Patent Grant
12100807
The present invention relates generally to additives for Li-ion batteries. More specifically, the present invention relates to nitrile-based additives for use in association with the electrolyte in Li-ion batteries.
Li-ion batteries are widely used as energy source, and the demand is increasing. Typically, such battery comprises a negative electrode or anode, a positive electrode or cathode, and an electrolyte provided between the two spaced-apart electrodes. The electrolyte may comprise organic molecules or polymers and generally also comprises a lithium salt such as LiPF6, LiTFSI or LiFSI. Moreover, the electrolyte may comprise linear carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) or cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC).
Various studies related to the nature and composition of electrolytes and aimed at improving the performance and safety of Li-ion batteries, are reported in the art. For example, the use of additives comprising one or more nitrile groups is reported [1-3]. Indeed, it is known in the art that organic compounds comprising nitrile groups present good electrochemical properties and stability at high voltage and temperature.
There is still a need for methods of improving the performance and safety of Li-ion batteries. In particular, there is a need for nitrile-based organic compounds for use as additives in electrolytes.
The inventors have designed and prepared an additive for use in association with the electrolyte in a Li-ion battery. The additive of the invention is an organic compound as described herein below and which comprises at least one nitrile group. The organic compound is compatible with the electrolyte as well as other components of the battery.
The invention thus provides the following in accordance with aspects thereof:
wherein:
wherein:
wherein:
wherein:
wherein: R1 to R5 are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO2, SO2, COOH and acyloxycarbonyl; preferably R1 to R5 are each independently selected from the group consisting of H, alkyloxy, halogen, halogeno alkyl, nitro and cyano; more preferably selected from the group consisting of H, halogen, nitro and cyano.
wherein:
wherein:
wherein:
wherein n is an integer from 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2; preferably n is an integer from 0 to 3; more preferably n is 0 or 1.
wherein:
wherein:
wherein:
wherein Y is Na, K or Li; preferably Y is Na.
wherein R1 and R2 are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO2, SO2, COOH and acyloxycarbonyl; preferably selected from the group consisting of H, alkyloxy, halogen, halogeno alkyl, nitro and cyano; more preferably selected from the group consisting of H, halogen, nitro and cyano.
wherein X is a halogen atom; preferably X is F.
Other objects, advantages and features of the present invention will become more apparent upon reading of the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings.
In the appended drawings:
Before the present invention is further described, it is to be understood that the invention is not limited to the particular embodiments described below, as variations of these embodiments may be made and still fall within the scope of the appended claims. It is also to be understood that the terminology employed is for the purpose of describing particular embodiments, and is not intended to be limiting. Instead, the scope of the present invention will be established by the appended claims.
In order to provide a clear and consistent understanding of the terms used in the present specification, a number of definitions are provided below. Moreover, unless defined otherwise, all technical and scientific terms as used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure pertains.
The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one”, but it is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”. Similarly, the word “another” may mean at least a second or more.
As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.
As used herein when referring to numerical values or percentages, the term “about” includes variations due to the methods used to determine the values or percentages, statistical variance and human error. Moreover, each numerical parameter in this application should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Term “alkyl” or “alk” as used herein, represents a monovalent group derived from a straight or branched chain saturated hydrocarbon comprising, unless otherwise specified, from 1 to 15 carbon atoms and is exemplified by methyl, ethyl, n- and iso-propyl, n-, sec-, iso- and tert-butyl, neopentyl and the like and may be optionally substituted with one, two, three or, in the case of alkyl groups comprising two carbons or more, four substituents.
The term “alkoxy” or “alkyloxy” as used interchangeably herein, represents an alkyl group attached to the parent molecular group through an oxygen atom.
The term “alkylthio” or “thioalkoxy” as used interchangeably herein, represents an alkyl group attached to the parent molecular group through a sulfur atom.
The term “alkylene” as used herein, represents a saturated divalent hydrocarbon group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms, and is exemplified by methylene, ethylene, isopropylene and the like.
The term “alkenyl” as used herein, represents monovalent straight or branched chain groups of, unless otherwise specified, from 2 to 15 carbons, such as, for example, 2 to 6 carbon atoms or 2 to 4 carbon atoms, containing one or more carbon-carbon double bonds and is exemplified by ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl and the like and may be optionally substituted with one, two, three or four substituents.
The term “alkynyl” as used herein, represents monovalent straight or branched chain groups of from two to six carbon atoms comprising a carbon-carbon triple bond and is exemplified by ethynyl, 1-propynyl, and the like and may be optionally substituted with one, two, three or four substituents.
The term “cycloalkyl” as used herein, represents a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbon atoms, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl and the like.
