# US 11,908,997 B2 · Development of a supercapacitive battery via in-situ lithiation

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- Number: US 11,908,997 B2
- Document ID: US11908997B2
- Status: Granted
- Kind: B2
- Application number: 17/409,036
- Filed: 2021-08-23
- Published: 2022-04-28
- Granted: 2024-02-20
- Earliest claimed: 2020-10-22
- Assignees: The University of Akron
- Applicants: Thein Kyu; Ran Li
- Inventors: Thein Kyu; Ran Li
- Web page: https://patentgrep.com/patent/US11908997B2

## CPC

- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 4/881: {Electrolytic membranes}
- H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane
- H01M 2300/0082: Organic polymers
- H01M 2300/0085: Immobilising or gelification of electrolyte
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- 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 solid-state polymer electrolyte membrane and a supercapacitive lithium-ion battery utilizing the solid-state polymer electrolyte membrane. The solid-state polymer electrolyte membrane comprising a mixture of a lithium salt, a plasticizer, and a co-network of a crosslinkable polyether addition and a crosslinkable amine addition. The co-network is crosslinked, and the solid-state polymer electrolyte membrane is conductive on the order of 10−3 S cm−1. The supercapacitive lithium-ion battery utilizing the solid-state polymer electrolyte membrane has an operating range of between about 0.01 and about 4.3 V without short-circuiting while also having a higher capacity relative to conventional liquid electrolyte lithium-ion batteries.

## Claims

### Claim 1

A solid-state polymer electrolyte membrane comprising:
a mixture of a lithium salt, a plasticizer, and a co-network of a crosslinkable polyether addition, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), poly(ethylene glycol)diacrylate (PEGDA), poly(ethylene glycol)dimethacrylate (PEGDMA), poly(propylene glycol) diacrylate (PPGDA), and poly(propylene glycol) dimethacrylate (PPGDMA), copolymers thereof, and mixtures thereof, and a crosslinkable amine addition, wherein the co-network is crosslinked, and the solid polymer electrolyte membrane is conductive on the order of 10−3 S cm−1.

### Claim 2 (depends on 1)

The solid-state polymer electrolyte membrane of claim 1, wherein the lithium salt is lithium bis-trifluoromethanesulfonylimide (LiTFSI), lithium bis-perfluoroethylsulfonylimide, lithium tetrafluoroborate, lithium perchlorate or mixtures thereof.

### Claim 3 (depends on 2)

The solid-state polymer electrolyte membrane of claim 2, wherein the plasticizer is succinonitrile (SCN), glutaronitrile (GCN), adiponitrile, camphor, dialkylsebacate, alkyl stearate, or mixtures thereof.

### Claim 4 (depends on 3)

The solid-state polymer electrolyte membrane of claim 3, wherein the crosslinkable amine addition is a polyether amine and wherein the polyether amine is either a polyether diamine or a polyether triamine.

### Claim 5 (depends on 4)

The solid-state polymer electrolyte membrane of claim 4, further comprising a crosslinking agent, wherein the crosslinking agent is trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, glycidyl methacrylate (GMA), or mixtures thereof.

### Claim 6 (depends on 1)

The solid-state polymer electrolyte membrane of claim 1, wherein the plasticizer is glutaronitrile (GCN), adiponitrile, camphor, dialkylsebacate, alkyl stearate, or mixtures thereof.

### Claim 7 (depends on 1)

The solid-state polymer electrolyte membrane of claim 1, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), poly(ethylene glycol)dimethacrylate (PEGDMA), poly(propylene glycol) diacrylate (PPGDA), and poly(propylene glycol) dimethacrylate (PPGDMA), copolymers thereof, and mixtures thereof.

### Claim 8 (depends on 1)

The solid-state polymer electrolyte membrane of claim 1, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), and the crosslinkable amine addition is a polyether amine and wherein the polyether amine is either a polyether diamine or a polyether triamine.

