FR3095204A1

FR3095204A1 - Solvants carbonates pour électrolytes non aqueux, électrolytes non aqueux et dispositifs électrochimiques, et leurs procédés de fabrication

Info

Publication number: FR3095204A1
Application number: FR1904075A
Authority: FR
Inventors: Matjaž Koželj; Cécile Petit; Sabrina PAILLET; Karim Zaghib
Original assignee: SCE France SAS
Current assignee: SCE France SAS
Priority date: 2019-04-16
Filing date: 2019-04-16
Publication date: 2020-10-23
Also published as: KR20210150435A; CA3134636A1; CN113795963A; EP3956288A1; WO2020212872A1; US20220209301A1; JP2022529217A

Abstract

Il est proposé un solvant carbonate pour des électrolytes non aqueux qui sont caractérisés par leur faible corrosivité vis-à-vis des collecteurs de courant en aluminium à des tensions supérieures à 4,2 V. Des électrolytes non aqueux comprenant le solvant carbonate ainsi que des dispositifs électrochimiques comprenant l’électrolyte non aqueux, sont également proposés. Des procédés de fabrication des solvants carbonates, de l’électrolyte non aqueux et des dispositifs électrochimiques sont proposés. Figure à publier avec l’abrégé : Fig. 1

Description

CARBONATE SOLVENTS FOR NON-AQUEOUS ELECTROLYTES, NON-AQUEOUS ELECTROLYTES, AND ELECTROCHEMICAL DEVICES, AND METHODS OF PRODUCTION THEREOF

Field of the Invention

The present invention relates to carbonate solvents for non-aqueous electrolytes and to a method for producing said carbonate solvents and non-aqueous electrolytes. More specifically, the present invention is concerned with carbonate solvents for non-aqueous electrolytes that are characterized by their low corrosiveness against aluminum current collectors at voltages higher than 4.2 V.

Background of the Invention

New technological solutions for telecommunications and especially electrification of transportation cells have been proposed for Li and Li-ion batteries. Their aim is to provide such batteries with the highest possible energy density in order to achieve higher voltage cathodes. This, however, requires high performance electrolytes which are resistant towards oxidation at the high potentials that occur during the operation of such a system. Also, other parasitic processes can cause deterioration and malfunctioning of the system. One such parasitic process is corrosion or electrolytic dissolution of the current collectors, which typically becomes significant at potentials beyond 4 V.

Conventional electrolytes used in most lithium and Li-ion battery systems, also in high voltage batteries, are based on LiPF₆salt, which has many good properties. For example, it passivates the majority of aluminum current collector materials, has good conductivity and it is relatively cheap. However, it also has some disadvantages, most notably sensitivity to moisture, causing HF to form, which causes rapid deterioration of battery performance. Another weakness is its limited thermal stability, limited solubility in polymers and emission of toxic decomposition products. The solvents used for the preparation of conventional electrolytes are cheaply available C₁-C₂dialkyl carbonates and lower cyclic carbonates, most notably ethylene carbonate and propylene carbonate.

In order to substitute the risky LiPF₆for safer alternatives, many salts have been proposed. One class of such salts are bissulfonyl amides; in fact, lithium bis(trifluoromethanesulfonyl)amide - LiTFSI, has been proposed as a salt for the preparation of electrolytes, including polymer electrolytes. In addition, other compounds of this class have been proposed. It has been discovered that LiTFSI produces serious anodic dissolution, erroneously called corrosion, of the aluminum current collector at voltages higher than 3.6 V. This means that the electrochemical charge that should be used for the charging of the battery is consumed for aluminum dissolution, such that the battery in fact cannot be charged. When this process occurs with a smaller rate (meaning only part of the charge is consumed by the corrosion process) the battery can be charged, but repeating the charging further dissolves the current collector. This slowly leads to diminished contact between the active electrode coating and the current collector, resulting in loss of capacity. This imposes a serious drawback for long-term operation, which entails many charges and discharges of the battery system.

For that reason, lithium bis(pentafluoroethanesulfonyl) amide – LiBETI was developed to overcome those problems, but its main disadvantages are its very high molecular weight, its high price and its accumulation in living organisms similar to all long chain perfluoroalkanes. On the other hand, two lighter salts have been proposed: lithium bis(fluorosulfonyl)amide – LiFSI and asymmetric lithium N-flurosulfonyl-trifluoromethanesulfonyl amide –LiFTFSI. Other asymmetric bisfluorosulfonyl amides have also been suggested.

It has been stated that electrolytes containing LiFSI can support voltages up to 4.2V. However, it is not clear, and there is no experimental proof, that these electrolytes can support higher voltages.

Anodic dissolution of an aluminum current collector in sulfone-based solvents has been examined. As an alternative to molecular solvents, ionic liquids were reported as a good solvent for the suppression of anodic dissolution of aluminum. However, ionic liquids are not easily available and their main drawback is their high price, which makes them less attractive for use in battery systems.

The influence of various solvents on anodic dissolution of aluminum collectors caused by LiTFSI has been examined. It has been found that collector corrosion depends on the electrolyte solvent, with strong corrosion in the presence of carbonates and lactones and minimal corrosion in the presence of nitriles. Such a conclusion discourages the utilisation of carbonate solvents for use with sulfonyl amide salts.

The inhibition of anodic dissolution of aluminum can be affected with fluoroborates, most effectively with lithium difluorooxalatoborate, LiDFOB; the drawback is the relatively high price of the additive.

Also, LiPF₆can be used as an aluminum anodic dissolution inhibitor. However, very high concentrations of LiPF₆are needed to effectively suppress the anodic dissolution of aluminum. In fact, due to the high concentrations, it would be more accurate to label such electrolytes as LiPF₆electrolytes, with LiFSI as an additive to the LiPF₆.

Another proposed solution is the use of highly concentrated electrolytes. However, there are several drawbacks, including the undesirable higher price of such a system and crystallisation problems at low temperatures.

There have also been more or less successful attempts to protect the aluminum current collector with a protective coating, but this increases the cost and weight of the battery. Furthermore, the most problematic point of this inhibition is that edges are not protected due to the cutting of electrodes to an appropriate size. Corrosion may propagate from the edges after many cycles, thus jeopardizing the long-term operation of such cells.

Possible solvents for lithium batteries have been discussed, but very little attention has been paid to unwanted processes on the current collectors. Most electrolytes used in the battery industry are based on the lower dialkyl carbonates: dimethyl, diethyl and ethylmethyl carbonate, mixed with additives, most notably ethylene carbonate. Syntheses of alkyl carbonates are very well developed, even on an industrial scale. Most suitable methods for their preparation in a laboratory are transesterifications.

Regarding high voltage applications, fluorinated carbonates have been proposed together with conventional LiPF₆salt. However, these solvents are very expensive and can represent a serious environmental risk, like all long chain fluorinated compounds. Insecticidal activity of some fluorinated carbonates has also been described.

The above solutions to inhibit aluminum corrosion do not represent an optimal solution to the problem of anodic aluminum dissolution and therefore they do not represent an optimal replacement for conventional solvents.

Summary of the Invention

In accordance with the present invention, there is provided:
1. A carbonate compound of formula (I):
(I),
wherein
R¹represents a C₃-C₂₄alkyl, a C₃-C₂₄alkoxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), or a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), and
R²represents a C₁-C₂₄alkyl, a C₁-C₂₄haloalkyl, a C₂-C₂₄alkoxyalkyl, a C₂-C₂₄alkyloyloxyalkyl, a C₃-C₂₄alkoxycarbonylalkyl, a C₁-C₂₄cyanoalkyl, a C₁-C₂₄thiocyanatoalkyl, a C₃-C₂₄trialkylsilyl, a C₄-C₂₄trialkylsilylalkyl, a C₄-C₂₄trialkylsilyloxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), or a C₆-C₂₄ω-O-silyl oligo(propylene glycol).
2. The carbonate compound of item 1, wherein R¹represents a C₃-C₂₄alkyl or a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), preferably a C₃-C₂₄alkyl.
3. The carbonate compound of item 1 or 2, wherein R²represents a C₁-C₂₄alkyl, a C₂-C₂₄alkoxyalkyl, a C₁-C₂₄cyanoalkyl, a C₄-C₂₄trialkylsilyloxyalkyl, a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), or a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), preferably a C₁-C₂₄alkyl.
4. The carbonate compound of any one of items 1 to 3, wherein the sum of the carbon atoms in R¹and R²is:
5 or more, preferably 6 or more, more preferably 7 or more, yet more preferably 8 or more, and most preferably 9 or more, and/or
24 or less, preferably 20 or less, more preferably 16 or less, yet more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less.
5. The carbonate compound of any one of items 1 to 4, wherein R²is methyl or ethyl.
6. The carbonate compound of any one of items 1 to 5, wherein R¹and/or R²is propyl, or isopropyl (2-propyl).
7. The carbonate compound of any one of items 1 to 6, wherein R¹and/or R²is butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl), or tertbutyl (2,2-dimethylethyl).
8. The carbonate compound of any one of items 1 to 7, wherein R¹and/or R²is pentyl or one of its isomers (including 2-pentyl and 3-pentyl), 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl, and 2-methyl-2-butyl).
9. The carbonate compound of any one of items 1 to 8, wherein R¹and/or R²is hexyl or one of its isomers (including 2-hexyl and 3-hexyl), 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2-ethylbutyl, and 3-ethyl-2-butyl).
10. The carbonate compound of any one of items 1 to 9, wherein R¹and/or R²is heptyl, one of its isomers, or 2-ethylhexyl.
11. The carbonate compound of any one of items 1 to 10, wherein R¹and/or R²is 2-methoxyethyl or 2-isopropoxyethyl.
12. The carbonate compound of any one of items 1 to 11, wherein R²is 2-cyanoethyl.
13. The carbonate compound of any one of items 1 to 12, wherein R²is (2-trimethylsilyloxy)ethyl.
14. The carbonate compound of any one of items 1 to 13, wherein R¹and/or R²is 2-methoxyethyl, 2-isopropoxyethyl, or 2-(2-methoxyethoxy)ethyl.
15. The carbonate compound of any one of items 1 to 14, wherein R²is 2-trimethylsilyloxyethyl.
16. The carbonate compound of any one of items 1 to 15, wherein the carbonate compound of formula (I) is didodecyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl propyl carbonate, diisopropyl carbonate, isopropyl methyl carbonate, ethyl dodecyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, diisobutyl carbonate, isobutyl methyl carbonate, dipentyl carbonate, methyl pentyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, methyl 2-pentyl carbonate, di(2-pentyl) carbonate, 2-butyl methyl carbonate, di(2-butyl) carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, isobutyl isopropyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-methoxyethyl) carbonate, 2-isopropoxyethyl methyl carbonate, di(2-isopropoxyethyl) carbonate, or di(2-(2-methoxyethoxy)ethyl) carbonate.
17. The carbonate compound of any one of items 1 to 16, wherein the compound of formula (I) is didodecyl carbonate, dibutyl carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, di(2-butyl) carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, di(2-pentyl) carbonate, ethyl dodecyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-isopropoxyethyl) carbonate, or diisobutyl carbonate.
18. The carbonate compound of any one of items 1 to 17, wherein the compound of formula (I) is didodecyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, ethyl dodecyl carbonate, or diisobutyl carbonate, preferably diisobutyl carbonate.
19. A non-aqueous electrolyte comprising as a solvent the carbonate compound of formula (I) as defined in any one of items 1 to 18 or a mixture thereof.
20. The non-aqueous electrolyte of item 19 further comprising a conducting salt dissolved in said solvent.
21. The non-aqueous electrolyte of item 20, wherein the conducting salt is LiClO₄; LiP(CN)_αF_6-α, where α is an integer from 0 to 6, preferably LiPF₆; LiB(CN)_βF₄ _- _β, where β is an integer from 0 to 4, preferably LiBF₄; LiP(C_nF_2n+1)_γF_6-γ, where n is an integer from 1 to 20, and γ is an integer from 1 to 6; LiB(C_nF_2n+1)_δF_4-δ, where n is an integer from 1 to 20, and δ is an integer from 1 to 4; Li₂Si(C_nF_2n+1)_εF_6-ε, where n is an integer from 1 to 20, and ε is an integer from 0 to 6; lithium bisoxalato borate; lithium difluorooxalatoborate; or compounds represented by the following general formulas:

