# US 12,224,397 B2 · Capsule for lithium-sulfur secondary battery and lithium-sulfur secondary battery comprising same

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- Number: US 12,224,397 B2
- Document ID: US12224397B2
- Status: Granted
- Kind: B2
- Application number: 17/636,296
- Filed: 2021-06-08
- Published: 2022-09-15
- Granted: 2025-02-11
- Earliest claimed: 2020-06-17
- Assignees: LG Energy Solution, Ltd.
- Applicants: LG Energy Solution, Ltd.
- Inventors: Kihyun Kim; Sangryeo Lee; Lucia Kim
- Web page: https://patentgrep.com/patent/US12224397B2

## CPC

- H01M 10/052: Li-accumulators
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 4/38: of elements or alloys
- H01M 4/405: {Alloys based on lithium}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0567: characterised by the additives
- H01M 2300/0065: Solid electrolytes
- 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 capsule for a lithium-sulfur secondary battery, wherein the capsule includes a core containing a material required for formation and restoration of a solid electrolyte interface layer (SEI layer) and a shell including a polymer surrounding the core. The shell maintains the material required for formation and restoration of the solid electrolyte interface layer (SEI layer) at a constant level during operation of the battery, thereby exhibiting the effect of maintaining the solid electrolyte interface layer (SEI layer) on the negative electrode for a long time.

## Claims

### Claim 1

A capsule for a lithium-sulfur secondary battery comprising:
a core comprising a material required for formation and restoration of a solid electrolyte interface layer (SEI layer); and
a shell comprising a polymer surrounding the core,
wherein the polymer is formed by crosslinking an epoxy compound having two or more epoxy groups and a crosslinking agent having two or more amino groups.

### Claim 2 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein the material required for formation and restoration of the solid electrolyte interface layer (SEI layer) is at least one selected from LiNO3, Be(NO3)2, NaNO3, Mg(NO3)2, Al(NO3)3, KNO3, Ca(NO3)2, Sc(NO3)3, Ti(NO3)4, VO(NO3)3, Cr(NO3)3, Mn(NO3)2, Fe(NO3)3, Fe(NO3)2, Co(NO3)2, Co(NO3)3, Ni(NO3)2, Cu(NO3)2, Zn(NO3)2, Ga(NO3)3, RbNO3, Sr(NO3)2, Y(NO3)3, Zr(NO3)4, Pd(NO3)2, AgNO3, Cd(NO3)2, Sb(NO3)3, Xe(NO3)2, CsNO3, Ba(NO3)2, Hg2(NO3)2, Hg(NO3)2, Tl(NO3)3, TlNO3, Pb(NO3)2, Bi(NO3)3, BiO(NO3), FrNO3, Ra(NO3)2, La(NO3)3, Ce(NO3)3, Ce(NO3)4, Nd(NO3)3, Eu(NO3)3, Gd(NO3)3, and Tb(NO3)3.

### Claim 3 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein the epoxy compound having two or more epoxy groups is at least one selected from the group consisting of 1,4-butanediol diglycidyl ether (BDDE), ethylene glycol diglycidyl ether (EGDGE), 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, poly(propylene glycol)diglycidyl ether, poly(tetramethylene glycol)diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, 1,2-bis(2,3-epoxypropoxy)ethane, pentaerythritol polyglycidyl ether, or sorbitol polyglycidyl ether.

### Claim 4 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein the crosslinking agent having two or more amino groups is at least one selected from the group consisting of ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentaamine, 1,3-diamino propane, 1,4-diamino butane, 1,6-diamino hexane, 1,8-diamino octane, 1,10-diamino decane, 1,12-diamino dodecane, isophoronediamine, 1,6-cyclohexane diamine, piperazine, 2,5-diamino pyridine, 4,4′-diamino dicyclohexyl methane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 1,3-bis(aminoethyl)cyclohexane, xylylene diamine, methaphenylene diamine, and diamino diphenyl methane.

### Claim 5 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein a particle diameter of the capsule for the lithium-sulfur secondary battery is 0.3 μm to 2.0 μm.

### Claim 6 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein a weight ratio of the core to the shell is 10:90 to 70:30.

### Claim 7

The lithium-sulfur secondary battery comprising:
a capsule for the lithium-sulfur secondary battery comprising:
a core comprising a material required for formation and restoration of a solid electrolyte interface layer (SEI layer); and
a shell comprising a polymer surrounding the core;
a positive electrode;
a negative electrode;
a separator; and
an electrolyte solution.

