This invention relates generally to lithium rechargeable batteries, and more specifically to additives and electrolyte system for lithium-sulfur rechargeable battery.
Lithium ion batteries (LIBs) have been developed into an important technology for energy storage applications, while the demand for materials with high energy density is urgent. A strong demand for low-cost and high-energy-density rechargeable batteries has spurred lithium-sulfur (Li—S) rechargeable battery research. First, sulfur is an abundant and low-cost material. Second, the Gibbs energy of the lithium (Li) and sulfur reaction is approximately 2,600 Wh/kg, assuming the complete reaction of Li with sulfur to form Li2S, more than five times the theoretical energy of transition metal oxide cathode materials and graphite coupling. With these advantages, Li—S batteries could be both high energy density and low cost, satisfying demand in energy storage for transportation application. The major obstacle is the loss of sulfur cathode material as a result of polysulfide dissolution into common electrolytes, which causes a shuttle effect and significant capacity fade. The polysulfide shuttle effect leads to poor sulfur utilization and fast-capacity fade, which have hindered widespread use of rechargeable Li—S batteries. Better electrolytes and additives for Li—S battery are needed for reduction of polysulfide dissolution. The ideal electrolyte for sulfur electrode should have moderate ion conductivity, have more stability towards polysulfide, and promotes the polysulfide affiliation with the electrode substrate to prevent polysulfide dissolution.
The present invention provides for an amphiphilic molecule having the following structure:
wherein R is
m is an integer from 1 to 21; a is an integer from 0 to 20; b is an integer from 0 to 4; and n is an integer from 1 to 20. In some embodiments, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21. In some embodiments, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, b is 0, 1, 2, 3, or 4. In some embodiments, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.
In some embodiments, the amphiphilic molecule has the following structure:
wherein m is an integer from 1 to 21, a is an integer from 0 to 20, b is an integer from 0 to 4, and n is an integer from 1 to 20.
In some embodiments, R is
wherein m is an integer from 1 to 21; a is an integer from 0 to 20.
In some embodiments, the amphiphilic molecule has the following structure:
wherein m is an integer from 1 to 21; a is an integer from 0 to 20.
In a particular embodiment, the amphiphilic molecule has Chemical Structure II and is F3EO1, wherein m is 3, a is 0, b is 1 and n is 1. In a particular embodiment, the amphiphilic molecule has Chemical Structure II and is F8EO4, wherein m is 8, a is 0, b is 1 and n is 4.
In some embodiments, the amphiphilic molecule is capable of self-formation of a micelle. In some embodiments, the micelle is an inverse micelle, prolate micelle, inverse prolate micelle, normal hexagonal phase, inverse hexagonal phase inverse, oblate micelle bilayered fragment, or the like. One skilled in the art can readily identify the polar and non-polar ends (or parts) of each amphiphilic molecule. The fluorinated alkyl is the polar end (or part), while the polyether and R group form the non-polar end (or part).
The present invention provides for an electrolyte composition comprising an amphiphilic molecule of the present invention, an electrolyte solvent, and a lithium salt.
In some embodiments, the electrolyte solvent is a highly fluorinated alkane, alkyl ether or alkyl tertiary amine comprising more F atoms than H atoms. In some embodiments, the alkane has a main chain having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. In some embodiments, the alkane has a straight or branched chain. In some embodiments, the alkane has a total of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. In some embodiments, the electrolyte solvent has the following chemical structure: R1—O—R2, or
wherein R1 is —CH3, —C2H5, or —R4; and R2, R3, and R4 are each independently -α-CyHzF2y+1−z, wherein α is —CHF—, —CF2—, or —CH2—; y is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; and z is 0 or 1. In some embodiments, —CyFy+2 is a straight chain alkyl. In some embodiments, —CyF2y+1 is a branched alkyl, and y is equal to or more than 3. In some embodiments, R1 and R2 are identical. In some embodiments, R2 and R3 are identical. In some embodiments, R1, R2, and R3 are identical.
