Carbonate Solvents for Non-Aqueous Electrolytes for Metal and Metal-Ion Batteries

Abstract

A metal or metal-ion battery is provided, comprising an aluminum current collector and a low-corrosion non-aqueous electrolyte containing a carbonate compound of formula (I):(I) as a solvent. The battery has an upper voltage limit of about 4.2 V or greater, and anodic dissolution of aluminum during battery operation at that voltage is suppressed. The present invention relates to carbonate solvents for non-aqueous electrolytes for batteries. More specifically, the present invention relates to carbonate solvents for non-aqueous electrolytes characterized by their low corrosiveness to aluminum current collectors at voltages greater than 4.2 V relative to Li metal. TIFF2022529217000021.tif1834

Description

[Technical field]

[0001] The present invention relates to carbonate solvents for non-aqueous electrolytes for batteries. More specifically, the present invention relates to carbonate solvents for non-aqueous electrolytes characterized by their low corrosivity towards aluminum current collectors at voltages higher than 4.2 V vs. Li metal. [Background technology]

[0002] New technical solutions are being presented for Li and Li-ion batteries for telecommunications, especially for the charging of transport cells. Their aim is to provide such batteries with as high an energy density as possible in order to achieve higher voltage cathodes. However, this requires high-performance electrolytes that are resistant to oxidation at the high potentials that arise during the operation of such systems. Also, other parasitic processes can cause degradation and failure of the system. One such parasitic process is the corrosion or electrolytic dissolution of the current collectors, which typically becomes significant at potentials above 4 V.

[0003] The conventional electrolyte used in most lithium and lithium-ion battery systems is also used in high voltage batteries and is based on LiPF6 salt, which has many good properties. For example, it passivates most of the aluminum current collector material, has good electrical conductivity, and is relatively inexpensive. However, it also has some disadvantages, most notably its sensitivity to moisture, which leads to the formation of HF, which causes rapid deterioration of the battery's performance. Another disadvantage is its limited thermal stability, limited solubility in polymers, and the release of toxic decomposition products. The solvents used in the preparation of conventional electrolytes are inexpensively available C1-C2 dialkyl carbonates and lower cyclic carbonates, most notably ethylene carbonate and propylene carbonate.

[0004] Many salts have been presented to replace the risky LiPF6 with safer alternatives. One class of such salts is the bissulfonylamides, and indeed lithium bis(trifluoromethanesulfonyl)amide-LiTFSI has been presented as a salt for the preparation of electrolytes, including polymer electrolytes. In addition, other compounds of this class have also been presented. LiTFSI has been found to cause severe anodic dissolution (erroneously called corrosion) of the aluminum current collectors at voltages higher than 3.6 V. This means that the electrochemical charge that should be used to charge the battery is consumed due to aluminum dissolution, thereby making the battery practically unchargeable. If this process occurs at a smaller rate (meaning that only a portion of the charge is consumed by the corrosion process), the battery can be charged, but repeated charging will cause further dissolution of the current collectors. This causes a slow decrease in the contact between the active electrode coating and the current collectors, leading to a loss of capacity. This creates serious drawbacks for long-term operation with many charging and discharging of the battery system.

[0005] For this reason, to overcome these problems, lithium bis(pentafluoroethanesulfonyl)amide-LiBETI was developed, but its main drawbacks are its very high molecular weight, its high price, and, like all long-chain perfluoroalkanes, its accumulation in the body. On the other hand, two lighter salts have been presented: lithium bis(fluorosulfonyl)amide-LiFSI and asymmetric lithium N-fluorosulfonyl-trifluoromethanesulfonylamide-LiFTFSI. Other asymmetric bisfluorosulfonylamides have also been presented.

[0006] Electrolytes containing LiFSI have been cited as being able to withstand voltages up to 4.2 V. However, it is not clear, and there is no experimental evidence, that these electrolytes can withstand higher voltages.

[0007] The anodic dissolution of aluminum current collectors in sulfonic solvents has been investigated. As an alternative to molecular solvents, ionic liquids have been reported as good solvents to suppress the anodic dissolution of aluminum. However, ionic liquids are not readily available and their main drawback is their high price, making them less attractive for use in battery systems.

[0008] The effect of various solvents on the anodic dissolution of aluminum collectors caused by LiTFSI has been investigated. Collector corrosion was found to be dependent on the electrolyte solvent, with strong corrosion in the presence of carbonates and lactones and minimal corrosion in the presence of nitriles. As a result, the use of carbonate solvents with sulfonylamide salts is not recommended.

[0009] The inhibition of the anodic dissolution of aluminum can be influenced by fluoroborates, most effectively lithium difluorooxalatoborate, LiDFOB, the disadvantage being the relatively high price of this additive.

[0010] LiPF6 may also be used as an aluminum anodic dissolution inhibitor. However, very high concentrations of LiPF6 are required to effectively inhibit the anodic dissolution of aluminum. In fact, due to the high concentrations, such electrolytes would be more accurately classified as LiPF6 electrolytes with LiFSI used as an additive to LiPF6.

[0011] Another proposed solution is the use of highly concentrated electrolytes, however there are several drawbacks to such systems including the undesirably high cost and crystallization problems at low temperatures.

[0012] Attempts to protect aluminum current collectors with protective coatings have been somewhat successful, but this increases the cost and weight of the battery. Moreover, the most problematic aspect of this inhibition is that the edges are not protected because the electrodes are cut to size. Corrosion can propagate from the edges after many cycles, thus compromising the long-term operation of such cells.

[0013] Possible solvents for lithium batteries have been discussed, but little attention has been paid to undesirable processes in the current collectors. Most electrolytes used in the battery industry are based on lower dialkyl carbonates, dimethyl, diethyl and ethyl methyl carbonate, mixed with additives, among them ethylene carbonate. The synthesis of alkyl carbonates, even on an industrial scale, is very well developed. The most suitable method for their preparation in the laboratory is the transesterification reaction.

[0014] For high voltage applications, fluorinated carbonates have been proposed along with conventional LiPF6 salts. However, these solvents are very expensive and, like all long-chain fluorinated compounds, may pose serious environmental risks. Insecticidal activity of some fluorinated carbonates has also been described.

[0015] Previous solutions for inhibiting aluminum corrosion do not represent an optimal solution to the problem of anodic aluminum dissolution and therefore do not represent optimal alternatives to conventional solvents. Summary of the Invention [Means for solving the problem]