The term “halogen” or “halo” as used interchangeably herein, represents F, Cl, Br and
The term “heteroatom”, as used herein, is understood as being oxygen, sulfur or nitrogen.
The inventors have designed and prepared an additive for use in association with the electrolyte in a Li-ion battery. The additive of the invention is an organic compound as described herein below and which comprises at least one nitrile group. Also, the organic compound is compatible with the electrolyte as well as other components of the battery.
More specifically, the additive of the invention for use in association with the electrolyte is a nitrile-based organic compound as described herein and having general formulae I-XI, A, B, C and D depicted below.
Such organic compounds are exemplified by compounds defined in Table 1 below, namely, Compounds A1-A4, B1-68, C1-C2 and D1.
B
C
D1
The present invention is illustrated in further details by the following non-limiting examples.
To a solution of aldehyde (1 eq.) in 15 mL of chloroform are added, molonodinitrile (1.5 eq.) and few drops of triethylamine. The mixture is refluxed one night under nitrogen. After return to room temperature, dichloromethane is added, and the solution is washed twice with water and dried over MgSO4. After solvent removal, the residue is chromatographed (silica gel/dichloromethane) to give a solid.
Bright yellow solid (70%). NMR 1H (400 MHz, CDCl3) δ: 7.69 (d, 1H, J=4 Hz); 7.64 (s, 1H); 7.38 (dd, 1H, J=4 Hz, J=12 Hz); 6.95 (d, 1H, J=12 Hz); 3.99 (s, 3H); 3.93 (s, 3H).
Yellow solid (40%). NMR 1H (400 MHz, CDCl3) δ: 7.77 (s, 1H). NMR 19F (400 MHz, CDCl3) δ: −132.55 (s, 2H); −143.68 (s, 1H); −158.50 (s, 1H).
White solid. NMR 1H (400 MHz, CDCl3) δ: 8.60 (d, 1H, J=4 Hz); 8.25 (dd, 1H, J=4 Hz, J=12 Hz); 8.18 (s, 1H); 8.15 (d, 1H, J=12 Hz).
Bright yellow solid. NMR 1H (400 MHz, CDCl3) δ: 8.12 (d, 1H, J=4 Hz); 8.03 (s, 1H); 7.67 (dd, 1H, J=4 Hz, J=12 Hz). NMR 19F (400 MHz, CDCl3) δ: −63.65 (s, 3F).
White solid. NMR 1H (400 MHz, CDCl3) δ: 8.02 (d, 2H, J=12 Hz); 7.83 (d, 2H, J=8 Hz); 7.80 (s, 1H). NMR 19F (400 MHz, CDCl3) δ: −63.48 (s, 3F).
White solid. NMR 1H (400 MHz, CDCl3) δ: 7.99 (d, 2H, J=8 Hz); 7.83 (d, 2H, J=8 Hz); 7.74 (s, 1H).
Pale orange solid. NMR 1H (400 MHz, CDCl3) δ: 8.39 (d, 2H, J=12 Hz); 8.07 (d, 2H, J=8 Hz); 7.88 (s, 1H).
Pink solid. NMR 1H (400 MHz, CDCl3) δ: 8.89 (d, 2H, J=12 Hz); 7.81 (s, 2H); 7.68 (d, 2H, J=8 Hz).
Compounds of the Series A and C and Compound D1 are commercially available and were used as received.
Referring to the figures,
As can be seen in
As will be understood by a skilled person, the additive for use in association with the electrolyte are adapted to be compatible with the components of the battery including the electrolyte and the cathode active material.
The invention is described in relation to lithium manganese iron phosphate (LMFP)—lithium titanium oxide (LTO) batteries. As will be understood by a skilled person, other lithium-ion batterie types may also be used. In other words, any battery wherein the cathode active material comprises a lithium-containing material may be used. Such lithium-containing material may be lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel oxide (LNO) and the like including olivines, lithium oxides, nickel manganese cobalt oxide (N M C).
Also, as will be understood by a skilled person, the anode material may be of any suitable type, such as for example lithium alloys, Si, SiOx, graphite and carbon mixtures, titanates, lithium titanates.
The scope of the claims should not be limited by the preferred embodiments set forth in the examples but should be given the broadest interpretation consistent with the description as a whole.
The present description refers to a number of documents, the content of which is herein incorporated by reference in their entirety.
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| PCT/CA2019/051415 | 10/3/2019 | WO |
| Publishing Document | Publishing Date | Country | Kind |
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| WO2020/069619 | 4/9/2020 | WO | A |
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| Number | Date | Country | |
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| 20210376381 A1 | Dec 2021 | US |
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