Development of a supercapacitive battery via in-situ lithiation

Patent metadata

Field	Value
Publication number	US-11908997-B2
Application number	US-202117409036-A
Country	US
Kind code	B2
Filing date	Aug 23, 2021
Priority date	Oct 22, 2020
Publication date	Feb 20, 2024
Grant date	Feb 20, 2024

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.

First claim

What is claimed is:

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 .

2. 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.

3. 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.

4. 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.

5. 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.

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

7. 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.

8. 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.

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.

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

11. 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.

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

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

14. 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.

15. 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.

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

17. 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.

18. 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.

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.

20. 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.

Assignees

• Kyu Thein
• Li Ran
• Univ Akron

Inventors

• Kyu Thein
• Li Ran

Classifications

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title