R³represents: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen, or an organic cation; and
R⁴, R⁵, R⁶, R⁷, R⁸represent: cyano, fluorine, chlorine, branched or linear alkyl radical with 1-24 carbon atoms, perfluorinated linear alkyl radical with 1-24 carbon atoms atoms, aryl or heteroaryl radical, or perfluorinated aryl or heterosaryl radical;
or their derivatives.
22. The non-aqueous electrolyte of item 20 or 21, wherein the conducting salt is a lithium salt, preferably a lithium sulfonyl amide salt.
23. The non-aqueous electrolyte of item 22, wherein the lithium sulfonyl amide salt is lithium bis(fluorosulfonyl)amide (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI), or lithium N-flurosulfonyl-trifluoromethanesulfonyl amide (LiFTFSI).
24. The non-aqueous electrolyte of item 23, wherein the conducting salt is LiFSI.
25. The non-aqueous electrolyte of item 20, wherein the conducting salt is a sodium, a potassium, calcium, aluminum, or a magnesium salt.
26. The non-aqueous electrolyte of any one of items 20 to 25, wherein the concentration of the conducting salt is at least about 0.05 M, at least about 0.1 M, at least about 0.5 M, or at least about 1 M, and/or at most about 3 M, at most about 2 M, at most about 1.5 M, or at most about 1 M.
27. The non-aqueous electrolyte of item 26, wherein the concentration of the conducting salt is 1 M.
28. The non-aqueous electrolyte of any one of items 19 to 27, wherein the electrolyte comprises one or more additives.
29. The non-aqueous electrolyte of item 28, wherein each of the one or more additives is an additive that improves solid electrolyte interphase and cycling properties; an unsaturated carbonate that improves stability at high and low voltages, and/or an organic solvent that diminishes viscosity and increases conductivity.
30. The non-aqueous electrolyte of item 29, wherein the one or more additives is ethylene carbonate (EC) and/or fluoroethylene carbonate (FEC).
31. The non-aqueous electrolyte of item 29 or 30, wherein the total amount of additives that improve solid electrolyte interphase and cycling properties and unsaturated carbonates represents at least about 0.1% w/w, at least 1% w/w, at least about 2% w/w, at least about 5% w/w, or at least about 7% w/w, and/or at most about 20% w/w, at most about 15% w/w, at most about 10% w/w, or at most about 7% w/w of the electrolyte.
32. The non-aqueous electrolyte of any one of items 29 to 31, wherein the one or more additives are ethylene carbonate (EC) and/or dimethyl carbonate (DEC).
33. The non-aqueous electrolyte of any one of items 29 to 32, wherein the amount of organic solvents that diminish viscosity and increase conductivity represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 7% v/v, and/or at most about 80% v/v, at most about 50% v/v, at most about 20% v/v, at most about 15% v/v, at most about 10% v/v, or at most about 7% v/v of the total volume of the electrolyte.
34. The non-aqueous electrolyte of any one of items 19 to 32, wherein the only solvent in the electrolyte is the carbonate compound of formula (I).
35. The non-aqueous electrolyte of any one of items item 28 to 34, wherein the one or more additives are fluoroethylene carbonate (FEC), ethylene carbonate (EC), diethyl carbonate (DEC), or a mixture thereof.
36. The non-aqueous electrolyte of any one of items 28 to 35, wherein the one or more additives are FEC, preferably about 2 w/w% of FEC, alone or together with:
- up to 5% w/w of EC,
- up to 10% w/w of EC,
- up to 15% w/w of EC,
- up to 20% w/w of EC,
- up to 30% w/w of EC,
- up to 20% w/w of a mixture of EC and DEC,
- up to 25% w/w of a mixture of EC and DEC,
- up to 30% w/w of a mixture of EC and DEC,
- up to 50% w/w of a mixture of EC and DEC,
- up to 70% w/w of a mixture of EC and DEC, or
- up to 75% w/w of a mixture of EC and DEC.
37. The non-aqueous electrolyte of any one of items 19 to 36, wherein the electrolyte comprises one or more corrosion inhibitors, such as LiPF6, lithium cyano fluorophosphates, lithium fluoro oxalatophosphates, LiDFOB, LiBF4, lithium fluro cyanoborates, and LiBOB.
38. The non-aqueous electrolyte of any one of items 19 to 37, wherein the total amount of corrosion inhibitors represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 10% v/v, and/or at most about 95% v/v, at most about 75% v/v, at most about 50% v/v, at most about 35% v/v, at most about 25% v/v, or at most about 15% v/v of the total weight of the electrolyte.
39. The non-aqueous electrolyte of any one of items 19 to 36, wherein the electrolyte is free of corrosion inhibitors.
40. The non-aqueous electrolyte of any one of items 19 to 39, wherein, when the electrolyte is free of corrosion inhibitors, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 50 % v/v, based on the total volume of the electrolyte, preferably at least about 60% v/v, more preferably at least about 70% v/v, even more preferably at least about 75% v/v, and most preferably at least about 80%, based on the volume of the electrolyte.
41. The non-aqueous electrolyte of any one of items 19 to 38, wherein, when the electrolyte comprises one or more corrosion inhibitors, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 10% v/v, based on the total volume of the electrolyte, preferably at least about 15% v/v, more preferably at least about 20% v/v, even more preferably at least about 25% v/v, and most preferably at least about 30%, based on the volume of the electrolyte.
42. An electrochemical device comprising the non-aqueous electrolyte of any one of items 19 to 41.
43. The electrochemical device of item 42, wherein the electrochemical device is a battery (preferably a lithium or lithium-ion battery), a capacitor, an electrochromic device, a sensor, or a metal–air electrochemical cell.
44. The electrochemical device of item 42 or 43, wherein the electrochemical device is a battery.
45. The electrochemical device of item 44, wherein the battery comprises (a) at least one positive electrode, (b) at least one negative electrode, (c) a separator membrane, and (d) the non-aqueous electrolyte of any one of items 19 to 41.
46. The electrochemical device of item 45, wherein the electrochemical device is a lithium, a lithium-ion battery or a lithium-air battery, preferably a lithium-ion battery.
47. The electrochemical device of item 45 or 46, wherein the negative electrode is made of lithium metal or graphite.
48. The electrochemical device of any one of items 45 to 47, wherein the cathode is an LMN cathode or an LCO cathode.
49. The electrochemical device of any one of items 45 to 47, wherein the cathode is made of lithiated oxides of transition metals such as LNO (LiNiO₂), LMO (LiMn₂O₄), LiCo_xNi_1-xO₂wherein x is from 0.1 to 0.9, LMC (LiMnCoO₂), LiCu_xMn_2−xO₄, NMC (LiNi_xMn_yCo_zO₂), NCA (LiNi_xCo_yAl_zO₂), lithium compounds with transition metals and complex anions, LFP (LiFePO₄), LNP (LiNiPO₄), LMP (LiMnPO₄), LCP (LiCoPO₄), Li₂FCoPO₄; LiCo_qFe_xNi_yMn_zPO₄, and Li₂MnSiO₄.
50. The electrochemical device of item 45, wherein the electrochemical device is a sodium battery, a sodium-ion battery, a sodium-air battery, a potassium battery, a potassium-ion battery, a potassium-air battery, a magnesium battery, a magnesium-ion battery, a magnesium-air battery, an aluminum battery, an aluminum ion battery, or an aluminum-air battery.
51. A solvent for a non-aqueous electrolyte for an electrochemical device, the solvent comprising a carbonate compound of formula (I) as defined in any one of items 1 to 18.
52. A carbonate compound of formula (I) as defined in any one of items 1 to 18 for use as a solvent in a non-aqueous electrolyte in an electrochemical device.
53. Use of a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in a non-aqueous electrolyte for an electrochemical device.
54. A non-aqueous electrolyte for an electrochemical device, the electrolyte comprising a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent.
55. Use of a non-aqueous electrolyte comprising a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent, in an electrochemical device.
56. A method of manufacturing a non-aqueous electrolyte for an electrochemical device, the method comprising using a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in the electrolyte.
57. A method of suppressing anodic dissolution of aluminum in an aluminum current collector in an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in the electrolyte.
58. A method of enabling the use of sulfonylamide salts in high voltage electrochemical devices, the method comprising using a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in the electrolyte.
59. A method of increasing the maximum operation voltage of an electrochemical device containing a non-aqueous electrolyte, said electrolyte preferably comprising sulfonylamide salts, the method comprising using a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in the electrolyte.
60. A method of broadening the operating temperature range of an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent in the electrolyte.
61. An electrochemical device comprising a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent.
62. A method of manufacturing an electrochemical device, the method comprising using a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as defined in any one of items 1 to 18 as a solvent.

Brief Description of the Drawings

In the appended drawings:

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in a conventional electrolyte comprising LIFSI and EC/DEC;

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in a conventional electrolyte comprising LIFTFSI and EC/DEC;

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in a conventional electrolyte comprising LITFSI and EC/DEC;

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in an electrolyte according to an embodiment of the present invention comprising LIFSI and diisobutyl carbonate;

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in an electrolyte according to an embodiment of the present invention comprising LIFTFSI and diisobutyl carbonate;

shows the chronoamperometry of an aluminum current collector versus Li metal at potentials increasing from 4 to 5.5 V by 0.1 V steps, 1h at each step, in an electrolyte according to an embodiment of the present invention comprising LITFSI and diisobutyl carbonate;

shows the charge/discharge curves of an LCO cathode versus Li metal in a conventional electrolyte comprising LIFSI and EC/DEC;

shows the charge/discharge curves of an LCO cathode versus Li metal in an electrolyte according to an embodiment of the present invention comprising LIFSI and diisobutyl carbonate;

shows the charge/discharge curves of an LCO cathode versus Li metal in an electrolyte according to an embodiment of the present invention comprising LIFSI and diisobutyl carbonate + EC;

shows the charge/discharge curves of an LMN cathode versus Li metal in a conventional electrolyte comprising LIFSI and EC/DEC;

shows the charge/discharge curves of an LMN cathode versus Li metal in an electrolyte according to an embodiment of the present invention comprising LIFSI and diisobutyl carbonate;

shows the discharge capacity of three cells versus cycle number, the first cell using LiFSI in diisobutyl carbonate, the second cell using LiFSI in 90% diisobutyl carbonate/10 % EC, and the third cell using a conventional electrolyte of 1 M LiPF6 in EC/DEC (3:7 vol).
Detailed Description of the Invention

An objective of the present invention is to provide a solvent for a non-aqueous electrolyte for an electrochemical device, the solvent comprising a carbonate compound of formula (I).

There is also provided a carbonate compound of formula (I) for use as a solvent in a non-aqueous electrolyte in an electrochemical device

There is also provided the use of a carbonate compound of formula (I) as a solvent in a non-aqueous electrolyte for an electrochemical device.

A further objective of the present invention is to provide a non-aqueous electrolyte for an electrochemical device, the electrolyte comprising a carbonate compound of formula (I) as a solvent.

There is also provided the use of a non-aqueous electrolyte comprising a carbonate compound of formula (I) as a solvent, in an electrochemical device.

There is also provided a method of manufacturing a non-aqueous electrolyte for an electrochemical device, the method comprising using a carbonate compound of formula (I) as a solvent in the electrolyte.

There is also provided a method of suppressing anodic dissolution of aluminum in an aluminum current collector in an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as a solvent in the electrolyte.

There is also provided a method of enabling the use of sulfonylamide salts in high voltage electrochemical devices, the method comprising using a carbonate compound of formula (I) as a solvent in the electrolyte.

There is also provided a method of increasing the maximum operation voltage of an electrochemical device containing a non-aqueous electrolyte, said electrolyte preferably comprising sulfonylamide salts, the method comprising using a carbonate compound of formula (I) as a solvent in the electrolyte.

There is also provided a method of broadening the operating temperature range of an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as a solvent in the electrolyte.

Another objective of the present invention is to provide an electrochemical device comprising a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as a solvent.

There is also provided a method of manufacturing an electrochemical device, the method comprising using a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as a solvent.

In all of the above, the electrochemical device preferably comprises an aluminum current collector.

In all of the above, the electrochemical device is preferably a lithium or lithium-ion battery.

In all of the above, the electrolyte preferably comprises a lithium sulfonylamide salt as a conducting salt.

More details on the carbonate compound of formula (I) as well as the other components of the non-aqueous electrolyte and the electrochemical device will be provided in the following sections.

The present inventors have found that carbonate compounds of formula (I) can advantageously be used as solvents in non-aqueous electrolytes in electrochemical devices because they are characterized by their low corrosiveness against aluminum, for example the aluminum contained in aluminum current collectors, even at voltages higher than 4.2 V, even in electrolytes containing lithium sulfonylamide salts. Utilization of these lithium sulfonylamide salts with conventional solvents in said high voltage systems is typically not possible as anodic dissolution of aluminum becomes the preferred electrochemical reaction and the vast majority of the charge is consumed for this detrimental corrosion process.

While the low corrosiveness of the carbonate compounds of formula (I) is especially advantageous when lithium sulfonylamide salts are the main conducting salt, the person skilled in the art would recognize the potential of these solvents for achieving high voltage lithium and lithium ion batteries in connection with other conducting salts. The skilled person would also understand that when the electrolyte is to be used in a different type of electrochemical device, such as sodium, potassium, calcium, aluminum and magnesium-based batteries, other salts can be dissolved in the solvents, for example sodium, potassium, calcium, aluminum and magnesium salts.

Indeed, the carbonate compounds of formula (I) are characterized by their capacity to suppress anodic dissolution of aluminum (e.g. an aluminum current collector or any other aluminum member in the electrochemical device) when used as solvents in electrolytes in electrochemical devices, even at potentials higher than 4.2 V vs a Li metal anode in a lithium or lithium-ion battery. For clarity, unless specified otherwise, all potentials in the present application are referenced to a Li metal anode. Anodic dissolution of the aluminum current collector is defined as the dissolution of an aluminum current collector at a certain externally forced potential (the critical potential), which is higher than the open circuit potential. At the critical potential, the components of the electrolyte react with the surface of the collector and form soluble compounds, which in turn dissolve in the electrolyte and cause dissolution of the aluminum i.e. quasi corrosion. Significant dissolution of the aluminum can lead to malfunctioning of the battery system, if its operating voltage surpasses the critical potential. Accordingly, suppressing anodic dissolution enables safer and more powerful battery technologies, especially lithium-ion batteries, as well as capacitors, electrochromic devices, sensors, metal–air electrochemical cells, fuel cells and the like.

This low corrosiveness of the carbonate compounds of formula (I) also enables the manufacture of electrolyte/electrochemical devices with extended operation voltages (in particular, operation voltages over 4.2 V), even for electrolytes containing lithium sulfonylamide salts and electrochemical devices containing aluminum current collectors, including lithium-ion batteries. This allows for the preparation of non-aqueous electrolytes containing lithium sulfonylamide salts without any corrosion inhibitors (while still maintaining said low corrosiveness against aluminum current collectors at voltages higher than 4.2 V).

Furthermore, when compared to conventional carbonate solvents (e.g. ethylene carbonate (EC), diethyl carbonate (DEC), and the like), the carbonate compounds of formula (I) have a wider operating temperature range, especially when used in lithium-ion batteries. Indeed, the temperature range in which the carbonate compounds of formula (I) are liquid (without crystallization) tends to be wider than that of these conventional carbonate solvents. For example, in embodiments, the carbonate compounds of formula (I) can have a melting point well below −10° C, and, in some cases, do not even have a melting point and thus stay liquid, without crystallizing, until they reach their glass transition point. Further, the melting point of the carbonate compounds tends to decrease with growing molecular mass to a certain point.

Further, the carbonate compounds of formula (I) have a higher boiling point than conventional carbonate solvents. For example, the boiling points of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate are 90, 126, 168 and 207 °C, respectively. This indicates that electrolytes prepared from higher carbonates can be used at higher temperatures without the risk of rapid evaporation. These higher boiling points translates into improved safety properties for the electrochemical devices containing the electrolyte using the carbonate compounds of formula (I) as solvent.

Finally, the carbonate compounds of formula (I) are a very green, that is environmentally benign, group of solvents.

The methods of the present invention are advantageous in that they produce the above-defined carbonate solvents, electrolytes, and electrochemical devices.

The inventors thus provide herein a novel solvent for a non-aqueous electrolyte for an electrochemical device, a non-aqueous electrolyte containing this solvent, and an electrochemical device containing such an electrolyte.
Carbonate compound of formula (I)

The carbonate compound of formula (I) is:
(I),
wherein
R¹represents a C₃-C₂₄alkyl, a C₃-C₂₄alkoxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), or a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), and
R²represents a C₁-C₂₄alkyl, a C₁-C₂₄haloalkyl, a C₂-C₂₄alkoxyalkyl, a C₂-C₂₄alkyloyloxyalkyl, a C₃-C₂₄alkoxycarbonylalkyl, a C₁-C₂₄cyanoalkyl, a C₁-C₂₄thiocyanatoalkyl, a C₃-C₂₄trialkylsilyl, a C₄-C₂₄trialkylsilylalkyl, a C₄-C₂₄trialkylsilyloxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), or a C₆-C₂₄ω-O-silyl oligo(propylene glycol).

In more preferred embodiments, R¹represents a C₃-C₂₄alkyl or a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol). In more preferred embodiments, R¹represents a C₃-C₂₄alkyl.

In more preferred embodiments, R²represents a C₁-C₂₄alkyl, a C₂-C₂₄alkoxyalkyl, a C₁-C₂₄cyanoalkyl, a C₄-C₂₄trialkylsilyloxyalkyl, a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), or a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol). In most preferred embodiments, R²represents a C₁-C₂₄alkyl.

