Non-aqueous fluoride salts, solutions, and their uses

Patent metadata

Field	Value
Publication number	US-11830983-B2
Application number	US-202117217428-A
Country	US
Kind code	B2
Filing date	Mar 30, 2021
Priority date	Aug 4, 2015
Publication date	Nov 28, 2023
Grant date	Nov 28, 2023

Abstract

Electrolyte solutions including at least one anhydrous fluoride salt and at least one non-aqueous solvent are presented. The fluoride salt includes an organic cation having a charge center (e.g., N, P, S, or O) that does not possess a carbon in the β-position or does not possess a carbon in the β-position having a bound hydrogen. This salt structure facilitates its ability to be made anhydrous without decomposition. Example anhydrous fluoride salts include (2,2-dimethylpropyl)trimethylammonium fluoride and bis(2,2-dimethylpropyl)dimethylammonium fluoride. Combining these fluoride salts with at least one fluorine-containing non-aqueous solvent (e.g., bis(2,2,2-trifluoroethyl)ether; (BTFE)) promotes solubility of the salt within the non-aqueous solvents. The solvent may be a mixture of at least one non-aqueous, fluorine-containing solvent and at least one other non-aqueous, fluorine or non-fluorine containing solvent (e.g., BTFE and propionitrile or dimethoxyethane). The electrolyte solutions may be employed in electrochemical cells, such as batteries, fuel cells, electrolysis systems, and capacitors.

First claim

What is claimed is:

1. An electrochemical cell, comprising:
a positive electrode;
a negative electrode; and
an electrolyte solution provided between said positive electrode and said negative electrode, said electrolyte solution comprising:
a first fluoride salt, comprising:
one or more first fluoride ions; and
a first organic cation, wherein:
the first organic cation does not possess a carbon in the β-position having a bound hydrogen;
the cation charge center of the first organic cation is N, P, S, or O; and
the first fluoride salt is a substituted or unsubstituted (2,2-dimethylpropyl)trimethylammonium fluoride (NpMe 3 NF) or a substituted or unsubstituted bis(2,2-dimethylpropyl)dimethylammonium fluoride (Np 2 Me 2 NF);

a second fluoride salt that is different than the first fluoride salt, the second fluoride salt comprising:
one or more second fluoride ions; and
a second organic cation, wherein
the cation charge center of the second organic cation is N, P, S, or O; and

one or more non-aqueous solvents, at least one of the one or more non-aqueous solvents being fluorinated and comprising at least one functional group characterized by the form [X—(CH 2 ) n —Y], where X and Y are polar functional groups having a combined effect to confer a partial positive charge on the CH 2 group or groups and n=1 or 2;
wherein said fluoride salt is provided to said one or more non-aqueous solvents in an anhydrous form; and
wherein the total concentration of said first and said second fluoride ions dissolved in said electrolyte solution is selected from the range of 0.5 M to 20 M.

2. The electrochemical cell of claim 1 , wherein the total concentration of said first and said second fluoride ions dissolved in said electrolyte solution is greater than or equal to 1 M and less than or equal to 20 M.

3. The electrochemical cell of claim 1 , wherein Y is O or S and X is a functional group selected from the group consisting of ethers, esters, acid anhydrides, amines, amides, carbonates, sulfones, sulfonyl esters, phosphites, phosphates, nitriles, nitro, aldehydes, acetates, SF 5 , or fluorocarbons.

4. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is characterized by the formula (FX7a) (FX7b), (FX7c), (FX7d), (FX7e), or (FX7g):

 or

5. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is a fluorinated phosphite or any combination thereof and the fluorinated phosphite is characterized by the formula (FX8a):

6. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is a fluorinated ester or anhydride or any combination thereof and the fluorinated ester or anhydride is characterized by the formula (FX9b):

7. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is a nitrile or any combination thereof and the nitrile is characterized by the formula (FX10c):

8. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is characterized by the formula (FX12a):

wherein R 7 is a halo group or a halogen-substituted C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 5 -C 30 aryl, C 5 -C 30 heteroaryl, C 1 -C 20 acyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 5 -C 20 alkylaryl, C 1 -C 20 alkyl, C 2 -C 20 alkoxycarbonyl, C 4 -C 30 aliphatic, C 4 -C 30 cycloaliphatic, or C 4 -C 30 aromatic; and
wherein n is an integer selected from the range of 1 to 20.

9. The electrochemical cell of claim 1 , wherein the electrolyte solution provides an ionic conductivity greater than or equal to 0.1 mS/cm at 25° C.

10. The electrochemical cell of claim 1 , wherein the one or more non-aqueous solvents comprises a second non-aqueous solvent being an ether or a glyme.

11. The electrochemical cell of claim 1 , wherein the at least one of the one or more non-aqueous solvents is selected from the group consisting of bis(2,2,2-trifluoroethyl)ether (BTFE), tris(2,2,2-trifluoroethyl)phosphite (TTFP), 2,2,2-trifluoroethyl trifluoroacetate (TFE-TFA), methoxyacetonitrile (MeOAN), 3-methoxypropionitrile (3-MeOPN), and fluoroethylene carbonate (FEC).

Assignees

• California Inst Of Techn
• Honda Motor Co Ltd

Inventors

• Jones Simon C
• Davis Victoria K
• Bates Christopher M
• Momcilovic Nebojsa
• Savoie Brett M
• Webb Michael A
• Miller Iii Thomas F
• Grubbs Robert H
• Brooks Christopher
• Omichi Kaoru

Classifications

• H01M10/0568 Primary

  characterised by the solutes · CPC title

• C07C209/68

  from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M10/0525

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

• H01M10/0569

  characterised by the solvents · CPC title