1. An electrolyte for a secondary battery, comprising an eutectic mixture consisting of:
(a) an amide group-containing compound with at least one electron donating group (EDG) introduced into the N-position thereof; and
(b) an ionizable lithium salt.
2. The electrolyte of claim 1, wherein the eutectic mixture has a decrease in reduction potential, caused by introducing the EDG.
3. The electrolyte of claim 1, wherein the EDG has a Hammett substituent constant value less than 0.
4. The electrolyte of claim 1, wherein the amide group-containing compound is represented by the following Formula 1 or Formula 2:
wherein in Formula 1, at least one of R2 and R3 is an EDG, and the other is hydrogen or halogen; and X is selected from the group consisting of hydrogen (H), carbon (C), silicon (Si), oxygen (O), nitrogen (N), phosphorous (P), and sulfur (S), with the proviso that i) when X\u2550H, m=0, ii) when X\u2550O or S, m=1, iii) when X\u2550N or P, m=2, and iv) when X\u2550C or Si, m=3, for each of which R1 is independently selected from the group consisting of hydrogen, halogen, a C1\u02dcC20 alkyl group, an alkylamine group, an alkenyl group, and an aryl group, and
wherein, in Formula 2, R5 is an EDG; X is selected from the group consisting of carbon (C), silicon (Si), oxygen (O), nitrogen (N), phosphorous (P), and sulfur (S), with the proviso that i) when X\u2550O or S, m=0, ii) when X\u2550N or P, m=1, and iii) when X\u2550C or Si, m=2, for each of which R4 is independently selected from the group consisting of hydrogen, halogen, a C1\u02dcC20 alkyl group, an alkylamine group, an alkenyl group, and an aryl group; and n is an integer of 1 to 10.
5. The electrolyte of claim 1, wherein the amide group-containing compound is selected from the group consisting of N-ethylacetamide, N-methylurea, N,N\u2032-dimethylurea, ethyl N-methylcarbamate, ethyl N-ethylcarbamate, ethyl N,N-dimethylcarbamate, methyl N-methylcarbamate, methyl N,N-dimethylcarbamate, N-methylcaprolactam, phenyl N,N-dimethylcarbamate, methyl N-butylcarbamate, methyl N-phenylcarbamate, methyl N-ethylcarbamate, and N-ethyl-N-phenylethylcarbamate.
6. The electrolyte of claim 1, wherein an anion of the lithium salt is selected from the group consisting of F\u2212, Cl\u2212, Br\u2212, I\u2212, NO3\u2212, N(CN)2\u2212, BF4\u2212, ClO4\u2212, PF6\u2212, (CF3)2PF4\u2212, (CF3)3PF3\u2212, (CF3)4PF2\u2212, (CF3)5PF\u2212, (CF3)6P\u2212, CF3SO3\u2212, CF3CF2SO3\u2212, (CF3SO2)2N\u2212, (FSO2)2N\u2212, CF3CF2(CF3)2CO\u2212, (CF3SO2)2CH\u2212, (SF5)3C\u2212, (CF3SO2)3C\u2212, CF3(CF2)7SO3\u2212, CF3CO2\u2212, CH3CO2\u2212, SCN\u2212, and (CF3CF2SO2)2N\u2212.
7. The electrolyte of claim 1, further comprising:
(a) a first compound capable of being reduced at a potential higher than a reduction potential vs. lithium potential (LiLi+) of the eutectic mixture to thereby form a passivation film; or
(b) a second compound having an oxidation potential higher than a cathode potential and thus consuming overcharge current; or
(c) both the first and second compounds.
8. The electrolyte of claim 1, wherein the electrolyte is a liquid-type electrolyte.
9. The electrolyte of claim 1, wherein the electrolyte is a gel polymer-type electrolyte.
10. The electrolyte of claim 9, wherein the electrolyte is formed by polymerizing an electrolyte precursor solution containing: (i) the eutectic mixture; and (ii) monomers capable of forming a gel polymer via polymerization.
11. The electrolyte of claim 9, wherein the electrolyte is prepared by impregnating a polymer or a gel polymer with the eutectic mixture.