[0016] According to the present invention, the following is provided: 1. A metal or metal-ion battery, (a) a cathode comprising an aluminum current collector and having an upper potential limit of about 4.2 V or more versus a Li metal reference electrode; (b) an anode; (c) a separator membrane separating the anode and the cathode; (d) a low-corrosivity, non-aqueous electrolyte in contact with the anode and the cathode; The battery has an upper voltage limit of about 4.2 V or more, Anodic dissolution of aluminum in the aluminum current collector is suppressed during battery operation at voltages up to the upper voltage limit; The electrolyte is a compound of formula (I): [ka] [In the formula, R 1 is C3~C 24 Alkyl, C3-C 24 Alkoxyalkyl, C3-C 24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 represents ω-O-alkyl oligo(propylene glycol), R 2 is C1~C 24 Alkyl, C1-C 24 Haloalkyl, C2-C 24 Alkoxyalkyl, C 2~ C 24 Alkyloxyalkyl, C3-C 24 Alkoxycarbonylalkyl, C1-C 24 Cyanoalkyl, C1-C 24 Thiocyanatoalkyl, C3-C 24 Trialkylsilyl, C4-C 24 Trialkylsilylalkyl, C4-C 24 Trialkylsilyloxyalkyl, C3-C 24 ω-O-Alkyl oligo(ethylene glycol), C4~C 24 ω-O-alkyl oligo(propylene glycol), C5~C 24 ω-O-trialkylsilyl oligo(ethylene glycol) or C6-C 24 ω-O-trialkylsilyl oligo(propylene glycol) and a conductive salt dissolved in said solvent. 2. The battery according to item 1, wherein the upper potential limit of the cathode is about 4.4 V or more, preferably about 4.6 V or more, about 4.8 V or more, about 5.0 V or more, about 5.2 V or more, about 5.4 V or more, or about 5.5 V or more, versus a Li metal reference electrode. 3. The battery according to item 1 or 2, wherein the upper voltage limit of the battery is about 4.4 V or more, preferably about 4.6 V or more, more preferably about 4.8 V or more, even more preferably about 5.0 V or more, even more preferably about 5.2 V or more, more preferably about 5.4 V or more, or most preferably about 5.5 V or more. 4.R 1 But, C3~C 24 Alkyl or C3-C 24 ω-O-alkyl oligo(ethylene glycol), preferably C3-C 24 The battery according to any one of items 1 to 3, wherein R represents an alkyl group. 5.R 2 But, C1~C 24 Alkyl, C2-C 24 Alkoxyalkyl, C1-C 24 Cyanoalkyl, C4-C 24 Trialkylsilyloxyalkyl, C5-C 24 ω-O-trialkylsilyl oligo(ethylene glycol) or C3-C 24 ω-O-alkyl oligo(ethylene glycol), preferably C1-C 24 5. The battery according to any one of items 1 to 4, wherein R represents an alkyl group. 6.R 1 and R 2 The total number of carbon atoms in 5 or more, preferably 6 or more, more preferably 7 or more, even more preferably 8 or more, and most preferably 9 or more, and / or The battery according to any one of items 1 to 5, wherein the number of particles is 24 or less, preferably 20 or less, more preferably 16 or less, still more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less. 7.R 2 is methyl or ethyl. 8.R1 and / or R 2 8. The battery according to any one of items 1 to 7, wherein is propyl or isopropyl (2-propyl). 9.R 1 and / or R 2 is butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl) or tertbutyl (2,2-dimethylethyl). 10.R 1 and / or R 2 is one of pentyl or its isomers (including 2-pentyl and 3-pentyl, 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl and 2-methyl-2-butyl). 11.R 1 and / or R 2 is one of hexyl or 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). 12.R 1 and / or R 2 is heptyl, one of its isomers, or 2-ethylhexyl. 13.R 1 and / or R 2 13. The battery according to any one of items 1 to 12, wherein is 2-methoxyethyl or 2-isopropoxyethyl. 14.R 2 14. The battery according to any one of items 1 to 13, wherein is 2-cyanoethyl. 15.R 2 15. The battery according to any one of items 1 to 14, wherein is (2-trimethylsilyloxy)ethyl. 16.R1 and / or R 2 is 2-methoxyethyl, 2-isopropoxyethyl, or 2-(2-methoxyethoxy)ethyl. 17.R 2 17. The battery according to any one of items 1 to 16, wherein is 2-trimethylsilyloxyethyl. 18. 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, 18. The battery according to any one of items 1 to 17, wherein the carbonate is 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. 19. The battery according to any one of items 1 to 18, 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. 20. The battery according to any one of items 1 to 19, wherein the compound of formula (I) is didodecyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexylmethyl carbonate, ethyldodecyl carbonate or diisobutyl carbonate, preferably diisobutyl carbonate. 21. A conductive salt is LiClO4, ·LiP(CN) α F 6-α [wherein α is an integer from 0 to 6], preferably LiPF6, LiB(CN) β F 4-β [wherein β is an integer from 0 to 4], preferably LiBF4, ·LiP(C n F 2n+1 ) γ F 6-γ [In the formula, n is an integer of 1 to 20, and γ is an integer of 1 to 6] · LiB(C n F 2n+1 ) δ F 4-δ [In the formula, n is an integer of 1 to 20, and δ is an integer of 1 to 4] Li2Si(C n F 2n+1 ) ε F 6-ε [In the formula, n is an integer of 1 to 20, and ε is an integer of 0 to 6] Lithium bis(oxalato)borate, Lithium difluorooxalatoborate or The general formula: [ka] [In the formula, R 3 represents Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen or an organic cation; R 4 , R 5 , R 6 , R 7 , R 8 represents cyano, fluorine, chlorine, a branched or linear alkyl radical having 1 to 24 carbon atoms, a perfluorinated linear alkyl radical having 1 to 24 carbon atoms, an aryl, a heteroaryl, a perfluorinated aryl or a heteroaryl] 21. The battery according to any one of items 1 to 20, wherein the compound represented by any one of the following formulas is a compound represented by any one of the following formulas: 22. The battery according to any one of items 1 to 21, wherein the conductive salt is a sulfonylamide salt. 23. The battery according to any one of items 1 to 22, wherein the conductive salt is a lithium salt, preferably a lithium sulfonylamide salt. 24. The battery of item 23, wherein the lithium sulfonylamide salt is lithium bis(fluorosulfonyl)amide (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI) or lithium N-fluorosulfonyl-trifluoromethanesulfonylamide (LiFTFSI). 25. The battery of item 24, wherein the conductive salt is LiFSI. 26. The battery according to any one of items 1 to 22, wherein the conductive salt is a sodium, potassium, calcium, aluminum or magnesium salt. 27. The battery according to any one of items 1 to 26, wherein the conductive salt is present in the electrolyte at a concentration of at least about 0.05M, at least about 0.1M, at least about 0.5M or at least about 1M, and / or at most about 3M, at most about 2M, at most about 1.5M or at most about 1M. 28. The battery according to item 27, wherein the concentration of the conductive salt in the electrolyte is 1M. 29. The battery of any one of items 1 to 28, wherein the electrolyte further comprises one or more additives. 30. One or more additives Agents for improving the solid electrolyte interface and cycle characteristics, unsaturated carbonates to improve stability at high and low voltages, and / or 30. The battery according to item 29, wherein the organic solvent reduces the viscosity and increases the conductivity. 31. The battery according to item 30, wherein the agent for improving the solid electrolyte interface (SEI) and cycling properties, and the unsaturated carbonate together represent in total at least about 0.1% w / w, at least about 1% w / w, at least about 2% w / w, at least about 5% w / w, or at least about 7% w / w, and / or up to about 20% w / w, up to about 15% w / w, up to about 10% w / w, or up to about 7% w / w of the total weight of the electrolyte. 32. The battery according to item 30 or 31, wherein the viscosity-reducing and conductivity-increasing organic solvents represent in total 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 up to about 80% v / v, up to about 50% v / v, up to about 20% v / v, up to about 15% v / v, up to about 10% v / v or up to about 7% v / v of the total volume of the electrolyte. 33. The battery according to any one of items 1 to 29, wherein the carbonate compound of formula (I) is the only solvent in the electrolyte. 34. The battery of any one of items 29 to 32, wherein the one or more additives are fluoroethylene carbonate (FEC), ethylene carbonate (EC), diethyl carbonate (DEC), or a mixture thereof. 35. One or more additives is FEC, preferably about 2 w / w% FEC, alone or together with EC, DEC or a mixture, thus preferably alone or EC of about 5% v / v, EC of about 10% v / v, EC of about 15% v / v, EC of about 20% v / v, EC of about 30% v / v, A mixture of EC and DEC at about 20% v / v, A mixture of EC and DEC at about 25% v / v, A mixture of EC and DEC at about 30% v / v, A mixture of EC and DEC at about 50% v / v, A mixture of EC and DEC at approximately 70% v / v, or Approximately 75% v / v mixture of EC and DEC and wherein the mixture preferably has an EC:DEC volume ratio of about 1:10 to about 1:1, preferably about 3:7; 35. The battery of item 34, wherein all w / w % are based on the total weight of the electrolyte and all v / v % are based on the total volume of the electrolyte. 36. The battery according to any one of items 1 to 35, wherein the carbonate compound of formula (I), the carbonate compound of formula (I) represents at least about 25% v / v, preferably at least about 50% v / v, more preferably at least about 75% v / v, even more preferably at least about 85% v / v, even more preferably at least about 90% v / v, and most preferably at least about 95% of the total volume of the electrolyte. 37. The battery of any one of items 1 to 36, wherein the electrolyte does not contain a corrosion inhibitor. 38. The battery of any one of items 1 to 36, wherein the electrolyte further comprises one or more corrosion inhibitors, such as LiPF6, lithium cyanofluorophosphate, lithium fluorooxalatophosphate, LiDFOB, LiBF4, lithium fluorocyanoborate, or LiBOB. 39. The battery according to item 37, wherein the corrosion inhibitors, in total, represent at least about 1% w / w, at least about 2% w / w, at least about 5% w / w, or at least about 10% w / w, and / or up to about 35% w / w, up to about 25% w / w, up to about 20% w / w, up to about 15% w / w, up to about 10% w / w, or up to about 7% w / w of the total weight of the electrolyte. 40. The battery according to any one of items 1 to 38, which is a lithium battery or a lithium ion battery, preferably a lithium ion battery. 41. The battery of item 40, wherein the anode is made of lithium metal or graphite. 42. The cathode comprises a lithium compound disposed on an aluminum current collector, the lithium compound preferably comprising: ·LNO(LiNiO2), LMO(LiMn2O4), LiCo x Ni 1-x O2 [wherein x is 0.1 to 0.9], LMC (LiMnCoO2), LiCu x Mn 2-x O4, NMC (LiNi x Mn y Co z O2) or NCA (LiNi x Co y Al z Lithiated oxides of transition metals, such as O2), or ·LFP(LiFePO4), LNP(LiNiPO4), LMP(LiMnPO4), LCP(LiCoPO4), Li2FCoPO4;LiCo q Fe x Ni y Mn z 42. The battery according to item 40 or 41, wherein the lithium compound is a lithium compound of a transition metal and a complex anion, such as PO4 or Li2MnSiO4. 43. The battery according to item 42, wherein the lithium compound is LMN or LCO. 44. The battery according to any one of items 1 to 39, which is a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery, a magnesium ion battery, an aluminum battery or an aluminum ion battery. 45. Formula (I): [ka] [In the formula, R 1 is C3~C 24 Alkyl, C3-C 24 Alkoxyalkyl, C3-C24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 represents ω-O-alkyl oligo(propylene glycol), R 2 is C1~C 24 Alkyl, C1-C 24 Haloalkyl, C2-C 24 Alkoxyalkyl, C2-C 24 Alkyloxyalkyl, C3-C 24 Alkoxycarbonylalkyl, C1-C 24 Cyanoalkyl, C1-C 24 Thiocyanatoalkyl, C3-C 24 Trialkylsilyl, C4-C 24 Trialkylsilylalkyl, C4-C 24 Trialkylsilyloxyalkyl, C3-C 24 ω-O-Alkyl oligo(ethylene glycol), C4~C 24 ω-O-alkyl oligo(propylene glycol), C5~C 24 ω-O-Silyl oligo(ethylene glycol) or C6~C 24 represents ω-O-silyl oligo(propylene glycol), However, R 2 is C1-C9 alkyl, R 1 is C 10 ~C 24 Alkyl, C3-C 24 Alkoxyalkyl, C3-C 24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 A carbonate compound of ω-O-alkyloligo(propylene glycol). 46.R 2 is C1-C9 alkyl, R 1 But, C3~C 24 Alkoxyalkyl, C3-C 24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 46. ​​The carbonate compound according to item 45, which represents an ω-O-alkyl oligo(propylene glycol). 47.R 1and R 2 The total number of carbon atoms in 5 or more, preferably 6 or more, more preferably 7 or more, even more preferably 8 or more, and most preferably 9 or more, and / or 47. The carbonate compound according to item 45 or 46, having 24 or less, preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less. 48.R 1 But, C3~C 24 Alkyl, C3-C 24 Alkoxyalkyl or C3-C 24 ω-O-alkyl oligo(ethylene glycol), preferably C3-C 24 Alkyl or C3-C 24 Alkoxyalkyl, more preferably C3-C 24 48. The carbonate compound according to any one of items 45 to 47, wherein R represents an alkyl group. 49.R 2 But, C1~C 24 Alkyl, C2-C 24 Alkoxyalkyl, C1-C 24 Cyanoalkyl, C4-C 24 Trialkylsilyloxyalkyl, C5-C 24 ω-O-Silyl oligo(ethylene glycol) or C3-C 24 ω-O-alkyl oligo(ethylene glycol), preferably C1-C 24 Alkyl or C2-C 24 Alkoxyalkyl, more preferably C1-C 24 49. The carbonate compound according to any one of items 45 to 48, wherein R represents an alkyl group. 50.R 1 C 10 ~C 24 Alkyl (preferably C 12 ~C 24 Alkyl, more preferably C 14 ~C 24 alkyl), and R 2 C1~C 2450. The carbonate compound according to any one of items 45 to 49, wherein R represents an alkyl group. 51.R 1 C3~C 24 represents alkyl, R 2 C1~C 24 50. The carbonate compound according to any one of items 45 to 49, which represents a cyanoalkyl. 52. The carbonate compound according to item 49, wherein the cyanoalkyl is 2-cyanoethyl. 53.R 1 C3~C 24 represents alkyl, R 2 C2~C 24 50. The carbonate compound according to any one of items 45 to 49, wherein the alkoxyalkyl is an alkoxyalkyl. 54.R 1 C3~C 24 represents an alkoxyalkyl group, and R 2 C1~C 24 50. The carbonate compound according to any one of items 45 to 49, wherein R represents an alkyl group. 55.R 1 and R 2 Both are C3~C 24 50. The carbonate compound according to any one of items 45 to 49, wherein the alkoxyalkyl is an alkoxyalkyl. 56. The carbonate compound according to any one of items 53 to 55, wherein the alkoxyalkyl is 2-methoxyethyl or 2-isopropoxyethyl. 57.R 1 C3~C 24 represents alkyl, R 2 C4~C 24 50. The carbonate compound according to any one of items 45 to 49, which represents a trialkylsilyloxyalkyl. 58. The carbonate compound according to item 57, wherein the trialkylsilyloxyalkyl is (2-trimethylsilyloxy)ethyl. 59.R 1 and R 2 Both are C3~C 2450. The carbonate compound according to any one of items 45 to 49, which represents an ω-O-alkyl oligo(ethylene glycol). 60. The carbonate compound according to item 59, wherein the ω-O-alkyl oligo(ethylene glycol) is 2-(2-methoxyethoxy)ethyl. 61. The carbonate compound according to any one of items 45 to 49, wherein the carbonate compound of formula (I) is didodecyl carbonate, ethyl dodecyl 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. 62. The carbonate compound according to item 61, wherein the compound of formula (I) is didodecyl carbonate, ethyl dodecyl carbonate, 2-cyanoethyl butyl carbonate, 2-methoxyethyl isobutyl carbonate, (2-trimethylsilyloxy)ethyl butyl carbonate or di(2-isopropoxyethyl)carbonate. 63. The carbonate compound according to item 62, wherein the compound of formula (I) is didodecyl carbonate or ethyl dodecyl carbonate. [Brief description of the drawings]

[0017] In the attached drawings, [Figure 1] Chronoamperometry of an aluminum current collector versus Li metal in conventional electrolytes containing LIFSI and EC / DEC at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each 1 h wide). [Diagram 2] Chronoamperometry of an aluminum current collector versus Li metal in conventional electrolytes with LIFTFSI and EC / DEC at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each 1 h wide). [Diagram 3]Chronoamperometry of an aluminum current collector versus Li metal in conventional electrolytes containing LITFSI and EC / DEC at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each 1 h wide). [Figure 4] 1 shows chronoamperometry of an aluminum current collector versus Li metal in an electrolyte according to an embodiment of the invention containing LIFSI and diisobutyl carbonate at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each width 1 h). [Diagram 5] 1 shows the chronoamperometry of an aluminum current collector versus Li metal in an electrolyte according to an embodiment of the invention containing LIFTFSI and diisobutyl carbonate at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each width 1 h). [Figure 6] 1 shows the chronoamperometry of an aluminum current collector versus Li metal in an electrolyte according to an embodiment of the invention containing LITFSI and diisobutyl carbonate at potentials increasing from 4 V to 5.5 V in 0.1 V steps (each width 1 h). [Figure 7] 1 shows the charge / discharge curves of an LCO cathode versus Li metal in conventional electrolytes including LIFSI and EC / DEC. [Figure 8] 1 shows charge / discharge curves of an LCO cathode versus Li metal in an electrolyte according to an embodiment of the invention comprising LIFSI and diisobutyl carbonate. [Figure 9] 1 shows charge / discharge curves of an LCO cathode versus Li metal in an electrolyte according to an embodiment of the invention including LIFSI and diisobutyl carbonate+EC. [Figure 10] 1 shows the charge / discharge curves of LMN cathode versus Li metal in conventional electrolytes including LIFSI and EC / DEC. [Figure 11] 1 shows charge / discharge curves of an LMN cathode versus Li metal in an electrolyte according to an embodiment of the invention comprising LIFSI and diisobutyl carbonate. [Figure 12]Discharge capacity versus cycle number for three cells is shown; the first cell uses LiFSI in diisobutyl carbonate, the second cell uses LiFSI in 90% diisobutyl carbonate / 10% EC, and the third cell uses a conventional electrolyte of 1 M LiPF6 in EC / DEC (3:7 by volume). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The inventors have found that the carbonate compounds of formula (I) can be advantageously used as solvents in non-aqueous electrolytes in batteries with one cathode with an aluminum current collector, since they are characterized by low corrosivity towards aluminum, even at voltages higher than 4.2 V, even in electrolytes containing lithium sulfonylamide salts. It is not usually possible to utilize these lithium sulfonylamide salts together with conventional solvents in such high voltage systems, since the anodic dissolution of aluminum becomes the dominant electrochemical reaction, and a large part of the charge is consumed for this detrimental corrosion process.

[0019] The low corrosiveness of the carbonate compounds of formula (I) is particularly advantageous when the lithium sulfonylamide salt is the primary conductive salt, but those skilled in the art will recognize the potential of these solvents in conjunction with other conductive salts to achieve high voltage lithium and lithium ion batteries. Those skilled in the art will also recognize that the electrolytes can be used in various types of batteries, such as sodium, potassium, calcium, aluminum and magnesium based batteries, and in so doing, other salts, such as sodium, potassium, calcium, aluminum and magnesium salts, can be dissolved in the solvent.

