CN103626682A - Imine alkali metal salt and ion liquid as well as application thereof as non-water electrolyte - Google Patents
Imine alkali metal salt and ion liquid as well as application thereof as non-water electrolyte Download PDFInfo
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Abstract
The invention discloses an application of imine alkali metal salt and an ion liquid as non-water electrolyte, and provides an ion liquid consisting of perfluoroalkyl sulfimide alkali metal salt with 'S-perfluoroalkyl sulfimide', perfluoroalkyl sulfimide anion with 'S-perfluoroalkyl sulfimide', as well as sulfonium salt, ammonium salt, microcosmic salt cation. According to the application, an intermediate fluoro-alkyl(S-perfluoroalkyl imino) sulfamide of perfluoroalkyl sulfimide is prepared by reacting (perfluoroalkyl sulfonyl)(perfluoroalkyl sulfinyl) imino with sulfur valence state of +4 and hydroxylamine oxygen sulfonic acid, the routes that fluoro-alkyl(S-perfluoroalkyl imino) sulfamide is prepared from (perfluoroalkyl sulfonyl)(perfluoroalkyl sulfinyl) imino through three steps of chlorination, fluorination and amination are effectively shortened, the operation is simple and convenient, the yield and the purity are high, the alkali metal salt has relatively good thermal stability and hydrolysis resistance, has high conductivity and oxidation potential in the conventional carbonic ester solution, and is good in compatibility with widely applied electrode materials, and the ion liquid can be applied to lithium ion batteries and carbon-based super capacitors.
Description
Technical field
The invention belongs to organic fluorine chemistry, novel material and advanced power technique fields, be specifically related to a kind of an alkali metal salt of the fluoroalkyl sulfimide containing " S-fluoroalkyl sulfimide base " and ionic liquid and preparation method thereof, and this alkali metal salt and ionic liquid application in secondary lithium (ion) battery and carbon back ultracapacitor as electrolyte.
Background technology
Fluorine-containing sulfimide and an alkali metal salt thereof, lithium salts particularly, it is important fluoride ion compound, at clean energy devices such as secondary lithium (ion) battery, ultracapacitor and aluminium electrolutic capacitors, with fields such as high-performance nonaqueous electrolyte material and efficient catalysts, all there is important commercial application and be worth.
At present, about the research of fluorine-containing sulfimide, focus mostly in the fluorine-containing sulfimide of monobasic (Coord.Chem.Revs., 1997,158,413.), namely in anion structure, contain a sulfimide (SO
2nSO
2-) unit, as two (fluoroalkyl sulphonyl) imines (H[(R
fsO
2)
2n], R
f=C
mf
2m+1, m=1-8) and an alkali metal salt (M[(R
fsO
2)
2n], M=Li, Na, K, Rb, Cs), wherein that representative is two (trimethyl fluoride sulfonyl) imine lithium (Li[(CF
3sO
2)
2n], be called for short LiTFSI).Due to CF in molecule
3strong electron attraction, and sulfimide group (SO
2-N-SO
2-) conjugation delocalization, make [(CF
3sO
2)
2n]
-(TFSI
-) negative charge high dispersing in negatively charged ion, and become the organic anion of weak coordination, so make HTFSI have extremely strong acidity and resistance to oxidation reducing property, its an alkali metal salt, ionic liquid have good chemistry and electrochemical stability.For this reason, people consider further will have the fluoroalkyl alkylsulfonyl (R of strong electron-withdrawing power
fsO
2) introduce above-mentioned two (fluoroalkyl sulphonyl) imines ([(R
fsO
2)
2n]
-) in negatively charged ion, as TFSI
-negatively charged ion, to developing, there is stronger organic super acid and the more weak fluorine-containing organic anion of coordination, as representational (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imines negatively charged ion (formula (A)), " the S-fluoroalkyl sulfimide (R such as two (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) imines negatively charged ion (formula (A))
fsO
2n=S) base " fluoroalkyl sulfimide negatively charged ion (Org.Biomol.Chem., 2005,3,2239).
