have a single phase. However, signs of high lithium mobility are found for this system in many samples.
More detailed investigations have, however, shown that the production of single-phase solids in the Li2S—P2S5 system is difficult and is greatly dependent, inter alia, on the starting materials and crucible materials used during the preparation, so that different byproducts form depending on the material used.
It is therefore an object of the present invention to provide a novel class of lithium-rich solid-state compounds which permit single-phase preparation in addition to high lithium ion mobility.
This object is achieved, according to the invention, by lithium argyrodites of the general formula (I):

Li+(12-n-x)Bn+X2−6-xY−x  (I)

in which

    Bn+ is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta,
    X2− is selected from the group consisting of S, Se and Te,
    Y− is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N3, and in which 0≦x≦2.


Advantageously, the inventive class of novel lithium-rich argyrodites permits preparation of single-phase solids. In addition, the inventive compounds of the novel class have high lithium ion mobility, which can preferably be employed in a use as solid electrolyte. In contrast to known lithium electrolytes, the lithium argyrodites according to the invention can be used in a wide temperature range from −150° C. to 600° C. Thus, the temperature sensitivity of electrochemical energy stores which has been observable to date can be reduced.
The component Bn+ can preferably be selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb and Ta. P, As, Sb and Ga are particularly preferred, especially with regard to use as an electrolyte constituent of a lithium accumulator.
The component X2− can be selected from the group consisting of S, Se and Te. In particular, components X2− selected from the group consisting of S and Se are favored in a preferred configuration of the invention, owing to their easier preparation.
The component Y− can preferably be selected from the group consisting of Cl, Br, I, F, OCN, SCN, N3, CN. Cl, Br and I are particularly preferred, especially with regard to use as an electrolyte constituent of a lithium accumulator.
The lithium argyrodites according to the invention can preferably be compounds of the general formula (II):

Li6PS5Z  (II),

in which the constituent Z may be a monovalent anion selected from the group consisting of the halides and the pseudohalides.

In a further preferred embodiment of the present invention, the component Z can be selected from the group consisting of Cl, Br, I.
Particularly when Z═I, these compounds show a high specific Li+ ion conductivity, in said case Z═I of about 7×10−3 Scm−1 at room temperature. NMR investigations on these compounds have also indicated a high specific Li+ mobility.
The compounds of the formula (II) where Z═Cl, Br or I can advantageously be prepared in a solid-state synthesis, for example according to the following reactions:

6Li2S+2P+1⁄2S8+I2→2Li6PS5I

5Li2S+2P+5⁄8S8+2LiBr→2Li6PS5Br

5Li2S+2P+5⁄8S8+2LiCl→2Li6PS5Cl

In a further preferred embodiment of the invention, the lithium argyrodites can be compounds of the general formula (III):

Li6B5+S5-aX2−aY−  (III)

in which

    B5+ is selected from the group consisting of P, As and Sb,
    X2− is selected from the group consisting of Se and Te,
    Y− is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N3, and in which 0≦a≦2.


Furthermore preferred are inventive lithium argyrodites of the general formula (IV):

Li7B5+S6-aX2−a  (IV)

in which

B5+ is selected from the group consisting of P, As, and Sb,

X2− is selected from the group consisting of Se and Te, and in which 0≦a≦2.

The invention moreover relates to a process for the preparation of lithium argyrodites of the general formula (I), characterized by the steps:

    
    
        mixing of the stoichiometric amounts of the starting substances under an inert gas atmosphere,
        pressing of the resulting powder mixture to give pellets, and
        heating of the pellets to temperatures from 400° C. to 700° C. for a duration of from 3 days to 10 days.
    
    


According to the invention, a process which permits a simple procedure in addition to a good single-phase character of the crystalline compounds can advantageously be provided.
The process according to the invention can be carried out in particular at a temperature of from 500° C. to 600° C., preferably at 550° C.
In a further advantageous embodiment of the process, a duration of from 4 days to 8 days, preferably a duration of 7 days, can be provided.
An inventive lithium argyrodite of the general formula (I) can preferably be used as a lithium ion electrolyte for primary and secondary electrochemical energy stores.
The invention is described further by the following examples without being limited thereto.


