CN1793121A - Fused salt containing asymmetrical sulfonium cation, its preparation process and application in electrochemical device - Google Patents
Fused salt containing asymmetrical sulfonium cation, its preparation process and application in electrochemical device Download PDFInfo
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- CN1793121A CN1793121A CNA2005101122083A CN200510112208A CN1793121A CN 1793121 A CN1793121 A CN 1793121A CN A2005101122083 A CNA2005101122083 A CN A2005101122083A CN 200510112208 A CN200510112208 A CN 200510112208A CN 1793121 A CN1793121 A CN 1793121A
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- melting salt
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- sulfonium cation
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Abstract
The invention relates to a manufacture method for fused salt that contains asymmetry matte positive ion and the application in electrochemistry component. It uses 1-bromine alkane or 1-iodine alkane and dialkyl sulfide as raw material, uses acetonitrile and acetone as reaction solution to gain bromized or iodinated fused salt. After taking anion exchange reaction of the inorganic salt or inorganic acid in the water solution to gain fused salt that contains asymmetry matte positive ion. The fused salt has the advantages of noninflammable, non-volatile, stable.
Description
Technical field
The present invention relates to a kind of sulfonium salt, particularly a kind ofly contain asymmetric sulfonium cation melting salt and preparation method and the application in electrochemical device.
Background technology
Arrival along with advanced IT application, environment symbiosis and aging society, clean energy movably there is bigger expectation, because the inherent defective of traditional electrolytic solution that organic solvent and inorganic salt are formed makes its needs that can't adapt to development, it is extremely urgent therefore to seek novel electrolytic solution.Room temperature melting salt (room temperaturemolten salt) is also referred to as ionic liquid at room temperature (room temperature ionic liquid), the i.e. liquid substance of in wide temperature range (comprising room temperature), forming fully by ion, characteristic with a series of excellences, such as high ionic conductivity, wide electrochemical window, extremely low vapour pressure and thermostability etc. very likely become novel green electrolytic solution of future generation.
Up to now, positively charged ion is a quaternary ammonium ion, [the assistant rattan is expensive etc. to comprise the aliphatic quaternary ammonium ion, Chinese patent, application number: 02808669.4, publication number: CN 1503778A] and aromatic series quaternary ammonium ion [A K Ah Du-Sha Da etc., Chinese patent, application number: 95190080.3, publication number: CN 1123031A; The J Vista is graceful, Chinese patent, and application number: 00810676.2, publication number: CN1361716A; Xu Danqian etc., Chinese patent, application number: 03104095.1, publication number: CN1524853A] and the melting salt of season phosphine ion [C.J.Bradaric, et al, Green Chem.5 (2003) 143-152] be widely studied and be applied to electrochemical cell.
Summary of the invention
The object of the invention provides a kind of electrolytic solution that contains asymmetric sulfonium cation melting salt and its preparation method and be used for electrochemical device (lithium-ion secondary cell, dye-sensitized solar cells, ultracapacitor).
The chemical structural formula that contains asymmetric sulfonium cation melting salt of the present invention is as follows:
R wherein1And R2Be selected from respectively a kind of in the straight chain aliphatic alkyl of carbon number C1～C8, R3Be selected from a kind of in the straight chain aliphatic alkyl of carbon number C1～C10 and R1、R
2、R
3Too many by two is same straight chain aliphatic alkyl; A-Be selected from Br-、I
-、BF
4 -、PF
6 -、C
4F
9SO
3 -、(CF
3SO
2)
2N
-、(C
2F
5SO
2)
2N
-、
(CF
3SO
2)(C
2F
5SO
2)N
-Or N (CN)2 -Groups include: benzyl group, (2 -, 3 - or 4 - methylbenzyl) amino, (2 -, 3 - or 4 - methoxybenzyl) amino, (2 -, 3 - or 4 - fluorophenyl benzyl) amino, (2 -, 3 - or 4 - chlorobenzyl) amino group, a phenethyl group, a (2 -, 3 - or 4 - methylphenethyl) amino, (2 -, 3 - or 4-