### Claim 8

A method for preparing a capsule for a lithium-sulfur secondary battery, comprising the steps of:
dissolving a material required for formation and restoration of a solid electrolyte interface layer (SEI layer) and a crosslinking agent having two or more amino groups in water to prepare an aqueous phase portion,
mixing the aqueous phase portion into an oil phase portion comprising an oil phase component and a surfactant to prepare a water-in-oil emulsion solution,
adding an epoxy compound having two or more epoxy groups to the water-in-oil emulsion solution to form an amine-epoxy crosslink, and
removing the oil phase component from the water-in-oil emulsion solution and drying the emulsion solution to obtain capsules.

### Claim 9 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the material required for formation and restoration of the solid electrolyte interface layer (SEI layer) is at least one selected from LiNO3, Be(NO3)2, NaNO3, Mg(NO3)2, Al(NO3)3, KNO3, Ca(NO3)2, Sc(NO3)3, Ti(NO3)4, VO(NO3)3, Cr(NO3)3, Mn(NO3)2, Fe(NO3)3, Fe(NO3)2, Co(NO3)2, Co(NO3)3, Ni(NO3)2, Cu(NO3)2, Zn(NO3)2, Ga(NO3)3, RbNO3, Sr(NO3)2, Y(NO3)3, Zr(NO3)4, Pd(NO3)2, AgNO3, Cd(NO3)2, Sb(NO3)3, Xe(NO3)2, CsNO3, Ba(NO3)2, Hg2(NO3)2, Hg(NO3)2, Tl(NO3)3, TlNO3, Pb(NO3)2, Bi(NO3)3, BiO(NO3), FrNO3, Ra(NO3)2, La(NO3)3, Ce(NO3)3, Ce(NO3)4, Nd(NO3)3, Eu(NO3)3, Gd(NO3)3, and Tb(NO3)3.

### Claim 10 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the crosslinking agent having two or more amino groups is at least one selected from the group consisting of ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentaamine, 1,3-diamino propane, 1,4-diamino butane, 1,6-diamino hexane, 1,8-diamino octane, 1,10-diamino decane, 1,12-diamino dodecane, isophoronediamine, 1,6-cyclohexane diamine, piperazine, 2,5-diamino pyridine, 4,4′-diamino dicyclohexyl methane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 1,3-bis(aminoethyl)cyclohexane, xylylene diamine, methaphenylene diamine, and diamino diphenyl methane.

### Claim 11 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the oil phase component is at least one selected from decane, hexane, pentane, cyclopentane, benzene, toluene, o-xylene, m-xylene, p-xylene, diethyl ether, ethyl methyl ketone, dichloromethane, tetrahydrofuran, mineral oil, paraffin oil, and plant-derived oil.

### Claim 12 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the surfactant has a hydrophilic/lipophilic balance (HLB) value of 1 to 6.

### Claim 13 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the surfactant is at least one selected from the group consisting of sorbitan isostearate, sorbitan sesquioleate, sorbitan ester, sorbitane monostearate, sorbitan monopalmitate, polyethylene glycol hexadecyl ether, polyethylene glycol octadecyl ether, polyethylene glycol oleyl ether, octylphenol ethoxylate and octylphenol ethoxylate.

### Claim 14 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the epoxy compound having two or more epoxy groups is at least one selected from the group consisting of 1,4-butanediol diglycidyl ether (BDDE), ethylene glycol diglycidyl ether (EGDGE), 1,6-hexanediol diglycidyl ether, propylene glycol diglycidyl ether, poly(propylene glycol)diglycidyl ether, poly(tetramethylene glycol)diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, 1,2-bis(2,3-epoxypropoxy)ethane, pentaerythritol polyglycidyl ether, or sorbitol polyglycidyl ether.

### Claim 15 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein a particle diameter of the capsule is 0.3 μm to 2.0 μm.

### Claim 16 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein a weight ratio of the core to the shell is 10:90 to 70:30.

### Claim 17 (depends on 1)

The capsule for the lithium-sulfur secondary battery according to claim 1, wherein the material required for formation and restoration of the solid electrolyte interface layer (SEI layer) is a metal nitrate.

### Claim 18 (depends on 8)

The method for preparing the capsule for the lithium-sulfur secondary battery according to claim 8, wherein the material required for formation and restoration of the solid electrolyte interface layer (SEI layer) is a metal nitrate.