Given that R¹and R²as defined above contain at least 3 and 1 carbon atoms, respectively, the sum of the carbon atoms in R¹and R²is at least 4. In preferred embodiments, the sum of the carbon atoms in R¹and R²is:
5 or more, preferably 6 or more, more preferably 7 or more, yet more preferably 8 or more, and most preferably 9 or more, and/or
24 or less, preferably 20 or less, more preferably 16 or less, yet more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less.

Each of the alkyl and substituted alkyl in R¹and R²are linear or branched.

Herein, “alkyl” has its usual meaning in the art. Specifically, it is a monovalent saturated aliphatic hydrocarbon radical of general formula -C_nH_2n+1.

Non-limiting examples of C₃-C₂₄alkyl in R¹include propyl, isopropyl (2-propyl), butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl), tertbutyl (2,2-dimethylethyl), 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl, 2-methyl-2-butyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2-ethylbutyl, 3-ethyl-2-butyl, 2-ethylhexyl, pentyl and its isomers (including 2-pentyl and 3-pentyl), hexyl and its isomers (including 2-hexyl and 3-hexyl), heptyl and its isomers, octyl and its isomers, nonyl and its isomers, decyl and its isomers, undecyl and its isomers, and dodecyl and its isomers. In preferred embodiments, the C₃-C₂₄alkyl in R¹is a C₃-C₁₈alkyl, preferably a C₃-C₁₂alkyl, preferably a C₃-C₁₁alkyl, preferably a C₃-C₁₀alkyl, preferably a C₃-C₉alkyl, more preferably a C₃-C₈alkyl, even more preferably a C₃-C₇alkyl (yet more preferably a C₄-C₇alkyl), yet more preferably a C₃-C₆alkyl (yet more preferably a C₄-C₆alkyl), more preferably a C₃-C₅alkyl, and most preferably a C₄-C₅alkyl.

Non-limiting examples of C₁-C₂₄alkyl chain in R²include the C₃-C₂₄alkyls listed above with regard to R¹, as well as methyl and ethyl. In preferred embodiments, R²is a C₁-C₁₈alkyl, preferably a C₁-C₁₂alkyl, a C₁-C₉alkyl, a C₁-C₈alkyl, a C₁-C₇alkyl, a C₂-C₇alkyl, a C₃-C₇alkyl (preferably a C₄-C₇alkyl), a C₃-C₆alkyl (preferably a C₄-C₆alkyl), a C₃-C₅alkyl, and most preferably a C₄-C₅alkyl.

In preferred embodiments, both R¹and R²are alkyl groups. In more preferred embodiments, R¹and R²are the same alkyl groups. In alternative preferred embodiments, R¹and R²are different alkyl groups.

Preferred C₃alkyls in R¹and R²include propyl, and isopropyl (2-propyl).

Preferred C₄alkyls in R¹and R²include butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl), and tertbutyl (2,2-dimethylethyl).

Preferred C₅alkyls in R¹and R²include pentyl and its isomers (including 2-pentyl and 3-pentyl), 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl, and 2-methyl-2-butyl.

Preferred C₆alkyls in R¹and R²include hexyl and its isomers (including 2-hexyl and 3-hexyl), 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2-ethylbutyl, and 3-ethyl-2-butyl.

Preferred C₇alkyls in R¹and R²include heptyl and its isomers.

Preferred C₈alkyls in R¹and R²include 2-ethylhexyl.

Herein, a “haloalkyl” refers to an alkyl group in which one or more (or even all) of the hydrogen atoms are each replaced by a halogen atom, wherein the halogen atoms are the same or different from one another (when more than one halogen atoms are present). Halogen atoms include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Preferably, the halogen atom is fluorine. Non-limiting examples of C₁-C₂₄haloalkyls in R²include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, 2,2,2-trifluoroethyl, and 1,1,1,3,3,3-hexafluoro-2-propyl.

Herein, an “alkoxyalkyl” refers to an alkyl group in which one or more, preferably one, of the hydrogen atoms are each replaced by an alkoxy group, wherein the alkoxy groups are the same or different from one another (when more than one alkoxy groups are present). In preferred embodiments, the alkoxyalkyl comprises only one alkoxy group. An alkoxy group is a radical of formula -O-alkyl, this alkyl being linear or branched, preferably linear. A C₂-C₂₄alkoxyalkyl is alkoxyalkyl radical, wherein the sum of the number of carbon atoms contained in the alkyl and alkoxy groups is between 2 and 24. In preferred embodiments, the alkoxyalkyl is a (C₁-C₂)alkoxy(C₂-C₆)alkyl. Non-limiting examples of alkoxyalkyls in R²or R¹include 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 5-methoxypentyl, 6-methoxyhexyl, and 2-isopropoxyethyl. In preferred embodiments, the alkoxyalkyl is 2-methoxyethyl or 2-isopropoxyethyl.

Herein, an “alkyloyloxyalkyl” refers to an alkyl group in which one or more, preferably one, of the hydrogen atoms are each replaced by an alkyloyloxy group, wherein the alkyloyloxy groups are the same or different when more than one alkyloyloxy groups are present). In preferred embodiments, the alkyloyloxyalkyl comprises only one alkyloyloxy group. An alkyloyloxy group is a radical of formula -O-C(=O)-alkyl, this alkyl being linear or branched. A C₂-C₂₄alkyloyloxyalkyl is alkyloyloxyalkyl wherein the sum of the number of carbon atoms contained in the alkyl and alkyloyloxy groups is between 2 and 24. Non-limiting examples of C₂-C₂₄alkyloyloxyalkyl in R²include 2-acetoxyethyl, 3-acetoxypropyl, 2-acetoxypropyl, and 4-acetoxybutyl.

Herein, an “alkoxycarbonylalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are each replaced by an alkoxycarbonyl group, wherein the alkoxycarbonyl groups are the same or different from one another (when more than one alkoxycarbonyl groups are present). In preferred embodiments, the alkoxycarbonylalkyl comprises only one alkoxycarbonyl group. An alkoxycarbonyl group is a radical of formula -C(=O)-O-alkyl, this alkyl being linear or branched. A C₂-C₂₄alkoxycarbonyl is an alkoxycarbonyl wherein the sum of the number of carbon atoms contained in the alkyl and alkoxycarbonyl groups is between 3 and 24. Non-limiting examples of C₃-C₂₄alkoxycarbonylalkyl in R²include 2-ethoxycarbonylethyl and 3-methoxycarbonylpropyl.

Herein, a “cyanoalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are each replaced by a cyano (-C≡N) group. In preferred embodiments, the cyanoalkyl comprises only one cyano group. In preferred embodiments, the cyanoalkyl is a C₁-C₅cyanoalkyl. Non-limiting examples of C₁-C₂₄cyanoalkyls in R²include cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, and 5-cyanopentyl. In preferred embodiments, the C₁-C₂₄cyanoalkyl in R²is 2-cyanoethyl.

Herein, a “thiocyanatoalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are each replaced by a thiocyanato (-S-C≡N) group. In preferred embodiments, the thiocyanatoalkyl comprises only one thiocyanato group. Non-limiting examples of C₁-C₂₄thiocyanatoalkyls in R²include thiocyanatomethyl, 2-thiocyanatoethyl, 3-thiocyanatopropyl, 4-thiocyanatobutyl, 5-thiocyanatopentyl, and 6-thiocyanatohexyl.

Herein, a “trialkylsilyl” refers to a radical of formula (alkyl)₃-Si-, wherein the alkyl groups are the same or different and are linear or branched. A C₃-C₂₄trialkylsilyl is a trialkylsilyl wherein the sum of the number of carbon atoms contained in all of the alkyl groups is between 3 and 24. In preferred embodiments, each of the alkyl groups in the trialkylsilyl is a C₁-C₄alkyl group. In preferred embodiments, the three alkyl groups are the same. Non-limiting examples of C₃-C₂₄trialkylsilyls in R²include trimethylsilyl, ethyldimethylsilyl, diethylmethylsilyl, triethylsilyl, dimethylpropylsilyl, dimethylisopropylsilyl, triisopropylsilyl, butyldimethylsilyl, and tertbutyldimethylsilyl.

Herein, a “trialkylsilylalkyl” is an alkyl group in which one or more of the hydrogen atoms are each replaced by a trialkylsilyl group, wherein the trialkylsilyl are as defined above and are the same or different from one another (when more than one trialkylsilyl groups are present). In a C₄-C₂₄trialkylsilylalkyl, the sum of the number of carbon atoms contained in all four of the alkyl groups is between 4 and 24. Preferably, the trialkylsilylalkyl comprises only one trialkylsilyl group. In preferred embodiments, the C₄-C₂₄trialkylsilylalkyl is a trialkylsilylalkyl(C₁-C₄)alkyl, preferably a trialkylsilylalkyl(C₂-C₄)alkyl. In preferred embodiments, the three alkyl groups attached to the Si atom are methyl groups. Non-limiting examples of C₄-C₂₄trialkylsilylalkyl in R²include trimethylsilylethyl, 2-trimethylsilyethyl, 3-trimethylsilylpropyl and 4-trimethylsilylbutyl.

Herein, a “trialkylsilyloxyalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are each replaced by a trialkylsilyloxy group, wherein the trialkylsilyloxy groups are the same or different from one another (when more than one trialkylsilyloxy groups are present). Preferably, the trialkylsilyloxyalkyl comprises only one trialkylsilyloxy group. Herein, a “trialkylsilyloxy” is a radical of formula (alkyl)₃-Si-O-, wherein the alkyl groups are the same or different from one another and are linear or branched. In a C₄-C₂₄trialkylsilyloxyalkyl, the sum of the number of carbon atoms contained in all four of the alkyl groups is between 4 and 24. In preferred embodiments, the C₄-C₂₄trialkylsilyloxyalkyl is a trialkylsilyloxy(C₃-C₄)alkyl. In preferred embodiments, the three alkyl groups attached to the Si atom are methyl groups. Non-limiting examples of C₄-C₂₄trialkylsilyloxyalkyl in R²include (2-trimethylsilyloxy)ethyl, 3-trimethylsilyloxypropyl and 4-trimethylsilyloxybutyl. In preferred embodiments, the C₄-C₂₄trialkylsilyloxyalkyl in R²is (2-trimethylsilyloxy)ethyl.

Herein an ω-O-alkyl oligo(ethylene glycol) is a radical of formula -(CH₂-CH₂-O-)_n-alkyl, wherein n is 1 or more. In a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), the sum of the number of carbon atoms contained in the alkyl and the (CH₂-CH₂-O-)repeating motif(s) is between 3 and 24. In preferred embodiments, n is an integer from 1 to 5. In preferred embodiments, the alkyl group is a C₁-C₄alkyl. Non-limiting examples of ω-O-alkyl oligo(ethylene glycol) in R²or R¹include 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butyloxyethyl, 2-(2-methoxyethoxy)ethyl, 2-(2-butoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethyl, 2-[2-(2-methoxyethoxy)ethoxy]ethyl, 2-[2-(2-ethoxyethoxy)ethoxy]ethyl, 2,5,8,11-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 2,5,8,11,14-pentaoxahexadecyl, or 3,6,9,12,15-pentaoxaheptadecyl. In preferred embodiments, the ω-O-alkyl oligo(ethylene glycol) of R²or R¹is 2-methoxyethyl, 2-isopropoxyethyl, or 2-(2-methoxyethoxy)ethyl.

Herein an ω-O-alkyl oligo(propylene glycol) is a radical of formula -(CH₂-CH₂-CH₂-O-)_n-alkyl, wherein n is 1 or more. In a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), the sum of the number of carbon atoms contained in the alkyl and the (CH₂-CH₂-CH₂-O-)repeating motif(s) is between 4 and 24. In preferred embodiments, n is 1. In preferred embodiments, the alkyl group is a C₁-C₄alkyl. Non-limiting examples of ω-O-alkyl oligo(propylene glycol) in R²or R¹include 2-methoxypropyl, 2-ethoxypropyl, 1-methoxy-2-propyl, 1-ethoxy-2-propyl, 1-propoxy-2-propyl, 1-isopropoxy-2-propyl, and 1-butoxy-2-propyl.

Herein an ω-O-silyl oligo(ethylene glycol) is a radical of formula -(CH₂-CH₂-O-)_n-Si-(alkyl)₃, wherein the alkyl groups are the same or different and are linear or branched and wherein n is 1 or more. In a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), the sum of the number of carbon atoms contained in the alkyl groups and the (CH₂-CH₂-O-)repeating motif(s) is between 5 and 24. In preferred embodiments, n is an integer from 1 to 5. In preferred embodiments, the three alkyl groups (attached to the Si atom) are methyl groups. Non-limiting examples of ω-O-silyl oligo(ethylene glycol) in R²include 2-trimethylsilyloxyethyl, 2-(2-trimethylsilyloxyethoxy)ethyl, 2-[2-(2-trimethylsilyloxyethoxy)-ethoxy]ethyl, 2-{2-[2-(2-trimethylsilyloxyethoxy)ethoxy]ethoxy}ethyl, and 2-(2-{2-[2-(2-trimethylsilyloxyethoxy)ethoxy]ethoxy}ethoxy)ethyl. In preferred embodiments, the ω-O-silyl oligo(ethylene glycol) of R²is 2-trimethylsilyloxyethyl.

Herein an ω-O-silyl oligo(propylene glycol) is a radical of formula -(CH₂-CH₂-CH₂-O-)_n-Si-(alkyl)₃, wherein the alkyl groups are the same or different and are linear or branched and wherein n is 1 or more. In a C₆-C₂₄ω-O-silyl oligo(ethylene glycol), the sum of the number of carbon atoms contained in the alkyl groups and the (CH₂-CH₂-CH₂-O-)repeating motif(s) is between 6 and 24. In preferred embodiments, n is 1. In preferred embodiments, the three alkyl groups (attached to the Si atom) are methyl groups. Non-limiting examples of ω-O-silyl oligo(propylene glycol) in R²include 2-trimethylsilyloxypropyl, and 1-trimethylsilyloxy-2-propyl.