- Methoxy-phenylethyl) amino, (2 -, 3 - or 4 - fluoro-phenylethyl) amino, (2 -, 3 - or 4 - chloro-phenethyl) amino, (3 - phenylpropyl) amino, (1 - methyl-1 - phenylethyl) amino, [1 - methyl -1 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [1 - methyl- -1 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - fluorophenyl) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - chlorophenyl) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - hydroxyphenyl) ethyl ] amino, [1 - methyl -1 - (2 -, 3 - or 4 - aminophenyl) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - methylamino-phenyl ) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - ethylamino) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - dimethylaminophenyl) ethyl] amino, [1 - methyl -1 - (2 -, 3 - or 4 - acetamidophenyl) ethyl] amino, [1 - methyl-1 - (2,3- -, 2,4 -, 2,5 -, 2,6 -, 3,4 -, 3,5 - or 3,6 - dimethoxyphenyl) ethyl] amino, (1,1 - dimethyl- -2 - phenylethyl) amino, [1,1 - dimethyl-2 - (2 -, 3 - or 4 - methylphenyl) ethyl] amino, [1,1 - dimethyl-2 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [1,1 - dimethyl-2 - (2 -, 3 - or 4 - fluorophenyl) ethyl] amino, [1,1 - dimethyl-2 - (2 -, 3 - or 4 - chlorophenyl) ethyl] amino, benzhydryl, [(2 -, 3 - or 4 -), (2 ' -, 3'-or 4'-) dimethyl diphenyl methyl] amino, [(2 -, 3 - or 4 -), (2'-, 3'-or 4'-) dimethoxy benzyl] amino, (2 -, 3 - or 4 -), (2'-, 3'-or 4'-) difluoro-benzhydryl] amino, [(2 -, 3 - or 4 - ), (2'-, 3'-or 4'-) dihydroxydiphenyl methyl] amino, [(2 -, 3 - or 4 -), (2'-, 3'-or 4'-) two
Amino diphenyl methyl] amino, [(2 -, 3 - or 4 -), (2'-, 3'-or 4'-) bis (dimethylamino) benzhydryl] amino, [(2 - , 3 - or 4 - methyl diphenyl methyl) amino, (2 -, 3 - or 4 - Methoxydiphenylmethyl) amino, (2 -, 3 - or 4 -) fluoro-benzhydryl ] amino, (2 -, 3 - or 4 -) chloro-benzhydryl] amino, (2 -, 3 - or 4 - hydroxy-diphenylmethyl) amino, (2 -, 3 - or 4 - aminodiphenylamine benzyl) amino, (2 -, 3 - or 4 - dimethylamino diphenylmethyl) amino, (1,1 - diphenyl-ethyl) amino, (1,2 - diphenyl-ethyl) amino, [ 2 - (2 -, 3 - or 4 - methylphenyl) -1 - phenylethyl] amino, [2 - (2 -, 3 - or 4 - methoxyphenyl) -1 - phenylethyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -1 - phenylethyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -1 - phenylethyl yl] amino, [1 - (2 -, 3 - or 4 - fluorophenyl) -2 - (2 -, 3 - or 4 - fluorophenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - chlorophenyl) -2 - (2 -, 3 - or 4 - chlorophenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - chlorophenyl) - 2 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - methylphenyl) -2 - (2 -, 3 - or 4- - methylphenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - hydroxyphenyl) -2 - (2 -, 3 - or 4 - hydroxyphenyl) ethyl] amino, [1 - (2 -, 3 -, or 4 - aminophenyl) -2 - (2 -, 3 -, or 4 - aminophenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - dimethylaminopyridine phenyl) -2 - (2 -, 3 - or 4 - dimethyl-aminophenyl) ethyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -1 - (2 -, 3 - or 4 - methylphenyl) ethyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -1 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [2 - (2 -, 3 - or 4 - hydroxyphenyl) -1 - phenylethyl] amino, [2 - (2 -, 3 -, or 4 - aminophenyl) -1 - phenyl ethyl] amino, [2 - (2
-, 3 - or 4 - dimethylamino-phenyl) -1 - phenylethyl] amino, [1 - (2 -, 3 - or 4 - methoxyphenyl) -2 - phenylethyl] amino, (1 - methyl -1,2 - diphenyl-ethyl) amino, (2,2 - diphenyl-ethyl) amino, [2 - (2 -, 3 - or 4 - methylphenyl) -2 - (2 -, 3 - or 4 - methylphenyl) ethyl] amino, [2 - (2 -, 3 - or 4 - methoxyphenyl) -2 - (2 -, 3 - or 4 - methoxyphenyl ) ethyl] amino, (1 - benzyl-4 - phenylbutyl) amino, (1,1 - diphenyl-ethyl) amino, [1 - (2 -, 3 - or 4 - fluorophenyl) -1 - (2 -, 3 - or 4 - fluorophenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - methylphenyl) -1 - (2 -, 3 - or 4- - methylphenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - methoxyphenyl) -1 - (2 -, 3 - or 4 - methoxyphenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - hydroxyphenyl) -1 - phenylethyl] amino, [1 - (2 -, 3 -, or 4 - aminophenyl) -1 - phenylethyl] amino, [1 - (2 -, 3 - or 4 - dimethylamino-phenyl) -1 - phenylethyl] amino, tritylamino, [(2 -, 3 - or 4 -), (2 ' -, 3'-or 4'-), (2 "-, 3" - or 4 "-) trimethyl-trityl methyl] amino, [(2, 3 -, or 4 -), (2'- , 3'-or 4'-), (2 "-, 3" - or 4 "-) trifluoromethyl trityl] amino, (1 - benzyl-2 - phenylethyl) amino, [1 - (2 -, 3 - or 4 - fluorobenzyl) -2 - (2 -, 3 - or 4 - fluorophenyl) ethyl] amino, (1 - benzyl-1 - methyl - 2 - phenyl ethyl) amino, [1 - (2 -, 3 - or 4 - chlorobenzyl) -2 - (2 -, 3 - or 4 - chlorophenyl) ethyl] amino, [1 - (2 -, 3 - or 4 - fluorobenzyl) -2 - (2 -, 3 - or 4 - fluorophenyl) -1 - methylethyl] amino, [1 - methyl - 2 - (2 -, 3 - or 4 - methyl yl-phenyl) -3 - (2 -, 3 - or 4 - methylphenyl) propyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -3 - (2 -, 3 - or 4 - fluorophenyl)