In some embodiments, the electrolyte solvent is methoxyperfluorobutane, profluorinated alkane, bis(2,2,2-trifluoroethyl)ether, 1,1,2,2-tetrafluoroethyl-2′,2′,2′-trifluoroethyl ether, perfluorotributylamine, hydrofluoroether (HFE), or a mixture thereof. In some embodiments, the profluorinated alkane is C(H or F)3[C(H or F)2]xC(H or F)3, wherein x is an integer from 0 to 20, and there are more F atoms than H atoms. In some embodiments, the profluorinated alkane is CF3(CF2)xCF3, wherein x is an integer from 0 to 20. In some embodiments, x is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some embodiments, the hydrofluoroether (HFE) is CHF2CF2—O—CH2CF2CHF2, C7F15—O—C2H5, C4F9—O—C2H5, n-C3F7—O—CH3), CF3CF2—O—CH3, CF3CHFCF2—O—CH3, CF3—O—CH3, CHF2—O—CHF2, CF3CF2—O—CH3), or CF3—O—CHFCF3. In some embodiments, the HFE is CHF2CF2—O—CH2CF2CHF2. Chemical structure of different electrolyte solvents is shown in
In some embodiments, the lithium salt is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxalato)borate (LiBOB), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), LiClO4, lithium bis(fluorosulfonyl)imide (LiFSI), LiPF6, LiAsF6, or a mixture thereof. In some embodiments, the lithium salt has an ionic association strength that is equal to or less than about the ionic association strength of LiBETI, and is equal to or more than about the ionic association strength of LiTFSI.
In some embodiments, the electrolyte composition comprises one or more amphiphilic molecule of the present invention, or a mixture thereof; methoxyperfluorobutane, profluorinated alkane, bis(2,2,2-trifluoroethyl)ether, 1,1,2,2-tetrafluoroethyl-2′,2′,2′-trifluoroethyl ether, perfluorotributylamine, or a mixture thereof; and, LiTFSI, LiBOB, LiBETI, LiClO4, LiFSI, LiPF6, LiAsF6, or a mixture thereof.
In some embodiments, the electrolyte composition comprises F3EO1,:HFE=1:5 (v/v) and 0.5 M LiTFSI, wherein HFE is CHF2CF2—O—CH2CF2CHF2. F3EO1 has the following chemical structure:
In some embodiments, the electrolyte composition comprises F8EO4,:HFE=2:3 (v/v) and 0.5 M LiTFSI, wherein HFE is CHF2CF2—O—CH2CF2CHF2.
The shorthand labeling of biphiphilic additives FnEOm is: “F” stands for the unit of —CF2— and ending CF3— moieties, and “n” is the number of the moieties; “EO” stands for the —CH2CH2O— ethyleneoxide moiety, the —CH2 end is covalently bond with CF2—, and the O— end is covalently bond with a methyl moiety, “m” is the number of the —CH2CH2O— repeating units. The “F” segment is profluorinated alkyl, and the “EO” segment is methyloligoethyleneoxide, wherein the two segments are linked by a covalent bond.
The present invention also provides for a lithium ion battery comprising the electrolyte composition of the invention.
The amphiphilic molecule and electrolyte composition of the present invention have more stability towards polysulfide, and promote polysulfide affiliation with the electrode substrate to prevent polysulfide dissolution.
The foregoing aspects and others will be readily appreciated by the skilled artisan from the following description of illustrative embodiments when read in conjunction with the accompanying drawings.
Before the invention is described in detail, it is to be understood that, unless otherwise indicated, this invention is not limited to particular sequences, expression vectors, enzymes, host microorganisms, or processes, as such may vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only and is not intended to be limiting.
In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:
The terms “optional” or “optionally” as used herein mean that the subsequently described feature or structure may or may not be present, or that the subsequently described event or circumstance may or may not occur, and that the description includes instances where a particular feature or structure is present and instances where the feature or structure is absent, or instances where the event or circumstance occurs and instances where it does not.
As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “molecules” includes a plurality of a molecule species as well as a plurality of molecules of different species.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
The term “about” refers to a value including 10% more than the stated value and 10% less than the stated value.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited.
The amphiphilic molecule and electrolyte composition of the present invention can be used for rechargeable Li—S battery, and can promote lithium salt (such as, LITFSI) dissolution into electrolyte, but preventing polysulfide dissolution during cell operation. In a particular embodiment, the new electrolyte comprises of a highly fluorinated solvent (such as, 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether), a lithium salt (such as, LiTFSI), and a “biphiphilic” additive F8EO4.
