Method of preparing sulfide-based solid electrolyte having excellent air stability

Patent metadata

Field	Value
Publication number	US-10020536-B2
Application number	US-201715404708-A
Country	US
Kind code	B2
Filing date	Jan 12, 2017
Priority date	Aug 22, 2016
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

A method for preparing a sulfide-based solid electrolyte which is stable upon exposure to the air is provided. Specifically, a stabilization layer is formed on the surface of a sulfide-based solid electrolyte particle through treatment with a reactive gas.
The sulfide-based solid electrolyte with superior air stability can be obtained because oxidation or reduction reactions with water, etc. in the air occur on the stabilization layer rather than on the sulfide-based solid electrolyte particle.

First claim

What is claimed is:

1. A method for preparing a sulfide-based solid electrolyte with superior air stability, comprising:
preparing a sulfide-based solid electrolyte particle; and
forming a stabilization layer on the surface of the sulfide-based solid electrolyte particle by treating the sulfide-based solid electrolyte particle under a reactive gas atmosphere,
wherein the reaction gas atmosphere is:
one or more nitrogen oxide-based gas of nitrogen monoxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), dinitrogen pentoxide (N2O5), and nitrogen (N2);
one or more oxygen-based gas of oxygen (O2) and ozone (O3);
an organic (CxHyOz) gas of diethyl ether (C2H10O);
one or more sulfur oxide (SxOy)-based gas of sulfur monoxide (SO), sulfur dioxide (SO2), and sulfur trioxide (SO3);
one or more chlorine (Cl)-based gas of chloroform (CH3Cl), chlorine monoxide (ClO), dichlorine monoxide (Cl2O), chlorine dioxide, (ClO2) and chlorine (Cl2);
one or more fluorine (F)-based gas of oxygen fluoride (OF2, O2F2, O3F2) and fluororesin gas; and
one or more silicon (Si)-based gas of a halosilane (SiF4, SiCl3F, SiCL2FBr), an organosilane, a heterosilane and a silanol.

2. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the sulfide-based solid electrolyte particle is crystallized by pre-heat treating, and then the crystallized sulfide-based solid electrolyte particle is treated under the reactive gas atmosphere.

3. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the stabilization layer is formed by heat treating or plasma treating under a reactive gas atmosphere.

4. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the stabilization layer is formed by heat-treating the sulfide-based solid electrolyte particle at 200-400° C. for 1 minute to 10 hours under a reactive gas atmosphere.

5. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 2 , wherein the stabilization layer is formed by heat-treating the sulfide-based solid electrolyte particle at 25-400° C. for 1 minute to 10 hours under a reactive gas atmosphere.

6. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the stabilization layer is formed as a reactant derived from the reactive gas is physically or chemically bound to the surface of the sulfide-based solid electrolyte particle.

7. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the reactive gas is supplied to the sulfide-based solid electrolyte particle at a pressure of 1-10 bars.

8. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein the preparing of the sulfide-based solid electrolyte particle includes the following steps:
preparing a mixture of phosphorus pentasulfide (P2S5) and lithium sulfide (Li2S); and
milling the mixture to obtain an amorphous sulfide-based solid electrolyte particle.

9. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 1 , wherein, in the forming of the stabilization layer the reactive gas atmosphere is provided by supplying nitrogen monoxide as a reactive gas at a pressure of 1-1.5 bars and then the stabilization layer comprising nitrogen functional groups derived from the nitrogen monoxide is formed on the surface of the sulfide-based solid electrolyte particle by heat-treating the sulfide-based solid electrolyte particle at 260-360° C. for 1-2 hours.

10. The method for preparing a sulfide-based solid electrolyte with superior air stability according to claim 2 , wherein
in the crystallizing of the sulfide-based solid electrolyte particle, the sulfide-based solid electrolyte particle is crystallized by pre-heat treating at 260-360° C. for 1-2 hours, and
in the forming of the stabilization layer, the reactive gas atmosphere is provided by supplying nitrogen monoxide as a reactive gas at a pressure of 1-1.5 bars and then the stabilization layer comprising nitrogen functional groups derived from the nitrogen monoxide is formed on the surface of the sulfide-based solid electrolyte particle by heat-treating the sulfide-based solid electrolyte particle at 25-200° C. for 1-2 hours.

Assignees

• Korea Inst Sci & Tech

Inventors

• Kim Hyoung Chul
• Choi Sung Jun
• Kim Jeong Hun
• Jung Wo Dum
• Jung Hun Gi
• Son Ji Won
• Lee Jong Ho
• Kim Byung Kook
• Lee Hae Weon

Classifications

• H01M10/0562 Primary

  Solid materials · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C01B17/20

  Methods for preparing sulfides or polysulfides, in general (ammonium sulfides or polysulfides C01C; sulfides or polysulfides of metals, other than alkali metals, magnesium, calcium, strontium and barium, see the relevant groups of subclasses C01F or C01G, according to the metal) · CPC title

• C01B17/22

  Alkali metal sulfides or polysulfides · CPC title

• H01M2300/0068

  inorganic · CPC title