-1 - Methyl-propyl] amino, (1,3 - diphenyl-propyl) amino, [1 - (2 -, 3 - or 4 - methylphenyl) -3 - (2 -, 3 - or 4- - methylphenyl) propyl] amino, [1 - (2 -, 3 - or 4 - methoxyphenyl) -3 - (2 -, 3 - or 4 - methoxyphenyl) propyl] amino, (1,4 - diphenyl butyl) amino, [1 - (2 -, 3 - or 4 - chlorophenyl) -4 - (2 -, 3 - or 4 - chlorophenyl) butyl] amino, [ 1 - (2 -, 3 - or 4 - methoxyphenyl) -4 - (2 -, 3 - or 4 - methoxyphenyl) butyl] amino, (1 - methyl -3,3 - diphenyl propyl) amino, [3 - (2 -, 3 - or 4 - fluorophenyl) -3 - (2 -, 3 - or 4 - fluorophenyl) -1 - methyl-propyl] amino, [1 - methyl-3 - (2 -, 3 - or 4 - methylphenyl) -3 - (2 -, 3 - or 4 - methylphenyl) propyl] amino, N-benzyl-N-methylamino , N-benzyl-N-ethylamino, N-benzyl-N-isopropylamino group, N-benzyl-N-isobutyl amino, N-benzyl-N-t-butylamino, N-(2 -, 3 - or 4 - fluorobenzyl)-N-isopropylamino group, N-(2 -, 3 - or 4 - chlorobenzyl)-N-isopropylamino group, N-(2 -, 3 - or 4 - methyl benzyl)-N-isopropylamino group, N-(2 -, 3 - or 4 - methoxybenzyl)-N-isopropylamino group, N-(2 -, 3 - or 4 - hydroxybenzyl)-N - isopropylamino, N, N-dibenzyl amino, N-benzyl-N-(2 -, 3 - or 4 - methoxybenzyl) amino, N-(2 -, 3 - or 4 - fluorobenzyl )-N-(2 -, 3 - or 4 - fluorobenzyl) amino, N-(2 -, 3 - or 4 - methylbenzyl)-N-(2 -, 3 - or 4 - methylbenzyl) amino, N-(2 -, 3 - or 4 - methoxybenzyl)-N-(2 -, 3 - or 4 - methoxybenzyl) amino, N-(2 -, 3 - or 4 - hydroxybenzyl yl)-N-(2 -, 3 - or 4 - hydroxybenzyl) amino, N-(2 -, 3 - or 4 - aminobenzyl)-N-(2 -, 3 - or 4 - aminobenzyl) amino- , N-(2 -, 3 - or 4 - dimethyl aminobenzyl)-N-(2 -, 3 - or 4 - dimethyl aminobenzyl) amino, N-benzyl-N-phenethyl group,
N-benzyl-N-(1 - phenylethyl) amino, N-benzyl-N-(1 - methyl-1 - phenylethyl) amino, N, N-diphenylethyl group, N, N- bis (1 - phenylethyl) amino, N-benzyl-N-(3 - phenylpropyl) amino, (2 - or 3 - furyl methyl) amino (2 - or 3 - thienylmethyl) amino, ( 2 -, 3 - or 4 - pyridylmethyl) amino, (2 - or 5 - methyl - 2 - or 3 - furylmethyl) amino, (2 - or 5 - methyl - 2 - or 3 - thenoyl yl) amino, [2 - (2 - or 3 - furyl) ethyl] amino, [2 - (2 - or 3 - thienyl) ethyl] amino, [3 - (2 - or 3 - furyl) propyl] amino, [3 - (2 - or 3 - thienyl) butyl] amino, [bis - (2 - or 3 - furyl) methyl] amino, [bis - (2 - or 3 - thienyl ) methyl] amino, [1,1 - bis - (2 - or 3 - furyl) ethyl] amino, [1,1 - bis (2 - or 3 - thienyl) ethyl] amino, [(2 - or 5 - methyl - 2 - or 3 - furylmethyl) amino, [(2 - or 5 - methyl - 2 - or 3 - furyl methyl] amino], (2 - or 5 - methyl - 2 - or 3 - thienylmethyl) amino, [1 - (2 - or 3 - furyl)-1 - methyl - ethyl] amino, [1 - (2 - or 3 - thienyl) -1 - methylethyl] amino, [1 - (2 - or 5 - methyl - 2 - or 3 - thienyl) -1 - methylethyl] amino, [1 - (2 - or 3 - furyl) -2 - (2 - or 3 - furyl) ethyl] amino, [1 - (2 - or 5 - methyl - 2 - or 3 - furyl)-1 - methylethyl] amino, [1 - (2 - or 3 - thienyl yl) -2 - (2 - or 3 - thienyl) ethyl] amino, [1 - (2 - or 3 - furyl)-2 - phenylethyl] amino, [1 - (2 - or 3 - furyl yl) -2 - (2 -, 3 - or 4 - methylphenyl) ethyl] amino, [2 - phenyl-1 - (2 - or 3 - thienyl) ethyl] amino, [1 - benzene -2 - (2 - or 3 - thienyl) ethyl] amino, [2 - (2 -, 3 - or 4 - methylphenyl) -1 - (2 - or 3 - thienyl) ethyl] amino, [2 - (2 -, 3 - or 4-
) - Chlorophenyl) -1 - (2 - or 3 - thienyl) ethyl] amino, [2 - (2 -, 3 - or 4 - fluorophenyl) -1 - (2 - or 3 - thienyl ) ethyl] amino, [2 - (2 -, 3 - or 4 - methoxyphenyl) -1 - (2 - or 3 - thienyl) ethyl] amino, N-(2 - or 3 - furoyl yl)-N-(2 - or 3 - furylmethyl) amino, N-(2 - or 3 - thienylmethyl)-N-(2 - or 3 - thienylmethyl) amino, [1 - (2 - , 3 - or 4 - fluorophenyl) -2 - (2 - or 3 - thienyl) ethyl] amino, N-benzyl-N-(2 - or 3 - furylmethyl) amino, (2 - hydroxy- -1,2 - diphenyl-ethyl) amino, N'N'-diphenyl hydrazine, N'-(2 -, 3 - or 4 - methylphenyl)-N'-phenyl hydrazino group, N'- (2 -, 3 - or 4 - methoxyphenyl)-N'-phenyl hydrazino group, N'-(2 -, 3 - or 4 - chlorophenyl)-N'-phenyl hydrazino group, N'-( 2 -, 3 - or 4 - fluorophenyl)-N'-phenyl hydrazino group, N'-(2 -, 3 - or 4 - hydroxyphenyl)-N'-phenyl hydrazino group, N'-(2 - , 3 - or 4 - aminophenyl)-N'-phenyl hydrazino group, N'-(2 -, 3 - or 4 - dimethyl-aminophenyl)-N'-phenyl hydrazino group, N'-(2 - , 3 - or 4 - acetamidophenyl)-N'-phenyl hydrazino group, N'-(2 -, 3 - or 4 - methylphenyl)-N'-(2 -, 3 - or 4 - methyl yl-phenyl)-hydrazine group, and N'-(2 -, 3 - or 4 - methoxyphenyl)-N'-(2 -, 3 - or 4 - methoxyphenyl) hydrazine.