Relevant fluoroalkyl sulfimide and an alkali metal salt thereof containing " S-fluoroalkyl sulfimide base " in existing technology of preparing, the fluoroalkyl that sulphur (S) valence state of generally take is+4 (S-fluoroalkyl sulfimide base)-sulfinate (R
f(R
fsO
2n) SOM, formula I) or its SULPHURYL CHLORIDE (R
f(R
fsO
2n) SOCl, formula II) for basic material, further transform, its synthetic method has:
1) with trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulfonic acid fluoride (CF
3(CF
3sO
2sOF) or phenyl (S-trifluoromethanesulp-onyl-onyl imide base) sulfonic acid fluoride (Ph (CF N)
3sO
2n) SOF) be raw material, reaction prepares trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (CF with liquefied ammonia at low temperatures
3(CF
3sO
2n) SONH
2, formula III) or phenyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (Ph (CF
3sO
2n) SONH
2, formula IV), then, under the existence of amine acid binding agent, by sulfonic acid fluoride and sulphonamide generation nucleophilic reaction, prepare (J.Chem.Soc., 2002,1,1887).But this preparation method's shortcoming is: (1) is with trimethyl fluoride sulfonyl lsothiocyanates (CF
3sO
2n=S=O) be raw material, the yield of synthetic this raw material is lower; (2) in this synthetic route process, use Ruppert reagent (trimethylammonium trifluoromethyl silane, CF
3siMe
3), price is comparatively expensive, is not suitable for extensive preparation; (3) from raw material trimethyl fluoride sulfonyl lsothiocyanates (CF
3sO
2n=S=O) to final product, synthetic route is longer, and overall productive rate is low.Thereby, a large amount of preparation manipulation inconvenience.
2) trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) SULPHURYL CHLORIDE (CF
3(CF
3sO
2n) SOCl, formula II) through fluoridation, make trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulfonic acid fluoride (CF
3(CF
3sO
2n) SOF), further and lithium nitride (Li
3n) synthetic two (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) imine lithium ([(CF of reaction
3(CF
3sO
2n) SO)
2n] Li formula (V)), but this synthetic route is only suitable in preparation symmetric target product (US6340716B1).
Containing " S-fluoroalkyl sulfimide (R
fsO
2n=S) base " imine intermediate fluoroalkyl (S-fluoroalkyl sulfimide base)-sulfinate (formula I) or the preparation method of its sulphinyl chlorine (formula II) have:
1) trimethyl fluoride sulfonyl lsothiocyanates (CF
3sO
2n=S=O) with MF(M be K or Cs) effect (J.Chem.Soc., 2002,1,1887), or at MF(M, be K or Cs) condition under trimethyl fluoride sulfonyl lsothiocyanates (CF
3sO
2n=S=O) and trimethylammonium trifluoromethyl silane (CF
3siMe
3) reaction, can obtain respectively (S-fluoroalkyl sulphonyl imino-) fluorine-sulfinate (F (CF
3sO
2n) SO
-m
+) and trifluoromethyl (S-fluoroalkyl sulphonyl imino-)-sulfinate (CF
3(CF
3sO
2n) SO
-m
+).
2) trifluoromethyl two sulphur (CF
3sSCF
3) and N, N-dichloro trimethyl fluoride sulfonyl amine (CF
3sO
2nCl
2) reaction directly obtains trifluoromethyl (S-fluoroalkyl sulphonyl imino-) SULPHURYL CHLORIDE (CF
3(CF
3sO
2n) SOCl), at stoichiometric trimethyl silanol an alkali metal salt (Me
3siOM, M=Li, Na, K) effect under further transform and obtain trifluoromethyl (S-fluoroalkyl sulphonyl imino-)-sulfinate (CF
3(CF
3sO
2n) SO
-m
+, M=Li, Na, K) and (J.Fluorine.Chem., 2002,115,129).
3) trifluoromethyl sulphinyl chlorine (CF
3sOCl) with (trimethyl silicon based) (trimethyl fluoride sulfonyl) imines sodium ([CF
3sO
2nSiMe
3] Na) in ether, react and prepare trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base)-sulfinic acid sodium (CF
3(CF
3sO
2n) SONa) (J.Fluorine.Chemistry, 2002,115,129).
4) (trimethyl fluoride sulfonyl) (butyl sulphonyl) imines sodium ([(CF
3sO
2) (C
4h
9sO
2) N] Na and oxalyl chloride (COCl)
2effect obtains butyl (S-trimethyl fluoride sulfonyl imino-) SULPHURYL CHLORIDE (C
4h
9(CF
3sO
2n) SOCl) (US6340716B1).
