# US 9,882,243 B2 · Lithium-sulfur battery and methods of reducing insoluble solid lithium-polysulfide depositions

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

- Number: US 9,882,243 B2
- Document ID: US9882243B2
- Status: Granted
- Kind: B2
- Application number: 14/037,993
- Filed: 2013-09-26
- Published: 2015-03-26
- Granted: 2018-01-30
- Earliest claimed: 2013-09-26
- Assignees: Eaglepicher Technologies, LLC
- Applicants: Eaglepicher Technologies, LLC
- Inventors: Ramanathan Thillaiyan; Wujun Fu; Mario Destephen; Greg Miller
- Web page: https://patentgrep.com/patent/US9882243B2

## CPC

- H01M 10/0567: characterised by the additives
- H01M 10/052: Li-accumulators
- H01M 10/44: Methods for charging or discharging (circuits for charging H02J7/00)
- H02J 7/933: {the cycle being controlled or terminated in response to electric parameters}
- H01M 4/38: of elements or alloys
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/5815: {Sulfides}
- H01M 10/058: Construction or manufacture
- H02J 7/963: {in response to battery voltage gradient}
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- Y10T 29/49108: Electric battery cell making
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H02J: ELECTRIC POWER NETWORKS; CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

An improved electrolyte including a strontium additive suitable for lithium-sulfur batteries, a battery including the electrolyte, and a battery including a separator containing a strontium additive are disclosed. The presence of the strontium additive reduces sulfur-containing deposits on the battery anode, thereby providing a battery with relatively high energy density and good partial discharge performance.

## Claims

### Claim 1

A lithium-sulfur battery, comprising:
an anode comprising lithium;
an electrolyte;
a cathode comprising a cathode material including sulfur;
a separator disposed between the anode and the cathode, wherein each of the separator and the electrolyte comprises a strontium additive; and
a sheet of surface-functionalized carbonaceous material disposed between the separator and the anode or the cathode, the surface-functionalized carbonaceous material being functionalized with amine or amide groups, wherein the sheet of surface-functionalized carbonaceous material comprises 1 to 30% of amine or amide groups by weight of the sheet of surface-functionalized carbonaceous material.

### Claim 2 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the strontium additive is one or more member selected from the group consisting of SrI2, SrI2.6H2O, SrBr2, SrBr2.6H2O, SrCl2, SrCl2.6H2O, SrF2, SrOH2, SrOH2.6H2O, SrCO3, SrHPO4, Sr(NO3)2, SrC2O4, and SrSO4.

### Claim 3 (depends on 2)

The lithium-sulfur battery of claim 2, wherein the strontium additive is SrI2.

### Claim 4 (depends on 2)

The lithium-sulfur battery of claim 2, wherein the strontium additive is soluble in the electrolyte.

### Claim 5 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the cathode material comprises about 20% to about 95% sulfur by weight based on a weight of the cathode.

### Claim 6 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the electrolyte comprises about 0.001% to about 25% strontium additive by weight based on a weight of the electrolyte.

### Claim 7 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the cathode further comprises an electron conducting material.

### Claim 8 (depends on 7)

The lithium-sulfur battery of claim 7, wherein the electron conducting material is one or more member selected from the group consisting of carbon black, graphite, carbon fiber, graphene, functionalized graphene, carbon nanotube and an electron conducting compound having at least one of a conjugated carbon-carbon double bond, a carbon-nitrogen double bond and carbon-oxygen bond.

### Claim 9

A non-aqueous lithium-sulfur electrochemical cell comprising:
an anode including an anode material comprising lithium;
a cathode including a cathode material comprising sulfur;
a separator disposed between the anode and the cathode;
a non-aqueous electrolyte which is in fluid communication with the anode, the cathode and the separator, wherein each of the separator and the non-aqueous electrolyte includes a strontium additive; and
a sheet of surface-functionalized carbonaceous material disposed between the separator and the anode or the cathode, the surface-functionalized carbonaceous material being functionalized with amine or amide groups, wherein the sheet of surface-functionalized carbonaceous material comprises 1 to 30% of amine or amide groups by weight of the sheet of surface-functionalized carbonaceous material.