...
It is raw material that the present invention contains asymmetric sulfonium cation melting salt employing 1-bromoalkane or 1-iodine alkane and dialkyl sulfide, is reaction solvent with acetonitrile or acetone, obtains bromination or iodate melting salt; This class bromination or iodate melting salt generate the melting salt that contains asymmetric sulfonium cation in the aqueous solution and behind various inorganic salt or the mineral acid generation anion exchange reaction.
The concrete preparation method that the present invention contains asymmetric sulfonium cation melting salt is as follows:
(1) dialkyl sulfide of the 1-bromoalkane of 3.0mol or 1-iodine alkane and 1.5～6.0mol is mixed after, add 50～450ml acetonitrile or acetone reaction 2～40 days again, after the filtration, use the ether thorough washing again, vacuum-drying 2～5 days obtains bromination or iodate melting salt.
(2) get 0.05mol bromination or iodate melting salt and be dissolved in 10～100ml water, add the NaBF that is dissolved with 0.05～0.08mol again
4, KC
4F
9SO
3, Li (CF
3SO
2)
2N, Li (C
2F
5SO
2)
2N, Li (CF
3SO
2) (C
2F
5SO
2) N, NaN (CN)
2Or HPF
6The aqueous solution in react and carried out anion exchange reaction in 0.5～36 hour, add 30～300ml methylene dichloride or chloroform extraction then, collect organic phase, solvent is removed in underpressure distillation, perhaps remove moisture, wash with water, last vacuum-drying obtained containing asymmetric sulfonium cation melting salt in 5～72 hours again.
The 1-bromoalkane that the present invention uses is selected from monobromethane, 1-N-PROPYLE BROMIDE, 1-bromine normal butane, 1-bromine Skellysolve A, 1-bromine normal hexane, 1-bromine normal heptane, 1-bromine octane, a kind of in 1-bromine n-decane or the positive nonane of 1-bromine.
The 1-iodine alkane that the present invention uses is selected from iodoethane, propyl iodide, 1-iodine normal butane, 1-iodine Skellysolve A, 1-iodine normal hexane, 1-iodine normal heptane, 1-iodine octane, a kind of in 1-iodine n-decane or the positive nonane of 1-iodine.
The dialkyl sulfide that the present invention uses is selected from dimethyl sulphide, diethyl thioether, propyl thioether, dibutyl sulfide ether, diamyl thioether, two own thioethers, two hepta-thioethers, a kind of in the two hot thioethers or first and second thioethers.
The present invention contains asymmetric sulfonium cation melting salt and is applied in the electrolytic solution of electrochemical device, and electrochemical device comprises lithium-ion secondary cell, dye-sensitized solar cells or ultracapacitor, yet these electrolytic solution should be low viscosity and high conductivity.
The present invention contain asymmetric sulfonium cation melting salt can be separately or with the mixture of other organic solvent or lithium salts as used for electrolyte in lithium-ion secondary cell, dye-sensitized solar cells or ultracapacitor; Wherein organic solvent is a NSC 11801, propylene carbonate, dimethyl carbonate, diethyl carbonate, the methylethyl carbonic ether, 1, the fluorine-based ethane of 2-diformazan, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl isophthalic acid, the 3-dioxolane, ether, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, 3-Jia Ji oxazolidinedione, 3-Yi Ji oxazolidinedione, methyl-formiate, methyl acetate, ethyl acetate, ethyl propionate, methyl propionate, methyl-butyrate, ethyl butyrate, N-methylformamide, N, dinethylformamide, N-methylacetamide, N-Methyl pyrrolidone, tetramethylene sulfone, dimethyl sulfoxide (DMSO), acetonitrile, methoxyacetonitrile, phosphotriester or its mixture; Lithium salts is LiBF
4, LiPF
6, LiClO
4, LiAsF
6, LiCF
3SO
3, LiC (CF
3SO
2)
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiN (CF
3SO
2) (C
2F
5SO
2) or its mixture.
When the present invention contained asymmetric sulfonium cation melting salt and is applied in electrolyte of lithium-ion secondary battery, lithium-ion secondary cell was made of barrier film between positive electrode material, negative material, the positive and negative pole material and electrolytic solution; Positive electrode material comprises that lithium ion can reversible embedding and take off the chalcogen compound that contains lithium ion and the polymer materials of embedding.The chalcogen compound that wherein contains lithium ion is selected from LiV
3O
8, LiMnO
2, LiMn
2O
4, LiCoO
2Or LiFePO
4Polymer materials is selected from polyacetylene, polyphenyl, polypyrrole, polyaniline, Polythiophene or active sulphur polymkeric substance and matrix material thereof; Negative material comprises that basic metal, alkali metal alloy, lithium ion can reversibly insert therein and take off slotting carbonaceous material, and at least a be nitride, oxide compound or the sulfide of the element of the periodic table of elements 8,9,10,11,12,13,14 and 15 families.Wherein basic metal is selected from lithium, sodium or potassium; Alkali metal alloy is selected from lithium-aluminium, lithium-magnesium or sodium-zinc; Lithium ion can reversibly insert and take off slotting carbonaceous material therein and be selected from carbon black, graphite, coke or vitreous carbon; The nitride that lithium ion can reversibly insert and take off slotting at least a element for the periodic table of elements 8,9,10,11,12,13,14 and 15 families therein is selected from and comprises the transition metal nitride that contains lithium; The oxide compound that lithium ion can reversibly insert and take off slotting at least a element for the periodic table of elements 8,9,10,11,12,13,14 and 15 families therein is selected from Li
3BiO
4, Li
2ZnO
2Or SnSiO
3The sulfide that lithium ion can reversibly insert and take off slotting at least a element for the periodic table of elements 8,9,10,11,12,13,14 and 15 families therein is selected from Li
xFeS
2(0≤x≤3) or Li
xCuS (0≤x≤3); Barrier film between the positive and negative pole material is selected from polyolefine or glass fibre; Wherein polyolefine is selected from multipolymer, the Natene of porousness polypropylene, propylene and ethene.
