ADDITIVES FOR ELECTROLYTES IN Li-IONS BATTERIES
20210376381 · 2021-12-02
Assignee
Inventors
- Charlotte MALLET (Montréal, Québec, CA)
- Sylviane ROCHON (Saint-Adèlphe, Québec, CA)
- Karim ZAGHIB (Longueuil, Québec, CA)
Cpc classification
H01M4/5825
ELECTRICITY
C07C255/55
CHEMISTRY; METALLURGY
H01M4/505
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C07C255/51
CHEMISTRY; METALLURGY
H01M4/525
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M10/4235
ELECTRICITY
C07C255/50
CHEMISTRY; METALLURGY
International classification
C07C255/50
CHEMISTRY; METALLURGY
C07C255/51
CHEMISTRY; METALLURGY
C07C255/55
CHEMISTRY; METALLURGY
H01M10/0525
ELECTRICITY
Abstract
Method of improving the performance and safety of a Li-ion battery. The method includes using a nitrile-based small organic compound of general formula I, V or IX outlined in the application in association with the electrolyte of the battery. An electrolyte including a nitrile-based small organic compound. A battery including the electrolyte.
Claims
1. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula I outlined below ##STR00037## wherein: Q is a 5 to 12-member ring or bicycle ring, optionally the ring comprises one or more heteroatom which are the same or different and selected from the group consisting of N, O and S; preferably Q is a 5-10-, or a 5-, or a 6-member ring or bicycle ring; L is present or absent and is a linker comprising one or more of alkyl, alkene and alkyne groups; and m in an integer from 1 to 10, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3.
2. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula II outlined below ##STR00038## wherein: X is C or N; L is present or absent and is a linker comprising one or more of alkyl, alkene and alkyne groups; Ri each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, 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; m is an integer from 1 to 5, or 1 to 4, or 1 to 3; and m′ is an integer from 0 to 5, or 0 to 4, or 0 to 3, or 1 to 5, or 1 to 4, or 1 to 3.
3. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula III outlined below ##STR00039## wherein: X is C or N; Ri are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, COOH and acyloxycarbonyl; preferably Ri 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; and m′ is an integer from 0 to 5, or 0 to 4, or 0 to 3, or 1 to 5, or 1 to 4, or 1 to 3.
4. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula IV outlined below ##STR00040## wherein: X is C or N; Ri are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, 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; and m′ is an integer from 0 to 5, or 0 to 4, or 0 to 3, or 1 to 5, or 1 to 4, or 1 to 3.
5. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula A outlined below ##STR00041## wherein: R.sub.1 to R.sub.5 are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, COOH and acyloxycarbonyl; preferably R.sub.1 to R.sub.5 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.
6. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula B outlined below ##STR00042## wherein: X is C and R.sub.3 is H; or X is N; and R.sub.1 to R.sub.5 are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, COOH and acyloxycarbonyl; preferably R.sub.1 to R.sub.5 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.
7. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound is A1, A2, A3 or A4 outlined below ##STR00043##
8. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound is B1, B2, B3, B4, B5, B6, B7 or B8 outlined below ##STR00044## ##STR00045##
9. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula V outlined below ##STR00046## wherein: L is present or absent and is a linker comprising one of more of alkyl, alkene and alkyne groups; and R.sub.1 to R.sub.3 are each independently alkyl groups; preferably C1 to C6 or C1 to C3 alkyl groups; more preferably at least one of R.sub.1 to R.sub.3 is CH.sub.3, or each of R.sub.1 to R.sub.3 is CH.sub.3.
10. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula VI outlined below ##STR00047## 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; and R.sub.1 to R.sub.3 are each independently alkyl groups; preferably C1 to C6 or C1 to C3 alkyl groups; more preferably at least one of R.sub.1 to R.sub.3 is CH.sub.3, or each of R.sub.1 to R.sub.3 is CH.sub.3.
11. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula C outlined below ##STR00048## 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.
12. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound is C1 or C2 outlined below ##STR00049##
13. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula IX outlined below ##STR00050## wherein: R.sub.1 is CN or CH.sub.3; L.sub.1 and L.sub.2 are each independently present or absent and are each independently a linker comprising alkyl, alkene and/or alkyne groups; and Y is Na, K or Li; preferably Y is Na.
14. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula X outlined below ##STR00051## wherein: L.sub.1 and L.sub.2 are each independently present or absent and are each independently a linker comprising one or more of alkyl, alkene and alkyne groups; and Y is Na, K or Li; preferably Y is Na.
15. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula XI outlined below ##STR00052## wherein: n1 and n2 are each independently an integer from 0 to 10, or 0 to 6, or 0 to 3; preferably at least one of n1 and n2 is 0, or both n1 and n2 are 0; and Y is Na, K or Li; preferably Y is Na.
16. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula D outlined below ##STR00053## wherein Y is Na, K or Li; preferably Y is Na.
17. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound has a general formula D1 outlined below ##STR00054##
18. A compound having a general formula VII outlined below ##STR00055## wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of H, alkyl, cycloalkyl, alkene, alkyne, aryl and alkylaryl, alkoxy, thioalkoxy, OH, SH, NH.sub.2, a halogen atom, a halogeno alkyl, a halogeno alkoxy, a halogeno thioalkoxy, a cyano alkyl, a cyano alkene, a cyano alkyne, CN, NO.sub.2, SO.sub.2, 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.
19. A compound having a general formula VIII outlined below ##STR00056## wherein X is a halogen atom; preferably X is F.
20. A compound of formula B4 outlined below ##STR00057##
21. A method of improving the performance and safety of a Li-ion battery, comprising using a nitrile-based organic compound in association with the electrolyte of the battery, wherein the compound as defined in any one of claims 18 to 20.
22. The method according to any one of claims 1 to 17 and 21, wherein the nitrile-based organic compound is added to the electrolyte; optionally an amount of the additive (nitrile-based organic compound) is between about 0.01 to about 5.0% wt, or about 0.01 to about 3.0% wt, or about 0.01 to about 1.0% wt, or about 0.05 to about 1.0% wt, or about 0.1 to about 1.0% wt, about 0.1 to about 0.8% wt, or about 0.1 to about 0.5% wt, or about 0.1 to about 0.3% wt, is 0.1% wt, or is 0.5% wt.
23. An electrolyte comprising a compound which is selected from the group consisting of: I, II, III, IV, A, B, A1, A2, A3, A4, B1, B2, B3, B4, B5, B6, B7, B8, V, VI, C, C1, C2, IX, X, XI, D, and D1 as defined in any one of method claims 1 to 17.
24. An electrolyte comprising the compound as defined in any one of claims 18 to 20.
25. A battery comprising the electrolyte as defined in claim 23 or 24.
26. An additive for an electrolyte for use in a Li-ion battery, comprising a compound which is selected from the group consisting of: I, II, III, IV, A, B, A1, A2, A3, A4, B1, B2, B3, B4, B5, B6, B7, B8, V, VI, C, C1, C2, IX, X, XI, D, and D1 as defined in any one of method claims 1 to 17.
27. An additive for an electrolyte for use in a Li-ion battery, comprising a compound as defined in any one of claims 18 to 20.
28. The method, electrolyte, battery or additive according to any one of claims 1 to 27, wherein the Li-ion battery is a battery wherein the cathode comprises a lithium-containing material;
29. The method, electrolyte, battery or additive according to any one of claims 1 to 27, wherein the Li-ion battery is a battery wherein the cathode comprises lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel oxide (LNO) and the like including olivines, lithium oxides, nickel manganese cobalt oxide (NMC).
30. The method, electrolyte, battery or additive according to claim 28 or 30, wherein the performance (capacity, reversibility) of the battery is improved.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
[0066] In the appended drawings:
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DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0078] 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.
[0079] 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.
[0080] 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.
[0081] 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.
[0082] 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.
[0083] 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.
[0084] The term “alkoxy” or “alkyloxy” as used interchangeably herein, represents an alkyl group attached to the parent molecular group through an oxygen atom.
[0085] The term “alkylthio” or “thioalkoxy” as used interchangeably herein, represents an alkyl group attached to the parent molecular group through a sulfur atom.
[0086] 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.
[0087] 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.
[0088] 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.
[0089] 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.
[0090] The term “halogen” or “halo” as used interchangeably herein, represents F, Cl, Br and
[0091] The term “heteroatom”, as used herein, is understood as being oxygen, sulfur or nitrogen.