12. The electrolyte of claim 9, wherein the electrolyte is prepared by dissolving a polymer and the eutectic mixture in a solvent, and then removing the solvent.
13. A secondary battery comprising:
a cathode;
an anode;
a separator; and
an electrolyte of claim 1 which comprises an eutectic mixture consisting of: (a) an amide group-containing compound with at least one electron donating group (EDG) introduced into the N-position thereof; and (b) an ionizable lithium salt.
14. The secondary battery of claim 13, wherein the anode has a reduction potential vs. lithium potential of 0 to 1V.
15. The secondary battery of claim 13, wherein the anode is selected from the group consisting of a carbonaceous material, a metal, a metalloid, and a metalloid-containing alloy.
16. The secondary battery of claim 13, wherein the secondary battery has a chargedischarge voltage ranging up to 4.35V.
17. A method of adjusting an electrochemical stability window of an eutectic mixture consisting of an amide group-containing compound and a lithium salt comprising regulating electron donating properties of at least one substituent group introduced into the N-position of the amide group-containing compound.
18. The method of claim 17, wherein said step of regulating electron donating properties of at least one substituent group comprises introducing at least one electron donating group (EDG) into the N-position of the amide group-containing compound, to intrinsically shift the electrochemical stability window of the eutectic mixture to a lower limit.
19. The secondary battery of claim 13, wherein the amide group-containing compound is represented by the following Formula 1 or Formula 2:
wherein in Formula 1, at least one of R2 and R3 is an EDG, and the other is hydrogen or halogen; and X is selected from the group consisting of hydrogen (H), carbon (C), silicon (Si), oxygen (O), nitrogen (N), phosphorous (P), and sulfur (S), with the proviso that i) when X\u2550H, m=0, ii) when X\u2550O or S, m=1, iii) when X\u2550N or P, m=2, and iv) when X\u2550C or Si, m=3, for each of which R1 is independently selected from the group consisting of hydrogen, halogen, a C1\u02dcC20 alkyl group, an alkylamine group, an alkenyl group, and an aryl group, and
wherein in Formula 2, R5 is an EDG; X is selected from the group consisting of carbon (C), silicon (Si), oxygen (O), nitrogen (N), phosphorous (P), and sulfur (S), with the proviso that i) when X\u2550O or S, m=0, ii) when X\u2550N or P, m=1, and iii) when X\u2550C or Si, m=2, for each of which R4 is independently selected from the group consisting of hydrogen, halogen, a C1\u02dcC20 alkyl group, an alkylamine group, an alkenyl group, and an aryl group; and n is an integer of 1 to 10.
20. The secondary battery of claim 13, wherein the electrolyte further comprises:
(a) a first compound capable of being reduced at a potential higher than a reduction potential vs. lithium potential (LiLi+) of the eutectic mixture to thereby form a passivation film; or
(b) a second compound having an oxidation potential higher than a cathode potential and thus consuming overcharge current; or
(c) both the first and second compounds.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1.-8. (canceled)
9. A process for isomerizing cis-2-pentenenitrile to 3-pentenenitriles, which comprises isomerizing cis-2-pentenenitrile with amidines, tertiary amines or mixtures thereof as a catalyst at a temperature of 80 to 200\xb0 C. and a pressure of 0.01 to 50 bar.
10. The process according to claim 9, wherein the catalyst used is a tertiary alkylamine, cycloalkylamine, alkylcycloalkylamine, aminopyridine, imidazole, bicyclic amidine IV or mixtures thereof.
11. The process according to claim 9, wherein the catalyst used is triethylamine.
12. The process according to claim 9, wherein the catalyst used has a boiling point equal to or lower than that of cis-2-pentenenitrile, and higher than that of cis-3-pentenenitrile.
13. The process according to claim 9, wherein the catalyst used has a boiling point 0 to 50\xb0 C. lower than that of cis-2-pentenenitrile, and 1 to 50\xb0 C. higher than that of cis-3-pentenenitrile.