When the present invention contained asymmetric sulfonium cation melting salt and is applied in dye-sensitized solar cells electrolytic solution, dye-sensitized solar cells was by the effect utmost point, form the utmost point and electrolytic solution; Act on the electrode that collector very and the porous membrane that has adsorbed pigment constitute; The collector of the effect utmost point is electroconductibility paper tinsel or plate such as metal, metal oxide, carbon or tNonwovens, film or plates such as the glass with surface conduction layer, plastics.From the viewpoint of the capture rate of light, adopt the photopermeability of glass with conductive layer or plastics etc. high tNonwovens, film or plate for well, from the viewpoint of price, electroconductibility paper tinsel such as metal, metal oxide, carbon or plate are for well; About the porous-film of adsorpting pigment of the effect utmost point, be to utilize coating method or sol-gel method dispersion liquid or colloidal solution film forming on collector with the semiconductor microactuator particle.Semi-conductor can use element semiconductors such as silicon, germanium, or the surface compound semi-conductor of metal and oxygen family element composition, or has perovskite-type compounds.The compound that metal and oxygen family element are formed comprises titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, plugs with molten metal, the oxide compound of cerium, yttrium, lanthanum, barium, niobium, tantalum, the sulfide of cadmium, zinc, lead, silver, antimony, bismuth, cadmium, plumbous selenide, the telluride of cadmium etc.Other compound semiconductor comprises the phosphide of zinc, gallium, indium, cadmium etc., gallium arsenide, copper-cadmium-selenium compound, copper-cadmium-sulfide etc.Perovskite-type compounds comprises strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium titanate etc.The mono crystalline semiconductor that adopts or many crystallizations all can, from the viewpoint of photoelectric transformation efficiency, single crystal is for well, from manufacturing price, the raw material resources consideration, many crystallizations are for well.Semi-conductive in addition particle diameter is more than 2nm, and 1 μ m is following to be best; Collector semiconductor-on-insulator micropartical is filmed, and forms porous membrane behind heating, the sintering, and collector because closely contact, has guaranteed the contact of electronics and the intensity of filming with each micropartical simultaneously; Porous membrane also can be in the two sides of collector film forming, and at this moment, the collector of employing is thin more, and photoelectric transformation efficiency is high more; Generally speaking, the thickness of semiconductor layer is thick more, and the dyestuff of unit shadow area absorption is many more, thereby the capture rate of light is also high more.But because the electron diffusion that generates distance is increasing, the combination again of electric charge increases.Therefore, the semi-conductor thickness preferably is controlled at 0.1～100 mu m range, and 1～30 μ m is best; The concrete example of porous membrane absorbing dye is: metal complexes colouring substance, merocyanine dyes, 9-propenyl santene compound pigment, three propylene ethane pigments, acridine (acridine) pigment, tonka bean camphor pigment, azoic dyestuff, phthalocyanine pigment, porphines dyestuff.These dyestuffs at least a or two above (comprising two kinds) mix as photoelectric conversion material and use; The electrode the same to the collector of the extremely available and above-mentioned effect utmost point.For further improving photoelectric transformation efficiency, can also can carry out surface treatment to it.Surface treatment method is, etching, splash, or method such as CVD.
When the present invention contained asymmetric sulfonium cation melting salt and is applied in electrolytic solution for super capacitor, ultracapacitor was made up of barrier film between a pair of polarizing electrode, the polarizing electrode and electrolytic solution; Polarizing electrode is by preparing the polarizing electrode coated materials on collector, the polarizing electrode material is selected from carbon materials, metal oxide materials or conducting polymer materials; Wherein carbon materials is selected from active carbon material, activated carbon fiber or carbon nanotube, in carbon materials, add electro-conductive material, electro-conductive material is selected from carbon black, acetylene black, graphite, titanium dioxide or steel fiber and composition thereof, for well, add-on is preferably 1～10 weight part/per 100 weight part carbon materialses to the average particle size particle size of electro-conductive material in 10～50nm scope; Metal oxide materials uses transition metal oxide, and wherein transition metal oxide is selected from α-RuO
2NH
2O, α-MnO
2NH
2O, α-V
2O
5NH
2O, H
3PMo
12O
40NH
2O, NiO
x, IrO
2, WO
3, PbO
2, Co
3O
4Or SrRuO
3Conducting polymer materials is selected from polyacetylene, polypyrrole, polyaniline, Polythiophene or polyurethane and their derived polymers thereof.
It is nonflammable that the present invention contains asymmetric sulfonium cation melting salt, not volatile, and excellent in stability when being applied in lithium-ion secondary cell, dye-sensitized solar cells and ultracapacitor, can solve performance and secure context hidden danger that conventional electrolysis liquid brings.
When the present invention contained asymmetric sulfonium cation melting salt and is applied in electrolytic solution for super capacitor, capability retention was better than the glyoxaline cation melting salt that contains commonly used at present.When containing the glyoxaline cation melting salt and being applied in electrolytic solution for super capacitor, 60 ℃ are the upper limit that it can discharge and recharge; And when containing asymmetric sulfonium cation melting salt and being applied in electrolytic solution for super capacitor, under 80 ℃, still can normally discharge and recharge.