In addition, by sulphur compound and the N of+divalent, N-dichloro trimethyl fluoride sulfonyl amine (CF
3sO
2nCl
2) effect, also can directly introduce " S-fluoroalkyl sulfimide (R
fsO
2n=S) base " group, the following reaction of reporting such as Yagupolskii etc.: CF
3sNR
2+ CF
3sO
2nCl
2→ CF
3(CF
3sO
2n) SNR
2; CHF
2sCl+CF
3sO
2nCl
2→ CHF
2(CF
3sO
2n) SCl; F-Ph (CF
3sO
2n) SF+CF
3sO
2nCl
2→ F-Ph (CF
3sO
2n)
2sCl (Russian JOC, 2006,42,1275; Tetrahedron, 1994,50,6891).
On the other hand, nonaqueous electrolytic solution is one of critical material of the energy storage devices such as high specific energy (secondary) lithium ion battery, its over-all properties, and as chemistry and electrochemical stability, security etc., directly affect the use of secondary lithium (ion) battery.At present, business-like (secondary) lithium-ion battery electrolytes mainly by organic carbonate as methylcarbonate (CH
3oCOOCH
3, DMC), diethyl carbonate (C
2h
5oCOOC
2h
5, DEC), vinyl carbonate (EC) etc., and ionogen conducting salt (is mainly LiPF
6) form.In this system, the inflammable and easy volatile of organic carbonate is main potential safety hazard (as burning, blast, leaks etc.) (J.Electrochem.Soc., 2001,148,1100 of current lithium ion battery; Chem.Rev., 2004,104,4303).Meanwhile, traditional ionogen conducting salt LiPF
6due to its chemical instability (comprising thermally labile and easily hydrolysis), make to use LiPF
6(secondary) lithium ion battery when the lower work of high temperature (>55 ℃), greatly reduce (Electrochem.Communs, 2005,7,669) in cycle performance and work-ing life.And in other common lithium salts, as lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), trifluoromethyl sulfonic acid lithium (Li[CF
3sO
3]), two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI), di-oxalate lithium borate (LiBOB) etc., owing to there being respectively the performance deficiency of different aspect, as LiClO
4there is potential explosivity, LiBF
4specific conductivity is too low, Li[SO
3cF
3] and LiTFSI anodal current collector material aluminium foil is corrosive, LiBOB solubleness in carbonic ether is low, makes these lithium salts fail to obtain and be widely used in lithium ion battery.Therefore, research and development chemical stability (as thermostability, water stability, etc.) height, the excellent novel conductive lithium salts electrolyte of chemical property (as high conductivity, wide electrochemical window, does not have corrodibility etc. to aluminium foil) replaces traditional lithium salts LiPF
6it is the important research direction of exploitation large-sized power battery and large-scale energy storage electron device.
Ionic liquid at room temperature, referring generally to be Chenged with single cation Zu by single negatively charged ion ﹑ lower at normal temperature (or room temperature) is liquid compound.Ionic liquid has the excellent properties such as the high and good chemistry of extremely low vapour pressure, difficult combustion, wider liquid journey, electric conductivity and thermo-chemical stability, is considered to the flame retardancy safety type electrolysis material that a new generation has application prospect.At present, ionic liquid is applied to (secondary) lithium ion battery, ultracapacitor etc. as the equivalent material of organic carbonate solvents, and the negatively charged ion of the ionic liquid of reporting is mainly TFSI
-.And these ionic liquids are as nonaqueous electrolyte material, the application in the energy storage devices such as (secondary) lithium ion battery, ultracapacitor, at present also in development.
Up to the present, relevant to " S-fluoroalkyl sulfimide (R
fsO
2n=S) " the synthetic report of the fluoroalkyl sulfimide of group and derivative thereof is less; and existing preparation method exists the deficiencies such as cost is high, productive rate is low; particularly this anion ion liquid and lithium salts thereof for example, the application at field of electronic devices (lithium ion battery; carbon back ultracapacitor) as electrolyte, is not yet seen in report.Particularly the preparation and application of (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluorine sulphonyl) imines and (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (two fluorine phosphinylidyne) imine compound and derivative thereof, also have no report.