Preferably, the carbonate compound of formula (I) is: isopropyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, dipropyl carbonate, isopropyl propyl carbonate, diisopropyl carbonate, butyl methyl carbonate, butyl ethyl carbonate, butyl propyl carbonate, dibutyl carbonate, butyl isopropyl carbonate, 2-butyl methyl carbonate, 2-butyl ethyl carbonate, 2-butyl propyl carbonate, di(2-butyl) carbonate, 2-butyl isopropyl carbonate, isobutyl methyl carbonate, isobutyl ethyl carbonate, isobutyl propyl carbonate, diisobutyl carbonate, isobutyl isopropyl carbonate, 2-butyl isobutyl carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, methyl pentyl carbonate, ethyl pentyl carbonate, pentyl propyl carbonate, butyl pentyl carbonate, dipentyl carbonate, isopropyl pentyl carbonate, 2-butyl pentyl carbonate, isobutyl pentyl carbonate, methyl 2-pentyl carbonate, ethyl 2-pentyl carbonate, 2-pentyl propyl carbonate, butyl 2-pentyl carbonate, di(2-pentyl) carbonate, isopropyl 2-pentyl carbonate, 2-butyl 2-pentyl carbonate, isobutyl 2-pentyl carbonate, methyl 3-pentyl carbonate, ethyl 3-pentyl carbonate, 3-pentyl propyl carbonate, butyl 3-pentyl carbonate, di(3-pentyl) carbonate, isopropyl 3-pentyl carbonate, 2-butyl 3-pentyl carbonate, isobutyl 3-pentyl carbonate, pentyl 2-pentyl carbonate, pentyl 3-pentyl carbonate, 2-pentyl 3-pentyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, propyl hexyl carbonate, butyl hexyl carbonate, pentyl hexyl carbonate, dihexyl carbonate, isopropyl hexyl carbonate, isobutyl hexyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, didodecyl carbonate, ethyl dodecyl carbonate, cyanomethyl propyl carbonate, butyl cyanomethyl carbonate, cyanomethyl isopropyl carbonate, 2-butyl cyanomethyl carbonate, isobutyl cyanomethyl carbonate, tertbutyl cyanomethyl carbonate, cyanomethyl pentyl carbonate, cyanomethyl 2-pentyl carbonate, cyanomethyl 3-pentyl carbonate, cyanomethyl hexyl carbonate, cyanomethyl heptyl carbonate, cyanomethyl octyl carbonate, cyanomethyl nonyl carbonate, cyanomethyl decyl carbonate, cyanomethyl undecyl carbonate, cyanomethyl dodecyl carbonate, cyanomethyl 2-ethylhexyl carbonate, 2-cyanoethyl propyl carbonate, butyl 2-cyanoethyl carbonate, 2-cyanoethyl isopropyl carbonate, 2-butyl 2-cyanoethyl carbonate, isobutyl 2-cyanoethyl carbonate, tertbutyl 2-cyanoethyl carbonate, 2-cyanoethyl pentyl carbonate, 2-cyanoethyl 2-pentyl carbonate, 2-cyanoethyl 3-pentyl carbonate, 2-cyanoethyl hexyl carbonate, 2-cyanoethyl heptyl carbonate, 2-cyanoethyl octyl carbonate, 2-cyanoethyl nonyl carbonate, 2-cyanoethyl decyl carbonate, 2-cyanoethyl undecyl carbonate, 2-cyanoethyl dodecyl carbonate, 2-cyanoethyl 2-ethylhexyl carbonate, 3-cyanopropyl propyl carbonate, butyl 3-cyanopropyl carbonate, 3-cyanopropyl isopropyl carbonate, 2-butyl 3-cyanopropyl carbonate, isobutyl 3-cyanopropyl carbonate, tertbutyl 3-cyanopropyl carbonate, 3-cyanopropyl pentyl carbonate, 3-cyanopropyl 2-pentyl carbonate, 3-cyanopropyl 3-pentyl carbonate, 3-cyanopropyl hexyl carbonate, 3-cyanopropyl heptyl carbonate, 3-cyanopropyl octyl carbonate, 3-cyanopropyl nonyl carbonate, 3-cyanopropyl decyl carbonate, 3-cyanopropyl undecyl carbonate, 3-cyanopropyl dodecyl carbonate, 3-cyanopropyl 2-ethylhexyl carbonate, 4-cyanobutyl propyl carbonate, butyl 4-cyanobutyl carbonate, 4-cyanobutyl isopropyl carbonate, 2-butyl 4-cyanobutyl carbonate, isobutyl 4-cyanobutyl carbonate, tertbutyl 4-cyanobutyl carbonate, 4-cyanobutyl pentyl carbonate, 4-cyanobutyl 2-pentyl carbonate, 4-cyanobutyl 3-pentyl carbonate, 4-cyanobutyl hexyl carbonate, 4-cyanobutyl heptyl carbonate, 4-cyanobutyl octyl carbonate, 4-cyanobutyl nonyl carbonate, 4-cyanobutyl decyl carbonate, 4-cyanobutyl undecyl carbonate, 4-cyanobutyl dodecyl carbonate, 4-cyanobutyl 2-ethylhexyl carbonate, propyl trimethylsilyl carbonate, butyl trimethylsilyl carbonate, isopropyl trimethylsilyl carbonate, 2-butyl trimethylsilyl carbonate, isobutyl trimethylsilyl carbonate, tertbutyl trimethylsilyl carbonate, pentyl trimethylsilyl carbonate, 2-pentyl trimethylsilyl carbonate, 3-pentyl trimethylsilyl carbonate, hexyl trimethylsilyl carbonate, heptyl trimethylsilyl carbonate, octyl trimethylsilyl carbonate, nonyl trimethylsilyl carbonate, decyl trimethylsilyl carbonate, trimethylsilyl undecyl carbonate, dodecyl trimethylsilyl carbonate, 2-ethylhexyl trimethylsilyl carbonate, ethyldimethylsilyl propyl carbonate, butyl ethyldimethylsilyl carbonate, ethyldimethylsilyl isopropyl carbonate, 2-butyl ethyldimethylsilyl carbonate, isobutyl ethyldimethylsilyl carbonate, tertbutyl ethyldimethylsilyl carbonate, ethyldimethylsilyl pentyl carbonate, ethyldimethylsilyl 2-pentyl carbonate, ethyldimethylsilyl 3-pentyl carbonate, ethyldimethylsilyl hexyl carbonate, ethyldimethylsilyl heptyl carbonate, ethyldimethylsilyl octyl carbonate, ethyldimethylsilyl nonyl carbonate, decyl ethyldimethylsilyl carbonate, ethyldimethylsilyl undecyl carbonate, dodecyl ethyldimethylsilyl carbonate, ethyldimethylsilyl 2-ethylhexyl carbonate, diethylmethylsilyl propyl carbonate, butyl diethylmethylsilyl carbonate, diethylmethylsilyl isopropyl carbonate, 2-butyl diethylmethylsilyl carbonate, isobutyl diethylmethylsilyl carbonate, tertbutyl diethylmethylsilyl carbonate, diethylmethylsilyl pentyl carbonate, diethylmethylsilyl 2-pentyl carbonate, diethylmethylsilyl 3-pentyl carbonate, diethylmethylsilyl hexyl carbonate, diethylmethylsilyl heptyl carbonate, diethylmethylsilyl octyl carbonate, diethylmethylsilyl nonyl carbonate, decyl diethylmethylsilyl carbonate, diethylmethylsilyl undecyl carbonate, diethylmethylsilyl dodecyl carbonate, 2-ethylhexyl diethylmethylsilyl carbonate, propyl triethylsilyl carbonate, butyl triethylsilyl carbonate, isopropyl triethylsilyl carbonate, 2-butyl triethylsilyl carbonate, isobutyl triethylsilyl carbonate, tertbutyl triethylsilyl carbonate, pentyl triethylsilyl carbonate, 2-pentyl triethylsilyl carbonate, 3-pentyl triethylsilyl carbonate, hexyl triethylsilyl carbonate, heptyl triethylsilyl carbonate, octyl triethylsilyl carbonate, nonyl triethylsilyl carbonate, decyl triethylsilyl carbonate, triethylsilyl undecyl carbonate, dodecyl triethylsilyl carbonate, 2-ethylhexyl triethylsilyl carbonate, dimethylisopropylsilyl propyl carbonate, butyl dimethylisopropylsilyl carbonate, dimethylisopropylsilyl isopropyl carbonate, 2-butyl dimethylisopropylsilyl carbonate, isobutyl dimethylisopropylsilyl carbonate, tertbutyl dimethylisopropylsilyl carbonate, dimethylisopropylsilyl pentyl carbonate, dimethylisopropylsilyl 2-pentyl carbonate, dimethylisopropylsilyl 3-pentyl carbonate, dimethylisopropylsilyl hexyl carbonate, dimethylisopropylsilyl heptyl carbonate, dimethylisopropylsilyl octyl carbonate, dimethylisopropylsilyl nonyl carbonate, decyl dimethylisopropylsilyl carbonate, dimethylisopropylsilyl undecyl carbonate, dimethylisopropylsilyl dodecyl carbonate, 2-ethylhexyl dimethylisopropylsilyl carbonate, propyl triisopropylsilyl carbonate, butyl triisopropylsilyl carbonate, isopropyl triisopropylsilyl carbonate, 2-butyl triisopropylsilyl carbonate, isobutyl triisopropylsilyl carbonate, tertbutyl triisopropylsilyl carbonate, pentyl triisopropylsilyl carbonate, 2-pentyl triisopropylsilyl carbonate, 3-pentyl triisopropylsilyl carbonate, hexyl triisopropylsilyl carbonate, heptyl triisopropylsilyl carbonate, octyl triisopropylsilyl carbonate, nonyl triisopropylsilyl carbonate, decyl triisopropylsilyl carbonate, triisopropylsilyl undecyl carbonate, dodecyl triisopropylsilyl carbonate, 2-ethylhexyl triisopropylsilyl carbonate, propyl tertbutyldimethylsilyl carbonate, butyl tertbutyldimethylsilyl carbonate, isopropyl tertbutyldimethylsilyl carbonate, 2-butyl tertbutyldimethylsilyl carbonate, isobutyl tertbutyldimethylsilyl carbonate, tertbutyl tertbutyldimethylsilyl carbonate, pentyl tertbutyldimethylsilyl carbonate, 2-pentyl tertbutyldimethylsilyl carbonate, 3-pentyl tertbutyldimethylsilyl carbonate, hexyl tertbutyldimethylsilyl carbonate, heptyl tertbutyldimethylsilyl carbonate, octyl tertbutyldimethylsilyl carbonate, nonyl tertbutyldimethylsilyl carbonate, decyl tertbutyldimethylsilyl carbonate, tertbutyldimethylsilyl undecyl carbonate, dodecyl tertbutyldimethylsilyl carbonate, 2-ethylhexyl tertbutyldimethylsilyl carbonate, propyl 2-trimethylsilyethyl carbonate, butyl 2-trimethylsilyethyl carbonate, isopropyl 2-trimethylsilyethyl carbonate, 2-butyl 2-trimethylsilyethyl carbonate, isobutyl 2-trimethylsilyethyl carbonate, tertbutyl 2-trimethylsilyethyl carbonate, pentyl 2-trimethylsilyethyl carbonate, 2-pentyl 2-trimethylsilyethyl carbonate, 3-pentyl 2-trimethylsilyethyl carbonate, hexyl 2-trimethylsilyethyl carbonate, heptyl 2-trimethylsilyethyl carbonate, octyl 2-trimethylsilyethyl carbonate, nonyl 2-trimethylsilyethyl carbonate, decyl 2-trimethylsilyethyl carbonate, 2-trimethylsilyethyl undecyl carbonate, dodecyl 2-trimethylsilyethyl carbonate, 2-ethylhexyl 2-trimethylsilyethyl carbonate, 2-methoxyethyl isobutyl carbonate, or (2-trimethylsilyloxy)ethyl butyl carbonate.

In more preferred embodiments, the carbonate compound of formula (I) is didodecyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl propyl carbonate, diisopropyl carbonate, isopropyl methyl carbonate, ethyl dodecyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, diisobutyl carbonate, isobutyl methyl carbonate, dipentyl carbonate, methyl pentyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, methyl 2-pentyl carbonate, di(2-pentyl) carbonate, 2-butyl methyl carbonate, di(2-butyl) carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, isobutyl isopropyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-methoxyethyl) carbonate, 2-isopropoxyethyl methyl carbonate, di(2-isopropoxyethyl) carbonate, or di(2-(2-methoxyethoxy)ethyl) carbonate.

In more preferred embodiments, the compound of formula (I) is didodecyl carbonate, dibutyl carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, di(2-butyl) carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, di(2-pentyl) carbonate, ethyl dodecyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-isopropoxyethyl) carbonate, or diisobutyl carbonate.

In even more preferred embodiments, the compound of formula (I) is didodecyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, ethyl dodecyl carbonate, or diisobutyl carbonate.

In a most preferred embodiment, the carbonate compound of formula (I) is diisobutyl carbonate.
Non-aqueous electrolyte comprising carbonate solvent

In a second aspect of the invention, a non-aqueous electrolyte comprising as a solvent the carbonate compound of formula (I) of the previous section is provided.

In embodiments, the non-aqueous electrolytes comprise:
i. a carbonate compound of formula (I) as defined above as a solvent, and
ii. a conducting salt dissolved in said solvent.

The carbonate compound of formula (I) is as described in the previous section. Mixtures of said carbonate compounds of formula (I) may also be used.

As previous discussed, the electrolyte of the present invention can be prepared using any known technique in the art. For example, to prepare electrolytes from the carbonate solvents of the present invention, the skilled person would know that an appropriate conducting salt can be dissolved in said carbonate solvents in an appropriate concentration. Depending on the application of the electrolyte, a different salt can be chosen. For example, as described above, a lithium salt can be chosen when the electrolyte will be used in a lithium battery. However, for sodium, potassium, calcium, aluminum and magnesium based electrochemical devices, other salts can be dissolved in the solvents, for example sodium, potassium, calcium, aluminum and magnesium salts.
Conducting Salt

The choice of the conducting salt has an impact on anodic dissolution. For example, for an electrolyte containing less of the carbonate compound of formula (I) of the present invention, the addition of a passivating conducting salt will produce an electrolyte which nonetheless prevents anodic dissolution of aluminum. Some inorganic salts like LiPF₆passivate the surface of the aluminum, as they form insoluble compounds and thus do not cause anodic dissolution up to more than 5 V vs Li anodes. In contrast, some salts do not passivate aluminum, especially lower fluorinated sulfonyl amides, which cause a very strong dissolution of aluminum. As mentioned, this can lead to malfunctioning of the battery system if its operating voltage surpasses the critical potential. When such conducting salts are used, it is preferable to include more of the carbonate compound of formula (I) in the electrolyte so as to further prevent anodic dissolution.

The conducting salt can be chosen from: LiClO₄; LiP(CN)_αF_6-α, where α is an integer from 0 to 6, preferably LiPF₆; LiB(CN)_βF₄ _- _β, where β is an integer from 0 to 4, preferably LiBF₄; LiP(C_nF_2n+1)_γF_6-γ, where n is an integer from 1 to 20, and γ is an integer from 1 to 6; LiB(C_nF_2n+1)_δF_4-δ, where n is an integer from 1 to 20, and δ is an integer from 1 to 4; Li₂Si(C_nF_2n+1)_εF_6-ε, where n is an integer from 1 to 20, and ε is an integer from 0 to 6; lithium bisoxalato borate; lithium difluorooxalatoborate; and compounds represented by the following general formulas:

R³represents: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen, or an organic cation; and
R⁴, R⁵, R⁶, R⁷, R⁸represent: cyano, fluorine, chlorine, branched or linear alkyl radical with 1-24 carbon atoms, perfluorinated linear alkyl radical with 1-24 carbon atoms, aryl or heteroaryl radical, or perfluorinated aryl or heterosaryl radical;
and their derivatives.