Description of drawings
Fig. 1 is ethyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
1H NMR spectrogram (no deuterated solvent).
Fig. 2 is an ethyl dimethyl sulfonium hexafluorophosphate
1H NMR spectrogram (deuterated solvent: deuterated methanol).
Fig. 3 is normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
1H NMR spectrogram (no deuterated solvent).
Fig. 4 is a normal-butyl dimethyl sulfonium hexafluorophosphate
1HNMR spectrogram (deuterated solvent: deuterated methanol).
Fig. 5 contains lithium-ion secondary cell at room temperature the cycle performance (10 circulation) of asymmetric sulfonium cation melting salt as electrolytic solution for using.
Fig. 6 contains asymmetric sulfonium cation melting salt as the capacity of super capacitor conservation rate of electrolytic solution and the graph of a relation of temperature for using.
Embodiment
The following examples are to further specify of the present invention, but do not limit the scope of the invention.
Embodiment 1: the preparation of ethyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
(1) with after new iodoethane that steams of 468g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, lucifuge condition, add the refining acetonitrile of 150ml; at room temperature reacted 3 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 2 days obtains 58.86g iodate ethyl dimethyl sulfonium.
(2) get 10.9g (0.05mol) iodate ethyl dimethyl sulfonium and be dissolved in the 20ml deionized water, add two (trifluoromethyl sulphonyl) the imines lithium aqueous solution that contains 14.35g (0.05mol), at room temperature reacted 12 hours, in reactant, add 100mlCH
2Cl
2, standing over night is divided oil-yielding stratum.Underpressure distillation removes and desolvates, and obtains 16.7g ethyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt at 80 ℃ of following vacuum-drying 24h at last, and it at room temperature is a colourless liquid.Fig. 1 is ethyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
1H NMR spectrogram (no deuterated solvent), δ: 2.77 (t, CH
2), 2.31 (s, 2CH
3), 0.89 (t, CH
3) ppm.
Embodiment 2: the preparation of ethyl dimethyl sulfonium hexafluorophosphate
(1) with after new monobromethane that steams of 327g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, add the refining acetonitrile of 150ml, at room temperature reacted 3 days, after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 2 days obtains 46g bromination ethyl dimethyl sulfonium.
(3) get 8.55g (0.05mol) bromination ethyl dimethyl sulfonium and be dissolved in the 10ml deionized water, drip the HPF that contains 8.76g (0.06mol)
6The aqueous solution reacted 0.5 hour, removed residual water-content, used the appropriate amount of deionized water washed product, made its PH ≈ 7.Obtain 10.15g ethyl dimethyl sulfonium hexafluorophosphate at 80 ℃ of following vacuum-drying 36h, it at room temperature is a white solid.Fig. 2 is an ethyl dimethyl sulfonium hexafluorophosphate
1H NMR spectrogram (deuterated solvent: deuterated methanol), δ: 3.31 (t, CH
2), 2.88 (s, 2CH
3), 1.47 (t, CH
3) ppm.
Embodiment 3: the preparation of normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
(1) with after new 1-iodine normal butane that steams of 552g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, lucifuge condition, add the 180ml purifying acetone; at room temperature reacted 20 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 3 days obtains 51.66g iodate normal-butyl dimethyl sulfonium.
(2) get 12.3g (0.05mol) iodate normal-butyl dimethyl sulfonium and be dissolved in the 50ml deionized water, add two (trifluoromethyl sulphonyl) the imines lithium aqueous solution that contains 14.35g (0.05mol), at room temperature reacted 24 hours, in reactant, add 200mlCH
2Cl
2, standing over night is divided oil-yielding stratum.Underpressure distillation removes and desolvates, and obtains 17.4g normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt at 80 ℃ of following vacuum-drying 24h at last, and it at room temperature is a colourless liquid.Fig. 3 is normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
1H NMR spectrogram (no deuterated solvent), δ: 2.76 (t, CH
2), 2.35 (s, 2CH
3), 1.23 (m, CH
2), 0.98 (m, CH
2), 0.45 (t, CH
3) ppm.
Embodiment 4: the preparation of normal-butyl dimethyl sulfonium hexafluorophosphate
(1) with after new 1-iodine normal butane that steams of 552g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, lucifuge condition, add the 180ml purifying acetone; at room temperature reacted 20 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 3 days obtains 51.66g iodate normal-butyl dimethyl sulfonium.
(3) get 12.3g (0.05mol) iodate normal-butyl dimethyl sulfonium and be dissolved in the 10ml deionized water, drip the HPF that contains 8.76g (0.06mol)
6The aqueous solution reacted 1 hour, removed residual water-content, used the appropriate amount of deionized water washed product, made its PH ≈ 7.Obtain 11.22g normal-butyl dimethyl sulfonium hexafluorophosphate at 80 ℃ of following vacuum-drying 36h, it at room temperature is a white solid.Fig. 4 is a normal-butyl dimethyl sulfonium hexafluorophosphate
1The HNMR spectrogram (deuterated solvent: deuterated methanol), δ: 2.89 (t, CH
2), 2.89 (s, 2CH
3), 1.79 (m, CH
2), 1.51 (m, CH
2), 1.00 (t, CH
3) ppm.
Embodiment 5: the preparation of n-hexyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt
(1) with after new 1-bromine normal hexane that steams of 495g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, add the refining acetonitrile of 300ml; at room temperature reacted 20 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 2 days obtains 36.1g bromination n-hexyl dimethyl sulfonium.
