IP Library Granted Patent US 11,387,488
Granted Patent B2
US 11,387,488 · App. 16/054,282 · Granted Jul 12, 2022

Gel polymer electrolyte compositions and electrochemical cells including the same

Inventors: Konstantinos Gerasopoulos (Odenton, MD); Adam W. Freeman (Laurel, MD); Christopher M. Hoffman, Jr. (Odenton, MD)
Assignee: The Johns Hopkins University
H01M10/0565H01M10/058H01M10/0525H01M2300/0002H01M2300/0082H01M2300/0085
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Quick Facts
Patent No.
US 11,387,488
App. No.
16/054,282
Granted
Jul 12, 2022
Kind
B2
Abstract

Gel polymer electrolyte compositions including a cross-linked three-dimensional polymer network and an electrolyte composition comprising an electrolyte and water are provided. The gel polymer electrolyte compositions can be included in an aqueous electrochemical cell, in which a gel polymer electrolyte can be positioned between an anode and a cathode. Methods of forming a gel polymer electrolyte in the form of a film are also provided. Methods of forming an aqueous electrochemical cell including a gel polymer electrolyte are also provided.

Claims (25)

1. A gel polymer electrolyte (GPE) composition, comprising:

(i) a cross-linked three-dimensional polymer network comprising the reaction product of at least (i) a first monomer including at least three thiol functional groups; (ii) a second monomer including at least two vinyl functional groups, at least one alkyne functional group, or a combination thereof, and (iii) a third monomer including at least two thiol functional groups, wherein the first monomer and the third monomer are different; and

(ii) an aqueous-based electrolyte composition comprising an electrolyte and water, wherein the GPE composition comprises less than 10% by weight of an organic solvent.

2. The GPE composition of claim 1 , wherein each of the first monomer, the second monomer, and the third monomer are substantially water soluble.

3. The GPE composition of claim 1 , wherein the GPE composition is provided in the form of a water-swellable hydrogel having a thickness from about 10 to 500 microns.

4. The GPE composition of claim 1 , wherein the cross-linked three-dimensional polymer network comprises from about 10% to about 75% by weight of the GPE composition.

5. The GPE composition of claim 1 , wherein the electrolyte comprises a salt selected from a lithium salt or a zinc salt, or combination thereof.

6. The GPE composition of claim 5 , wherein the salt comprises lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium chloride (LiCl), lithium hexafluorophosphate (LiPF 6 ), a lithium polysulfide, lithium perchlorate (LiClO 4 ), lithium bromide (LiBr), lithium iodide (LiI), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium bis(oxalate)borate, zinc trifluoromethanesulfonate (Zn(OTf) 2 ), or zinc di[bis(trifluoromethanesulfonyl)imide)] Zn(TFSI) 2 and mixtures thereof.

7. The GPE composition of claim 1 , wherein the GPE composition is devoid of an organic solvent.

8. An electrochemical cell, comprising:

(i) an anode;

(ii) a cathode;

(iii) a gel polymer electrolyte (GPE) positioned between and in contact with the anode and the cathode; wherein the GPE includes a GPE-composition comprising (a) a cross-linked three-dimensional polymer network and (b) an aqueous-based electrolyte composition absorbed by the GPE, in which the electrolyte composition comprises an electrolyte and water, and wherein the GPE-composition comprises less than 10% by weight of an organic solvent.

wherein the cross-linked three-dimensional polymer network comprises the reaction product of at least (i) a first monomer including at least three thiol functional groups; (ii) a second monomer including at least two vinyl functional groups, at least one alkyne functional group, or a combination thereof, and (iii) a third monomer including at least two thiol functional groups, wherein the first monomer and the third monomer are different.

9. The electrochemical cell of claim 8 , wherein

(i) the anode comprises an anode-composition comprising (a) an active anode species and (b) the GPE-composition; wherein the active anode species and the GPE-composition are admixed together; or

(ii) the cathode comprises a cathode-composition comprising (a) an active cathode species and (b) the GPE-composition; wherein the active cathode species and the GPE-composition are admixed together; or

(iii) the combination of (i) and (ii).

10. The electrochemical cell of claim 8 , wherein the GPE-composition is devoid of an organic solvent.

11. A method of forming a gel polymer electrolyte (GPE), comprising radically-curing an aqueous composition of a mixture of monomers in an oxygen-containing environment; wherein the mixture of monomers comprise a first group of monomers comprising at least (a) a first monomer including at least three thiol functional groups, (b) a second monomer including at least two vinyl functional groups, at least one alkyne functional group, or a combination thereof, and (c) a third monomer including at least two thiol functional groups, wherein the first monomer and the third monomer are different.

12. The method of claim 11 , further comprising a step of mixing the first group of monomers with an electrolyte in water to provide the aqueous composition, and depositing a coating of aqueous composition onto a substrate prior to radically-curing the aqueous composition.

13. A method of forming an electrochemical cell, comprising:

depositing a gel polymer electrolyte (GPE) between and in contact with an anode and a cathode; wherein depositing the GPE comprises positioning a pre-fabricated GPE between the anode and the cathode or forming the GPE directly onto the anode or the cathode, and wherein the GPE includes a GPE-composition comprising (a) a cross-linked three-dimensional polymer network comprising the reaction product of at least (i) a first monomer including at least three thiol functional groups; (ii) a second monomer including at least two vinyl functional groups, at least one alkyne functional group, or a combination thereof, and (iii) a third monomer including at least two thiol functional groups, wherein the first monomer and the third monomer are different, and (b) an aqueous-based electrolyte composition absorbed by the GPE, in which the electrolyte composition comprises an electrolyte and water, and wherein the GPE-composition comprises less than 10% by weight of an organic solvent.

14. The method of claim 13 , wherein the depositing the GPE comprises forming a first GPE-layer directly onto the anode and forming a second GPE-layer directly onto the cathode, and further comprising a step of joining the first GPE-layer and the second GPE-layer together such that the first GPE-layer and the second GPE-layer are located between the anode and the cathode.

15. The method of claim 13 , wherein depositing the GPE comprises forming the GPE directly onto the anode or the cathode, and wherein forming the GPE directly onto the anode or the cathode comprises radically-curing an aqueous composition of a mixture of monomers in an oxygen-containing environment; wherein the mixture of monomers comprises a first group of monomers comprising at least the first monomer, the second monomer, and the third monomer.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 13, 2018
From: GERASOPOULOS, KONSTANTINOS; FREEMAN, ADAM W.; HOFFMAN, JR., CHRISTOPHER M.
To: THE JOHNS HOPKINS UNIVERSITY
Reel/Frame 046626/0892 →
Continuity (2)
Provisional Application 62622203 · Jan 26, 2018
Related Publication 20190237803A1 · Aug 1, 2019