[0020] Indeed, the carbonate compounds of formula (I) are characterized by their ability to inhibit anode dissolution of aluminum (e.g., in an aluminum current collector, and any other aluminum components in a battery), when used as a solvent in an electrolyte in a battery, even at potentials higher than 4.2 V, measured against a lithium metal reference electrode. Examples of such batteries are lithium or lithium-ion batteries. For clarity, unless otherwise specified, all electrode potentials in this application are referenced to a Li metal anode.

[0021] Anodic dissolution of an aluminum current collector is defined as the dissolution of the aluminum current collector at a certain external forced potential (critical potential) higher than the open circuit potential. At the critical potential, components of the electrolyte react with the surface of the collector to form soluble compounds that then dissolve in the electrolyte, causing dissolution of the aluminum, i.e., quasi corrosion. Significant dissolution of aluminum can result in failure of the battery system if its operating voltage exceeds the critical potential. Thus, inhibiting anode dissolution enables safer and more powerful battery technology, especially lithium-ion batteries. As used herein, "inhibiting" anode dissolution means that anode dissolution does not occur or is reduced to a level that is not harmful to the battery.

[0022] This low corrosiveness of the carbonate compounds of formula (I) also allows the fabrication of batteries containing aluminum current collectors with extended operating voltages, even in the case of lithium sulfonyl amide salt-containing electrolytes and lithium ion batteries, particularly operating voltages greater than 4.2 V vs. Li metal reference electrode, which allows the preparation of lithium sulfonyl amide salt-containing non-aqueous electrolytes that are free of corrosion inhibitors, while still maintaining said low corrosiveness to aluminum current collectors at voltages greater than 4.2 V.

[0023] Furthermore, compared to conventional carbonate solvents (e.g., ethylene carbonate (EC), diethyl carbonate (DEC), etc.), the carbonate compounds of formula (I) have a wider operating temperature range, especially when used in lithium-ion batteries. In fact, the temperature range in which the carbonate compounds of formula (I) are liquid (without crystallizing) tends to be wider than the temperature range of these conventional carbonate solvents. For example, in embodiments, the carbonate compounds of formula (I) may have a melting point well below -10°C, or even no melting point, and thus remain liquid without crystallizing until the carbonate compounds of formula (I) reach their glass transition point. Furthermore, the melting point of carbonate compounds tends to decrease to a certain point with increasing molecular weight.

[0024] In addition, the carbonate compounds of formula (I) have higher boiling points than conventional carbonate solvents. For example, the boiling points of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and dibutyl carbonate are 90°C, 126°C, 168°C and 207°C, respectively. This means that electrolytes prepared from higher carbonates can be used at higher temperatures without the risk of rapid evaporation. These higher boiling points improve the safety of batteries containing electrolytes that use the carbonate compounds of formula (I) as a solvent.

[0025] Finally, the carbonate compounds of formula (I) are a very green, or environmentally friendly, class of solvents.

[0026] Accordingly, the inventors herein provide a metal or metal-ion battery comprising: (a) a cathode comprising an aluminum current collector and having an upper potential limit of about 4.2 V or more versus a Li metal reference electrode; (b) an anode; (c) a separator membrane separating the anode and the cathode; (d) a low-corrosivity, non-aqueous electrolyte in contact with the anode and the cathode; The battery has an upper voltage limit of about 4.2 V or more, Anodic dissolution of aluminum in the aluminum current collector is suppressed during battery operation at voltages up to the upper voltage limit; A metal or metal ion battery is provided in which the electrolyte comprises a carbonate compound of formula (I) as a solvent and a conductive salt dissolved in the solvent.

[0027] In embodiments, the upper potential limit of the cathode is preferably about 4.4 V or more, about 4.6 V or more, about 4.8 V or more, about 5.0 V or more, about 5.2 V or more, about 5.4 V or more, or about 5.5 V or more versus a Li metal reference electrode.

[0028] In embodiments, the upper potential limit of the cathode is preferably about 6.0 V or less, about 5.6 V or less, about 5.5 V or less, about 5.4 V or less, about 5.2 V or less, about 5.0 V or less, or about 4.8 V or less versus a Li metal reference electrode.

[0029] In embodiments, the upper voltage limit of the battery is preferably about 4.4V or more, about 4.6V or more, about 4.8V or more, about 5.0V or more, about 5.2V or more, about 5.4V or more, or about 5.5V or more.

[0030] In embodiments, the upper voltage limit of the battery is preferably about 6.0V or less, about 5.6V or less, about 5.5V or less, about 5.4V or less, about 5.2V or less, about 5.0V or less, about 4.8V or less.

[0031] The lower potential limit of the cathode and the lower voltage limit of the cell are not substantially affected by using the carbonate compound of formula (I) as a solvent in the cell of the present invention. In fact, these lower limits are not critical to the present invention, since anodic dissolution occurs only at elevated potentials. Furthermore, the lower potential limit of the cathode is typically not affected by the solvent used in the electrolyte. Thus, these lower limits are those found in the corresponding conventional cells using other solvents.

[0032] In fact, the cathode is characterized by a potential window that goes from a lower potential limit to an upper potential limit. The lower potential limit is the potential beyond which further discharging may damage the cathode. The upper potential limit is the potential beyond which further charging may damage the cathode. These potential values ​​are always given relative to a certain reference. For example, for all lithium batteries, this reference is the Li metal reference electrode. In this specification, the potential values ​​are all relative to the Li metal reference electrode, even when referring to other types of batteries (sodium-based batteries, magnesium-based batteries, etc.).

[0033] Furthermore, batteries are characterized by an operating voltage window that goes from a lower voltage limit to an upper voltage limit. The lower voltage limit is the voltage at which the battery is considered fully discharged and above which further discharging may damage the battery (or its components). The upper potential limit is the voltage at which the battery is considered fully charged and above which further charging may damage the battery (or its components). Thus, batteries operate at voltages within their operating voltage window, i.e., they are charged / discharged so that their voltages fall within their operating voltage window, ideally as close as possible to the upper voltage limit when charged to provide maximum energy.

[0034] It should be noted that the cell voltage is the difference between the potential of the cathode and the potential of the anode. Battery voltage = (cathode potential) - (anode potential) Therefore, no reference is needed when providing the battery voltage value.

[0035] If the anode of the battery is lithium metal, it (always) has a potential of 0V. Thus, in such a case, the upper and lower voltage limits of the battery are equal to the upper and lower potential limits of the cathode. In other cases, such as when the anode is made of graphite, the anode has a potential of >0V. When the anode has a potential of >0V, the upper and lower voltage limits of the battery are lower than the upper and lower potential limits of the cathode, respectively. For example, a graphite anode (in most cases) has a potential of about 0.1V, but this potential can nevertheless vary from about 2.5V to very close to 0V. An LTO anode has a potential of about 1.5V in most cases.

[0036] As mentioned above, the anodic dissolution of aluminum in the aluminum current collector is inhibited during the operation of the cell at least up to the upper voltage limit. In this specification, "inhibition" of anodic dissolution means that the phenomenon does not occur at all or is limited so that the cell can be charged up to the upper voltage limit without losing a significant portion of the charge due to anodic dissolution of aluminum. For example, less than 0.01%, preferably less than 0.001%, more preferably less than 0.0001% of the charge is lost. In another scale, the corrosion current density is about 1 μA / cm 2 It is preferable that the anodic dissolution voltage is less than 1000 V. In fact, if significant anodic dissolution occurs within the operating voltage window of the battery, a significant amount of charge is lost, a significant amount of aluminum is dissolved, the contact between the current collector and the active material is lost, and the effective capacity is further lost. In the worst case, when the battery is first charged, most of the charge is consumed by aluminum dissolution, which means that the amount of charge stored by the battery (i.e., the effective amount of charge) is very small. In other words, the battery does not work. In particular, electrolytes containing bis(sulfonyl amide) salts (e.g., of lithium or of other metals in batteries based on other metals) can cause such severe anodic dissolution of aluminum. In contrast, dissolving such salts in the carbonate compound of formula (I) as a solvent successfully suppresses anodic dissolution.

[0037] In a preferred embodiment, the battery is a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery, a magnesium ion battery, an aluminum battery or an aluminum ion battery. Preferably, the battery is a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery or a magnesium ion battery. In a more preferred embodiment, the battery of the present invention is a lithium battery or a lithium ion battery, and even more preferably a lithium ion battery.

[0038] Further details of the various components of the batteries of the present invention are provided in the following sections.

[0039] Also provided is a method of making and / or operating a battery as described above, the method comprising charging the battery to an upper voltage limit of about 4.2 V or greater, preferably about 4.4 V or greater, about 4.6 V or greater, about 4.8 V or greater, about 5.0 V or greater, about 5.2 V or greater, about 5.4 V or greater, or about 5.5 V or greater.

[0040] Carbonate compounds of formula (I) The carbonate compound of formula (I) is [ka] where: R 1 is C3~C 24 Alkyl, C3-C 24 Alkoxyalkyl, C3-C 24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 represents ω-O-alkyl oligo(propylene glycol), R 2 is C1~C 24 Alkyl, C1-C 24 Haloalkyl, C2-C 24 Alkoxyalkyl, C 2~ C 24 Alkyloxyalkyl, C3-C24 Alkoxycarbonylalkyl, C1-C 24 Cyanoalkyl, C1-C 24 Thiocyanatoalkyl, C3-C 24 Trialkylsilyl, C4-C 24 Trialkylsilylalkyl, C4-C 24 Trialkylsilyloxyalkyl, C3-C 24 ω-O-Alkyl oligo(ethylene glycol), C4~C 24 ω-O-alkyl oligo(propylene glycol), C5~C 24 ω-O-trialkylsilyl oligo(ethylene glycol) or C6-C 24 It represents ω-O-trialkylsilyl oligo(propylene glycol).

[0041] In a more preferred embodiment, R 1 is C3~C 24 Alkyl or C3-C 24 In a more preferred embodiment, R 1 is C3~C 24 Represents alkyl.

[0042] In a more preferred embodiment, R 2 is C1~C 24 Alkyl, C2-C 24 Alkoxyalkyl, C1-C 24 Cyanoalkyl, C4-C 24 Trialkylsilyloxyalkyl, C5-C 24 ω-O-trialkylsilyl oligo(ethylene glycol) or C3-C 24 In the most preferred embodiment, R 2 is C1~C 24 Represents alkyl.

[0043] The previously defined R 1 and R 2 containing at least 3 and 1 carbon atoms, respectively, R 1 and R 2The total number of carbon atoms in R is at least 4. 1 and R 2 The total number of carbon atoms in 5 or more, preferably 6 or more, more preferably 7 or more, even 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, even more preferably 14 or less, even more preferably 12 or less, and most preferably 10 or less.

[0044] R 1 and R 2 Each of the alkyl and substituted alkyl in is linear or branched.

[0045] As used herein, "alkyl" has its usual meaning in the art. Specifically, it refers to a group of the general formula -C n H 2n+1 is a monovalent saturated aliphatic hydrocarbon radical.

[0046] R 1 C3~C in 24Non-limiting examples of alkyl include 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 a preferred embodiment, R 1 C3~C in 24 Alkyl is C3-C 18 Alkyl, preferably C3-C 12 Alkyl, preferably C3-C 11 Alkyl, preferably C3-C 10 Alkyl, preferably C3-C9 alkyl, more preferably C3-C8 alkyl, even more preferably C3-C7 alkyl (still more preferably C4-C7 alkyl), still more preferably C3-C6 alkyl (still more preferably C4-C6 alkyl), more preferably C3-C5 alkyl, and most preferably C4-C5 alkyl.

[0047] R 2 C1~C in 24 Non-limiting examples of alkyl chains include R 1 Regarding C3 to C 24 alkyl, as well as methyl and ethyl. In a preferred embodiment, R 2 is C1~C 18 Alkyl, preferably C1-C 12alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C2-C7 alkyl, C3-C7 alkyl (preferably C4-C7 alkyl), C3-C6 alkyl (preferably C4-C6 alkyl), C3-C5 alkyl, and most preferably C4-C5 alkyl.

[0048] In a preferred embodiment, R 1 and R 2 are both alkyl groups. In a more preferred embodiment, R 1 and R 2 are the same alkyl group. In an alternative preferred embodiment, R 1 and R 2 are different alkyl groups.

[0049] R 1 and R 2 Preferred C3 alkyl in the formula (I) include propyl and isopropyl (2-propyl).

[0050] R 1 and R 2 Preferred C4 alkyl in the formula (I) include butyl, 2-butyl, 3-butyl, isobutyl (3-methylpropyl) and tertbutyl (2,2-dimethylethyl).

[0051] R 1 and R 2 Preferred C5 alkyl in the formula (I) include pentyl and its isomers (including 2-pentyl and 3-pentyl), 2-methylbutyl, 3-methylbutyl, 1-methyl-2-butyl and 2-methyl-2-butyl.