EXAMPLES
1. Preparation of the Compound Li6PS5I According to the Invention
For the preparation of the compound Li6PS5I, the starting materials I2, S8, Li2S and P2S5 were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li6PS5I were obtained as a white solid.
2. Preparation of the Compound Li6PS5Br According to the Invention
For the preparation of the compound Li6PS5Br, the starting materials LiBr, Li2S and P2S5 were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li6PS5Br were obtained as a white solid.
3. Preparation of the Compound Li6PS5Cl According to the Invention
For the preparation of the compound Li6PS5Cl, the starting materials LiCl, Li2S and P2S5 were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li6PS5Cl were obtained as a white solid.
4. Preparation of the Compound Li7PS5Se According to the Invention
For the preparation of the compound Li7PS5Se, the starting materials S8, Li2S and P2Se5 were weighed out in the stoichiometric ratio under an argon inert gas atmosphere, transferred to a graphitized quartz ampoule and melted in vacuo. The sample was heated in a tubular furnace at a temperature of 500° C.-550° C. for 6 days and then slowly cooled. Single-phase crystals of the compound Li7PS5Se were obtained as a white solid.

## Claims

1. A lithium argyrodite of the general formula (I):


Li+(12-n-x)Bn+X2−6-xY−x  (I)


in which
Bn+ is selected from the group consisting of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, and Ta,
X2− is selected from the group consisting of S, Se, and Te,
Y− is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, and N3, and in which 0≦x≦2.

2. The lithium argyrodite as claimed in claim 1, characterized in that the component Bn+ is selected from the group consisting of P, As, and Ga.

3. The lithium argyrodite as claimed in claim 1, characterized in that the component X2− is selected from the group consisting of S and Se.

4. The lithium argyrodite as claimed in claim 1, characterized in that the component Y− is selected from the group consisting of Cl, Br, and I.

5. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (II):


Li6PS5Z  (II)


in which the constituent Z is a monovalent anion selected from the group consisting of the halides and pseudohalides.

6. The lithium argyrodite as claimed in claim 5, characterized in that the component Z is selected from the group consisting of Cl, Br, and I.

7. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (III):


Li6B5+S5-aX2−aY−  (III)


in which
B5+ is selected from the group consisting of P, As, and Sb,
X2− is selected from the group consisting of Se and Te,
Y− is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N3, and in which 0≦a≦2.

8. The lithium argyrodite as claimed in claim 1, characterized in that it is a compound of the general formula (IV):


Li7B5+S6-aX2−a  (IV)


in which
B5+ is selected from the group consisting of P, As, and Sb,
X2− is selected from the group consisting of Se and Te, and in which 0≦a≦2.

9. A process for the preparation of a lithium argyrodite of the general formula (I), characterized by the steps:
mixing of the stoichiometric amounts of the starting substances under an inert gas atmosphere,
pressing of the resulting powder mixture to give pellets, and
heating of the pellets to temperatures from 400° C. to 700° C. for a duration of from 3 days to 10 days.

10. The process for the preparation of a lithium argyrodite as claimed in claim 9, characterized in that temperatures of from 500° C. to 600° C. are established.

11. The process for the preparation of a lithium argyrodite as claimed in claim 9, characterized in that the heating is carried out for a duration of from 4 days to 8 days.

12. Primary and secondary electrochemical energy stores comprising a lithium ion electrolyte, wherein the lithium ion electrolyte is the lithium argyrodite as claimed in claim 1.

13. The lithium argyrodite as claimed in claim 2, characterized in that the component X2− is selected from the group consisting of S and Se.

14. The lithium argyrodite as claimed in claim 2, characterized in that the component Y− is selected from the group consisting of Cl, Br, and I.

15. The lithium argyrodite as claimed in claim 3, characterized in that the component Y− is selected from the group consisting of Cl, Br, and I.

16. The lithium argyrodite as claimed in claim 13, characterized in that the component Y− is selected from the group consisting of Cl, Br, and I.

17. The lithium argyrodite as claimed in claim 2, characterized in that it is a compound of the general formula (II):


Li6PS5Z  (II)


in which the constituent Z is a monovalent anion selected from the group consisting of the halides and pseudohalides.

18. The lithium argyrodite as claimed in claim 3, characterized in that it is a compound of the general formula (II):


Li6PS5Z  (II)


in which the constituent Z is a monovalent anion selected from the group consisting of the halides and pseudohalides.

19. The lithium argyrodite as claimed in claim 4, characterized in that it is a compound of the general formula (II):


Li6PS5Z  (II)


in which the constituent Z is a monovalent anion selected from the group consisting of the halides and pseudohalides.

20. The lithium argyrodite as claimed in claim 14, characterized in that it is a compound of the general formula (II):


Li6PS5Z  (II)


in which the constituent Z is a monovalent anion selected from the group consisting of the halides and pseudohalides.