(2) get 11.35g (0.05mol) bromination n-hexyl dimethyl sulfonium and be dissolved in the 60ml deionized water, add two (trifluoromethyl sulphonyl) the imines lithium aqueous solution that contains 14.35g (0.05mol), at room temperature reacted 16 hours, in reactant, add 200mlCH
2Cl
2, standing over night is divided oil-yielding stratum.Underpressure distillation removes and desolvates, and obtains 17.47g n-hexyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt at 80 ℃ of following vacuum-drying 24h at last, and it at room temperature is a white solid.
Embodiment 6: the preparation of n-pentyl dihexyl sulfonium nine fluorine butyl sulfosalts
(1) with after new 1-bromine Skellysolve A that steams of 453g (3.0mol) and 606g (3.0mol) the two own thioethers mixing; under nitrogen protection, add the refining acetonitrile of 300ml; at room temperature reacted 30 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 3 days obtains 50.83g bromination n-pentyl dihexyl sulfonium.
(2) get 17.65g (0.05mol) bromination n-pentyl dihexyl sulfonium and be dissolved in the 50ml deionized water, add the nine fluorine butyl sulfonic acid aqueous solutions of potassium that are dissolved with 16.9g (0.05mol), at room temperature reacted 24 hours.In reactant, add 150mlCH
2Cl
2, standing over night is divided oil-yielding stratum.Underpressure distillation removes and desolvates, and obtains 23.49g n-pentyl dihexyl sulfonium nine fluorine butyl sulfosalts at 70 ℃ of following vacuum-drying 36h at last, and it at room temperature is a white solid.
Embodiment 7: the preparation of n-octyl dimethyl sulfonium two (pentafluoroethyl group sulphonyl) inferior amine salt
(1) with after new 1-bromine octane that steams of 579g (3.0mol) and the mixing of 186g (3.0mol) dimethyl sulphide; under nitrogen protection, add the refining acetonitrile of 200ml; at room temperature reacted 30 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 3 days obtains 29.84g bromination n-octyl dimethyl sulfonium.
(2) get 12.75g (0.05mol) bromination n-octyl dimethyl sulfonium and be dissolved in the 50ml deionized water, add two (pentafluoroethyl group sulphonyl) the imines lithium aqueous solution that contains 0.05mol, at room temperature reacted 24 hours, in reactant, add 200mlCH
2Cl
2, standing over night is divided oil-yielding stratum.Underpressure distillation removes and desolvates, and obtains 15.79g n-octyl dimethyl sulfonium two (pentafluoroethyl group sulphonyl) inferior amine salt at 80 ℃ of following vacuum-drying 24h at last, and it at room temperature is a white solid.
Embodiment 8: the preparation of methylethyl normal-butyl sulfonium dicyan amine salt
(1) with after new 1-bromine normal butane that steams of 411g (3.0mol) and the mixing of 228g (2.5mol) first and second thioethers; under nitrogen protection, add the refining acetonitrile of 120ml; at room temperature reacted 20 days; after product is used the anhydrous diethyl ether thorough washing; vacuum-drying at room temperature 3 days obtains 26.84g Diethylaminoethyl ethyl normal-butyl sulfonium.
(2) getting 10.65g (0.05mol) Diethylaminoethyl ethyl normal-butyl sulfonium is dissolved in the 50ml deionized water, dropping is dissolved with the aqueous solution of 3.65g (0.05mol) dicyanamide lithium, at room temperature reacted 24 hours, and filtered removal of solvent under reduced pressure, residue is dissolved in the 100ml trichloromethane, use anhydrous magnesium sulfate drying, filter, underpressure distillation removes and desolvates, obtain 7.36g methylethyl normal-butyl sulfonium dicyan amine salt at 70 ℃ of following vacuum-drying 36h at last, it at room temperature is a white solid.
The preparation of the application lithium-ion secondary cell of embodiment 9 normal-butyl dimethyl sulfoniums two (trifluoromethyl sulphonyl) inferior amine salt in lithium-ion secondary cell
(1) anodal preparation
LiCoO with 85 parts by weight
2As the acetylene black of positive active material, 7 parts by weight as poly-inclined to one side 1 of conducting material, 8 parts by weight, 1-difluoroethylene (PVDF) is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 265 parts by weight and fully mixes into pasty state, with scraper it is coated on the aluminium foil then, then following dry 2 hours at 80 ℃, under 5Mpa pressure, be pressed into the disk of diameter 14cm, 110 ℃ of following vacuum-dryings 5 hours, obtain LiCoO again
2Positive electrode material.
(2) preparation of electrolytic solution
7 parts by weight two (trifluoromethyl sulphonyl) imines lithium is dissolved in normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt that 80 parts by weight obtain by embodiment 3 makes electrolytic solution.
(3) assembling of lithium-ion secondary cell
Fibreglass diaphragm is placed between above-mentioned positive pole and the lithium anode (diameter 14cm), and with above-mentioned electrolytic solution impouring and be full of the entire cell assembly, obtain the coin shape lithium-ion secondary cell.
The above-mentioned lithium-ion secondary cell that assembles is at room temperature carried out the cycle performance test, and the result as can be seen, is 90.6% of the 1st circulation back loading capacity through the loading capacity after 10 circulations as shown in Figure 5, still can normally discharge and recharge.
The preparation of dye-sensitized solar cells
TiO
2The water that adds equivalent in the slurry, making by particle diameter after reaction in 12 hours at 250 ℃ is the Detitanium-ore-type TiO of 30nm
2The paste that colloidal solution forms is coated this paste (20mm * 25mm, NHTechno company on the transparency electrode of glass matrix, 1.1mmFTO transparency conducting layer resistance 15 Ω/square), then, in electric furnace, calcined 30 minutes for 450 ℃, promptly on collector, form porous film.
The Ruthenium535-bisTBA dyestuff that SOLARONIX company is produced is dissolved in ethanol, and adjusting its concentration is 5 * 10
-4M immerses in this dye solution 12 hours with absorbing dye with above-mentioned test film, cleans electrode surface after painted with ethanol, and drying is as the effect utmost point.