[0052] R 1 and R 2Preferred C6 alkyl in the formula (I) include 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.

[0053] R 1 and R 2 Preferred C7 alkyl in the formula (I) include heptyl and its isomers.

[0054] R 1 and R 2 A preferred C8 alkyl in the formula (I) is 2-ethylhexyl.

[0055] As used herein, "haloalkyl" refers to an alkyl group in which one or more (or even all) of the hydrogen atoms are respectively replaced by halogen atoms, which may be the same or different from each other (when more than one halogen atom is present). Halogen atoms include fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). Preferably, the halogen atom is fluorine. R 2 C1~C in 24 Non-limiting examples of haloalkyls include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, 2,2,2-trifluoroethyl, and 1,1,1,3,3,3-hexafluoro-2-propyl.

[0056] As used herein, "alkoxyalkyl" refers to an alkyl group in which one or more, preferably one, of the hydrogen atoms are each replaced by an alkoxy group, which alkoxy groups are identical or different from each other (when more than one alkoxy group is present). In a preferred embodiment, the alkoxyalkyl contains only one alkoxy group. An alkoxy group is a radical of the formula -O-alkyl, where the alkyl is linear or branched, preferably linear. C2-C 24 An alkoxyalkyl is an alkoxyalkyl radical in which the sum of the number of carbon atoms in the alkyl and alkoxy groups is 2 to 24. In a preferred embodiment, the alkoxyalkyl is a (C1-C2)alkoxy(C2-C6)alkyl. R 2 or R 1 Non-limiting examples of alkoxyalkyl in include 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 5-methoxypentyl, 6-methoxyhexyl and 2-isopropoxyethyl. In a preferred embodiment, the alkoxyalkyl is 2-methoxyethyl or 2-isopropoxyethyl.

[0057] As used herein, "alkyloyloxyalkyl" refers to an alkyl group in which one or more, preferably one, of the hydrogen atoms are each replaced by an alkyloyloxy group, and if more than one alkyloyloxy group is present, the alkyloyloxy groups are the same or different). In a preferred embodiment, the alkyloyloxyalkyl contains only one alkyloyloxy group. An alkyloyloxy group is a radical of the formula -OC(=O)-alkyl, where the alkyl is linear or branched. C2-C 24 The alkyloyloxyalkyl is an alkyloyloxyalkyl having 2 to 24 carbon atoms in total contained in the alkyl and alkyloyloxy groups. 2 C2~C in 24Non-limiting examples of alkyloyloxyalkyl include 2-acetoxyethyl, 3-acetoxypropyl, 2-acetoxypropyl, and 4-acetoxybutyl.

[0058] As used herein, "alkoxycarbonylalkyl" refers to an alkyl group in which one or more of the hydrogen atoms are respectively replaced by an alkoxycarbonyl group, the alkoxycarbonyl groups being identical or different from each other (when more than one alkoxycarbonyl group is present). In a preferred embodiment, the alkoxycarbonylalkyl contains only one alkoxycarbonyl group. An alkoxycarbonyl group is a radical of the formula -C(=O)-O-alkyl, where the alkyl is linear or branched. C2-C 24 The alkoxycarbonyl is an alkoxycarbonyl having 3 to 24 carbon atoms in total in the alkyl and alkoxycarbonyl groups. 2 C3~C in 24 Non-limiting examples of alkoxycarbonylalkyl include 2-ethoxycarbonylethyl and 3-methoxycarbonylpropyl.

[0059] As used herein, "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 contains only one cyano group. In preferred embodiments, the cyanoalkyl is a C1-C5 cyanoalkyl. R 2 C1~C in 24 Non-limiting examples of cyanoalkyl include cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, and 5-cyanopentyl. In a preferred embodiment, R 2 C1~C in 24 Cyanoalkyl is 2-cyanoethyl.

[0060] As used herein, "thiocyanatoalkyl" refers to an alkyl group in which one or more of the hydrogen atoms are each replaced by a thiocyanato (-SC≡N) group. In preferred embodiments, a thiocyanatoalkyl contains only one thiocyanato group. R 2 C1~C in 24 Non-limiting examples of thiocyanatoalkyls include thiocyanatomethyl, 2-thiocyanatoethyl, 3-thiocyanatopropyl, 4-thiocyanatobutyl, 5-thiocyanatopentyl, and 6-thiocyanatohexyl.

[0061] As used herein, "trialkylsilyl" refers to a radical of the formula (alkyl)3-Si-, where the alkyl groups are the same or different and linear or branched. C3 to C 24 The trialkylsilyl is a trialkylsilyl having a total number of carbon atoms contained in all the alkyl groups of 3 to 24. In a preferred embodiment, each of the alkyl groups in the trialkylsilyl is a C1 to C4 alkyl group. In a preferred embodiment, the three alkyl groups are the same. R 2 C3~C in 24 Non-limiting examples of trialkylsilyls include trimethylsilyl, ethyldimethylsilyl, diethylmethylsilyl, triethylsilyl, dimethylpropylsilyl, dimethylisopropylsilyl, triisopropylsilyl, butyldimethylsilyl, and tertbutyldimethylsilyl.

[0062] As used herein, "trialkylsilylalkyl" refers to alkyl groups in which one or more of the hydrogen atoms are respectively replaced by trialkylsilyl groups, where trialkylsilyl is as defined above and may be the same or different (when more than one trialkylsilyl group is present). 24 In the trialkylsilylalkyl, the total number of carbon atoms contained in all four alkyl groups is 4 to 24. Preferably, the trialkylsilylalkyl contains only one trialkylsilyl group. In a preferred embodiment, 24Trialkylsilylalkyl is trialkylsilylalkyl(C1-C4)alkyl, preferably trialkylsilylalkyl(C2-C4)alkyl. In a preferred embodiment, the three alkyl groups bonded to the Si atom are methyl groups. R 2 C4~C in 24 Non-limiting examples of trialkylsilylalkyl include trimethylsilylethyl, 2-trimethylsilylethyl, 3-trimethylsilylpropyl, and 4-trimethylsilylbutyl.

[0063] As used herein, "trialkylsilyloxyalkyl" refers to an alkyl group in which one or more of the hydrogen atoms are respectively replaced by a trialkylsilyloxy group, and the trialkylsilyloxy groups are the same or different from each other (when more than one trialkylsilyloxy group is present). Preferably, a trialkylsilyloxyalkyl contains only one trialkylsilyloxy group. As used herein, "trialkylsilyloxy" refers to a radical of formula (alkyl)3-Si-O-, where the alkyl groups are the same or different from each other and are linear or branched. C4 to C 24 In the trialkylsilyloxyalkyl, the total number of carbon atoms contained in all four alkyl groups is 4 to 24. In a preferred embodiment, 24 Trialkylsilyloxyalkyl is trialkylsilyloxy(C3-C4)alkyl. In a preferred embodiment, the three alkyl groups bonded to the Si atom are methyl groups. R 2 C4~C in 24 Non-limiting examples of trialkylsilyloxyalkyl include (2-trimethylsilyloxy)ethyl, 3-trimethylsilyloxypropyl, and 4-trimethylsilyloxybutyl. In a preferred embodiment, R 2 C4~C in 24 Trialkylsilyloxyalkyl is (2-trimethylsilyloxy)ethyl.

[0064] As used herein, ω-O-alkyloligo(ethylene glycol) has the formula -(CH-CH-O-) n -alkyl radical, where n is 1 or more. C3-C 24 In the ω-O-alkyl oligo(ethylene glycol), the total number of carbon atoms in the alkyl and (CH2-CH2-O-) repeating motif is 3 to 24. In a preferred embodiment, n is an integer from 1 to 5. In a preferred embodiment, the alkyl group is a C1 to C4 alkyl. R 2 or R 1 Non-limiting examples of ω-O-alkyloligo(ethylene glycol) in include 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. 2 or R 1 The ω-O-alkyl oligo(ethylene glycol) is 2-methoxyethyl, 2-isopropoxyethyl or 2-(2-methoxyethoxy)ethyl.

[0065] As used herein, ω-O-alkyl oligo(propylene glycol) refers to a group having the formula -(CH-CH-CH-O-) n -alkyl radical, where n is 1 or more. C4-C 24 In ω-O-alkyl oligo(propylene glycol), the total number of carbon atoms in the alkyl and (CH2-CH2-CH2-O-) repeating motifs is 4 to 24. In a preferred embodiment, n is 1. In a preferred embodiment, the alkyl group is a C1 to C4 alkyl. R 2 or R 1Non-limiting examples of ω-O-alkyl oligo(propylene glycol)s include 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.

[0066] As used herein, ω-O-trialkylsilyl oligo(ethylene glycol) refers to a group having the formula -(CH-CH-O-) n -Si-(alkyl)3 radical, where the alkyl groups are the same or different, linear or branched, and n is 1 or more. C5-C 24 In ω-O-trialkylsilyl oligo(ethylene glycol), the total number of carbon atoms in the alkyl groups and the (CH2-CH2-O-) repeating motif is 5 to 24. In a preferred embodiment, n is an integer from 1 to 5. In a preferred embodiment, the three alkyl groups (bonded to the Si atom) are methyl groups. R 2 Non-limiting examples of ω-O-trialkylsilyloligo(ethylene glycol)s in include 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 a preferred embodiment, R 2 The ω-O-trialkylsilyl oligo(ethylene glycol) is 2-trimethylsilyloxyethyl.

[0067] As used herein, ω-O-trialkylsilyl oligo(propylene glycol) refers to a compound of the formula -(CH-CH-CH-O-) n -Si-(alkyl)3 radicals, where the alkyl groups are the same or different, linear or branched, and n is 1 or more. C6 to C 24In ω-O-trialkylsilyl oligo(ethylene glycol), the total number of carbon atoms in the alkyl groups and the (CH2-CH2-CH2-O-) repeating motif is 6 to 24. In a preferred embodiment, n is 1. In a preferred embodiment, the three alkyl groups (bonded to the Si atom) are methyl groups. R 2 Non-limiting examples of ω-O-trialkylsilyloligo(propylene glycol)s include 2-trimethylsilyloxypropyl and 1-trimethylsilyloxy-2-propyl.

[0068] 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, methylhexyl carbonate, ethylhexyl carbonate, propylhexyl carbonate, butylhexyl carbonate, pentylhexyl carbonate, dihexyl carbonate, isopropylhexyl carbonate, isobutylhexyl 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, tert-butyl 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 butyl 2-cyanoethyl 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, tert-butyl 2-cyanoethyl carbonate, 2-cyanoethyl pentyl carbonate, 2-cyanoethyl 2-pentyl carbonate, 2-cyanoethyl 3-Pentyl carbonate, 2-cyanoethylhexyl carbonate, 2-cyanoethylheptyl carbonate, 2-cyanoethyloctyl carbonate, 2-cyanoethylnonyl carbonate, 2-cyanoethyldecyl carbonate, 2-cyanoethylundecyl carbonate, 2-cyanoethyldodecyl carbonate, 2-cyanoethyl2-ethylhexyl carbonate, 3-cyanopropyl propyl carbonate, butyl 3-cyanopropyl carbonate, 3-cyanopropyl isopropyl carbonate, 2-butyl 3-cyanopropyl carbonate , isobutyl 3-cyanopropyl carbonate, tert-butyl 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, tert-butyl 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 Chiloctyl 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, tert-butyl trimethylsilyl carbonate, pentyl trimethylsilyl carbonate , 2-pentyltrimethylsilyl carbonate, 3-pentyltrimethylsilyl carbonate, hexyltrimethylsilyl carbonate, heptyltrimethylsilyl carbonate, octyltrimethylsilyl carbonate, nonyltrimethylsilyl carbonate, decyltrimethylsilyl carbonate, trimethylsilyl undecyl carbonate, dodecyltrimethylsilyl carbonate, 2-ethylhexyltrimethylsilyl carbonate, ethyldimethylsilyl propyl carbonate, butylethyldimethylsilyl carbonate, ethyldimethylsilyl Isopropyl carbonate, 2-butylethyldimethylsilyl carbonate, isobutylethyldimethylsilyl carbonate, tertbutylethyldimethylsilyl carbonate, ethyldimethylsilyl pentyl carbonate, ethyldimethylsilyl 2-pentyl carbonate, ethyldimethylsilyl 3-pentyl carbonate, ethyldimethylsilyl hexyl carbonate, ethyldimethylsilyl heptyl carbonate, ethyldimethylsilyl octyl carbonate, ethyldimethylsilyl nonyl carbonate, decylethyldimethylsilyl carbonate,Ethyl dimethylsilyl undecyl carbonate, dodecyl ethyl dimethylsilyl carbonate, ethyl dimethylsilyl 2-ethylhexyl carbonate, diethyl methylsilyl propyl carbonate, butyl diethyl methylsilyl carbonate, diethyl methylsilyl isopropyl carbonate, 2-butyl diethyl methylsilyl carbonate, isobutyl diethyl methylsilyl carbonate, tert butyl diethyl methylsilyl carbonate, diethyl methylsilyl pentyl carbonate, diethyl methylsilyl 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 triethyl Silyl carbonate, 2-butyl triethylsilyl carbonate, isobutyl triethylsilyl carbonate, tert-butyl 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, dimethyl isopropyl silyl propyl carbonate, butyl dimethyl isopropyl silyl carbonate, dimethyl isopropyl silyl isopropyl carbonate, 2-butyl dimethyl isopropyl silyl carbonate, isobutyl dimethyl isopropyl silyl carbonate, tert butyl dimethyl isopropyl silyl carbonate, dimethyl isopropyl silyl pentyl carbonate, dimethyl isopropyl silyl 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, tert-butyl triisopropylsilyl carbonate, pentyl triisopropylsilyl carbonate, 2-pentyl triisopropylsilyl carbonate, 3-pentyl triisopropylsilyl carbonate, hexyl triisopropylsilyl carbonate, heptyl triisopropylsilyl carbonate, octyl triisopropylsilyl carbonate, Nyl triisopropylsilyl carbonate, decyl triisopropylsilyl carbonate, triisopropylsilyl undecyl carbonate, dodecyl triisopropylsilyl carbonate, 2-ethylhexyl triisopropylsilyl carbonate, propyl tert-butyl dimethylsilyl carbonate, butyl tert-butyl dimethylsilyl carbonate, isopropyl tert-butyl dimethylsilyl carbonate, 2-butyl tert-butyl dimethylsilyl carbonate, isobutyl tert-butyl dimethylsilyl carbonate, tert-butyl 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 tert-butyl dimethyl silyl carbonate, 2-ethylhexyl tert-butyl dimethyl silyl carbonate, propyl 2-trimethylsilyl ethyl carbonate, butyl 2-trimethylsilyl ethyl carbonate, isopropyl 2-trimethylsilyl ethyl carbonate, 2-butyl 2-trimethylsilyl ethyl carbonate, isobutyl, 2-trimethylsilylethyl carbonate, tertbutyl 2-trimethylsilylethyl carbonate, pentyl 2-trimethylsilylethyl carbonate, 2-pentyl 2-trimethylsilylethyl carbonate, 3-pentyl 2-trimethylsilylethyl carbonate, hexyl 2-trimethylsilylethyl carbonate, heptyl 2-trimethylsilylethyl carbonate, octyl 2-trimethylsilylethyl carbonate, nonyl 2-trimethylsilylethyl carbonate, decyl 2-trimethylsilylethyl carbonate, 2-trimethylsilylethyl undecyl carbonate, dodecyl 2-trimethylsilylethyl carbonate, 2-ethylhexyl 2-trimethylsilylethyl carbonate, 2-methoxyethyl isobutyl carbonate or (2-trimethylsilyloxy)ethyl butyl carbonate.