### Claim 9

A method of creating a lithium-ion battery comprising the steps of:
a. providing an anode;
b. providing a cathode;
c. preparing a solid-state electrolyte polymer membrane comprising the steps of:
i. mixing a lithium salt, a plasticizer, and a co-network of a crosslinkable polyether addition, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), poly(ethylene glycol)diacrylate (PEGDA), poly(ethylene glycol)dimethacrylate (PEGDMA), poly(propylene glycol) diacrylate (PPGDA), and poly(propylene glycol) dimethacrylate (PPGDMA), copolymers thereof, and mixtures thereof, and a crosslinkable amine addition; and
ii. crosslinking the mixture to form said solid-state electrolyte polymer membrane; and
d. combining the anode, the cathode, and the solid-state electrolyte polymer membrane to create a lithium-ion battery.

### Claim 10 (depends on 9)

The method of claim 9, wherein the anode is lithium metal, graphite, silicon, tin, germanium, or combinations thereof.

### Claim 11 (depends on 10)

The method of claim 10, wherein the cathode is Lithium Iron Phosphate (LFP), Lithium Nickel Cobalt Manganese Oxide (NMC), Lithium Nickel Manganese Spinel (LMN) Lithium Nickel Cobalt Aluminum Oxide (NCA), Lithium Cobalt Oxide (LCO), Lithium Manganese Oxide (LMO), or combinations thereof.

### Claim 12 (depends on 11)

The method of claim 11, wherein the lithium salt is lithium bis-trifluoromethanesulfonylimide (LiTFSI), lithium bis-perfluoroethylsulfonylimide, lithium tetrafluoroborate, lithium perchlorate or mixtures thereof.

### Claim 13 (depends on 12)

The method of claim 12, wherein the plasticizer is succinonitrile (SCN), glutaronitrile (GCN), adiponitrile, camphor, dialkylsebacate, alkyl stearate, or mixtures thereof.

### Claim 14 (depends on 13)

The method of claim 13, wherein the crosslinkable amine addition is a polyether amine and wherein the polyether amine is either a polyether diamine or a polyether triamine.

### Claim 15 (depends on 13)

The method of claim 13, wherein the step of mixing further includes mixing in a crosslinking agent, wherein the crosslinking agent is trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, glycidyl methacrylate (GMA), or mixtures thereof.

### Claim 16 (depends on 9)

The method of claim 9, wherein the plasticizer is glutaronitrile (GCN), adiponitrile, camphor, dialkylsebacate, alkyl stearate, or mixtures thereof.

### Claim 17 (depends on 9)

The method of claim 9, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), poly(ethylene glycol)dimethacrylate (PEGDMA), poly(propylene glycol) diacrylate (PPGDA), and poly(propylene glycol) dimethacrylate (PPGDMA), copolymers thereof, and mixtures thereof.

### Claim 18 (depends on 9)

The method of claim 9, wherein the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), and the crosslinkable amine addition is a polyether amine and wherein the polyether amine is either a polyether diamine or a polyether triamine.

### Claim 19

A method of creating a supercapacitive lithium-ion battery comprising the steps of:
a. providing an anode;
b. providing a cathode;
c. preparing a solid-state electrolyte polymer membrane comprising the steps of:
i. mixing a lithium salt, a plasticizer, and a co-network of a crosslinkable polyether addition and a crosslinkable amine addition; and
ii. crosslinking the mixture to form said solid-state electrolyte polymer membrane;
d. combining the anode, the cathode, and the solid-state electrolyte polymer membrane to create a lithium-ion battery; and
e. lithiating the lithium-ion battery by deep discharging the lithium-ion battery, wherein deep discharging includes lowering the voltage to −0.5 V and then increasing the voltage to 0.5 V during a first cycle of the lithium-ion battery so as to form a supercapacitive lithium-ion battery, wherein the supercapacitive lithium-ion battery has an operating range of between about 0.01 and about 4.3 V without short-circuiting.

### Claim 20 (depends on 19)

The method of claim 19, wherein the provided anode is a lithium metal, the provided cathode is Lithium Iron Phosphate (LFP), the lithium salt is lithium bis-trifluoromethanesulfonylimide (LiTFSI), the plasticizer is succinonitrile (SCN), the crosslinkable polyether addition is poly(ethylene glycol) diglycidyl ether (PEGDGE), and the crosslinkable amine addition is a polyether amine and wherein the polyether amine is either a polyether diamine or a polyether triamine.