### Claim 10 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the strontium additive is one or more member selected from the group consisting of SrI2, SrI2.6H2O, SrBr2, SrBr2.6H2O, SrCl2, SrCl2.6H2O, SrF2, SrOH2, SrOH2.6H2O, SrCO3, SrHPO4, Sr(NO3)2, SrC2O4, and SrSO4.

### Claim 11 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the strontium additive is SrI2.

### Claim 12 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the strontium additive is soluble in the non-aqueous electrolyte.

### Claim 13 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the cathode material comprises about 20% to about 95% sulfur by weight based on a weight of the cathode.

### Claim 14 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the non-aqueous electrolyte comprises about 0.001% to about 25% strontium additive by weight based on a weight of the non-aqueous electrolyte.

### Claim 15 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the separator comprises about 0.001% to about 90% strontium additive by weight based on a weight of the separator.

### Claim 16 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the cathode material is loaded onto a surface of a substrate in an average loading amount in a range of from about 1 to about 40 mg/cm′.

### Claim 17 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the cathode material comprising sulfur is present in the non-aqueous electrochemical cell in a range of from about 0.001 wt % to about 10 wt % with respect to a weight of the strontium additive.

### Claim 18 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the non-aqueous electrolyte comprises one or more organic solvents selected from a group consisting of dimethyl carbonate (DMC), diethyl carbonate, dioxolane (DOL), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), methyl acetate (MA), glycol ethers, diglyme, triglyme, tetraglyme, propylene carbonate (PC), ethylene carbonate (EC), acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-butyrolactone (GBL), and N-methyl-pyrrolidinone (NMP).

### Claim 19 (depends on 18)

The non-aqueous lithium-sulfur electrochemical cell of claim 18, wherein the non-aqueous electrolyte comprises a salt having a formula LiMF6 or LiMF4, wherein M is an element selected from the group consisting of phosphorous, arsenic, antimony and boron.

### Claim 20 (depends on 19)

The non-aqueous electrochemical cell of claim 19, wherein the salt is one or more member selected from the group consisting of LiPF6, LiAsF6, LiTFSI, LiFSI, LiSbF6, LiBF4, LiClO4, LiAlCl4, LiGaCl4, LiC(SO2CF3)3, LiB(C6H4O2)2, LiN(CF3SO2)2 and Li(CF3SO3).

### Claim 21 (depends on 19)

The non-aqueous lithium-sulfur electrochemical cell of claim 19, wherein a concentration of the salt in the organic solvent is in a range of from about 0.001 M to about 2 M.

### Claim 22 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the anode further comprises a metal selected from the group consisting of magnesium, sodium, and potassium.

### Claim 23 (depends on 21)

The non-aqueous lithium-sulfur electrochemical cell of claim 21, wherein the anode further comprises one or more members selected from the group consisting of LiMg, LiAl, LiAlMg, LiSi, LiB and LiSiB.

### Claim 24 (depends on 9)

A method of charging the lithium-sulfur electrochemical cell of claim 9, comprising:
supplying electrical energy to the lithium-sulfur electrochemical cell at a constant current;
monitoring the voltage during charging; and
terminating the charge when the monitored voltage is in a range of about 2.1 volts to about 3.0 volts.

### Claim 25 (depends on 24)

The method of claim 24, wherein the electrolyte further comprises one or more lithium salts.

### Claim 26 (depends on 24)

The method of claim 24, wherein the termination voltage is in a range of about 2.4 volts to about 2.6 volts.

### Claim 27 (depends on 24)

The method of claim 24, wherein the strontium additive is one or more member selected from the group consisting of SrI2, SrI2.6H2O, SrBr2, SrBr2.6H2O, SrCl2, SrCl2.6H2O, SrF2, SrOH2, SrOH2.6H2O, SrCO3, SrHPO4, Sr(NO3)2, SrC2O4, SrI2, and SrSO4.