0.13 parts by weight lithium iodide, 0.3 parts by weight iodine, 1.35 parts by weight 4-butyl-pyridinium, 2.7 parts by weight iodate ethyl dimethyl sulfoniums are dissolved in 16 parts by weight ethyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salts make electrolytic solution, to the platinum foil of 0.1mm very.
, inject electrolytic solution at two interpolars and promptly make electrooptical device as pad with the thick resin molding of 25 μ m of chemical company of Mitsui Du Pont system.
Adopt the solar simulator of (day) beam split gauge company product, mix the antireflective film of corresponding 1.5G, adjust to 100mW/cm with quantorecorder
2The back is measured with the potentiostat (HSV-100F) that (day) Big Dipper electrician company produces as measuring light source, and its photoelectric transformation efficiency is 1.5%.
The application of embodiment 11 normal-butyl dimethyl sulfoniums two (trifluoromethyl sulphonyl) inferior amine salt in ultracapacitor
The preparation of ultracapacitor
With activated carbon, acetylene black, polytetrafluoroethylsolution solution was by 9: 1: 1 (weight ratio) mixed and fully stir into pasty state, with scraper it is coated on the aluminium sheet then, at 5Mpa pressure lower sheeting, thickness is 0.2mm, 110 ℃ of following vacuum-dryings 5 hours, obtain polarizable electrode.Electrolytic solution is selected normal-butyl dimethyl sulfonium two (trifluoromethyl sulphonyl) inferior amine salt that is obtained by embodiment 3 for use.Fibreglass diaphragm is placed between a pair of polarizable electrode, and with above-mentioned electrolytic solution impouring and be full of the entire cell assembly, obtain ultracapacitor.
The above-mentioned ultracapacitor that assembles is carried out test under the differing temps, the result as shown in Figure 6, as can be seen, when temperature rose to 70 ℃, its degradation was still less, can normally discharge and recharge.
Claims (6)
1. one kind contains asymmetric sulfonium cation melting salt, it is characterized in that chemical structural formula is as follows:
R wherein
1And R
2Be selected from a kind of in the straight chain aliphatic alkyl of carbonatoms C1～C8, R respectively
3Be selected from a kind of in the straight chain aliphatic alkyl of carbonatoms C1～C10 and R
1, R
2, R
3Too many by two is with a kind of straight chain aliphatic alkyl; A
-Be selected from Br
-, I
-, BF
4 -, PF
6 -, C
4F
9SO
3 -, (CF
3SO
2)
2N
-, (C
2F
5SO
2)
2N
-, (CF
3SO
2) (C
2F
5SO
2) N
-Or N (CN)
2 -In a kind of.
2. as claimed in claim 1ly contain asymmetric sulfonium cation melting salt, it is characterized in that being used for the electrolytic solution of electrochemical device, wherein electrochemical device is lithium-ion secondary cell, dye-sensitized solar cells or ultracapacitor.
3. the preparation method who contains asymmetric sulfonium cation melting salt as claimed in claim 1 is characterized in that the preparation method is as follows:
(1) dialkyl sulfide of the 1-bromoalkane of 3.0mol or 1-iodine alkane and 1.5～6.0mol is mixed after, add 50～450ml acetonitrile or acetone reaction 2～40 days again, after the filtration, use the ether thorough washing again, vacuum-drying 2～5 days obtains bromination or iodate melting salt;
(2) get 0.05mol bromination or iodate melting salt and be dissolved in 10～100ml water, add the NaBF that is dissolved with 0.05～0.08mol again
4, KC
4F
9SO
3, Li (CF
3SO
2)
2N, Li (C
2F
5SO
2)
2N, Li (CF
3SO
2) (C
2F
5SO
2) N, NaN (CN)
2Or HPF
6The aqueous solution in react and carried out anion exchange reaction in 0.5～36 hour, add 30～300ml methylene dichloride or chloroform extraction then, collect organic phase, solvent is removed in underpressure distillation, perhaps remove moisture, wash with water, last vacuum-drying obtained containing asymmetric sulfonium cation melting salt in 5～72 hours again.
4. the preparation method who contains asymmetric sulfonium cation melting salt according to claim 3 is characterized in that the 1-bromoalkane is selected from monobromethane, 1-N-PROPYLE BROMIDE, 1-bromine normal butane, 1-bromine Skellysolve A, 1-bromine normal hexane, 1-bromine normal heptane, 1-bromine octane, a kind of in 1-bromine n-decane or the positive nonane of 1-bromine.
5. the preparation method who contains asymmetric sulfonium cation melting salt according to claim 3 is characterized in that 1-iodine alkane is selected from iodoethane, propyl iodide, 1-iodine normal butane, 1-iodine Skellysolve A, 1-iodine normal hexane, 1-iodine normal heptane, 1-iodine octane, a kind of in 1-iodine n-decane or the positive nonane of 1-iodine.
6. the preparation method who contains asymmetric sulfonium cation melting salt according to claim 3 is characterized in that dialkyl sulfide is selected from dimethyl sulphide, the diethyl thioether, propyl thioether, dibutyl sulfide ether, diamyl thioether, two own thioethers, two hepta-thioethers, a kind of in the two hot thioethers or first and second thioethers.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092412B (en) * | 2007-07-24 | 2012-12-12 | 中国科学院长春应用化学研究所 | Ion liquor in onium category of tetrahydrothiophene, preparation method, and application |
-
2005
- 2005-12-29 CN CNA2005101122083A patent/CN1793121A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092412B (en) * | 2007-07-24 | 2012-12-12 | 中国科学院长春应用化学研究所 | Ion liquor in onium category of tetrahydrothiophene, preparation method, and application |
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