[0092] 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.
[0093] 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.
##STR00022## ##STR00023## ##STR00024##
[0094] Such organic compounds are exemplified by compounds defined in Table 1 below, namely, Compounds A1-A4, B1-68, C1-C2 and D1.
TABLE-US-00001 TABLE 1 Organic compounds according to the invention (Series A, B, C and D) R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X n Cycle A A1 H H OMe OMe H 0.1% 300 A2 F F F F F 0.1% 300 A3 F F CN F F 0.1% 300 A4 CN H CN CN H 0.1% 300 B B1 H H OMe OMe H C 0.5% 300 B2 F F F F F C 0.5% 200 B3 H H NO.sub.2 H NO.sub.2 C 0.5% poor results B4 H H CF.sub.3 H NO.sub.2 C 0.5% 300 B5 H H CF.sub.3 H H C 0.5% 300 B6 H H CN H H C 0.5% 300 B7 H H NO.sub.2 H H C 0.5% poor results B8 H H H H H N 0.5% 300 C C1 0 0.5% 300 C2 1 0.5% 300 D D1 0.5% 300 A
[0095] The present invention is illustrated in further details by the following non-limiting examples.
Nitrile-Based Organic Compounds for Use as Additive in Association with Li-Ion Electrolytes
Example 1—General Procedure for the Preparation of the Compounds
[0096] 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 MgSO.sub.4. After solvent removal, the residue is chromatographed (silica gel/dichloromethane) to give a solid.
Example 2—Compound B1
[0097] ##STR00029##
[0098] Bright yellow solid (70%). NMR .sup.1H (400 MHz, CDCl.sub.3) 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).
Example 3—Compound B2
[0099] ##STR00030##
[0100] Yellow solid (40%). NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 7.77 (s, 1H). NMR .sup.19F (400 MHz, CDCl.sub.3) δ: −132.55 (s, 2H); −143.68 (s, 1H); −158.50 (s, 1H).
Example 4—Compound B3
[0101] ##STR00031##
[0102] White solid. NMR .sup.1H (400 MHz, CDCl.sub.3) 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).
Example 5—Compound B4
[0103] ##STR00032##
[0104] Bright yellow solid. NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 8.12 (d, 1H, J=4 Hz); 8.03 (s, 1H); 7.67 (dd, 1H, J=4 Hz, J=12 Hz). NMR .sup.19F (400 MHz, CDCl.sub.3) δ: −63.65 (s, 3F).
Example 6—Compound B5
[0105] ##STR00033##
[0106] White solid. NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 8.02 (d, 2H, J=12 Hz); 7.83 (d, 2H, J=8 Hz); 7.80 (s, 1H). NMR .sup.19F (400 MHz, CDCl.sub.3) δ: −63.48 (s, 3F).
Example 7—Compound B6
[0107] ##STR00034##
[0108] White solid. NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 7.99 (d, 2H, J=8 Hz); 7.83 (d, 2H, J=8 Hz); 7.74 (s, 1H).
Example 8—Compound B7
[0109] ##STR00035##
[0110] Pale orange solid. NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 8.39 (d, 2H, J=12 Hz); 8.07 (d, 2H, J=8 Hz); 7.88 (s, 1H).
Example 9—Compound B8
[0111] ##STR00036##
[0112] Pink solid. NMR .sup.1H (400 MHz, CDCl.sub.3) δ: 8.89 (d, 2H, J=12 Hz); 7.81 (s, 2H); 7.68 (d, 2H, J=8 Hz).
[0113] Compounds of the Series A and C and Compound D1 are commercially available and were used as received.
[0114] Referring to the figures,
[0115] As can be seen in
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[0119] 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.
[0120] 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).
[0121] 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.
[0122] 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.
[0123] The present description refers to a number of documents, the content of which is herein incorporated by reference in their entirety.
REFERENCES
[0124] 1. Rohan R. et al. J. Phys. Chem. C (2016), 120 (12), 6450-6458. [0125] 2. Kim Y.-S. et al. ACS Appl. Mater. Interfaces (2014), 6 (11), 8913-8920. [0126] 3. Pohl B. et al. J. Electrochem. Soc. (2015), 162 (3), A460-A464.