IP Library Granted Patent US 12,057,556
Granted Patent B2
US 12,057,556 · App. 17/346,673 · Granted Aug 6, 2024

Aqueous and hybrid electrolytes with wide electrochemical stability windows

Inventors: Kang Xu (Potomac, MD); Arthur Von Wald Cresce (Beltsville, MD); Oleg A. Borodin (Laurel, MD); Chunsheng Wang (Silver Spring, MD); Liumin Suo (Greenbelt, MD)
Assignees: University of Maryland, College Park; The United States of America as Represented by the Secretary of the Army
H01M10/36H01M4/505H01M4/525H01M4/5815H01M4/5825H01M10/056H01M10/0568H01M10/0569H01M10/26H01M2300/0002H01M2300/0014H01M2300/0025H01M2300/0091
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Quick Facts
Patent No.
US 12,057,556
App. No.
17/346,673
Granted
Aug 6, 2024
Kind
B2
Abstract

The present invention is directed to aqueous and hybrid aqueous electrolytes that comprise a lithium salt. The present invention is also directed to methods of making the electrolytes and methods of using the electrolytes in batteries and other electrochemical technologies.

Claims (25)

1. An electrolyte, comprising:

(a) at least one metal salt; and

(b) a solvent comprising between about 1% and about 100% water by weight and at least one non-aqueous solvent; wherein the molal concentration of the metal salt in the electrolyte is between 15 m and about 22 m, wherein the at least one non-aqueous solvent is selected from the group consisting of an alcohol, a ketone, a carboxylic acid, an ester of a carboxylic acid, a carbonic acid, an ester of a carbonic acid, an amine, an amide, a nitrile, an inorganic acid, an ester of an inorganic acid, an ether, a sulfone, a sulfoxide, a sulfate, a phosphate ester, a hydrocarbon, and combinations thereof, and wherein the electrochemical stability window of the electrolyte is between about 2.0 V and about 5.0 V.

2. The electrolyte of claim 1 , wherein the at least one metal salt comprises an anion selected from the group consisting of bis(trifluoromethane sulfonyl)imide (TFSI), trifluoromethane sulfonate (TF), bis(fluorosulfonyl)imide (FSI), tetrafluorophosphate (BF 4 ), hexafluorophosphate (PF 6 ), bis(pentafluoroethane sulfonyl) imide (BETI), 4,5-dicyano-2-trifluoromethanoimidazole (DCMI), [fluoro(nonafluorobutane) sulfonyl]imide (FNF), perchlorate (ClO 4 ), sulfate (SO 4 ), and nitrate (NO 3 ).

3. The electrolyte of claim 1 , wherein the at least one metal salt is selected from the group consisting of LiTFSI, LiTF, LiFSI, LiBETI, LiDCMI, LiFNF, LiClO 4 , LiSO 4 , LiNO 3 , NaTFSI, NaTF, NaFSI, NaBETI, NaDCMI, NaFNF, NaClO 4 , NaSO 4 , NaNO 3 , KTFSI, KTF, KFSI, KBETI, KDCMI, KFNF, KClO 4 , KSO 4 , KNO 3 , Mg(TFSI) 2 , Mg(TF) 2 , Mg(FSI) 2 , Mg(BETI) 2 , Mg(DCMI) 2 , Mg(FNF) 2 , Mg(ClO 4 ) 2 , Mg(SO 4 ) 2 , Mg(NO 3 ) 2 , Al(TFSI) 3 , Al(TF) 3 , Al(FSI) 3 , Al(BETI) 3 , Al(DCMI) 3 , Al(FNF) 3 , Al(ClO 4 ) 3 , Al(SO 4 ) 3 , and Al(NO 3 ) 3 .

4. The electrolyte of claim 1 , wherein the at least one metal salt is selected from the group consisting of LiTFSI, LiTF, NaTFSI, NaFSI, KTFSI, KBETI, and Mg(TFSI) 2 .

5. The electrolyte of claim 1 , wherein the weight ratio of the at least one non-aqueous solvent in the solvent is between about 10% and about 90%.

6. The electrolyte of claim 1 , comprising two non-aqueous solvents.

7. The electrolyte of claim 1 , wherein the electrolyte has an electrochemical stability window of between about 2.3 V and about 5.0 V.

8. An electrochemical battery cell comprising the electrolyte of claim 1 ; an anode; and a cathode.

9. The electrochemical battery cell of claim 8 , wherein the cathode is selected from the group consisting of LiMn 2 O 4 , LiCoO 2 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0.5 Mn 1.5 O 2 , LiCoPO 4 , and LiNiPO 4 .

10. The electrochemical battery cell of claim 8 , wherein the anode is selected from the group consisting of lithium, magnesium, aluminum, zinc, chromium, iron, nickel, tin, lead, hydrogen, copper, silver, palladium, mercury, platinum, gold, molybdenum, sulfur, combinations thereof, and oxides thereof.

11. The electrochemical battery cell of claim 8 , wherein the anode is Mo 6 S 8 and the cathode is LiMn 2 O 4 .

12. The electrochemical battery cell of claim 8 , wherein a number of cycles of the electrochemical battery cell at a C-rate of about 4.5 C is between about 10 and about 500.

13. The electrochemical battery cell of claim 8 , wherein a number of cycles of the electrochemical battery cell at a C-rate of about 1.5 C is between about 500 and about 2000.

14. An electrolyte, comprising:

(a) at least one metal salt; and

(b) a solvent comprising between about 1% and about 100% water by weight and two non-aqueous solvents; wherein the molal concentration of the metal salt in the electrolyte is between 15 m and about 22 m, and wherein the electrochemical stability window of the electrolyte is between about 2.0 V and about 5.0 V.

15. An electrochemical battery cell comprising:

an electrolyte, comprising:

(a) at least one metal salt; and

(b) a solvent comprising between about 1% and about 100% water by weight;

wherein the molal concentration of the metal salt in the electrolyte is between 15 m and about 22 m when water is the only solvent or the molal concentration of the metal salt in the electrolyte is between 15 m and about 22 m when the solvent comprises water and a non-aqueous solvent, and wherein the electrochemical stability window of the electrolyte is between about 2.0 V and about 5.0 V;

an anode; and

a cathode, wherein the cathode is selected from the group consisting of LiMn 2 O 4 , LiCoO 2 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 , LiNi 0.5 Mn 1.5 O 2 , LiCoPO 4 , and LiNiPO 4 .

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 26, 2024
From: WANG, CHUNSHENG; SUO, LIUMIN
To: UNIVERSITY OF MARYLAND, COLLEGE PARK
Reel/Frame 067847/0822 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 26, 2024
From: XU, KANG; VON WALD CRESCE, ARTHUR; BORODIN, OLEG
To: THE UNITED STATES OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE ARMY
Reel/Frame 067847/0825 →
CONFIRMATORY LICENSE Recorded Apr 19, 2023
From: UNIVERSITY OF MARYLAND COLLEGE PK
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 063397/0045 →
Continuity (3)
Continuation 15763652
Provisional Application 62233902 · Sep 28, 2015
Related Publication 20220045349A1 · Feb 10, 2022