14. The process according to claim 9, wherein the isomerization of cis-2-pentenenitrile to 3-pentenenitriles is performed in a reaction column.
15. A process for continuously isomerizing cis-2-pentenenitrile to 3-pentenenitriles, by
a) hydrocyanating 3-pentenenitriles or a mixture comprising 3-pentenenitriles to adiponitrile in the presence of nickel(0)-phosphorus ligand complex as a catalyst,
b) removing adiponitrile, 2-methylglutaronitrile and nickel(0)-phosphorus ligand complex from the hydrocyanation output,
c) isomerizing the cis-2-pentenenitrile in the organic phase thus obtained, comprising unsaturated C5-mononitriles with the aid of a nitrogen base of the formula I as a catalyst,
R1R2R3N\u2003\u2003(I)
wherein
R\u2032, R2, and R3 are each independently a C1- to C20-alkyl, C3- to C12-cycloalkyl, C3- to C12-cycloalkyl mono- to trisubstituted by C1- to C4-alkyl or mixtures thereof, or two of the R1, R2, R3 radicals together are a linear C4- to C9 chain, which is optionally substituted by C1- to C4-alkyl and may additionally comprise a nitrogen, oxygen or sulfur atom or
R1, R2 and R3 radicals may also be joined so as to form a tertiary amine which independently comprises two five- to seven-membered rings,
the boiling point of which is equal to or lower than that of cis-2-pentenenitrile at standard pressure, which comprises
d) feeding the organic phase which comprises essentially unsaturated C5-mononitriles and is obtained in c) to a distillation column K1, removing cis-2-pentenenitrile and cis- and trans-2-methyl-2-butenenitrile via the top of the distillation column K1, and 3-pentenenitrile and trans-2-pentenenitrile via the bottom, and recycling the latter into the reaction step for hydrocyanation of 3-pentenenitriles,
e) feeding the top product of column K1 to a distillation column K2, and removing and discharging trans-2-methyl-2-butenenitrile as the bottom product of column K2,
f) feeding the top product of column K2 and a nitrogen base having a boiling point equal to or lower than that of cis-2-pentenenitrile at standard pressure to a reactor R1, and feeding the reaction product of the reactor R1 and the tertiary amine having a boiling point equal to or lower than that of cis-2-pentenenitrile to a distillation column K3,
g) recycling the top product of the distillation column K3, which consists predominantly of the tertiary amine, into the reactor R1 and discharging a substream of the top product comprising cis-2-methyl-2-butenenitrile, tertiary amine and cis-2-pentenenitrile, recycling a mixture of cis-2-pentenenitrile, trans-3-pentenenitrile, trans-2-pentenenitrile and tertiary base from a side draw into distillation column K1, and discharging high boilers as the bottom product.
16. The process according to claim 15, wherein said step c) is isomerizing the cis-2-pentenenitrile in the organic phase thus obtained, consisting essentially of unsaturated cis- and trans-3-pentenenitrile, 4-pentenenitrile, trans-2-pentenenitrile, cis-2-methyl-2-butenenitrile, trans-2-methyl-2-butenenitrile, 2-methyl-3-butenenitrile, to 3-pentenenitriles with the aid of a nitrogen base of the formula I as a catalyst, the boiling point of which is equal to or lower than that of cis-2-pentenenitrile at standard pressure
R1R2R3N\u2003\u2003(I)
wherein
R1, R2, and R3 are each independently a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl, cycloheptyl,
C4- to C8-cycloalkyl mono- to trisubstituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or two of the R1, R2, R3 radicals together are a linear C5- to C7 chain, which is optionally substituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, and optionally comprise a nitrogen, oxygen or sulfur atom or R1, R2, R3 radicals may also be joined so as to form a tertiary amine which independently comprises two five- to seven-membered rings.
17. The process according to claim 15, wherein the isomerization of cis-2-pentenenitrile to 3-pentenenitriles is performed in a reaction column.
18. A catalyst for the isomerization of cis-2-pentenenitrile to 3-pentenenitrile which comprises an amidine, tertiary amine or mixture thereof.