# US 11,114,691 B2 · Sulfide-based solid electrolyte for lithium battery, method of preparing the same, and lithium battery including the sulfide-based solid electrolyte

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,114,691 B2
- Document ID: US11114691B2
- Status: Granted
- Kind: B2
- Application number: 16/449,910
- Filed: 2019-06-24
- Published: 2020-02-13
- Granted: 2021-09-07
- Earliest claimed: 2018-08-10
- Assignees: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd.
- Inventors: Hongsoo Choi; Dongjin Lee; Joonseon Jeong
- Web page: https://patentgrep.com/patent/US11114691B2

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/5815: {Sulfides}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0562: Solid materials
- H01M 2300/0068: inorganic
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

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

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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<σ2/μ<1, Formula 1
wherein σ2 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.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein the sulfide electrolyte comprises Li2S—P2S5, LiI—Li2S—B2S3, Li3PO4—Li2S—Si2S, Li3PO4—Li2S—SiS2, LiPO4—Li2S—SiS, LiI—Li2S—P2O5, LiI—Li3PO4—P2S5, Li3PS4, Li2S—P2S5—LiI, Li2S—Si2S5—LiI, Li2S—B2S3—LiI, Li2S—Si2S5—Li3N, Li4Ge1−xPxS4 wherein 0<x<1, Li10±1MP2X12 wherein M is Ge, Si, Sn, Al, or a combination thereof, Li3PS4, Li4SnS4, Li4−xSn4−aAsaS4 wherein 0≤x<4 and 0<a<4, Li6Z5+S5−aXa2−T− wherein Z5+is P, As, or Sb, X2−is Se, Te, or a combination thereof, T−is Cl, Br, I, F, CN, OCN, SCN, N3, or a combination thereof, and 0≤a≤2, Li7Z5+S6−aXa2−, wherein Z5+is P, As, Sb, or a combination thereof, X2−is Se or Te, and 0≤a≤2, or a combination thereof.

### Claim 5 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein the sulfide electrolyte is Li6Z5+S5−aXa2−T− wherein Z5+is P, As, or Sb, X2−is Se, Te, or a combination thereof, T−is Cl, Br, I, F, CN, OCN, SCN, N3, or a combination thereof, and 0≤a≤2, comprising an argyrodite crystal structure.

### Claim 6 (depends on 5)

The sulfide solid electrolyte of claim 5,
wherein the sulfide electrolyte is Li6PS5Cl, Li7PS6, Li6PS5SeCl, or a combination thereof.

### Claim 7 (depends on 1)

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 —CS2H, a methane dithio acid anion functional group of the formula —CS2−, a pyridine functional group, or a pyrazine functional group, a combination thereof.

### Claim 8 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein the metal-organic framework is a compound represented by Formula 1:
MmOkXlLp, Formula 1
wherein, in Formula 1,
M is Ti4+, Zr4+, Mn4+, Si4+, Al3+, Cr3+, V3+, Ga3+, Mn3+, Zn+3, Mn2+, Mg2+, Fe2+, Fe3+, 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−, SO42−, NO3−, ClO4−, PF6−, BF3−, R1—(COO)n−, R1—(SO3)n−, or R1—(PO3)n−, wherein R1 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.

### Claim 9 (depends on 1)

The sulfide solid electrolyte of claim 1, wherein the metal-organic framework is a compound represented by Formula 2:
M′mOkX′lL′p Formula 2
wherein
M′ is Ti4+, Zr4+, V3+, Zn+3, Fe2+, Fe3+, 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−, CH3COO−, PF6−, ClO4−, 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.

### Claim 10 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein the metal-organic framework is Ti8O8(OH)4[O2C—C6H4—CO2]6, Cu(bpy)(H2O)2(BF4)2(bpy) wherein bpy is 4,4′-bipyridine, Zn4O(O2C—C6H4—CO2), Al(OH){O2C—C6H4—CO2}, Ti8O8(OH)4[O2C—C6H3(NH2)—CO2]6, VO[C6H4(CO2)2], Cr(OH)[C6H4(CO2)2], Al(OH)[C10H6(CO2)2], Al1O(OH)18(H2O)3[C6H3—(CO2)3]6·nH2O, Cr3OX1[C6H4(CO2)2]3 wherein X is H, OH−, Cl−, F−, CH3COO−, PF6−, ClO4−, or a combination thereof, and 1 is an integer from 0 to 8, Cr3OX1[C12H8(CO2)2]3, where X is H, OH−, Cl−, F−, CH3COO−, PF6−, ClO4−, or a combination thereof; and 1 is an integer from 0 to 8, Al8(OH)15(H2O)3[C6H3(CO2)3]3, V3OX1[C6H3(CO2)3]3, wherein X is H, OH−, Cl−F−, CH3COO−, PF6−, ClO4−, or a combination thereof, and 1 is an integer from 0 to 8, ZrO[C6H4(CO2)2], or a combination thereof.

### Claim 11 (depends on 1)

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

### Claim 12 (depends on 1)

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.

### Claim 13 (depends on 1)

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 is reduced by about 20% to about 30%, as compared with a sulfide solid electrolyte not including the metal-organic framework.

### Claim 14 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein the sulfide solid electrolyte has a thickness of about 1 nanometer to about 1,000 micrometers.

### Claim 15 (depends on 1)

The sulfide solid electrolyte of claim 1,
wherein, the sulfide solid electrolyte has a major peak at less than or equal to 5 degrees two-theta, when analyzed by X-ray diffraction analysis using Cu Kα radiation.

### Claim 16

A lithium battery comprising:
a cathode, wherein the cathode does not comprise sulfur;
an anode; and
a sulfide solid electrolyte comprising
a sulfide electrolyte, and
a metal-organic framework between the cathode and the anode, the metal-organic framework comprising hydrogen sulfide adsorbed in a pore of the metal-organic framework.

### Claim 17 (depends on 16)

The lithium battery of claim 16,
wherein the anode is a lithium metal electrode or a lithium metal alloy electrode, and
wherein the anode comprises an anode active material, wherein the anode active material comprises a carbonaceous material, silicon, a silicon oxide, a silicon alloy, a silicon-carbon composite, tin, a tin alloy, a tin-carbon composite, a metal or metalloid alloyable with lithium, an alloy thereof, an oxide thereof, or a combination thereof.

### Claim 18 (depends on 16)

The lithium battery of claim 16, wherein the lithium battery is an all-solid battery.

### Claim 19 (depends on 16)

The lithium battery of claim 16,
wherein the sulfide solid electrolyte of the lithium battery has an ion conductivity of greater than or equal to 1 millisiemens per centimeter after exposure to dry air, and
wherein an ion conductivity of the sulfide solid electrolyte is reduced about 5% to about 15% less than an ion conductivity of a sulfide solid electrolyte not including the metal-organic framework when exposed to air at a dew point of −32° C. to −28° C. and a temperature of 20° C. to 25° C.

### Claim 20 (depends on 1)

A method of preparing the sulfide solid electrolyte of claim 1, comprising:
mixing the metal-organic framework with the sulfide electrolyte to obtain a mixture; and
pressure-molding the mixture to prepare the sulfide solid electrolyte.