[0069] In a more preferred embodiment, 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.

[0070] In a more preferred embodiment, 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.

[0071] In a further preferred embodiment, the compound of formula (I) is didodecyl carbonate, di(2-ethylhexyl) carbonate, 2-ethylhexylmethyl carbonate, ethyldodecyl carbonate or diisobutyl carbonate.

[0072] In a most preferred embodiment, the carbonate compound of formula (I) is diisobutyl carbonate.

[0073] In another aspect of the invention, the present invention relates to all preferred subgroups thereof, in particular R 2 is C1-C9 alkyl, R 1 The present invention provides all of the above carbonate compounds per se, including those in which R is not a C3-C9 alkyl. Preferred such compounds include those in which R 2 is C1-C9 alkyl, R 1 But, C3~C 24 Alkoxyalkyl, C3-C 24 ω-O-alkyl oligo(ethylene glycol) or C4~C 24 Examples include those representing ω-O-alkyl oligo(propylene glycol).

[0074] Nonaqueous electrolyte As mentioned above, the low corrosive non-aqueous electrolyte comprises the carbonate compound of formula (I) of the previous section as a solvent and a conductive salt dissolved in the solvent.

[0075] In embodiments, a mixture of the carbonate compounds of formula (I) may be used as the solvent.

[0076] The electrolyte of the present invention can be prepared using any technique known in the art. For example, to prepare the electrolyte from the carbonate solvent of the present invention, a person skilled in the art would know that a suitable conductive salt can be dissolved in the carbonate solvent at a suitable concentration. Depending on the application of the electrolyte, various salts can be selected. For example, as described above, when the electrolyte is used in a lithium battery, a lithium salt can be selected. However, for sodium, potassium, calcium, aluminum and magnesium based batteries, other salts can be dissolved in the solvent, such as sodium, potassium, calcium, aluminum and magnesium salts.

[0077] Conductive Salt The selection of conductive salts affects the anode dissolution. For example, in the case of electrolytes containing less carbonate compound of formula (I) of the present invention, the addition of a passivating conductive salt produces an electrolyte that still prevents the anode dissolution of aluminum. Some inorganic salts, such as LiPF6, passivate the surface of aluminum because they form insoluble compounds and therefore do not cause anode dissolution until more than 5V against the Li anode. In contrast, some salts do not passivate aluminum, especially low-fluorinated sulfonyl amides, which cause very strong dissolution of aluminum. As mentioned above, this can lead to the failure of the battery system when the operating voltage of the battery system exceeds the critical potential. When using such conductive salts, it is preferable to include more carbonate compound of formula (I) in the electrolyte to further prevent anode dissolution.

[0078] The conductive salt may be selected from: LiClO4; LiP(CN) α F 6-α [wherein α is an integer from 0 to 6], preferably LiPF6; LiB(CN) β F 4-β [wherein β is an integer of 0 to 4], preferably LiBF4; LiP(C n F 2n+1 ) γ F 6-γ [wherein n is an integer of 1 to 20, and γ is an integer of 1 to 6]; LiB(C n F 2n+1 ) δ F 4-δ [wherein n is an integer from 1 to 20, and δ is an integer from 1 to 4]; Li2Si(C n F 2n+1 ) ε F 6-ε [wherein n is an integer of 1 to 20 and ε is an integer of 0 to 6]; lithium bisoxalatoborate; lithium difluorooxalatoborate; and compounds of the general formula: [ka] [ka] [In the formula, R 3 represents Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen or an organic cation; R 4 , R 5 , R 6 , R 7 , R 8 represents cyano, fluorine, chlorine, a branched or linear alkyl radical having 1 to 24 carbon atoms, a perfluorinated linear alkyl radical having 1 to 24 carbon atoms, an aryl or heteroaryl radical, or a perfluorinated aryl or heteroaryl radical. and derivatives thereof.

[0079] In a preferred embodiment, the conductive salt is a lithium salt. This is appropriate, for example, when the electrolyte is to be used in a lithium battery or a lithium ion battery. Non-limiting examples of lithium salts include the above-mentioned salts, preferably lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium sulfonylamide salts (e.g., lithium bis(fluorosulfonyl)amide, lithium N-fluorosulfonyl-trifluoromethanesulfonylamide (LiFTFSI) and lithium bis(trifluoromethanesulfonyl)amide) and their derivatives. In a preferred embodiment, the conductive salt is a lithium sulfonylamide salt. In a preferred embodiment, the lithium sulfonylamide salt is lithium bis(fluorosulfonyl)amide (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSI) or lithium N-fluorosulfonyl-trifluoromethanesulfonylamide (LiFTFSI). In a more preferred embodiment, the conductive salt is LiFSI. This is appropriate, for example, when the electrolyte is to be used in a lithium ion battery. Indeed, a significant advantage of the electrolyte of the present invention is that it enables the use of lithium sulfonyl amide salts in battery systems where the upper cathode potential limit is greater than 4.2 V vs. Li metal.

[0080] In alternative embodiments, the salt is a sodium, potassium, calcium, aluminum or magnesium salt as listed above, which is appropriate, for example, if the electrolyte is to be used in a sodium-, potassium-, calcium-, aluminum- or magnesium-based battery.

[0081] The concentration of the conductive salt present in the electrolyte can vary. One skilled in the art will understand that the amount of conductive salt should not have a significant adverse effect on the effectiveness of the electrolyte. The concentration of the conductive salt refers to the molar concentration of the conductive salt in the carbonate solvent and any other solvents (if present), regardless of the presence of additives. This can be represented by the following formula:

number

[0082] In embodiments, the concentration of the conductivity salt is at least about 0.05 M and / or at most about 3 M. In embodiments, the concentration of the conductivity 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.

[0083] In a preferred embodiment, the concentration of the conductive salt is 1M.

[0084] Additives that improve the electrochemical properties of electrolytes In an embodiment, the electrolyte further comprises one or more additives used to improve the electrochemical properties of the electrolyte. Non-limiting examples of additives that improve the electrochemical properties of the electrolyte include the following: Agents for improving the solid electrolyte interface (SEI) and cycling characteristics, Unsaturated carbonates for improved stability at high and low voltages, and · Organic solvents that reduce viscosity and increase conductivity.

[0085] Those skilled in the art will appreciate that an additive may 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 depending on the desired effect of the additive.

[0086] The agent for improving the solid electrolyte interface and cycle characteristics is preferably present in the electrolyte.Non-limiting examples of the agent for improving the solid electrolyte interface and cycle characteristics 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 agents for improving the solid electrolyte interface and cycle characteristics include ethylene carbonate (EC) and fluoroethylene carbonate (FEC).

[0087] An unsaturated carbonate is 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 (i.e., vinyl compounds), such as methyl vinyl carbonate, divinyl carbonate, and ethyl vinyl carbonate.

[0088] An organic solvent that reduces viscosity and increases conductivity is optionally present in the electrolyte. In a preferred embodiment, such an organic solvent is present. Non-limiting examples of organic solvents that reduce 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, methoxypropionitrile, propionitrile, butyronitrile, succinonitrile, glutaronitrile, adiponitrile, acetate, propionate, cyclic esters such as γ-butyrolactone, ε-caprolactone, trifluoroacetate, sulfolane, dimethylsulfone, ethylmethylsulfone, or peralkylated sulfamide. In embodiments, ionic liquids may also be added to reduce flammability and increase conductivity. Preferred organic solvents that reduce viscosity and increase conductivity include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC).

[0089] In embodiments, the agent improving the solid electrolyte interface (SEI) and cycling properties and the unsaturated carbonate together represent 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 together 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 total weight of the electrolyte.

[0090] In embodiments, the viscosity reducing and conductivity increasing organic solvents represent, in total, at least about 1% v / v and / or up to about 80% v / v of the total volume of the electrolyte. In embodiments, the organic solvents represent, in total, 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 up to about 80% v / v, up to about 50% v / v, up to about 20% v / v, up to about 15% v / v, up to about 10% v / v or up to about 7% v / v of the total volume of the electrolyte.

[0091] In a preferred embodiment, the additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), diethyl carbonate (DEC) or a mixture thereof.

[0092] In a more preferred embodiment, the additive is FEC, preferably about 2 w / w% FEC, alone or together with EC, DEC or mixtures thereof, preferably alone or EC up to about 5% v / v, EC up to approximately 10% v / v, EC up to approximately 15% v / v, EC up to approximately 20% v / v, EC up to approximately 30% v / v, Mixtures of EC and DEC up to about 20% v / v, A mixture of EC and DEC up to about 25% v / v, Mixtures of EC and DEC up to about 30% v / v, Mixtures of EC and DEC up to about 50% v / v, A mixture of EC and DEC up to about 70% v / v, or Mixtures of EC and DEC up to approximately 75% v / v where all w / w% are based on the total weight of the electrolyte and all v / v% are based on the total volume of the electrolyte.

[0093] In an embodiment, 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, and preferably, the volume ratio is about 3:7.

[0094] In a preferred embodiment, the additives are ethylene carbonate and fluoroethylene carbonate only (preferably in the amounts described above).

[0095] In a more preferred embodiment, the additive is fluoroethylene carbonate alone (preferably in the amounts described above).

[0096] Corrosion Inhibitors In a preferred embodiment, the electrolyte does not contain a corrosion inhibitor. Indeed, as mentioned above, one of the advantages of the carbonate compounds of formula (I) is that they are characterized by their low corrosiveness towards aluminum current collectors, even at voltages higher than 4.2 V.

[0097] In an alternative embodiment, the electrolyte further comprises one or more corrosion inhibitors. Non-limiting examples of corrosion inhibitors include LiPF6, lithium cyanofluorophosphate, lithium fluorooxalatophosphate, LiDFOB, LiBF4, lithium fluorocyanoborate, and LiBOB.

[0098] In embodiments, the corrosion inhibitors represent, in total, at least about 1% and / or up to about 35% of the total weight of the electrolyte. In embodiments, the total amount of corrosion inhibitor represents at least about 1% w / w, at least about 2% w / w, at least about 5% w / w, or at least about 10% w / w, and / or up to about 35% w / w, up to about 25% w / w, up to about 20% w / w, up to about 15% w / w, up to about 10% w / w, or up to about 7% w / w of the total weight of the electrolyte.

[0099] Minimum concentration of compound of formula (I) in electrolyte Those skilled in the art will appreciate that the concentration of the carbonate compound of formula (I) in the electrolyte will be influenced by various factors, such as the desired concentration of the conductive salt and the amount of the preceding additives and corrosion inhibitors.