Summary of the invention
Task of the present invention is to provide a kind of imine alkali metal salt its preparation method and application.Another task of the present invention be to provide a kind of ionic liquid and preparation method thereof with its in lithium cell, lithium ion battery and carbon back ultracapacitor as electrolytical application.Realizing concrete scheme of the present invention is: imine alkali metal salt provided by the invention has structure shown in following formula VI or (VII) or (VIII),
In formula VI:
M
+li, Na, K, Rb or Cs;
R
f 1=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2and R
f 3can be identical or different.
In formula (VII):
M
+li, Na, K, Rb or Cs;
R
f 1=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 4=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2, R
f 3and R
f 4can be identical or different.
In formula (VIII):
M
+li, Na, K, Rb or Cs;
R
f 5=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 6=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 7=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 8=C
mf
2m+1, m=0-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 5, R
f 6, R
f 7, R
f 8can be identical or different;
R in formula (VIII)
f 5=R
f 6=R
f 7=R
f 8=C
mf
2m+1or H (CF (m=1-8)
2cF
2o)
ncF
2cF
2, or F (CF
2cF
2o)
ncF
2cF
2when (n=1,2,3,4,5,6), this imine alkali metal salt is (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl phosphinylidyne) imine alkali metal salt.
R in formula (VIII)
f 5=C
mf
2m+1or H (CF (m=1-8)
2cF
2o)
ncF
2cF
2, or F (CF
2cF
2o)
ncF
2cF
2(n=1,2,3,4,5,6); R
f 6=C
mf
2m+1or H (CF (m=1-8)
2cF
2o)
ncF
2cF
2, or F (CF
2cF
2o)
ncF
2cF
2(n=1,2,3,4,5,6); R
f 7=R
f 8during=F, this imine alkali metal salt is (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (two fluorine phosphinylidyne) imine alkali metal salt.
R in formula (VIII)
f 5=R
f 6=R
f 7=R
f 8=F, this imine alkali metal salt is ((S-fluorine sulfimide base) fluorine sulphonyl) (two fluorine phosphinylidyne) imine alkali metal salt.
The method of the imine alkali metal salt of structure shown in the imine alkali metal salt of preparing structure shown in formula VI provided by the invention and formula (VII), comprises the following steps:
Step 1: by fluoroalkyl-sulfinate (R
fsO
2m), thionyl chloride (SOCl
2) by stoichiometry mol ratio, be 1:1～1:10, preferably 1:2～1:4 mixing is placed in reaction flask, and adding chlorobenzene is solvent, at 30～100 ℃, preferably temperature is 40～70 ℃, reacts 2～8 hours, the preferred reaction time is 3～5 hours, then by fluoroalkyl sulphinyl chlorine (R
fsOCl) steam;
Step 2: under argon shield, by fluoroalkyl sulphinyl chlorine (R
fsOCl), fluoroalkyl sulphonamide (R
fsO
2nH
2) by stoichiometry mol ratio, be 1:1～3:1, the ratio of preferred 1.5:1～2:1, add appropriate organic solvent to be under agitation mixed in reaction flask, by said mixture at-20～60 ℃, at preferably-5～30 ℃, react 8～48 hours, the preferred reaction time is 10～12 hours, then decompress filter is removed solid by-product, under agitation, gradation is by 1.2～5 times, preferably 1.5～3 times of Anhydrous potassium carbonates to group with imine moiety mole number, Carbon Dioxide caesium or Carbon Dioxide rubidium solids, join in above-mentioned organic solution; Add after Anhydrous potassium carbonate, Carbon Dioxide caesium or Carbon Dioxide rubidium, continue reaction 5～20 hours, preferably 10～12 hours, filtration under diminished pressure, elimination insolubles, obtains product (fluoroalkyl sulphonyl) (fluoroalkyl sulfinyl) imine alkali metal salt ([(R
fsO
2) (R
fsO) N] M, M=K, Rb, Cs);
Step 3: (fluoroalkyl sulphonyl) (fluoroalkyl sulfinyl) imine alkali metal salt of preparing in step 2 is soluble in water, by stoichiometry mol ratio, be 1:1～1:5, preferably 1:1～1:3 adds azanol oxygen sulfonic acid (H
2nOSO
3h), at-20～60 ℃, preferably stir at-10～40 ℃, the reaction times is 4～24 hours, preferably 8～12 hours, after completion of the reaction, add extracted with diethyl ether product, and obtain fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonamide (R