In preferred embodiments, the conducting salt is a lithium salt. This is appropriate when, for example, the electrolyte will be used in a lithium battery. Non-limiting examples of lithium salts include lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium sulfonyl amide salts (such as lithium bis(fluorosulfonyl)amide, lithium N-flurosulfonyl-trifluoromethanesulfonyl amide (LiFTFSI), and lithium bis(trifluoromethanesulfonyl)amide) and their derivatives. In preferred embodiments, the conducting salt is a lithium sulfonyl amide salt. In preferred embodiments, the lithium sulfonyl amide salt is lithium bis(fluorosulfonyl)amide (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI), or lithium N-flurosulfonyl-trifluoromethanesulfonyl amide (LiFTFSI). In more preferred embodiments, the conducting salt is LiFSI. This is appropriate when, for example, the electrolyte is to be used in a lithium-ion battery. Indeed, an important advantage of the electrolyte of the present invention is that it enables use of lithium sulfonyl amide salts in battery systems where the charging/discharging potential of the cathode is above 4.2 V vs Li metal.

In alternative embodiments, the salt is a sodium, a potassium, calcium, aluminum, or a magnesium salt. This is appropriate when, for example, the electrolyte is to be used in a sodium, potassium, calcium, aluminum, or magnesium based electrochemical device.

The concentration of the conducting salt present in the electrolyte may vary; the skilled person would understand that the quantity of conducting salt should not severely negatively impact the efficacy of the electrolyte. The concentration of the conducting salt refers to the molarity of the conducting salt in the carbonate solvent and any other solvents (if present), disregarding the presence of additives. This can be represented by the following equation:
wherein the volume of the electrolyte is the final total volume of the carbonate compound of formula (I), the dissolved salt, and any liquid additive present.

In embodiments, the concentration of the conducting salt is at least about 0.05 M and/or at most about 3 M. In embodiments, the concentration of the conducting salt is at least about 0.05 M, at least about 0.1 M, at least about 0.5 M, or at least about 1 M, and/or at most about 3 M, at most about 2 M, at most about 1.5 M, or at most about 1 M.

In preferred embodiments, the concentration of the conducting salt is 1 M.
Additives that Improve the Electrochemical Properties of the Electrolyte

In embodiments, the electrolyte comprises one or more additives, which are used to improve the electrochemical properties of the electrolyte. Non-limiting examples of additives that improve the electrochemical properties of the electrolyte include:

additives that improve solid electrolyte interphase and cycling properties,
unsaturated carbonates that improve stability at high and low voltages, and
organic solvents that diminish viscosity and increase conductivity.

It will be understood by the skilled person that one additive can have more than one specific technical effect on the electrolyte and thus may be cited in more than one of the above lists of exemplary additives with different preferred concentration ranges according to the effect desired of the additive.

Additives that improve solid electrolyte interphase and cycling properties are preferably present in the electrolyte. Non-limiting examples of additives that improve solid electrolyte interphase and cycling properties include ethylene carbonate, vinylene carbonate, fluorovinylene carbonate, succinic anhydride, maleic anhydride, fluoroethylene carbonate, difluoroethylene carbonate, methylene-ethylene carbonate, prop-1-ene-1,3-sultone, acrylamide, fumaronitrile, and triallyl phosphate. Preferred additives that improve solid electrolyte interphase and cycling properties include ethylene carbonate (EC) and fluoroethylene carbonate (FEC).

Unsaturated carbonates are optionally present in the electrolyte. Non-limiting examples of unsaturated carbonates that improve stability at high and low voltages include vinylene carbonate and derivatives of ethene (that is, vinyl compounds) like methyl vinyl carbonate, divinylcarbonate, and ethyl vinyl carbonate.

In embodiments, the total amount of additives that improve solid electrolyte interphase and cycling properties and unsaturated carbonates represents at least about 0.1% and/or at most about 20% of the total mass of the electrolyte. In embodiments, the amount of these additives represents at least about 0.1% w/w, at least 1% w/w, at least about 2% w/w, at least about 5% w/w, or at least about 7% w/w, and/or at most about 20% w/w, at most about 15% w/w, at most about 10% w/w, or at most about 7% w/w of the electrolyte.

Organic solvents that diminish viscosity and increase conductivity are optionally present in the electrolyte. In preferred embodiments, such organic solvents are present. Non-limiting examples of organic solvents that diminish viscosity and increase conductivity include polar solvents, preferably alkyl carbonates, alkyl ethers, and alkyl esters. For example, the organic solvent may be ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dimethoxyethane, diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetraglyme ((tetraethylene glycol dimethyl ether), tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 1,4-dioxane, 1,3-dioxane, methoxypropionitril, propionitril, butyronitrile, succinonitrile, glutaronitrile, adiponitrile, esters of acetic acid, esters of propionic acid, cyclic esters like γ-butyrolactone, ε-caprolactone, esters of trifluoroacetic acid, sulfolane, dimethyl sulfone, ethyl methyl sulfone, or peralkylated sulfamides. In embodiments, ionic liquids could also be added in order to diminish flammability and to increase conductivity. Preferred organic solvents that diminish viscosity and increase conductivity include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC).

In embodiments, the total amount of organic solvents that diminish viscosity and increase conductivity represents at least about 1% v/v and/or at most about 80% v/v of the total volume of the electrolyte. In embodiments, the amount of organic solvents that diminish viscosity and increase conductivity represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 7% v/v, and/or at most about 80% v/v, at most about 50% v/v, at most about 20% v/v, at most about 15% v/v, at most about 10% v/v, or at most about 7% v/v of the total volume of the electrolyte.

In preferred embodiments, the electrolyte of the invention is free of other solvents. In other words, the only solvent is the carbonate compound of formula (I).

In preferred embodiments, the additives are fluoroethylene carbonate (FEC), ethylene carbonate (EC), diethyl carbonate (DEC), or a mixture thereof.

In more preferred embodiments, the additives are FEC, preferably about 2 w/w% of FEC, alone or together with:

up to 5% w/w of EC,
up to 10% w/w of EC,
up to 15% w/w of EC,
up to 20% w/w of EC,
up to 30% w/w of EC,
up to 20% w/w of a mixture of EC and DEC,
up to 25% w/w of a mixture of EC and DEC,
up to 30% w/w of a mixture of EC and DEC,
up to 50% w/w of a mixture of EC and DEC,
up to 70% w/w of a mixture of EC and DEC, or
up to 75% w/w of a mixture of EC and DEC.

In embodiments, the volume ratio of ethylene carbonate (EC) to diethyl carbonate (DEC) in the mixture of EC and DEC is from about 1:10 to about 1:1, preferably this ratio is about 3:7.

In preferred embodiments, the additives are ethylene carbonate and fluoroethylene carbonate only (preferably in the above-mentioned quantities).

In more preferred embodiments, the additive is fluoroethylene carbonate only (preferably in the above-mentioned quantity).

In more preferred embodiments, the amount of additives present represents 7% w/w of the electrolyte.

These amounts may represent the amount of any individual additive present (for example, each additive present may represent 7% w/w of the electrolyte), or the total amount of additives present (for example, the sum of the weight of all the additives present in the electrolyte may represent 7% w/w of the electrolyte).
Corrosion Inhibitors

In embodiments, the electrolyte comprises one or more corrosion inhibitors.

In alternative preferred embodiments, the electrolyte is free of corrosion inhibitors. Indeed, as noted above, one of the advantages of the carbonate compounds of formula (I) is that they are characterized by their low corrosiveness against aluminum current collectors, even at voltages higher than 4.2 V.

Non-limiting examples of corrosion inhibitors include LiPF6, lithium cyano fluorophospahates, lithium fluoro oxalatophosphates, LiDFOB, LiBF4, lithium fluro cyanoborates, and LiBOB.

In embodiments, the total amount of corrosion inhibitors represents at least about 1% and/or at most about 85% of the total weight of the electrolyte. In embodiments, the total amount of corrosion inhibitors represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 10% v/v, and/or at most about 95% v/v, at most about 75% v/v, at most about 50% v/v, at most about 35% v/v, at most about 25% v/v, or at most about 15% v/v of the total weight of the electrolyte.
Minimum Concentration of Compound of Formula (I) in the Electrolyte

The skilled person would understand that the concentration of carbonate compound of formula (I) in the electrolyte will be influenced by various factors, such as the desired concentration of the conducting salt, and the quantity of the above additives and corrosion inhibitors.

Nevertheless, the electrolyte of the present invention should contain the carbonate compound of formula (I) in a concentration sufficient to achieve a desired anodic dissolution suppression.

In practice, the concentration of carbonate compound of formula (I) necessary to achieve suppression of anodic dissolution will vary depending on various factors, such as the intended operating voltage and presence of corrosion inhibitors. Generally, when corrosion inhibitors are present, a lower concentration of the carbonate compound of formula (I) will be needed to achieve a desired suppression of anodic dissolution.

In embodiments, when the electrolyte is free of corrosion inhibitors, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 50 % v/v, based on the total volume of the electrolyte. In preferred embodiments, this concentration is at least about 60% v/v, preferably at least about 70% v/v, more preferably at least about 75% v/v, and most preferably at least about 80%, based on the volume of the electrolyte.

In embodiments, when the electrolyte comprises one or more corrosion inhibitors as described in the previous section, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 10% v/v, based on the total volume of the electrolyte. In preferred embodiments, this concentration is at least about 15% v/v, preferably at least about 20% v/v, more preferably at least about 25% v/v, and most preferably at least about 30%, based on the volume of the electrolyte.
Electrochemical devices comprising the electrolyte

The electrochemical device can be any known electrochemical device in the art for which the above non-aqueous electrolyte may be used. In embodiments, the electrolytes of the present invention can be used in other electrochemical devices such as batteries (preferably lithium or lithium-ion batteries), capacitors, electrochromic devices, sensors, and metal–air electrochemical cells. In preferred embodiments, the electrochemical device is a sodium battery, a sodium-ion battery, a sodium-air battery, a potassium battery, a potassium-ion battery, a potassium-air battery, a magnesium battery, a magnesium-ion battery, a magnesium-air battery, an aluminum battery, an aluminum ion battery, or an aluminum-air battery.
Capacitors

In embodiments, the electrochemical device of the present invention is a capacitor. In general, capacitors comprise at least two electrical conductors, typically metallic plates or surfaces separated by a dielectric medium. When an electrolyte is used in the capacitor, the capacitor is known as an electrolytic capacitor. Many electrolytic capacitors are made of tantalum or aluminum, although other materials may be used.

In an aluminum electrolytic capacitor, there are two aluminum foils, one of which is the anode. The anode foil comprises a thin layer of aluminum oxide that acts as the dielectric of the capacitor. The second aluminum foil, known as cathode foil, contacts the electrolyte and serves as the electrical connection to the negative terminal of the capacitor. In capacitors, the anode has a positive voltage in relation to the cathode. An electrolyte, typically a non-solid electrolyte, is placed between the two foils. In embodiments, the electrolyte used in the electrolytic capacitor is the electrolyte of the present invention.

In embodiments, the anode, electrolyte (generally in a soaked paper), and cathode are stacked on top of each other. The stack is subsequently rolled, placed into an enclosure (generally cylindrical) and connected to a circuit.

Variations in terms of structure and materials used for electrolytic capacitors would be known to the person of skill in the art.
Electrochromic Devices

In embodiments, the electrochemical device of the present invention is an electrochromic device. Electrochromic devices typically comprise five superimposed layers. These five layers are generally on one substrate or positioned between two substrates. The middle layer is an ion conducting layer, which typically comprises an electrolyte. On one side of the electrolyte is an electrochromic layer, which can conduct electrons as well as ions. On the other side of the electrolyte is another electrochromic layer, which serves as an ion storage layer. Bookending the electrochemical device (as the first and fifth layer) are two electron conductors, which are generally transparent, although one of the conductive layers can be reflective instead of transparent, depending on the intended use of the device. By applying voltage to the electrochromic device, the optical properties thereof can be controlled.

The electrochromic layers are made of electrochromic materials, which can include metal oxides, such as tungsten oxide, nickel oxide, or even various organic materials, such as conducting polymers, including polypyrrole, PEDOT, polyaniline, Prussian blue, and viologen used in conjunction with titanium dioxide (TiO2).

Such electrochromic devices have a wide variety of uses, such as electrochromic windows (smart glass), electrochromic mirrors (e.g. self darkening mirrors), and electrochromic displays.

In embodiments, the electrolyte used in the electrochromic device is the electrolyte of the present invention.

Variations in terms of structure and materials used for electrochromic devices would be known to the person of skill in the art.
Sensors

In embodiments, the electrochemical device of the present invention is a sensor. Various sensors use electrolytes; for example, an electrolyte–insulator–semiconductor (EIS) sensor is a sensor that, along with a reference electrode, is made of these three components:

an electrolyte;
an insulator; and
a semiconductor.

Typically, in such a sensor, the electrolyte contains the chemical to be measured, while the insulator allows field-effect interaction. The purpose of the semiconductor is generally to register chemical changes. The EIS sensor can be used with other devices and structures, for example to build a light-addressable potentiometric sensor (LAPS).

In embodiments, the electrolyte used in the sensor is the electrolyte of the present invention.

Variations in terms of structure and materials used for the sensor would be known to the person of skill in the art.
Metal–air electrochemical cell

In embodiments, the electrochemical device of the present invention is a metal–air electrochemical cell (also called a metal–air battery). A metal–air electrochemical cell is an electrochemical cell that generally uses an anode made from pure metal, while ambient air functions as an external cathode. The electrolyte is typically aqueous or aprotic. This type of electrochemical cell generally involves a reduction reaction at the ambient air cathode during discharging, while the metal anode is oxidized.

In embodiments, the metal–air electrochemical cell is a lithium air, magnesium air, aluminum air, or zinc air electrochemical cell.

In embodiments, the electrolyte used in the metal–air electrochemical cell is the electrolyte of the present invention.

Variations in terms of structure and materials used for the metal–air electrochemical cell would be known to the person of skill in the art.
Batteries

In preferred embodiments, the electrochemical device of the present invention is a battery. In embodiments, batteries comprise (a) at least one positive electrode, (b) at least one negative electrode, (c) a separator membrane, and (d) a non-aqueous electrolyte.

For example, the electrochemical device may be lithium or a lithium-ion battery, or even a sodium-, a potassium-, or a magnesium-based battery. In preferred embodiments, the electrochemical device of the present invention is a lithium or lithium-ion battery, even more preferably a lithium-ion battery.

The choice of non-aqueous solvent, anode, cathode, and separator membrane will vary depending on the type of battery. If the electrochemical device is a lithium-ion battery, it would be more appropriate to choose, for example, an electrolyte comprising lithium sulfonyl amide as a conducting salt. However, if the electrochemical device is a sodium-based battery, it would be more appropriate to choose, for example, an electrolyte comprising a sodium salt as a conducting salt.

The non-aqueous electrolyte is the electrolyte defined in the previous section.