[0100] Nevertheless, the electrolyte of the present invention should contain the carbonate compound of formula (I) in a concentration sufficient to achieve the desired anodic dissolution inhibition.

[0101] In practice, the concentration of the carbonate compound of formula (I) required to achieve inhibition of anodic dissolution will vary depending on various factors, such as the intended operating voltage and the presence of a corrosion inhibitor. Generally, when a corrosion inhibitor is present, a lower concentration of the carbonate compound of formula (I) will be required to achieve the desired inhibition of anodic dissolution.

[0102] In preferred embodiments, the carbonate compound of formula (I) represents at least about 25% v / v of the total volume of the electrolyte, preferably at least about 50% v / v, more preferably at least about 75% v / v, even more preferably at least about 85% v / v, even more preferably at least about 90% v / v, and most preferably at least about 95%.

[0103] In alternative embodiments in which the electrolyte includes one or more corrosion inhibitors as described in the previous section, the carbonate compound of formula (I) can be present in lower concentrations, such as at least about 10% v / v, 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.

[0104] In a preferred embodiment, the electrolyte of the present invention does not contain other solvents, in other words, the only solvent in the electrolyte is the carbonate compound of formula (I).

[0105] Battery Remaining Components As mentioned above, the battery of the present invention comprises: (a) a cathode comprising an aluminum current collector; (b) an anode; (c) a separator membrane separating the anode and the cathode; (d) a low-corrosivity non-aqueous electrolyte in contact with the anode and the cathode.

[0106] As mentioned above, the battery is in preferred embodiments a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery, a magnesium ion battery, an aluminum battery or an aluminum ion battery.

[0107] The selection of non-aqueous solvent, anode, cathode and separator membrane varies according to the type of battery.If the battery is a lithium ion battery, it will be more appropriate to select an electrolyte that contains, for example, lithium salt, such as lithium sulfonyl amide salt, as conductive salt.However, if the battery is a sodium-based battery, it will be more appropriate to select an electrolyte that contains, for example, sodium salt, as conductive salt.

[0108] The non-aqueous electrolyte is an electrolyte as defined in the previous section.

[0109] The anode can be any anode typically used in batteries.

[0110] In a preferred embodiment, the anode is one suitable for lithium or lithium-ion batteries. Such anodes are typically 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 (Li4Ti5O 12Typically, these materials are mixed with a solvent, a polymer binder, and an electrically conductive additive (including various forms of conductive carbon such as carbon nanotubes and carbon black) and then coated onto a copper current collector to obtain the anode. In preferred embodiments, the anode is made of lithium metal or graphite.

[0111] The cathode can be any cathode typically used in batteries that contain aluminum current collectors, since one advantage of using the electrolyte of the present invention is the prevention of anodic dissolution of the aluminum current collector.

[0112] In a preferred embodiment, the cathode is suitable for lithium or lithium-ion batteries. Such cathodes typically include lithium compounds. These lithium compounds are typically mixed with a solvent, a polymer binder, and an electrically conductive additive (including various forms of conductive carbon such as carbon nanotubes and carbon black) and then coated onto an aluminum current collector to obtain the cathode. The aluminum current collector is susceptible to anodic dissolution at elevated potentials, especially when the electrolyte contains non-passivating conductive salts. Such lithium compounds include LCO (LiCoO2), LNO (LiNiO2), LMO (LiMn2O4), LiCoO2, LCO3 (LiCoO4), LCO4 (LiNiO2), LMO (LiMn2O4), LCO5 (LiNiO2), LCO6 (LiNiO2), LCO7 (LiNiO2), LCO8 (LiNiO2), LCO9 (LiNiO2), LCO10 (LiNiO2), LCO11 (LiNiO2), LCO12 (LiNiO2), LCO13 (LiNiO2), LCO14 (LiNiO2), LCO15 (LiNiO2), LCO16 (LiNiO2), LCO17 (LiNiO2), LCO18 (LiNiO2), LCO19 (LiNiO2), LCO10 (LiNiO2), LCO15 ... x Ni 1-x O2 [wherein x is 0.1 to 0.9], LMN (LiMn 3 / 2 Ni 1 / 2 O4), LMC (LiMnCoO2), LiCu x Mn 2-x O4, NMC (LiNi x Mn y Co z O2), NCA(LiNi x Co y Al z O2), lithium compounds with transition metals and complex anions, LFP (LiFePO4), LNP (LiNiPO4), LMP (LiMnPO4), LCP (LiCoPO4), Li2FCoPO4, LiCo q Fe x Ni yMn z These include lithiated oxides of transition metals such as PO4 and Li2MnSiO4.

[0113] In a preferred embodiment, the cathode of the present invention is an LMN cathode or an LCO cathode.

[0114] In an embodiment, the cathode comprises only a current collector.

[0115] In an embodiment, the cathode is made by coating a current collector with the lithium compounds described above, preferably LMN or LCO. In a preferred embodiment, the current collector is an aluminum current collector.

[0116] A separator membrane is usually placed between the electrodes to prevent physical contact between them, and can be any separator membrane typically used in batteries.

[0117] In a preferred embodiment, the separator membrane is suitable for lithium or lithium-ion batteries. Another function of such separator membranes is to prevent lithium dendrites from causing short circuits between electrodes. Such separator membranes typically include (i) polyolefin-based porous polymer membranes, preferably made from polyethylene "PE", polypropylene "PP" or a combination of PE and PP, such as a three-layer PP / PE / PP membrane, (ii) heat-activatable microporous membranes, (iii) porous materials made from textiles, including glass, ceramic or synthetic textiles (woven or non-woven), (iv) porous membranes made from polymeric materials such as poly(vinyl alcohol), poly(vinyl acetate), cellulose and polyamide, (v) porous polymer membranes equipped with an additional ceramic layer to improve performance at high potentials, and (vi) polymer electrolyte membranes. However, as mentioned, the separator membrane can be any separator membrane typically used in batteries, preferably lithium or lithium ion batteries, such as Celgard 3501™ or Celgard Q20S1HX™.

[0118] Depending on the type of battery, different cathodes, anodes and separator membranes may be provided or prepared. As with the electrolyte, the cathodes, anodes and separator membranes may be prepared using any technique known in the art, and the batteries may be prepared using any technique known in the art.

[0119] As previously mentioned, the batteries of the present invention have a wide variety of applications that will be readily appreciated by those skilled in the art, including electric vehicles, power tools, grid energy storage, medical devices and equipment, toys, hybrid electric vehicles, cell phones, laptops, and various military and aerospace applications.

[0120] Carbonate solvent, non-aqueous electrolyte and method for producing battery In another aspect of the present invention, methods of making the above carbonate solvents and batteries are provided.

[0121] The carbonate solvents, electrolytes and batteries of the present invention can each be prepared using any technique known in the art.

[0122] For example, the carbonate solvents of the present invention can be synthesized according to the following scheme: [ka] [ka]

[0123] In the above formula, R 6 is the previously defined R 1 and R 2 The synthesis of alkyl carbonates is a very well developed process. The most convenient methods are discussed below, but those skilled in the art will recognize that other synthetic methods are available.

[0124] The preparation of the carbonate solvents of the present invention on a smaller scale is most conveniently accomplished by base-catalyzed transesterification of readily available dimethyl carbonate, diethyl carbonate, ethylene carbonate or propylene with an aliphatic alcohol in the presence of a suitable catalyst. The transesterification of carbonate esters follows the same rules as the transesterification of other esters, which are typical equilibration reactions, and can be easily controlled by using Le Chatelier's principle. The ratio of alcohol to carbonate ester determines the ratio of products in a fully equilibrated reaction mixture. If complete substitution is desired, an excess of alcohol should be used. If the desired product is a mixed carbonate, the molar ratio should be close to 1, or a small excess of starting carbonate should be used. During the reaction, it is desirable to constantly remove the reaction products from the reaction mixture. This allows the reaction to proceed to completion more quickly. Separation is most conveniently accomplished by fractional distillation of the lower alcohol. For this reason, the use of lower carbonates is preferred over higher carbonates, since the alcohol formed has a lower boiling point, but care must be taken to avoid the formation of azeotropes which can complicate separation.

[0125] The catalyst used in this conversion can be selected from acids and bases, with bases such as carbonates, oxides, hydroxides and alkoxides of alkali and alkaline earth metals being preferred as they can be easily separated from the volatile products.

[0126] In a suitable reaction vessel equipped for fractional distillation, an appropriate amount of the desired aliphatic alcohol is placed and a specific amount of metallic sodium is added. The amount of sodium should be selected so as to react with and consume all the water present in the reaction. In this way, an anhydrous solvent can be isolated. The process of sodium dissolution can be accelerated by heating and stirring, which is required for 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. Once the sodium has dissolved, the starting carbonate ester is added and the mixture is refluxed at a temperature such that the alcohol formed during the reaction is distilled from the reaction mixture, while all the reactants remain in the reactor. After the reaction is finished, the components of the reaction mixture are separated by fractional distillation under vacuum for the higher alkyl carbonates. In the case where no azeotrope is formed, the solvent can be isolated in this way in high purity.

[0127] However, the industrial preparation of symmetrical carbonates can be carried out by phosgenating the corresponding alcohols.

[0128] When small amounts of mixed carbonates are desired, the most suitable method appears to be the reaction of an aliphatic alcohol with an aliphatic chloroformate in an aprotic solvent in the presence of a suitable base to bind the HCl formed. Although this method is well established, it can sometimes give erroneous results.

[0129] definition In the context of describing the invention (particularly in the context of the claims which follow), the use of the terms "a" and "an" and "the" and similar referents are to be construed to encompass both the singular and the plural, unless otherwise indicated in the specification or clearly contradicted by context.

[0130] 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 specified.

[0131] The recitation of ranges of values ​​herein, unless otherwise stated herein, is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, and each separate value is incorporated herein as if it were individually recited herein. Every subset of values ​​within a range is also incorporated herein as if it were individually recited herein.

[0132] Similarly, the general chemical structure with various substituents and various radicals listed for these substituents herein is intended to serve as a shorthand way of individually referring to each and every molecule obtained by combining any radicals for any of the substituents. Each individual molecule is incorporated herein as if it were individually listed herein. Furthermore, all subsets of the molecules in the general chemical structure are also incorporated herein as if it were individually listed herein.

[0133] All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context.

[0134] Any and all examples provided herein, or the use of exemplary language (e.g., "etc.") are intended merely to further clarify the invention, and do not limit the scope of the invention unless otherwise stated.

[0135] No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0136] As used herein, the term "about" has its ordinary meaning. In embodiments, the term can mean plus or minus 10% or plus or minus 5% of the numerical value it is modified by.

[0137] 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.

[0138] To avoid any mistakes, please keep the following in mind: Alkylyl is alkyl-C(=O)-, Aryl is aryl-C(=O)-, Alkyloxycarbonyl is alkyl-OC(=O)-, Aryloxycarbonyl is aryl-OC(=O)-.

[0139] As used herein, the term "alkyl" has its usual meaning in the art. Note that unless otherwise specified, the hydrocarbon chain of an alkyl group can be linear or branched.

[0140] In this specification, the term "aryl" has its usual meaning in the art.Unless otherwise specified, it should be noted that an aryl group can contain 5-30 atoms, including carbon and heteroatoms, preferably not including heteroatoms, more specifically, can contain 5-10 atoms, or can contain 5 or 6 atoms.

[0141] 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 cobalt oxide, LMN-LiMn 3 / 2 Ni 1 / 2 O4.

[0142] Other objects, advantages and features of the present invention will become more apparent upon reading the following non-limiting description of particular embodiments of the invention, given by way of example only with reference to the accompanying drawings, in which: EXAMPLES

[0143] Description of exemplary embodiments The present invention is further illustrated by the following non-limiting examples. A brief summary of the contents of each example is as follows: Examples 1-4 include the preparation of various carbonate solvents of the present invention. Examples 5-7 are comparative examples that measure anodic dissolution in button cells containing conventional electrolytes. Examples 8-10 measure anodic dissolution in button cells containing an electrolyte of the present invention. Examples 11-54 involve measuring the onset potential of anodic dissolution of various electrolytes of the present invention. Examples 55 and 58 are comparative examples in which the charging and discharging of button-type cells containing a conventional electrolyte was measured. Examples 56, 57 and 59 involve measuring the charge and discharge of button cells containing electrolytes of the present invention. Example 60 involves measuring the temperature ranges of the electrolytes of the present invention and conventional electrolytes by performing digital scanning calorimetry (DSC) experiments. Example 61 involves measuring the discharge capacity versus cycle number of three cells, two of which contain the electrolyte of the present invention and one of which contains a conventional electrolyte.

