IP Library Patent Application 17999796
Patent Application
App. No. 17/999,796

NEW SOLID SULFIDE ELECTROLYTES

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Patent No.
US None
App. No.
17/999,796
Abstract

The present invention concerns a new solid material according to general formula (I) as follows: Li 4−2x Zn x P 2 S 6 (I) wherein 0<x≤1. The invention also refers to a method for producing a solid material comprising at least bringing at least lithium sulfide, phosphorous sulfide, and a zinc compound, optionally in one or more solvents. The invention also refers to said solid materials and their use as solid electrolytes notably for electrochemical devices.

Claims (51)

1 . A solid material comprising Li, Zn, P and S elements and exhibiting at least peaks at position of: 13.4°+/−0.5°, 16.9°+/−0.5°, 27.1°+/−0.5°, 32.1°+/−0.5°, 32.6°+/−0.5° when analyzed by x-ray diffraction using CuKα radiation at 25° C.

2 . (canceled)

3 . The solid material according to claim 1 wherein the solid material is of general formula (I) as follows:

Li 4−2x Zn x P 2 S 6   (I)

wherein 0<x≤1.

4 . The solid material according to claim 1 wherein x is chosen from 0.33 to 0.5.

5 . The solid material according to claim 1 wherein it is in powder form with a distribution of particle diameters having a D50 comprised between 0.05 μm and 10 μm.

6 . The solid material according to claim 1 wherein the solid is selected from a group consisting of: Li 3.8 Zn 0.1 P 2 S 6 , Li 3.6 Zn 0.2 P 2 S 6 , Li 3.5 Zn 0.25 P 2 S 6 , Li 3.33 Zn 0.33 P 2 S 6 , Li 3.2 Zn 0.4 P 2 S 6 , Li 3 Zn 0.5 P 2 S 6 , and Li 2.666 Zn 0.666 P 2 S 6 .

7 . A method for producing the solid material according to claim 1 comprising at least bringing at least lithium sulfide, phosphorous sulfide and zinc compound, optionally in one or more solvents, then proceeding with a heat treatment at a temperature in the range of from 375° C. to 900° C., under an inert atmosphere, thereby forming the solid material.

8 . A process for the preparation of a solid material comprising Li, Zn, P and S elements and exhibiting at least peaks at position of: 13.4°+/−0.5°, 16.9°+/−0.5°, 27.1°+/−0.5°, 32.1°+/−0.5°, 32.6°+/−0.5° when analyzed by x-ray diffraction using CuKα radiation at 25° C., said process comprising at least the process steps of:

a) obtaining a composition by admixing stoichiometric amounts of lithium sulfide, phosphorous sulfide, and a zinc compound, optionally in one or more solvents, under an inert atmosphere;

b) applying a mechanical treatment to the composition obtained in step a);

c) optionally removing at least a portion of the one or more solvents from the composition obtained on step b), so that to obtain a solid residue;

d) heating the obtained residue obtained in step c) at a temperature in the range of from 370° C. to 900° C., under an inert atmosphere, thereby forming the solid material; and

e) optionally treating the solid material obtained in step d) to the desired particle size distribution.

9 . A process for the preparation of a solid material according to general formula (I) as follows:

Li 4−2x Zn x P 2 S 6   (I)

wherein 0<x≤1, preferably x is chosen from 0.2 to 0.7;

said process comprising at least the process steps of:

a) obtaining a composition by admixing stoichiometric amounts of lithium sulfide, phosphorous sulfide, and a zinc compound in order to obtain Li 4−2x Zn x P 2 S 7 , optionally in one or more solvents, under an inert atmosphere;

b) applying a mechanical treatment to the composition obtained in step a);

c) optionally removing at least a portion of the one or more solvents from the composition obtained on step b), so that to obtain a solid residue;

d) heating the obtained residue obtained in step c) at a temperature in the range of from 375° C. to 900° C., under an inert atmosphere, thereby forming the solid material; and

e) optionally treating the solid material obtained in step d) to the desired particle size distribution.

10 . The process according to claim 8 wherein the zinc compound is chosen in the group consisting of ZnS and Zn.

11 . The process according to claim 8 wherein lithium sulfide is Li2S, phosphorous sulfide is P2S5, and zinc compound is ZnS.

12 . The process according to claim 8 wherein the solvent is selected in the group consisting of alkanols, notably having 1 to 6 carbon atoms, such as methanol, ethanol, propanol and butanol; carbonates, such as dimethyl carbonate; acetates, such as ethyl acetate; ethers, such as dimethyl ether, tetrahydrofuran; organic nitriles, such as acetonitrile; aliphatic hydrocarbons, such as hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane; and aromatic hydrocarbons, such as xylene and toluene.

13 . The process according to claim 8 wherein in step b) the mechanical treatment is performed by wet or dry milling.

14 . The process according to claim 8 wherein the heat treatment is carried out in step d) at a temperature in the range of from 400° C. to 700° C.

15 . (canceled)

16 . The solid electrolyte of claim 17 , wherein the solid material is of formula (I) as follows:

Li 4−2x Zn x P 2 S 6   (I)

wherein 0<x≤1.

17 . A solid electrolyte comprising at least the solid material of claim 1 .

18 . An electrochemical device comprising at least a solid electrolyte comprising at least the solid material of claim 1 .

19 . A solid state battery comprising at least a solid electrolyte comprising at least the solid material of claim 1 .

20 . A vehicle comprising at least a solid state battery comprising at least a solid electrolyte comprising at least the solid material of claim 1 .

21 . An electrode comprising at least:

a metal substrate;

directly adhered onto said metal substrate, at least one layer made of a composition comprising:

(i) the solid material according to claim 1 ;

(ii) at least one electro-active compound (EAC);

(iii) optionally at least one lithium ion-conducting material (LiCM) other than the solid material of the invention;

(iv) optionally at least one electro-conductive material (ECM);

(v) optionally a lithium salt (LIS); and

(vi) optionally at least one polymeric binding material (P).

22 . A separator comprising at least:

the solid material according to claim 1 ;

optionally at least one polymeric binding material (P);

optionally at least one metal salt, notably a lithium salt; and

optionally at least one plasticizer.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 1, 2024
From: SOLVAY SA
To: SYENSQO SA
Reel/Frame 066406/0174 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 15, 2023
From: BRAIDA, MARC-DAVID; LE MERCIER, THIERRY; KUDU, ÖMER ULAS
To: SOLVAY SA
Reel/Frame 063641/0291 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 15, 2023
From: MASQUELIER, CHRISTIAN
To: UNIVERSITE DE PICARDIE JULES VERNE
Reel/Frame 063641/0311 →