The negative electrode can be any negative electrode typically used for a battery.

In preferred embodiments, the negative electrode (the anode) is one that is suitable for a lithium or a lithium ion battery. Such negative electrodes are usually made of Li metal, carbonaceous materials (graphite, coke, and hard carbon), silicon and its alloys, tin and its alloys, antimony and its alloys, and/or lithium titanate (Li₄Ti₅O₁₂). These materials are usually mixed with a solvent, a polymer binder and electro-conductive additives – which include various forms of conductive carbon, such as carbon nanotubes and carbon black - and subsequently coated on a copper current collector in order to obtain the anode.

In preferred embodiments, the negative electrode is made of lithium metal or graphite. In preferred embodiments, the negative electrode is a disk, more preferably a 16 mm, 200 μm thick disc. In even more preferred embodiments, the negative electrode is a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD, or a 16 mm graphite disk.

The positive electrode can also be any positive electrode typically used for a battery.

In preferred embodiments, the positive electrode (the cathode) is one that is suitable for a lithium or a lithium ion battery. Such positive electrodes are usually made of lithium compounds. Such lithium compounds include lithiated oxides of transition metals like LCO (LiCoO₂), LNO (LiNiO₂), LMO (LiMn₂O₄), LiCo_xNi_1-xO₂wherein the x is from 0.1 to 0.9, LMN (LiMn_3/2Ni_1/2O₄), LMC (LiMnCoO₂), LiCu_xMn_2−xO₄, NMC (LiNi_xMn_yCo_zO₂), NCA (LiNi_xCo_yAl_zO₂), lithium compounds with transition metals and complex anions, LFP (LiFePO₄), LNP (LiNiPO₄), LMP (LiMnPO₄), LCP (LiCoPO₄), Li₂FCoPO₄; LiCo_qFe_xNi_yMn_zPO₄, and Li₂MnSiO₄. In addition, these lithium compounds are usually mixed with a solvent, polymer binder and electro-conductive additives - which include various forms of conductive carbon, such as carbon nanotubes and carbon black - and subsequently coated on an aluminum current collector in order to obtain the cathode. This aluminum current collector is susceptible to anodic dissolution at elevated potential, especially if the electrolyte contains non-passivating conducting salts.

As one advantage of using the electrolyte of the present invention is the prevention of anodic dissolution of aluminum current collectors, it is preferable that the positive electrode comprise an aluminum current collector. However, other positive electrodes can still be used.

In preferred embodiments, the cathode of the present invention is an LMN cathode or an LCO cathode.

In embodiments, the cathode comprises only the current collector.

In embodiments, the cathode is made by coating the current collector with the above described lithium compounds, preferably LMN or LCO. In preferred embodiments, the current collector is an aluminum current collector, provided by UACJ Corporation. In more preferred embodiments, the current collector is a 16 mm aluminum disc that is 15 μm thick, provided by UACJ Corporation.

In more preferred embodiments, the cathode is a disc of 16 mm in diameter made from coating a 15 μm thick aluminum current collector, provided by UACJ Corporation, with the above described lithium compounds.

In more preferred embodiments, the cathode is the 15 μm thick aluminum current collector, provided by UACJ Corporation.

In order to prevent physical contact between electrodes, a separator membrane is usually placed between them. The separator membrane can be any separator membrane typically used for a battery.

In preferred embodiments, the separator membrane is one that is suitable for a lithium or a lithium ion battery. Another function of such a separator membrane is to prevent lithium dendrite from causing a short-circuit between electrodes. Such separator membranes typically include (i) a polyolefin based porous polymer membrane, preferably made of polyethylene “PE”, polypropylene “PP”, or a combination of PE and PP, such as a trilayer PP/PE/PP membrane; (ii) heat-activatable microporous membranes; (iii) porous materials made of fabric including glass, ceramic or synthetic fabric (woven or non-woven fabric); (iv) porous membranes made of polymer materials such as poly(vinyl alcohol), poly(vinyl acetate), cellulose, and polyamide; (v) porous polymeric membranes provided with an additional ceramic layer in order to improve the performance at high potentials; and (vi) polymer electrolyte membranes. However, as mentioned, the separator membrane can also be any separator membrane typically used for a battery, preferably for a lithium or a lithium ion battery; for example Celgard 3501^TMor Celgard Q20S1HX^TM.

Depending on the type of electrochemical device, a different cathode, anode, and separator membrane may be provided or prepared. Much like the electrolyte, the cathode, anode, and separator membrane can be prepared using any known technique in the art, and the electrochemical device can be prepared using any known technique in the art.

As noted above, the electrochemical devices, in particular the batteries, of the present invention have a wide variety of applications that would be readily understood by the person of skill in the art. Such applications include electric vehicles, power tools, grid energy storage, medical devices and equipment, toys, hybrid electric vehicles, cell phones, laptops, and various military and aerospace applications.
Method of producing the carbonate solvents, the non-aqueous electrolytes, and the electrochemical devices

In a second aspect of the invention, a method for producing the above carbonate solvents, electrolytes, and electrochemical devices is provided.

Each of the carbonate solvent, the electrolyte, and the electrochemical device of the present invention can be prepared using any known technique in the art.

For example, the carbonate solvents of the invention can be synthesised according to the following formula:

In the above formula, R⁶represents both R¹and R², defined above. Syntheses of alkyl carbonates are very well-developed processes. While the most convenient methods are discussed below, the skilled person would understand that other synthesis methods can be used.

Preparation of the carbonate solvents of the present invention in smaller scale is most conveniently accomplished by a base catalyzed transesterification of readily available dimethyl carbonate, diethyl carbonate, ethylene carbonate, or propylene with aliphatic alcohols in the presence of a suitable catalyst. The transesterification of carbonate esters obeys the same rules as transesterification of other esters, which is a typical equilibrium reaction, and can be easily controlled by the use of Le Chateliers’ principle. The ratio between the alcohol and the carbonate ester determines the ratio of the products in a fully equilibrated reaction mixture. If a full substitution is desired, the excess of alcohol should be used. If the desired product is the mixed carbonate, the molar ratio should be close to 1, or a slight excess of starting carbonate should be used. During the reaction, it is desirable that the reaction products are steadily removed from the reaction mixture; this allows the reaction to proceed faster to completion. The separation is most conveniently done by fractional distillation of a lower alcohol. For this reason, the use of lower carbonates is preferred over higher carbonates because the formed alcohol has a lower boiling point; however, attention must be paid to the formation of azeotropic mixtures which may complicate the separation.

The catalysts used for this transformation can be chosen from acids and from bases, but bases like alkali and earthalkali carbonates, oxides, hydroxides and alkoxides are preferred as they can be separated easily from the volatile products.

In a suitable reaction vessel equipped for a fractioning distillation, there is placed the appropriate amount of desired aliphatic alcohol and a certain amount of metallic sodium is added. The amount of sodium should be chosen so that it will react with the water present in the reactants and consume it all. In this way, a water free solvent can be isolated. The process of sodium dissolution can be accelerated by heating and stirring, which is necessary with all higher alcohols. A protective atmosphere of nitrogen or argon should be used to exclude the uptake of carbon dioxide and water from the atmosphere. When sodium is dissolved, the starting carbonate ester is added and the mixture is refluxed at such a temperature that the alcohol which is formed during the reaction distills from the reaction mixture, while all reactants remain in the reactor. After the reaction is finished, the components of the reaction mixture are separated by fractional distillation, under vacuum for higher alkyl carbonates. In this manner the solvents can be isolated in high purity if no azeotropes are formed.

However, the industrial preparation of symmetric carbonates can be performed by phosgenation of the corresponding alcohols.

When small amounts of mixed carbonate are desired, the most suitable method seems to be the reaction of an aliphatic alcohol with an aliphatic chloroformate in an aprotic solvent in the presence of a suitable base which binds the formed HCl. Even though this method is well established, it may sometimes give erroneous results.
Definitions

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

The terms "comprising", "having", "including", and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted.

Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All subsets of values within the ranges are also incorporated into the specification as if they were individually recited herein.

Similarly, herein a general chemical structure with various substituents and various radicals enumerated for these substituents is intended to serve as a shorthand method of referring individually to each and every molecule obtained by the combination of any of the radicals for any of the substituents. Each individual molecule is incorporated into the specification as if it were individually recited herein. Further, all subsets of molecules within the general chemical structures are also incorporated into the specification as if they were individually recited herein.

All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed.

No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Herein, the term "about" has its ordinary meaning. In embodiments, it may mean plus or minus 10% or plus or minus 5% of the numerical value qualified.

Unless otherwise defined, 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.

For certainty, it should be noted that:

alkyloyl is alkyl-C(=O)-,
aryloyl is aryl-C(=O)-,
alkyloxycarbonyl is alkyl-O-C(=O)-, and
aryloxycarbonyl is aryl-O-C(=O)-.

Herein, the terms "alkyl" has its ordinary meaning in the art. It is to be noted that, unless otherwise specified, the hydrocarbon chain of the alkyl groups can be linear or branched.

Herein, the terms "aryl" has its ordinary meaning in the art. It is to be noted that, unless otherwise specified, the aryl groups can contain between 5 and 30 atoms, including carbon and heteroatoms, preferably without heteroatoms, more specifically between 5 and 10 atoms, or contain 5 or 6 atoms.

For clarity, the following abbreviations are used:EC – ethylene carbonate, PC – propylene carbonate, DEC – diethyl carbonate, EMC – ethyl methyl carbonate, DMC – dimethyl carbonate, FEC – fluoroethylene carbonate, VC – vinylene carbonate, LCO – LiCoO₂- lithium cobaltate, LMN – LiMn_3/2Ni_1/2O₄,

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.
Description of Illustrative Embodiment

The present invention is illustrated in further details by the following non-limiting examples.

A brief summary of the nature of each Example is as follows:

Examples 1-4involve the preparation of various carbonate solvents of the present invention.

Examples 5-7are comparative examples wherein anodic dissolution is measured in button cells comprising conventional electrolytes.

Examples 8-10measure anodic dissolution in button cells comprising electrolytes of the present invention.

Examples 11-54involve measuring the starting potentials of anodic dissolution of various electrolytes of the present invention.

Examples 55 and 58are comparative examples where charging and discharging of button cells comprising conventional electrolytes was measured.

Examples 56, 57, and 59involve measuring the charging and discharging of button cells comprising electrolytes of the present invention.

Example 60involves measuring the temperature range of an electrolyte of the present invention and a conventional electrolyte by performing a digital scanning calorimetry (DSC) experiment.

Example 61involves measuring the discharge capacity of three cells versus cycle number; two of the cells comprise electrolytes of the present invention, while one comprises a conventional electrolyte.
Preparation of carbonate solvents of the invention
Example 1: Preparation of diisobutyl carbonate (Solvent no. 10) by transesterification

In a 250 ml round bottom flask equipped with a Vigreux column is placed 128 g (1.73 mol) of isobutanol, in which 0.3g sodium was dissolved at the boiling point and 59 g (0.66 mol) of dimethyl carbonate was added. The mixture was refluxed overnight with the separation of methanol formed. After the separation of the methanol ceased, the remainder was subjected to a fractional distillation, giving 120 g of diisobutyl carbonate as a colourless liquid. Unreacted isobutanol, dimethyl carbonate and isobutyl methyl carbonate were also detected in the preceding fraction. The structure of the products was confirmed by NMR (nuclear magnetic resonance spectroscopy), IR (infra-red spectroscopy) and GC/MS (gas chromatography with mass selective detector) analyses.
Example 2: Preparation of di( 2-pentyl) carbonate (Solvent no. 17) and methyl 2-pentyl carbonate (Solvent no. 16) by transesterification

In a 250 ml round bottom flask equipped with a Vigreux column is placed 116 g (1316 mmol) of 2-pentanol, in which 1 g sodium was dissolved at 100 °C and 98 g (1088 mmol) of dimethyl carbonate was added. The mixture was refluxed over 48h with the separation of methanol formed. After the separation of the methanol ceased, the remainder was subjected to a vacuum fractional distillation, giving a smaller fraction of 40 g containing pure methyl 2-pentyl carbonate and a main fraction of 70 g of di(2-pentyl) carbonate as a colourless liquid. Unreacted dimethyl carbonate, 2-pentanol and methanol were also detected in the preceding fractions. The structure of the products was confirmed by NMR, IR and GC/MS analyses.
Example 3: Preparation of 2-cyanoethyl butyl carbonate (Solvent no. 23) by reaction of butyl chloroformate and 3-hydroxypropinonitril

In a 250 ml round bottom flask is placed 7.1 g (100 mmol) of 3-hydroxypropinonitril, 11 g of a freshly distilled triethyl amine, and 150 ml dry dichloromethane. The mixture was cooled under nitrogen in an ice water bath and a solution of 13,66 g (100 mmol) of butyl chloroformate in 30 ml of dichloromethane was added dropwise. After the addition, the mixture was stirred at room temperature for 2h, after which water and sulfuric acid were added and the mixture was separated by means of a separation funnel. The organic phase was washed 4 times with water, and then dried with anhydrous magnesium sulfate, filtered, and evaporated. Distillation of the remaining clear oil gave pure product (13.1 g). Structure of the products was confirmed by NMR, IR and GC/MS analyses.
Example 4: Preparation of other carbonate solvents of the present invention

Other dialkylcarbonates were prepared similarly to the procedures in examples 1-3 and all are listed in the following table (Table 1) together with their¹H and¹³C NMR spectroscopy data.

Measurement of anodic dissolution of aluminum current collector

In the following examples, anodic dissolution of an aluminum current collector was measured. Detection of anodic dissolution of an aluminum current collector can be realised by many electrochemical methods. One indicator of anodic dissolution is the current which appears between the reference electrode and the bare aluminum electrodes at a certain potential. Anodic dissolution is strongly dependant on the applied potential, so the variation of the potential during anodic dissolution probing is essential.

In light of the above, in the following Examples, anodic dissolution of an aluminum current collector was measured using chronoamperometry, CA. Chronoamperometry involves measuring the current at a given potential and is usually performed over a longer period of time; accordingly, even the slowest processes can be detected in that manner. For the following examples, chronoamperometry was used for 1h at potentials between 4–5.5 V vs Li metal by 0.1 V steps (1 hour of CA at 4.0, 4.1, 4.2, etc., until 5.5 V). This enables relatively fast screening of the electrolytes.

The chronoamperometry results are shown in Figures 1 to 6.

In general, it was found that in electrolytes obtained by dissolution of LiFSI, LiFTFSI and LiTFSI in mixtures of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC) and propylene carbonate (PC), significant anodic dissolution appeared between 4.1 and 4.3 V vs Li metal, detected as a high current/current density between electrodes (Figures 1-3).