[0144] Preparation of the Carbonate Solvent of the Present Invention Example 1: Preparation of diisobutyl carbonate (solvent no. 10) by transesterification In a 250 ml round-bottom flask equipped with a Vigreux column, 128 g (1.73 mol) of isobutanol was placed, in which 0.3 g of sodium was dissolved at the boiling point, and 59 g (0.66 mol) of dimethyl carbonate was added. The mixture was refluxed overnight while separating the formed methanol. After the separation of methanol ceased, the remainder was subjected to fractional distillation, yielding 120 g of diisobutyl carbonate as a colorless liquid. Unreacted isobutanol, dimethyl carbonate and isobutyl methyl carbonate were also detected in the previous fractions. The structure of the product was confirmed by NMR (nuclear magnetic resonance spectroscopy), IR (infrared spectroscopy) and GC / MS (gas chromatography with mass selective detection) analyses.

[0145] Example 2: Preparation of di(2-pentyl)carbonate (solvent no. 17) and methyl 2-pentylcarbonate (solvent no. 16) by transesterification A 250 ml round bottom flask equipped with a Vigreux column was charged with 116 g (1316 mmol) of 2-pentanol, in which 1 g of sodium was dissolved at 100° C., and 98 g (1088 mmol) of dimethyl carbonate was added. The mixture was refluxed for 48 h while separating the formed methanol. After the separation of methanol ceased, the remainder was subjected to vacuum fractional distillation, which gave 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 colorless liquid. Unreacted dimethyl carbonate, 2-pentanol and methanol were also detected in the previous fractions. The structure of the product was confirmed by NMR, IR and GC / MS analysis.

[0146] Example 3: Preparation of 2-cyanoethyl butyl carbonate (solvent no. 23) by reaction of butyl chloroformate with 3-hydroxypropinonitrile A 250 ml round bottom flask was charged with 7.1 g (100 mmol) of 3-hydroxypropinonitrile, 11 g of freshly distilled triethylamine and 150 ml of anhydrous dichloromethane. The mixture was cooled in an ice-water bath under nitrogen 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 2 hours, after which water and sulfuric acid were added and the mixture was separated by a separatory funnel. The organic phase was washed four times with water, then dried over anhydrous magnesium sulfate, filtered and evaporated. The remaining clear oil was distilled to give the pure product (13.1 g). The structure of the product was confirmed by NMR, IR and GC / MS analysis.

[0147] Example 4: Preparation of other carbonate solvents of the present invention Other dialkyl carbonates were prepared similarly to the procedures of Examples 1-3. 1 H and 13 The C NMR spectroscopy data are listed in the table below (Table 1). [Table 1-1] [Table 1-2] [Table 1-3]

[0148] Measurement of anodic dissolution of aluminum current collectors. In the following example, the anodic dissolution of an aluminum current collector was measured. Detection of anodic dissolution of an aluminum current collector can be achieved by a number of electrochemical methods. One indication of anodic dissolution is the current that occurs at a particular potential between a reference electrode and a bare aluminum electrode. Anodic dissolution is strongly dependent on the applied potential, so variation of the potential during probing of anodic dissolution is essential.

[0149] With the foregoing in mind, in the following examples, chronoamperometry (CA) was used to measure the anodic dissolution of an aluminum current collector. Chronoamperometry involves measuring the current at a given potential and is usually carried out over a relatively long period of time. Thus, even the slowest processes can be detected with this technique. For the following examples, chronoamperometry was used over a period of 1 hour at potentials between 4 and 5.5 V versus Li metal in 0.1 V steps (1 hour CA at 4.0, 4.1, 4.2, etc. up to 5.5 V). This allows for a relatively fast screening of the electrolyte.

[0150] The results of chronoamperometry are shown in Figures 1 to 6.

[0151] Typically, in electrolytes obtained by dissolving 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 was found to occur between 4.1 and 4.3 V vs. Li metal, detected as high current / current density between the electrodes (Figures 1-3).

[0152] However, LiFSI, LiFTFSI and LiTFSI, when dissolved in higher, preferably branched, dialkyl carbonates having a total number of carbon atoms equal to or greater than 4, were found not to cause anodic dissolution of the aluminum current collector, even at potentials of greater than 5 V versus Li metal in some cases (Figures 4-6).

[0153] Example 5 (Comparative): Anodic Dissolution of Aluminum Current Collector in LiFSI-EC-DEC Electrolyte A solution of 1 M LiFSI (Nippon Shokubai) in a conventional industrial solvent mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 3:7 (EC / DEC) was prepared and 2 wt % fluoroethylene carbonate was added.

[0154] A button cell was assembled using a 16 mm diameter disk as the cathode with a 15 μm thick uncoated aluminum current collector provided by UACJ. Celgard 3501 was used as the separator membrane, as was the LiFSI-EC-DEC electrolyte described above. A 200 μm thick 16 mm lithium metal disk provided by China Energy Lithium Co.,LTD. was used as the anode. This cell was used at potentials of 4 to 5.5 V vs. Li metal in 0.1 V steps over 1 h during chronoamperometry to probe the anodic dissolution of the cathode (chronoamperometry for 1 h at 4.0, 4.1, 4.2…5.5 V). The results of this experiment can be seen in Figure 1. Already at 4.3 V a significant appearance of current was observed, indicating anodic dissolution. Therefore, this electrolyte cannot be used for cells with a cathode potential above 4.3 V.

[0155] 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 as electrolyte a solution of 1 M LiFTFSI in a conventional industrial solvent mixture of ethylene carbonate / diethyl carbonate (EC / DEC) in a volume ratio of 3:7 and 2% by weight of fluoroethylene carbonate. The results of this experiment can be seen in FIG. 2. Already at 4.1 V a significant appearance of current was observed, indicating anodic dissolution. Therefore, this electrolyte cannot be used in batteries with a cathode potential above 4.2 V.

[0156] 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 as electrolyte a conventional industrial solvent mixture of ethylene carbonate and diethyl carbonate (EC / DEC) in a volume ratio of 3:7 and a solution of 1 M LiTFSI in 2 wt. % fluoroethylene carbonate (available from 3M™). The results of this experiment can be seen in FIG. 3. Already at 4.1 V a significant appearance of current was observed, indicating anodic dissolution. Therefore, this electrolyte cannot be used in cells with a cathode potential above 4.2 V.

[0157] Example 8: Inhibition of anodic dissolution of aluminum current collectors in LiFSI-diisobutylcarbonate electrolyte A solution of 1 M LiFSI (Nippon Shokubai) in diisobutyl carbonate (solvent No. 10 prepared according to Example 1) was prepared, and 2 wt % fluoroethylene carbonate was added to the solution.

[0158] Button cells were constructed and tested according to Example 5, but using the LiFSI-diisobutylcarbonate electrolyte described above. The results of this experiment can be seen in Figure 4. At all potentials tested (4-5.5 V), the current density was greater than 1 μA / cm. 2 , which means that this electrolyte can be used, inter alia, with cathodes having a cutoff potential of at least 5.5 V.

[0159] Example 9: Inhibition of anodic dissolution of aluminum current collectors in LiFTFSI-diisobutylcarbonate electrolyte A solution of 1 M LiFTFSI in diisobutyl carbonate (solvent number 10) was prepared according to Example 1, and 2 wt % fluoroethylene carbonate was added to the solution.

[0160] Button cells were constructed and tested according to Example 5, but using the LiFTFSI-diisobutylcarbonate electrolyte described above. The results of this experiment can be seen in Figure 5. At all potentials tested (4-5.5 V), the current density was greater than 1 μA / cm. 2 , which means that the electrolyte can be used, among others, in battery systems with voltages above 5.5 V. As mentioned above, electrolytes prepared from conventional solvents containing FSI are typically unsafe at operating voltages above 4.3 V (see Examples 5-7).

[0161] Example 10: Inhibition of anodic dissolution of aluminum current collectors in LiTFSI-diisobutylcarbonate electrolyte A solution of 1 M LiTFSI in diisobutyl carbonate (solvent number 10) was prepared according to Example 1, and 2 wt % fluoroethylene carbonate was added to the solution.

[0162] Button cells were constructed and tested according to Example 5, but using the LiTFSI-diisobutylcarbonate electrolyte described above. The results of this experiment can be seen in Figure 6. At all potentials tested (4-5.5 V), the current density was greater than 1 μA / cm 2 , which means that this electrolyte can be used, inter alia, in battery systems with voltages above 5.5 V.

[0163] Examples 11-54: Onset potentials of anodic dissolution for various electrolytes Button cells were constructed and tested according to Example 5, but using each of the electrolytes listed in the table below (Table 2) with the results as described above. The results of this experiment are presented as the potential at which significant anodic dissolution of aluminum occurs, and represent the safe usage limits of the electrolyte. Several examples were made to illustrate the possibility of blending different solvents to obtain electrolytes with enhanced conductivity while maintaining the effectiveness of inhibiting anodic dissolution.

[0164] In the tables below, "EC / DEC (3:7 by volume)" refers to an EC / DEC mixture with a volume ratio of 3:7. [Table 2-1] [Table 2-2] [Table 2-3]

[0165] Charge / discharge test of button type cells Example 55 (Comparative): Poor Results of Charging and Discharging LCO in LiFSI-EC-DEC Electrolyte A mixture of LCO, VGCF (vapour grown carbon nanotubes), carbon black and polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP) at a weight ratio of 89:3:3:5 was used to prepare the LCO cathode material. The mixture was then coated onto a 15 μm thick uncoated aluminum current collector provided by UACJ. The electrode material was calendared, cut into disks and dried in a vacuum oven at 120° C. for 12 hours before use.

[0166] A button-type cell was assembled using one of the above LCO disks (16 mm in diameter) as the cathode, Celgard Q20S1HX (i.e., the electrolyte of Comparative Example 5) as the separator membrane, and a 16 mm lithium metal disk with a thickness of 200 μm as the anode provided by China Energy Lithium Co., LTD.

[0167] This cell was used to probe charge and discharge from 3 to 4.5 V at a C / 24 rate. The results of this experiment can be seen in Figure 7. The first charge / discharge cycle is of normal shape, but during the second charge, an unexpected plateau occurs at 4.2 V. This plateau can be attributed to the anodic dissolution of the aluminum current collector, which results in a loss of charge and a very low discharge capacity. Therefore, this electrolyte is not tolerable for operation with LCO electrodes.

[0168] Example 56: Successful charging and discharging of LCO in LiFSI-diisobutylcarbonate electrolyte A button cell was assembled using a 16 mm diameter LCO disk (prepared using the process described in Example 55) as the cathode, Celgard Q20S1HX (i.e., the electrolyte of Example 8) as the separator membrane, and a 200 μm thick 16 mm lithium metal disk as the anode provided by China Energy Lithium Co., LTD.

[0169] This cell was used to probe charge and discharge from 3 to 4.5 V at a C / 24 rate. The results of this experiment can be seen in Figure 8. Although the charge-discharge curves are deformed, no signs of any parasitic processes can be detected that may manifest as a plateau similar to the second cycle in Figure 7. Thus, this electrolyte can withstand operation with LCO electrodes, potentially with some additives to further improve its performance (as shown in Example 57).

[0170] Example 57: Successful charging and discharging of LCO in LiFSI-EC-diisobutyl carbonate electrolyte The electrolyte of Example 33 was prepared (i.e., a solution of 1M LiFSI (Nippon Shokubai) in a mixture of ethylene carbonate (EC) and diisobutyl carbonate (solvent number 10) at 1:9 by volume, respectively, to which 2% fluoroethylene carbonate was added). Note that this electrolyte is similar to that of Example 56, except that solvent number 10 was replaced with a mixture of EC and solvent number 10 at 1:9 by volume. In other words, EC is used as an additive herein.

[0171] A button cell was assembled using a 16 mm diameter LCO disk (prepared using the process described in Example 55) as the cathode coated on a 15 μm thick aluminum current collector provided by UACJ, Celgard Q20S1HX as the separator membrane, the LiFSI-EC-diisobutyl carbonate electrolyte described above, and a 200 μm thick 16 mm lithium metal disk as the anode provided by China Energy Lithium Co., LTD.

[0172] This cell was used to probe charge and discharge from 3 to 4.5 V at a C / 24 rate. The results of this experiment can be seen in Figure 9. The charge-discharge curves have a regular shape and no signs of any parasitic processes can be detected that may manifest as a plateau similar to the second cycle in Figure 7. Therefore, this electrolyte can withstand the operation of the LCO electrode quite well.

[0173] Example 58 (Comparative): Poor Results of Charging and Discharging LMN in LiFSI-EC-DEC Electrolyte A mixture of LMN, VGCF (vapor grown carbon nanotubes), carbon black and polyvinylidene fluoride (PVDF) in NMP at a weight ratio of 94:1.5:1.5:3 was used to prepare LiMn 3 / 2 Ni 1 / 2O4(LMN) cathode material was prepared. The mixture was then coated onto a 15 μm thick uncoated aluminum current collector provided by UACJ. The electrode material was calendered, cut into disks, and dried in a vacuum oven at 120° C. for 12 hours before use.

[0174] A button-type cell was assembled using a 16 mm diameter LMN disk as the cathode, Celgard Q20S1HX (i.e., the electrolyte of Comparative Example 5) as the separator membrane, and a 16 mm thick lithium metal disk with a thickness of 200 μm as the anode provided by China Energy Lithium Co., LTD.

