Sulfide-based solid electrolyte for lithium battery, method of preparing the same, and lithium battery including the sulfide-based solid electrolyte

Patent metadata

Field	Value
Publication number	US-11114691-B2
Application number	US-201916449910-A
Country	US
Kind code	B2
Filing date	Jun 24, 2019
Priority date	Aug 10, 2018
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A sulfide solid electrolyte including: a sulfide electrolyte for a lithium battery; and a metal-organic framework.

First claim

What is claimed is:

1. A sulfide solid electrolyte comprising:
a sulfide electrolyte for a lithium battery; and
a metal-organic framework comprising hydrogen sulfide adsorbed in a pore of the metal-organic framework.

2. The sulfide solid electrolyte of claim 1 ,
wherein the metal-organic framework has a primary particle size of about 1 nanometer to about 1 micrometer, and
wherein the primary particle size of the metal-organic framework is in accordance with Formula 1:
0<σ 2 /μ<1,  Formula 1

wherein σ 2 is a size variance of a plurality of primary particles obtained by dynamic laser scattering, and μ is an average particle diameter of the plurality of primary particles.

3. The sulfide solid electrolyte of claim 1 ,
wherein a content of the metal-organic framework is about 0.1 parts by weight to about 50 parts by weight, based on 100 parts by weight of the sulfide solid electrolyte.

4. The sulfide solid electrolyte of claim 1 ,
wherein the sulfide electrolyte comprises Li 2 S—P 2 S 5 , LiI—Li 2 S—B 2 S 3 , Li 3 PO 4 —Li 2 S—Si 2 S, Li 3 PO 4 —Li 2 S—SiS 2 , LiPO 4 —Li 2 S—SiS, LiI—Li 2 S—P 2 O 5 , LiI—Li 3 PO 4 —P 2 S 5 , Li 3 PS 4 , Li 2 S—P 2 S 5 —LiI, Li 2 S—Si 2 S 5 —LiI, Li 2 S—B 2 S 3 —LiI, Li 2 S—Si 2 S 5 —Li 3 N, Li 4 Ge 1−x P x S 4 wherein 0<x<1, Li 10±1 MP 2 X 12 wherein M is Ge, Si, Sn, Al, or a combination thereof, Li 3 PS 4 , Li 4 SnS 4 , Li 4−x Sn 4−a As a S 4 wherein 0≤x<4 and 0<a<4, Li 6 Z 5+ S 5−a X a 2− T − wherein Z 5+ is P, As, or Sb, X 2− is Se, Te, or a combination thereof, T − is Cl, Br, I, F, CN, OCN, SCN, N 3 , or a combination thereof, and 0≤a≤2, Li 7 Z 5+ S 6−a X a 2− , wherein Z 5+ is P, As, Sb, or a combination thereof, X 2− is Se or Te, and 0≤a≤2, or a combination thereof.

5. The sulfide solid electrolyte of claim 1 ,
wherein the sulfide electrolyte is Li 6 Z 5+ S 5−a X a 2− T − wherein Z 5+ is P, As, or Sb, X 2− is Se, Te, or a combination thereof, T − is Cl, Br, I, F, CN, OCN, SCN, N 3 , or a combination thereof, and 0≤a≤2, comprising an argyrodite crystal structure.

6. The sulfide solid electrolyte of claim 5 ,
wherein the sulfide electrolyte is Li 6 PS 5 Cl, Li 7 PS 6 , Li 6 PS 5 SeCl, or a combination thereof.

7. The sulfide solid electrolyte of claim 1 ,
wherein the metal-organic framework is a porous crystalline compound comprising a Group 2 to Group 15 metal ion or a Group 2 to Group 15 metal ion cluster, and an organic ligand chemically bound to the Group 2 to Group 15 metal ion or the Group 2 to Group 15 metal ion cluster,
wherein the Group 2 to Group 15 metal ion is cobalt, nickel, molybdenum, tungsten, ruthenium, osmium, cadmium, beryllium, calcium, barium, strontium, iron, manganese, chromium, vanadium, aluminum, titanium, zirconium, copper, zinc, magnesium, hafnium, niobium, tantalum, rhenium, rhodium, iridium, palladium, platinum, silver, scandium, yttrium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, or a combination thereof, and
wherein the organic ligand is derived from an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, an imidazole compound, a tetrazole, 1,2,3-triazole, 1,2,4-triazole, pyrazole, an aromatic sulfonic acid, an aromatic phosphoric acid, an aromatic sulfinic acid, an aromatic phosphinic acid, a bipyridine, an amino functional group, an imino functional group, an amide functional group, a methane dithio acid functional group of the formula —CS 2 H, a methane dithio acid anion functional group of the formula —CS 2 − , a pyridine functional group, or a pyrazine functional group, a combination thereof.