However, it was found that LiFSI, LiFTFSI and LiTFSI, when dissolved in higher, preferably branched, dialkyl carbonate, where the total number of carbon atoms was equal to or greater than 4, did not cause anodic dissolution of the aluminum current collector, in some cases even at potentials over 5 V vs Li metal (Figures 4-6).
Example 5 (comparative): anodic dissolution of aluminum current collector in LiFSI -EC-DEC electrolyte

1M solution of LiFSI (Nippon Shokubai) in a conventional industrial solvent mixture of ethylene carbonate and diethyl carbonate (EC/DEC), in volume ratio of 3:7, was prepared and 2 % of fluoroethylene carbonate was added.

A button cell was assembled using a disc of 16 mm diameter, with a 15 μm thickness of non-coated aluminum current collector, provided by UACJ as a cathode. Celgard 3501 was used as a separator membrane and the aforementioned LiFSI-EC-DEC electrolyte was also used. A 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., was used as an anode. The cell was used for probing the anodic dissolution of the cathode during chronoamperometry for 1h at potentials between 4 and 5.5 V vs Li metal at 0.1 V steps (1 hour of chronoamperaometry at 4.0, 4.1, 4.2…5.5 V). The results of this experiment can be seen inFIG. 1.Already at 4.3 V a significant appearance of current is observed, which indicates anodic dissolution. Accordingly, this electrolyte cannot be used for batteries where the potential of the cathode surpasses 4.3 V.
Example 6 (comparative): anodic dissolution of aluminum current collector in LiFTFSI -EC-DEC electrolyte

A button cell was assembled and tested according to example 5 but using a 1M solution of LiFTFSI in a conventional industrial solvent mixture of ethylene carbonate/diethyl carbonate, EC/DEC, in a volume ratio of 3:7, and 2 % of fluoroethylene carbonate, as an electrolyte. The results of this experiment can be seen inFIG. 2.Already at 4.1 V a significant appearance of current is observed, which indicates anodic dissolution. Accordingly, this electrolyte cannot be used for batteries where the potential of the cathode surpasses 4.2 V.
Example 7 (comparative): anodic dissolution of aluminum current collector in LiTFSI -EC-DEC electrolyte

A button cell was assembled and tested according to example 5 but using a 1M solution of LiTFSI (available from 3M^TM) in a conventional industrial solvent mixture of ethylene carbonate and diethyl carbonate, EC/DEC, in a volume ration of 3:7, and 2 % of fluoroethylene carbonate, as an electrolyte. The results of this experiment can be seen onFIG. 3.Already at 4.1 V, a significant appearance of current is observed, which indicates anodic dissolution. Accordingly, this electrolyte cannot be used for batteries where the potential of the cathode surpasses 4.2 V.
Example 8: Suppression of anodic dissolution of aluminum current collector in LiFSI-diisobutyl carbonate electrolyte

1M solution of LiFSI (Nippon Shokubai) in diisobutyl carbonate (Solvent no. 10 prepared according to Example 1) was prepared, to which 2 % of fluoroethylene carbonate was added.

A button cell was assembled and tested according to Example 5 but using the preceding LiFSI-diisobutyl carbonate electrolyte. The results of this experiment can be seen inFIG. 4.On all potentials tested (4-5.5V), the current density stays well below 1μA/cm², meaning this electrolyte can be used inter alia with cathodes with a cut off potential of at least at 5.5 V.
Example 9: Suppression of anodic dissolution of aluminum current collector in LiFTFSI-diisobutyl carbonate electrolyte

1M solution of LiFTFSI in diisobutyl carbonate (Solvent no. 10) was prepared according to example 1, to which 2 % of fluoroethylene carbonate was added.

A button cell was assembled and tested according to example 5 but using the preceding LiFTFSI-diisobutyl carbonate electrolyte. The results of this experiment can be seen inFIG. 5.On all potentials tested (4-5.5V), the current density stays well below 1μA/cm², meaning this electrolyte can be used inter alia in battery systems where the voltage surpasses 5.5 V. As mentioned, electrolytes prepared from conventional solvents containing FSI typically become unsafe when the operating voltage surpasses 4.3 V (see Examples 5 to 7).
Example 10: Suppression of anodic dissolution of aluminum current collector in LiTFSI-diisobutyl carbonate electrolyte

1M solution of LiTFSI in diisobutyl carbonate (Solvent no. 10) was prepared according to example 1, to which 2 % of fluoroethylene carbonate was added.

A button cell was assembled and tested according to example 5 but using the preceding LiTFSI-diisobutyl carbonate electrolyte. The results of this experiment can be seen inFIG. 6.On all potentials tested (4-5.5V), the current density stays below 1μA/cm², meaning this electrolyte can be used inter alia in battery systems where the voltage surpasses 5.5 V.
Examples 11-54: Starting potentials of anodic dissolution of various electrolytes

Button cells were assembled and tested according to example 5 but using each of the electrolytes listed in the following table (Table 2) with the previous results. The results of this experiment are presented as the potential where significant anodic dissolution of aluminum occurs and represents a safe use limit for said electrolyte. Several examples have been made in order to illustrate the mixing possibilities of different solvents in order to get an electrolyte with enhanced conductivity, while maintaining the effect of suppressing anodic dissolution.

Button cell charge-discharge tests
Example 55 (comparative): Unsuccessful charging and discharging of LCO in LiFSI -EC-DEC electrolyte

An LCO cathode material was prepared using a mixture of LCO, VGCF (vapour grown carbon nanotubes), carbon black and polyvinylidene fluoride (PVDF) in a ratio 89:3:3:5 by weight in N-methyl-2-pyrrolidone (NMP). The mixture was then coated on a 15 μm thick non-coated aluminum current collector, provided by UACJ. The electrode material was calendered, cut into discs and dried at 120° C in a vacuum oven for 12 h before use.

A button cell was assembled using one of the above-described discs (16 mm diameter) of LCO as a cathode, Celgard Q20S1HX as separator membrane, the electrolyte ofcomparative example 5, and a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., as an anode.

The cell was used for probing the charging and discharging between 3 and 4.5 V at C/24 rate. The results of this experiment can be seen inFIG. 7.The first charge/discharge cycle has a normal shape, but during second charging an unexpected plateau appears at 4.2 V. This plateau could be attributed to the anodic dissolution of aluminum current collector, which leads to a loss of charge and a very low discharge capacity. Accordingly, this electrolyte does not support the operation of an LCO electrode.
Example 56: Successful charging and discharging of LCO in LiFSI-diisobutyl carbonate electrolyte

A button cell was assembled using a disc of 16 mm diameter LCO as a cathode (prepared using the process described in Example 55), Celgard Q20S1HX as separator membrane, the electrolyte ofexample 8, and a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., as an anode.

The cell was used for probing the charging and discharging between 3 and 4.5 V at C/24 rate. The results of this experiment can be seen inFIG. 8.The charge-discharge curves are deformed, but one cannot detect any sign of a parasitic process, which would manifest as a plateau similar to the second cycle in FIG 7. Accordingly, this electrolyte can support the operation of an LCO electrode, potentially with some additives to further improve its performance (which is shown in Example 57).
Example 57: Successful charging and discharging of LCO in LiFSI -EC- diisobutyl carbonate electrolyte

The electrolyte ofexample 33(i.e. a 1M solution of LiFSI (Nippon Shokubai) in a 1:9 mixture by volume of ethylene carbonate (EC) and diisobutyl carbonate (solvent no.10), respectively, to which 2 % of fluoroethylene carbonate was added) was prepared. Note that this electrolyte is similar to the electrolyte of example 56 except that solvent no.10 was replaced by a 1:9 mixture by volume of EC and solvent no.10. In other words, EC is used as an additive herein.

A button cell was assembled using a disc of 16 mm diameter LCO coated on a 15 μm thick aluminum current collector (prepared using the process described in Example 55), provided by UACJ, as a cathode; Celgard Q20S1HX as a separator membrane; the preceding LiFSI-EC-diisobutyl carbonate electrolyte; and a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., as an anode.

The cell was used for probing the charging and discharging between 3 and 4.5 V at C/24 rate. The results of this experiment can be seen inFIG. 9. The charge-discharge curves have a normal shape and one cannot detect any sign of the parasitic process which would manifest as a plateau similar to the second cycle in FIG 7. Accordingly, this electrolyte can support quite well the operation of an LCO electrode.
Example 58 (comparative): Unsuccessful charging and discharging of LMN in LiFSI -EC-DEC electrolyte

A LiMn_3/2Ni_1/2O₄(LMN) cathode material was prepared using a mixture of LMN, VGCF (vapour grown carbon nanotubes), carbon black and polyvinylidene fluoride (PVDF) in a ratio of 94:1.5:1.5:3 by weight in NMP. The mixture was then coated on a 15 μm thickness of non-coated aluminum current collector, provided by UACJ. The electrode material was calendered, cut into discs and dried at 120° C in a vacuum oven for 12 h before use.

A button cell was assembled using a disc of 16 mm diameter LMN as a cathode, Celgard Q20S1HX as a separator membrane, the electrolyte ofcomparative example 5, and a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., as an anode.

The cell was used for probing the charging and discharging between 3.5 and 4.9 V at C/24 rate. The results of this experiment can be seen inFIG. 10. The first charge cycle shows an abnormal shape. First, the potential increases to approximately 4.5 V but then decreases down to an unexpected plateau at approximately 4.3 V. This plateau could be attributed to the anodic dissolution of the aluminum current collector, which lead to the extreme malfunctioning of the battery, as not even one normal cycle could be performed. Therefore, this electrolyte cannot be used at all with an LMN electrode.
Example 59: Successful charging and discharging of LMN in LiFSI-diisobutyl carbonate electrolyte

A button cell was assembled using a disc of 16 mm diameter LMN as a cathode (prepared using the process described in Example 58), Celgard Q20S1HX as separator membrane, the electrolyte ofexample 8, and a 16 mm, 200 μm thick disc of lithium metal, provided by China Energy Lithium Co., LTD., as an anode.

The cell was used for probing the charging and discharging between 3.5 and 4.9V at C/24 rate. The results of this experiment can be seen inFIG. 11. The charge-discharge curves appear normal and one cannot detect any sign of parasitic process, which would manifest as a plateau similar to that found in FIG 10. This electrolyte can therefore support the operation of an LMN electrode, possibly with some additives to further improve its performance.
Example 60: Extended temperature range of a diisobutyl carbonate-based electrolyte compared to conventional solvent

A digital scanning calorimetry experiment was performed on the electrolyte ofexample 33and on the electrolyte ofcomparative example 5.

The electrolyte of comparative example 5 exhibited a melting point of -10 °C and a glass transition point of -111 °C. In contrast, the electrolyte of the invention showed no melting point and a glass transition point of -98°C. In other words, the electrolyte ofexample 33stayed in liquid form and eventually in amorphous solid form, without crystallizing, until it reached its glass transition point of -98°C. This indicates that the electrolyte of the invention can be used at lower temperatures than conventional electrolytes without crystallisation.
Example 61: Full Li-ion cell

Electrolytes fromexample 8(LiFSI in diisobutyl carbonate, 2% of FEC) andexample 33(LiFSI in 90% diisobutyl carbonate:10 % EC, 2% of FEC) and a conventional electrolyte of 1 M LiPF₆in EC/DEC (3:7 vol) with 2% of FEC were tested.

A graphite electrode was prepared by Cumstomcells Company by mixing 96% of modified graphite (SMG), 2 % of water-based binder, and 2 % of electronic conductivity enhancer in water; coating the mixture onto a 14 μm thick copper foil; drying it and calendering it. The resulting electrode material was cut into discs and dried at 120° C in a vacuum oven for 12 h before use.

Li-ion button cells were assembled using a disc of 16 mm diameter LCO coated on 15 μm thick aluminum current collector (as in example 55), provided by UACJ, as a cathode; Celgard Q20S1HX as separator membrane; one of the above-listed electrolytes; and the above-prepared 16 mm disc of graphite electrode as an anode.

The cells were subjected to three formation cycles – the charging and discharging between 3 and 4.4 V at C/24 rate. After that, the cells were subjected to long term cycling with charging at C/4, followed by a 30 min float at 4.4 V and C/4 discharge. The results of this experiment – the discharge capacity of the cells versus cycle number - can be seen inFIG. 12. The LiPF₆electrolyte provides the highest starting discharge capacity, but then one can observe relatively linear diminution of the capacity over cycle number. LiFSI in pure diisobutyl carbonate has approximately 10% less of the starting capacity, but degradation of the capacity is slower than in the case of LiPF₆. The addition of 10 % of EC to pure diisobutyl carbonate electrolyte increases the starting capacity, but the speed of degradation approaches to that of LiPF₆.

With this experiment, the utilisation electrolytes prepared of LIFSI in the solvents of the present invention in high voltage Li-ion batteries has been demonstrated, while the utilisation of LiFSI in conventional solvents is not possible for this battery system.

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.

References

The present description refers to a number of documents, the content of which is herein incorporated by reference in their entirety. These documents include, but are not limited to, the following:

US5072040
EP 858994
US 5,446,134
Beran, M.; Příhoda, J.; Žák, Z.; Černík, M.Polyhedron2006,25, 1292.
Beran, M.; Příhoda, J.; Taraba, J.Polyhedron 2010,29, 991.
WO 2018072024
Han, H.-B.; Zhou, S.-S.; Zhang, D.-J.; Feng, S.-W.; Li, L.-F.; Liu, K.; Feng, W.-F.; Nie, J.; Li, H.; Huang, X.-J.; Armand, M.; Zhou, Z.-B.J. Power Sources 2011,196, 3623.
Meister, P.; Qi, X.; Kloepsch, R.; Krämer, E.; Streipert, B.; Winter, M.; Placke, T.ChemSusChem 2017,10, 804.
Kraemer, E.; Passerini, S.; Winter, M.ECS Electrochem . Lett. 2012,1, C9.
Park, K.; Yu, S.; Lee, C.; Lee, H.J. Power Sources 2015,296, 197.
US9698447
Xia, L.; Jiang, Y.; Pan, Y.; Li, S.; Wang, J.; He, Y.; Xia, Y.; Liu, Z.; Chen, G. Z.ChemistrySelect 2018,3, 1954.
Yamada, Y.; Chiang, C. H.; Sodeyama, K.; Wang, J.; Tateyama, Y.; Yamada, A.ChemElectroChem 2015,2, 1687.
Flamme, B.; Rodriguez Garcia, G.; Weil, M.; Haddad, M.; Phansavath, P.; Ratovelomanana-Vidal, V.; Chagnes, A.Green Chemistry 2017,19, 1828.
Shaikh, A.-A. G.; Sivaram, S.Chem. Rev. 1996,96, 951., Parrish, J. P.; Salvatore, R. N.; Jung, K. W.Tetrahedron 2000,56, 8207.
Buysch, H.-J. InUllmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000; Vol. 7, p 45, doi : 10.1002/14356007.a05_197
Tundo, P.; Aricò, F.; Rosamilia Anthony, E.; Rigo, M.; Maranzana, A.; Tonachini, G. InPure Appl . Chem. 2009; Vol. 81, p 1971.
Kenar, J. A.; Knothe, G.; Copes, A. L.J. Am. Oil Chem. Soc. 2004,81, 285.
Chen, Z.; Zhang, Z.; Amine, K. InAdvanced Fluoride-Based Materials for Energy Conversion; Groult, H., Ed.; Elsevier:2015, p 1.
US3359296
https://en.wikipedia.org/wiki/Electrolytic_capacitor
https://en.wikipedia.org/wiki/Electrochromic_devices
https://en.wikipedia.org/wiki/Electrolyte%E2%80%93insulator%E2%80%93semiconductor_sensor
https://en.wikipedia.org/wiki/Metal%E2%80%93air_electrochemical_cell