[0175] This cell was used to probe charge and discharge from 3.5 to 4.9 V at a C / 24 rate. The results of this experiment can be seen in Figure 10. The first charge cycle shows an abnormal shape. Initially, the potential increases to about 4.5 V, but then drops to an unexpected plateau at about 4.3 V. This plateau may be due to the anodic dissolution of the aluminum current collector, thereby resulting in extreme failure of the cell since even one normal cycle cannot be performed. Therefore, this electrolyte cannot be used at all with LMN electrodes.

[0176] Example 59: Successful charge / discharge of LMN in LiFSI-diisobutylcarbonate electrolyte A button-type cell was assembled using a 16 mm diameter LMN disk (prepared using the process described in Example 58) as the cathode, Celgard Q20S1HX (i.e., the electrolyte of Example 8) as the separator membrane, and a 200 μm thick 16 mm lithium metal disk as the anode provided by China Energy Lithium Co., LTD.

[0177] This cell was used to probe charge and discharge from 3.5 to 4.9 V at a C / 24 rate. The results of this experiment can be seen in Figure 11. The charge-discharge curves appear normal and no signs of any parasitic processes can be detected that may manifest as plateaus similar to those seen in Figure 10. Therefore, this electrolyte can withstand operation with LMN electrodes, potentially with some additives to further improve its performance.

[0178] Example 60: Extended temperature range of diisobutyl carbonate-based electrolytes compared to conventional solvents Digital scanning calorimetry experiments were carried out on the electrolyte of Example 33 and the electrolyte of Comparative Example 5.

[0179] 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 present invention exhibited no melting point and a glass transition point of -98°C. In other words, the electrolyte of Example 33 remained in liquid form without crystallization until it reached its glass transition point of -98°C, and finally remained in amorphous solid form. This indicates that the electrolyte of the present invention can be used at a lower temperature than conventional electrolytes without crystallizing.

[0180] Example 61: Complete Lithium-Ion Cell The electrolytes of Example 8 (LiFSI in diisobutyl carbonate, 2% FEC) and Example 33 (LiFSI in 90% diisobutyl carbonate:10% EC, 2% FEC) were tested, as well as a conventional electrolyte of 1 M LiPF6 in EC / DEC (3:7 by volume) with 2% FEC.

[0181] A graphite electrode was prepared by Cumstomcells Company by mixing 96% modified graphite (SMG), 2% water-based binder and 2% electronic conductivity enhancer in water, and the mixture was coated on a 14 μm thick copper foil, which was dried and calendered. The resulting electrode material was cut into disks and dried in a vacuum oven at 120° C. for 12 hours before use.

[0182] Lithium ion button cells were assembled using a 16 mm diameter LCO disk (similar to Example 55) as the cathode coated on a 15 μm thick aluminum current collector provided by UACJ, Celgard Q20S1HX as the separator membrane, one of the electrolytes listed above, and a 16 mm disk of the previously prepared graphite electrode as the anode.

[0183] The cells were subjected to three formation cycles (charge and discharge from 3 to 4.4 V at a C / 24 rate). The cells were then subjected to an extended cycle involving a charge at C / 4, followed by a 30 minute float at 4.4 V, and a C / 4 discharge. The results of this experiment (cell discharge capacity versus cycle number) can be seen in Figure 12. The LiPF6 electrolyte provides the highest starting discharge capacity, but then a relatively linear capacity degradation over cycle number can be observed. LiFSI in pure diisobutyl carbonate has about 10% less starting capacity, but the capacity degradation is slower than for LiPF6. Adding 10% EC to the pure diisobutyl carbonate electrolyte increases the starting capacity, but the degradation rate approaches that of LiPF6.

[0184] This experiment demonstrates the use of electrolytes prepared from LIFSI in a solvent of the present invention in a high voltage Li-ion battery, whereas the use of LiFSI in a conventional solvent is not possible in this battery system.

[0185] The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be accorded the broadest interpretation consistent with the specification as a whole.

[0186] References This specification references a number of documents, the contents of which are incorporated herein by reference in their entireties. These documents include, but are not limited to, the following: US3359296 US5072040 US5292601 US5446134 US9698447 ·US2002 / 122988 ·US2005 / 241145 EP858994 WO2017 / 221908 WO2018 / 072024 ·Beran, M.; Prihoda, J.; Zak, Z.; Cernik, M. Polyhedron 2006,25,1292. ·Beran, M.; Prihoda, J.; Taraba, J. Polyhedron 2010,29,991. ·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.-BJPower Sources 2011,196,3623. ·Meister,P.;Qi,X.;Kloepsch,R.;Kramer,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,HJPower Sources 2015,296,197. ·Xia, L.;Jiang,Y.;Pan,Y.;Li,S.;Wang,J.;He,Y.;Xia,Y.;Liu,Z.;Chen,GZChemistrySelect 2018,3,1 ·Yamada,Y.;Chiang,CH;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.-AG;Sivaram,S.Chem.Rev.1996,96,951.,Parrish,JP;Salvatore,RN;Jung,KWTetrahedron 2000,56,8207. ·Buysch,H.-J.In Ullmann's Encyclopedia of Industrial Chemistry;Wiley-VCH Publishing GmbH&Co.KGaA:2000;Vol.7,p45,doi:10.1002 / 14356007.a05_197 ·Tundo ,P.;Arico ,F.;Rosamilia Anthony ,E.;Rigo ,M.;Maranzana ,A.;Tonachini ,G.In Pure Appl.Chem.2009;Vol.81,p1971. ·Kenar,JA;Knothe,G.;Copes,ALJAm.Oil Chem.Soc.2004,81,285. ·Chen, Z.; Zhang, Z.; Amine, K. In Advanced Fluoride - Based Materials for Energy Conversion; Groult, H., Ed.; Elsevier: 2015, p1. In one embodiment, for example, the following items are provided: (Item 1) A metal or metal-ion battery, (a) a cathode comprising an aluminum current collector and having an upper potential limit of about 4.2 V or more versus a Li metal reference electrode; (b) an anode; (c) a separator membrane separating the anode and the cathode; and (d) a low-corrosivity, non-aqueous electrolyte in contact with the anode and the cathode; The battery has an upper voltage limit of about 4.2 V or more; anodic dissolution of aluminum in the aluminum current collector is suppressed during battery operation at a voltage up to the upper voltage limit; The electrolyte is a solvent having the formula (I):

Chem.

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Claims

1. A metal or metal-ion battery, (a) a cathode comprising an aluminum current collector and having an upper potential limit greater than 4.2 V versus a Li metal reference electrode; (b) an anode; (c) a separator membrane separating the anode and the cathode; and (d) a low-corrosivity, non-aqueous electrolyte in contact with the anode and the cathode; The battery has an upper voltage limit higher than 4.2 V; anodic dissolution of aluminum in the aluminum current collector is suppressed during battery operation at a voltage up to the upper voltage limit; The electrolyte is a solvent having the formula (I): 【Chemistry 11】 [In the formula, R １ is C ３ ~C ２４ Alkyl, C ３ ~C ２４ Alkoxyalkyl, C ３ ~C ２４ ω-O-alkyl oligo(ethylene glycol) or C ４ ~C ２４ represents ω-O-alkyl oligo(propylene glycol); R ２ is C ２ ~C ２４ Alkoxyalkyl, C ２～ C ２４ Alkyloxyalkyl, C ３ ~C ２４ Alkoxycarbonylalkyl, C １ ~C ２４ Cyanoalkyl, C １ ~C ２４ Thiocyanatoalkyl, C ３ ~C ２４ Trialkylsilyl, C ４ ~C ２４ Trialkylsilylalkyl, C ４ ~C ２４ Trialkylsilyloxyalkyl, C ３ ~C ２４ ω-O-alkyl oligo(ethylene glycol), C ４ ~C ２４ ω-O-alkyl oligo(propylene glycol), C ５ ~C ２４ ω-O-trialkylsilyl oligo(ethylene glycol) or C ６ ~C ２４ ω-O-trialkylsilyl oligo(propylene glycol)] and a conductive salt dissolved in the solvent; Including, The electrolyte does not contain a corrosion inhibitor. Metal or metal-ion batteries.

2. 2. The battery of claim 1, wherein the upper potential limit of the cathode is 4.4 V or greater versus a Li metal reference electrode.

3. 3. The battery according to claim 1, wherein the upper limit voltage of the battery is 4.4 V or higher.

4. R １ But, C ３ ~C ２４ Alkyl or C ３ ~C ２４ A battery according to any one of claims 1 to 3, which represents an ω-O-alkyl oligo(ethylene glycol).

5. R ２ But, C ２ ~C ２４ Alkoxyalkyl, C １ ~C ２４ Cyanoalkyl, C ４ ~C ２４ Trialkylsilyloxyalkyl, C ５ ~C ２４ ω-O-trialkylsilyl oligo(ethylene glycol) or C ３ ~C ２４ The battery of any one of claims 1 to 4, which represents ω-O-alkyl oligo(ethylene glycol).

6. R １ and R ２ The battery according to any one of claims 1 to 5, wherein the total number of carbon atoms in

7. The battery according to any one of claims 1 to 6, wherein the carbonate compound of formula (I) is 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.

8. The conductive salt is ・LiClO ４ 、 LiP (CN) α F ６－α [wherein α is an integer from 0 to 6] ・LiB (CN) β F ４－β [wherein β is an integer from 0 to 4] LiP (C ｎ F ２ｎ＋１ ) γ F ６－γ [In the formula, n is an integer from 1 to 20, and γ is an integer from 1 to 6] ・LiB(C ｎ F ２ｎ＋１ ) δ F ４－δ [In the formula, n is an integer from 1 to 20, and δ is an integer from 1 to 4] Li ２ Si(C ｎ F ２ｎ＋１ ) ε F ６－ε [In the formula, n is an integer from 1 to 20, and ε is an integer from 0 to 6] Lithium bis(oxalato)borate, Lithium difluorooxalatoborate or The following general formula: 【Chemistry 12】 【Chemistry 13】 [In the formula, R ３ represents Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, hydrogen or an organic cation; R ４ , R ５ , R ６ , R ７ , R ８ represents cyano, fluorine, chlorine, a branched or linear alkyl radical having 1 to 24 carbon atoms, a perfluorinated linear alkyl radical having 1 to 24 carbon atoms, an aryl, a heteroaryl, a perfluorinated aryl or a heteroaryl. The battery according to any one of claims 1 to 7, wherein the compound is a compound represented by one of the following formulas:

9. The battery according to any one of claims 1 to 8, wherein the conductive salt is a sulfonylamide salt.

10. The battery of any one of claims 1 to 9, wherein the carbonate compound of formula (I) is the only solvent in the electrolyte.

11. The battery according to any one of claims 1 to 10, which is a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery, a magnesium ion battery, an aluminum battery or an aluminum ion battery.

12. A carbonate solvent for a non-aqueous electrolyte, comprising: a carbonate solvent having formula (I): 【Chemistry 14】 [In the formula, R １ is C ３ ~C ２４ Alkyl, C ３ ~C ２４ Alkoxyalkyl, C ３ ~C ２４ ω-O-alkyl oligo(ethylene glycol) or C ４ ~C ２４ represents ω-O-alkyl oligo(propylene glycol); R ２ is C ２ ~C ２４ Alkyloxyalkyl, C ３ ~C ２４ Alkoxycarbonylalkyl, C １ ~C ２４ Cyanoalkyl, C １ ~C ２４ Thiocyanatoalkyl, C ３ ~C ２４ Trialkylsilyl, C ４ ~C ２４ Trialkylsilylalkyl, C ４ ~C ２４ Trialkylsilyloxyalkyl, C ３ ~C ２４ ω-O-alkyl oligo(ethylene glycol), C ４ ~C ２４ ω-O-alkyl oligo(propylene glycol), C ５ ~C ２４ ω-O-silyl oligo(ethylene glycol) or C ６ ~C ２４ represents ω-O-silyl oligo(propylene glycol), where ω-O-alkyloligo(ethylene glycol) is a radical of the formula —(CH 2 —CH 2 —O—) n -alkyl, where n is 2 or greater; wherein ω-O-alkyloligo(propylene glycol) is a radical of the formula -(CH 2 -CH 2 -CH 2 -O-) n -alkyl, where n is 2 or greater.

13. R １ and R ２ The carbonate solvent of claim 12, wherein the total number of carbon atoms in is 5 or more.

14. R １ C ３ ~C ２４ represents alkyl, R ２ C １ ~C ２４ 14. The carbonate solvent of claim 12 or 13, which represents a cyanoalkyl.

15. R １ C ３ ~C ２４ represents alkyl, R ２ C ４ ~C ２４ 14. The carbonate solvent of claim 12 or 13, which represents a trialkylsilyloxyalkyl.

16. R １ and R ２ But both are C ３ ~C ２４ 14. The carbonate solvent of claim 12 or 13, which represents an ω-O-alkyl oligo(ethylene glycol).

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