The additive molecules can form micelles in the highly fluorinated solvent. The micelle core is methyloligoethyleneoxide, and the profluorinated alkyls extend to the highly fluorinated solvent. The highly fluorinated solvent does not dissolve polysulfide. The combination solvent can effectively dissolvent LiTFSI to 0.5M concentration in the micelle core for any of the amphiphilic molecule, including but not limited to F8EO4 and F3EO1. The main solvent body is any highly fluorinated solvent, which prevents polysulfide dissolution.
All the current electrolytes and additives for electrolyte are distributed homogenously. This invention uses a bi-functional additive to form micelle structures within the electrolyte. The micelle core selectively dissolves lithium salt, and the bulk of electrolyte solvent of highly fluorinated solvent prevents polysulfide dissolution.
Amphiphilic molecules of the present invention can be synthesized using the following method (with this particular example provided for the synthesis of F8EO4):
Reaction 1:
Reaction 2:
The EO3-Tosylate (shown in Reaction 1 above) is synthesized according to J. Org. Chem. 2018, 83, 1903-1912. The synthetic procedure of FEO is stated as follows: 5.088 g EO3-Tosylate (16 mmol) and 3.72 g F—OH (8 mmol) are added to 4.8 mL NMP and followed by adding 4.8 mL 48 wt % KOH solution. The mixture is heated at 50° C. for 5 hours and 70° C. for another 2 h. After cooling down, 50 mL of ether is added and extracted against water to remove the impurities. The FEO (3.5 g, yield: 76%) was finally obtained after evaporating the solvent under vacuum.
In some embodiments, the present invention can be used in a high voltage lithium ion and lithium metal battery. In some embodiments, the cathode comprises NMC622 materials (LiNi0.6Mn0.2Co0.2O). In some embodiments, the anode comprises lithium metal. In some embodiments, the electrolyte comprising 0.5M LiTFSI in F4/TTE (1:5) electrolyte. In some embodiments, the battery is a coin cell. In some embodiments, the battery has an operational voltage 2.75V-4.4V.
A high voltage lithium ion and lithium metal battery is fabricated comprising the following: the cathode comprises NMC622 materials (LiNi0.6Mn0.2Co0.2O), the anode comprises lithium metal, the electrolyte comprising 0.5M LiTFSI in F4/TTE (1:5) electrolyte. The battery is tested as follows: C/10 first 2 cycles, and C/3 cycling subsequent cycling.
The electrolytes can be used for high voltage lithium metal cells. In some embodiments, the cathode is an NMC material (such as (111, 532, 622 or 811)), NCA materials (such as LiNi0.8Co0.15Al0.05O2), or Nickelate material (such as LiNiO2). In some embodiments, the cell voltage can range from 2.5 V to 6 V. In some embodiments, the anode is a Cu, Ni, or Ti, Lithium metal; a Si based material (such as Si, Si/C, SiOx), carbon base materials (such as graphite), or a mixture thereof (such as a mixture of Si based materials and carbon based materials). In some embodiments, the electrolyte is any combination of the amphiphilic electrolyte and compositions disclosed herein.
It is to be understood that, while the invention has been described in conjunction with the preferred specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
All patents, patent applications, and publications mentioned herein are hereby incorporated by reference in their entireties.
The invention having been described, the following examples are offered to illustrate the subject invention by way of illustration, not by way of limitation.
The Li—S cell performance results obtained are reported herein. F8EO4 and F3EO1 are separately synthesized using the method taught herein.
LiTFSI does not dissolve in the 1:9 electrolyte with a concentration of 0.5 M.
“FEO” in Table 2 is F3EO1.
While the present invention has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, process, process step or steps, to the objective, spirit and scope of the present invention. All such modifications are intended to be within the scope of the claims appended hereto.
All cited references are hereby each specifically incorporated by reference in their entireties.
This application claims priority as a continuation application to PCT International Patent Application No. PCT/US2020/058064, filed Oct. 29, 2020, which claims priority to U.S. Provisional Patent Application Ser. No. 62/929,678, filed Nov. 1, 2019, both of which are hereby incorporated by reference.
The invention was made with government support under Contract No. DE-AC02-05CH11231 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
Number | Date | Country | |
---|---|---|---|
62929678 | Nov 2019 | US |
Number | Date | Country | |
---|---|---|---|
Parent | PCT/US2020/058064 | Oct 2020 | US |
Child | 17734585 | US |