Claims

A carbonate compound of formula (I):
(I),
wherein
R¹represents a C₃-C₂₄alkyl, a C₃-C₂₄alkoxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), or a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), and
R²represents a C₁-C₂₄alkyl, a C₁-C₂₄haloalkyl, a C₂-C₂₄alkoxyalkyl, a C₂-C₂₄alkyloyloxyalkyl, a C₃-C₂₄alkoxycarbonylalkyl, a C₁-C₂₄cyanoalkyl, a C₁-C₂₄thiocyanatoalkyl, a C₃-C₂₄trialkylsilyl, a C₄-C₂₄trialkylsilylalkyl, a C₄-C₂₄trialkylsilyloxyalkyl, a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), a C₄-C₂₄ω-O-alkyl oligo(propylene glycol), a C₅-C₂₄ω-O-silyl oligo(ethylene glycol), or a C₆-C₂₄ω-O-silyl oligo(propylene glycol).
The carbonate compound of claim 1, wherein R¹represents a C₃-C₂₄alkyl or a C₃-C₂₄ω-O-alkyl oligo(ethylene glycol), preferably a C₃-C₂₄alkyl.
The carbonate compound of claim 1 or 2, wherein R2 represents a C1-C24 alkyl, a C2-C24 alkoxyalkyl, a C1-C24 cyanoalkyl, a C4-C24 trialkylsilyloxyalkyl, a C5-C24 ω-O-silyl oligo(ethylene glycol), or a C3-C24 ω-O-alkyl oligo(ethylene glycol), preferably a C1-C24 alkyl.
The carbonate compound of any one of claims 1 to 3, wherein the sum of the carbon atoms in R1 and R2 is:
5 or more, preferably 6 or more, more preferably 7 or more, yet more preferably 8 or more, and most preferably 9 or more, and/or
24 or less, preferably 20 or less, more preferably 16 or less, yet more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less.
The carbonate compound of any one of claims 1 to 4, wherein R²is methyl or ethyl.
The carbonate compound of any one of claims 1 to 5, wherein R¹and/or R²is propyl, or isopropyl (2-propyl).
The carbonate compound of any one of claims 1 to 6, wherein R¹and/or R²is butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl), or tertbutyl (2,2-dimethylethyl).
The carbonate compound of any one of claims 1 to 7, wherein R¹and/or R²is pentyl or one of its isomers (including 2-pentyl and 3-pentyl), 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl, and 2-methyl-2-butyl).
The carbonate compound of any one of claims 1 to 8, wherein R¹and/or R²is hexyl or one of its isomers (including 2-hexyl and 3-hexyl), 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-2-butyl, 2-ethylbutyl, and 3-ethyl-2-butyl).
The carbonate compound of any one of claims 1 to 9, wherein R¹and/or R²is heptyl, one of its isomers, or 2-ethylhexyl.
The carbonate compound of any one of claims 1 to 10, wherein R¹and/or R²is 2-methoxyethyl or 2-isopropoxyethyl.
The carbonate compound of any one of claims 1 to 11, wherein R²is 2-cyanoethyl.
The carbonate compound of any one of claims 1 to 12, wherein R²is (2-trimethylsilyloxy)ethyl.
The carbonate compound of any one of claims 1 to 13, wherein R¹and/or R²is 2-methoxyethyl, 2-isopropoxyethyl, or 2-(2-methoxyethoxy)ethyl.
The carbonate compound of any one of claims 1 to 14, wherein R²is 2-trimethylsilyloxyethyl.
The carbonate compound of any one of claims 1 to 15, wherein the carbonate compound of formula (I) is didodecyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl propyl carbonate, diisopropyl carbonate, isopropyl methyl carbonate, ethyl dodecyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, diisobutyl carbonate, isobutyl methyl carbonate, dipentyl carbonate, methyl pentyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, methyl 2-pentyl carbonate, di(2-pentyl) carbonate, 2-butyl methyl carbonate, di(2-butyl) carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, isobutyl isopropyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-methoxyethyl) carbonate, 2-isopropoxyethyl methyl carbonate, di(2-isopropoxyethyl) carbonate, or di(2-(2-methoxyethoxy)ethyl) carbonate.
The carbonate compound of any one of claims 1 to 16, wherein the compound of formula (I) is didodecyl carbonate, dibutyl carbonate, 2-ethylbutyl methyl carbonate, di(2-ethylbutyl) carbonate, di(2-butyl) carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, di(2-pentyl) carbonate, ethyl dodecyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate, di(2-isopropoxyethyl) carbonate, or diisobutyl carbonate.
The carbonate compound of any one of claims 1 to 17, wherein the compound of formula (I) is didodecyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexyl methyl carbonate, ethyl dodecyl carbonate, or diisobutyl carbonate, preferably diisobutyl carbonate.
A non-aqueous electrolyte comprising as a solvent the carbonate compound of formula (I) as defined in any one of claims 1 to 18 or a mixture thereof.
The non-aqueous electrolyte of claim 19 further comprising a conducting salt dissolved in said solvent.
The non-aqueous electrolyte of claim 20, wherein the conducting salt is LiClO₄; LiP(CN)_αF_6-α, where α is an integer from 0 to 6, preferably LiPF₆; LiB(CN)_βF₄ _- _β, where β is an integer from 0 to 4, preferably LiBF₄; LiP(C_nF_2n+1)_γF_6-γ, where n is an integer from 1 to 20, and γ is an integer from 1 to 6; LiB(C_nF_2n+1)_δF_4-δ, where n is an integer from 1 to 20, and δ is an integer from 1 to 4; Li₂Si(C_nF_2n+1)_εF_6-ε, where n is an integer from 1 to 20, and ε is an integer from 0 to 6; lithium bisoxalato borate; lithium difluorooxalatoborate; or compounds represented by the following general formulas:

R³represents: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen, or an organic cation; and
R⁴, R⁵, R⁶, R⁷, R⁸represent: cyano, fluorine, chlorine, branched or linear alkyl radical with 1-24 carbon atoms, perfluorinated linear alkyl radical with 1-24 carbon atoms atoms, aryl or heteroaryl radical, or perfluorinated aryl or heterosaryl radical;
or their derivatives.
The non-aqueous electrolyte of claim 20 or 21, wherein the conducting salt is a lithium salt, preferably a lithium sulfonyl amide salt.
The non-aqueous electrolyte of claim 22, wherein the lithium sulfonyl amide salt is lithium bis(fluorosulfonyl)amide (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI), or lithium N-flurosulfonyl-trifluoromethanesulfonyl amide (LiFTFSI).
The non-aqueous electrolyte of claim 23, wherein the conducting salt is LiFSI.
The non-aqueous electrolyte of claim 20, wherein the conducting salt is a sodium, a potassium, calcium, aluminum, or a magnesium salt.
The non-aqueous electrolyte of any one of claims 20 to 25, wherein the concentration of the conducting salt is at least about 0.05 M, at least about 0.1 M, at least about 0.5 M, or at least about 1 M, and/or at most about 3 M, at most about 2 M, at most about 1.5 M, or at most about 1 M.
The non-aqueous electrolyte of claim 26, wherein the concentration of the conducting salt is 1 M.
The non-aqueous electrolyte of any one of claims 19 to 27, wherein the electrolyte comprises one or more additives.
The non-aqueous electrolyte of claim 28, wherein each of the one or more additives is an additive that improves solid electrolyte interphase and cycling properties; an unsaturated carbonate that improves stability at high and low voltages, and/or an organic solvent that diminishes viscosity and increases conductivity.
The non-aqueous electrolyte of claim 29, wherein the one or more additives is ethylene carbonate (EC) and/or fluoroethylene carbonate (FEC).
The non-aqueous electrolyte of claim 29 or 30, wherein the total amount of additives that improve solid electrolyte interphase and cycling properties and unsaturated carbonates represents at least about 0.1% w/w, at least 1% w/w, at least about 2% w/w, at least about 5% w/w, or at least about 7% w/w, and/or at most about 20% w/w, at most about 15% w/w, at most about 10% w/w, or at most about 7% w/w of the electrolyte.
The non-aqueous electrolyte of any one of claims 29 to 31, wherein the one or more additives are ethylene carbonate (EC) and/or dimethyl carbonate (DEC).
The non-aqueous electrolyte of any one of claims 29 to 32, wherein the amount of organic solvents that diminish viscosity and increase conductivity represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 7% v/v, and/or at most about 80% v/v, at most about 50% v/v, at most about 20% v/v, at most about 15% v/v, at most about 10% v/v, or at most about 7% v/v of the total volume of the electrolyte.
The non-aqueous electrolyte of any one of claims 19 to 32, wherein the only solvent in the electrolyte is the carbonate compound of formula (I).
The non-aqueous electrolyte of any one of claims claim 28 to 34, wherein the one or more additives are fluoroethylene carbonate (FEC), ethylene carbonate (EC), diethyl carbonate (DEC), or a mixture thereof.
The non-aqueous electrolyte of any one of claims 28 to 35, wherein the one or more additives are FEC, preferably about 2 w/w% of FEC, alone or together with:
up to 5% w/w of EC,
up to 10% w/w of EC,
up to 15% w/w of EC,
up to 20% w/w of EC,
up to 30% w/w of EC,
up to 20% w/w of a mixture of EC and DEC,
up to 25% w/w of a mixture of EC and DEC,
up to 30% w/w of a mixture of EC and DEC,
up to 50% w/w of a mixture of EC and DEC,
up to 70% w/w of a mixture of EC and DEC, or
up to 75% w/w of a mixture of EC and DEC.
The non-aqueous electrolyte of any one of claims 19 to 36, wherein the electrolyte comprises one or more corrosion inhibitors, such as LiPF6, lithium cyano fluorophosphates, lithium fluoro oxalatophosphates, LiDFOB, LiBF4, lithium fluro cyanoborates, and LiBOB.
The non-aqueous electrolyte of any one of claims 19 to 37, wherein the total amount of corrosion inhibitors represents at least about 1% v/v, at least about 2% v/v, at least about 5% v/v, or at least about 10% v/v, and/or at most about 95% v/v, at most about 75% v/v, at most about 50% v/v, at most about 35% v/v, at most about 25% v/v, or at most about 15% v/v of the total weight of the electrolyte.
The non-aqueous electrolyte of any one of claims 19 to 36, wherein the electrolyte is free of corrosion inhibitors.
The non-aqueous electrolyte of any one of claims 19 to 39, wherein, when the electrolyte is free of corrosion inhibitors, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 50 % v/v, based on the total volume of the electrolyte, preferably at least about 60% v/v, more preferably at least about 70% v/v, even more preferably at least about 75% v/v, and most preferably at least about 80%, based on the volume of the electrolyte.
The non-aqueous electrolyte of any one of claims 19 to 38, wherein, when the electrolyte comprises one or more corrosion inhibitors, the carbonate compound of formula (I) is present in the electrolyte in a concentration of at least about 10% v/v, based on the total volume of the electrolyte, preferably at least about 15% v/v, more preferably at least about 20% v/v, even more preferably at least about 25% v/v, and most preferably at least about 30%, based on the volume of the electrolyte.
An electrochemical device comprising the non-aqueous electrolyte of any one of claims 19 to 41.
The electrochemical device of claim 42, wherein the electrochemical device is a battery (preferably a lithium or lithium-ion battery), a capacitor, an electrochromic device, a sensor, or a metal–air electrochemical cell.
The electrochemical device of claim 42 or 43, wherein the electrochemical device is a battery.
The electrochemical device of claim 44, wherein the battery comprises (a) at least one positive electrode, (b) at least one negative electrode, (c) a separator membrane, and (d) the non-aqueous electrolyte of any one of claims 19 to 41.
The electrochemical device of claim 45, wherein the electrochemical device is a lithium, a lithium-ion battery or a lithium-air battery, preferably a lithium-ion battery.
The electrochemical device of claim 45 or 46, wherein the negative electrode is made of lithium metal or graphite.
The electrochemical device of any one of claims 45 to 47, wherein the cathode is an LMN cathode or an LCO cathode.
The electrochemical device of any one of claims 45 to 47, wherein the cathode is made of lithiated oxides of transition metals such as LNO (LiNiO₂), LMO (LiMn₂O₄), LiCo_xNi_1-xO₂wherein x is from 0.1 to 0.9, LMC (LiMnCoO₂), LiCu_xMn_2−xO₄, NMC (LiNi_xMn_yCo_zO₂), NCA (LiNi_xCo_yAl_zO₂), lithium compounds with transition metals and complex anions, LFP (LiFePO₄), LNP (LiNiPO₄), LMP (LiMnPO₄), LCP (LiCoPO₄), Li₂FCoPO₄; LiCo_qFe_xNi_yMn_zPO₄, and Li₂MnSiO₄.
The electrochemical device of claim 45, wherein the electrochemical device is a sodium battery, a sodium-ion battery, a sodium-air battery, a potassium battery, a potassium-ion battery, a potassium-air battery, a magnesium battery, a magnesium-ion battery, a magnesium-air battery, an aluminum battery, an aluminum ion battery, or an aluminum-air battery.
A solvent for a non-aqueous electrolyte for an electrochemical device, the solvent comprising a carbonate compound of formula (I) as defined in any one of claims 1 to 18.
A carbonate compound of formula (I) as defined in any one of claims 1 to 18 for use as a solvent in a non-aqueous electrolyte in an electrochemical device.
Use of a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in a non-aqueous electrolyte for an electrochemical device.
A non-aqueous electrolyte for an electrochemical device, the electrolyte comprising a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent.
Use of a non-aqueous electrolyte comprising a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent, in an electrochemical device.
A method of manufacturing a non-aqueous electrolyte for an electrochemical device, the method comprising using a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in the electrolyte.
A method of suppressing anodic dissolution of aluminum in an aluminum current collector in an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in the electrolyte.
A method of enabling the use of sulfonylamide salts in high voltage electrochemical devices, the method comprising using a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in the electrolyte.
A method of increasing the maximum operation voltage of an electrochemical device containing a non-aqueous electrolyte, said electrolyte preferably comprising sulfonylamide salts, the method comprising using a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in the electrolyte.
A method of broadening the operating temperature range of an electrochemical device containing a non-aqueous electrolyte, the method comprising using a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent in the electrolyte.
An electrochemical device comprising a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent.
A method of manufacturing an electrochemical device, the method comprising using a non-aqueous electrolyte, wherein the electrolyte comprises a carbonate compound of formula (I) as defined in any one of claims 1 to 18 as a solvent.