### Claim 28 (depends on 24)

The method of claim 24, wherein the strontium additive is SrI2.

### Claim 29 (depends on 24)

The method of claim 24, wherein the strontium additive is insoluble in the non-aqueous electrolyte.

### Claim 30 (depends on 24)

The method of claim 24, wherein the cathode material comprises about 20% to about 95% sulfur by weight based on a weight of the cathode material.

### Claim 31 (depends on 24)

The method of claim 24, wherein the non-aqueous electrolyte comprises about 0.001% to about 25% strontium additive by weight based on a weight of the electrolyte.

### Claim 32 (depends on 24)

The method of claim 24, wherein the separator comprises about 0.001% to about 90% strontium additive by weight based on a weight of the separator.

### Claim 33 (depends on 24)

The method of claim 24, wherein the cathode material comprising sulfur is present in the non-aqueous electrochemical cell in a range of from about 0.001 wt % to about 10 wt % with respect to a weight of the strontium additive.

### Claim 34 (depends on 24)

The method of claim 24, wherein the non-aqueous electrolyte comprises one or more organic solvents selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate, dioxolane (DOL), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), methyl acetate (MA), glycol ethers, diglyme, triglyme, tetraglyme, propylene carbonate (PC), ethylene carbonate (EC), acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, gamma-butyrolactone (GBL), and N-methyl-pyrrolidinone (NMP).

### Claim 35 (depends on 9)

A method for manufacturing a non-aqueous lithium-sulfur electrochemical cell of claim 9, comprising:
preparing a separator including a strontium additive, or
preparing a non-aqueous electrolyte including a strontium additive; and
introducing the separator and the non-aqueous electrolyte into the lithium-sulfur electrochemical cell.

### Claim 36 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the electrolyte comprises an ionic liquid of 1-n-butyl-methyl pyrrolidiniurn bis(trifluoromethylsulfonyl)imide (PYR14TFSI).

### Claim 37 (depends on 36)

The lithium-sulfur battery of claim 36, wherein the electrolyte further comprises one or more organic solvents selected from the group consisting of hexamethylphosphoramide (HMPA) and dimethyl sulfoxide (DMSO).

### Claim 38 (depends on 9)

The non-aqueous lithium-sulfur electrochemical cell of claim 9, wherein the non-aqueous electrolyte comprises an ionic liquid of 1-n-butyl-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR14TFSI).

### Claim 39 (depends on 38)

The non-aqueous lithium-sulfur electrochemical cell of claim 38, wherein the non-aqueous electrolyte further comprises one or more organic solvents selected from the group consisting of hexamethylphosphoramide (HMPA) and dimethyl sulfoxide (DMSO).

### Claim 40 (depends on 1)

The lithium-sulfur battery of claim 1, wherein the cathode material further comprises a binder, a polymeric material and a surface-functionalized carbonaceous material.

### Claim 41 (depends on 40)

The lithium-sulfur battery of claim 40, wherein the binder includes a polymeric binder that is at least one of polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF).

### Claim 42 (depends on 40)

The lithium-sulfur battery of claim 40, wherein the polymeric material and the surface-functionalized carbonaceous material is present in an amount of about 0.001% to about 30% by weight of the sulfur in the cathode material.

### Claim 43 (depends on 9)

The lithium-sulfur battery of claim 9, wherein the cathode material further comprises a binder, a polymeric material and a surface-functionalized carbonaceous material.

### Claim 44 (depends on 43)

The lithium-sulfur battery of claim 43, wherein the binder includes a polymeric binder that is at least one of polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF).

### Claim 45 (depends on 43)

The lithium-sulfur battery of claim 43, wherein the polymeric material and the surface-functionalized carbonaceous material is present in an amount of about 0.001% to about 30% by weight of the sulfur in the cathode material.