8. The sulfide solid electrolyte of claim 1 ,
wherein the metal-organic framework is a compound represented by Formula 1:
M m O k X l L p,   Formula 1

wherein, in Formula 1,
M is Ti 4+ , Zr 4+ , Mn 4+ , Si 4+ , Al 3+ , Cr 3+ , V 3+ , Ga 3+ , Mn 3+ , Zn +3 , Mn 2+ , Mg 2+ , Fe 2+ , Fe 3+ , Cu +2 , or a combination thereof,
m is an integer from 1 to 10,
k is 0 or an integer from 1 to 10,
l is 0 or an integer from 1 to 10,
p is an integer from 1 to 10,
X is H, OH − , Cl − , F − , F − , Br − , SO 4 2− , NO 3 − , ClO 4 − , PF 6 − , BF 3 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , or R 1 —(PO 3 ) n − , wherein R 1 is hydrogen, a C1-C30 alkyl group, or a combination thereof,
n is an integer from 1 to 4, and
L is a ligand of the formula R—(*COO— # ) q , wherein q is an integer from 1 to 6, * indicates a binding site of the carboxylate group to R, # indicates a binding site of the carboxylate group to metal ion M, and R is a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted monocyclic C6-C30 aryl group, a substituted or unsubstituted polycyclic C10-C30 aryl group, a substituted or unsubstituted monocyclic C3-C30 heteroaryl group, or a substituted or unsubstituted polycyclic C10-C30 heteroaryl group.

9. The sulfide solid electrolyte of claim 1 , wherein the metal-organic framework is a compound represented by Formula 2:
M′ m O k X′ l L′ p   Formula 2

wherein
M′ is Ti 4+ , Zr 4+ , V 3+ , Zn +3 , Fe 2+ , Fe 3+ , Cu +2 , or a combination thereof,
L′ is terephthalate), fumarate, muconate, 2,5-thiophenedicarboxylate, 2,5-pyrazine dicarboxylate, succinate, glutarate, adipate, naphthalene-2,6-dicarboxylate, biphenyl-4,4′-dicarboxylate, azobenzenedicarboxylate, benzene-1,2,4-tricarboxylate, benzene-1,3,5-tricarboxylate, benzene-1,3,5-tribenzoate, benzene-1,2,4,5-tetracarboxylate, naphthalene-2,3,6,7-tetracarboxylate, naphthalene-1,4,5,8-tetracarboxylate, and biphenyl-3,5,3′,5′-tetracarboxylate, or a combination thereof,
X′ is OH − , Cl − , F − , CH 3 COO − , PF 6 − , ClO 4 − , or a combination thereof, and
m is an integer from 1 to 8, k is an integer from 0 to 8,1 is an integer from 0 to 8, and p is an integer from 1 to 8.

10. The sulfide solid electrolyte of claim 1 ,
wherein the metal-organic framework is Ti 8 O 8 (OH) 4 [O 2 C—C 6 H 4 —CO 2 ] 6 , Cu(bpy)(H 2 O) 2 (BF 4 ) 2 (bpy) wherein bpy is 4,4′-bipyridine, Zn 4 O(O 2 C—C 6 H 4 —CO 2 ), Al(OH){O 2 C—C 6 H 4 —CO 2 }, Ti 8 O 8 (OH) 4 [O 2 C—C 6 H 3 (NH 2 )—CO 2 ] 6 , VO[C 6 H 4 (CO 2 ) 2 ], Cr(OH)[C 6 H 4 (CO 2 ) 2 ], Al(OH)[C 10 H 6 (CO 2 ) 2 ], Al 1 O(OH) 18 (H 2 O) 3 [C 6 H 3 —(CO 2 ) 3 ] 6 ·nH 2 O, Cr 3 OX 1 [C 6 H 4 (CO 2 ) 2 ] 3 wherein X is H, OH − , Cl − , F − , CH 3 COO − , PF 6 − , ClO 4 − , or a combination thereof, and 1 is an integer from 0 to 8, Cr 3 OX 1 [C 12 H 8 (CO 2 ) 2 ] 3 , where X is H, OH − , Cl − , F − , CH 3 COO − , PF 6 − , ClO 4 − , or a combination thereof; and 1 is an integer from 0 to 8, Al 8 (OH) 15 (H 2 O) 3 [C 6 H 3 (CO 2 ) 3 ] 3 , V 3 OX 1 [C 6 H 3 (CO 2 ) 3 ] 3 , wherein X is H, OH − , Cl − F − , CH 3 COO − , PF 6 − , ClO 4 − , or a combination thereof, and 1 is an integer from 0 to 8, ZrO[C 6 H 4 (CO 2 ) 2 ], or a combination thereof.

11. The sulfide solid electrolyte of claim 1 ,
wherein the metal-organic framework has a pore size of less than or equal to 5 nanometers.

12. The sulfide solid electrolyte of claim 1 ,
wherein an amount of hydrogen sulfide generated from the sulfide solid electrolyte is less than or equal to 10 cubic centimeters per gram when the sulfide solid electrolyte is exposed to air.

13. The sulfide solid electrolyte of claim 1 ,
wherein, when the sulfide solid electrolyte is exposed to air at a dew point of −32° C. to −28° C. and a temperature of 20° C. to 25° C., an amount of hydrogen sulfide generated from the sulfide solid electrolyte is reduced by about 40% to about 60% and a maximum hydrogen sulfide discharge time

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Choi Hongsoo
• Lee Dongjin
• Jeong Joonseon

Classifications

• H01M10/052 Primary

  Li-accumulators · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title

• H01M10/0562 Primary

  Solid materials · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title