f(R
fsO
2n) SONH
2);
Step 4: be in 1:1～1.5:1 fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonamide of being added drop-wise to step 3 and obtaining by stoichiometry mol ratio by corresponding sulfonic acid fluoride, 1～5 times of amount by sulphonamide volume adds organic solvent, described organic solvent can be methylene dichloride, trichloromethane, ether, acetone, acetonitrile, Nitromethane 99Min., methylcarbonate or propylene carbonate, at-40～60 ℃, at preferably-20～20 ℃, stir, reaction times is 4～24 hours, preferably 8～12 hours, after completion of the reaction, decompress filter is removed solid by-product, under agitation, gradation is by 1.2～5 times, preferably 1.5～3 times to the Anhydrous potassium carbonate of group with imine moiety mole number, Carbon Dioxide caesium or Carbon Dioxide rubidium solid join in above-mentioned organic solution, continue reaction 5～20 hours, preferably 10～12 hours, filtration under diminished pressure, after elimination insolubles, obtain corresponding product (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl sulphonyl) imines sylvite, (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl sulphonyl) imines cesium salt or (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl sulphonyl) imines rubidium salt ([(R
f(R
fsO
2n) SO) (R
fsO
2) N] M, M=K, Rb or Cs),
Step 5: the fluoroalkyl that step 3 is obtained (S-fluoroalkyl sulfimide base) sulphonamide, thionyl chloride are by stoichiometry 1:1～1:5, preferably 1:1～1:3 mixing is placed in reaction flask, adding with (S-fluoroalkyl sulfimide base) (fluoroalkyl) sulphonamide mol ratio is 1:1～1:3, preferably chlorsulfonic acid (the ClSO of 1:1～1:2
3h), at 60～150 ℃, preferably stir at 100～120 ℃, the reaction times is 4～24 hours, preferably 8～12 hours.After completion of the reaction, underpressure distillation obtains (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (chlorine sulphonyl) imines ((R
f(R
fsO
2n) SO) (ClSO
2) NH), by stoichiometry, adding mol ratio is 1:1～1:3, and the preferred antimony trifluoride of 1:1～1:2, at 0～60 ℃, preferably stirs at 20～40 ℃, and the reaction times is 4～24 hours, preferably 8～12 hours.After completion of the reaction, underpressure distillation obtains (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluorine sulphonyl) imines ((R
f(R
fsO
2n) SO) (FSO
2) NH), add polar aprotic solvent, described hungry polar aprotic solvent can be acetonitrile, Nitromethane 99Min. or methylcarbonate, gradation is by 1.2～5 times, preferably 1.5～3 times to the Anhydrous potassium carbonate of group with imine moiety mole number, Carbon Dioxide caesium or Carbon Dioxide rubidium solid join in above-mentioned organic solution, continue reaction 5～20 hours, preferably 10～12 hours, press filtration, elimination insolubles is corresponding obtaining ((S-fluoroalkyl sulfimide base) (fluoroalkyl) sulphonyl) (fluorine sulphonyl) imines sylvite, ((S-fluoroalkyl sulfimide base) (fluoroalkyl) sulphonyl) (fluorine sulphonyl) imines cesium salt or ((S-fluoroalkyl sulfimide base) (fluoroalkyl) sulphonyl) (fluorine sulphonyl) imines rubidium salt ([(R
f(R
fsO
2n) SO) (FSO
2) N] M, M=K, Rb, Cs), (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl sulphonyl) imines potassium or (fluoro-alkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluorine sulphonyl) imines potassium prepared by above-mentioned steps four and this step are dissolved in polar aprotic solvent, with the MClO that waits mole number
4or MBF
4, M=Li, or Na carries out metathesis exchange reaction, obtains colourless lithium salts or sodium salt, and wherein said polar aprotic solvent can be methylcarbonate, diethyl carbonate, acetonitrile or acetone.
Preparation provided by the invention, with the method for the imine alkali metal salt of structure shown in following formula (VIII), comprises the following steps:
Step (1) is by phosphorus oxychloride (POCl
3) in molar ratio for 1:1～1.5:1 is added drop-wise to (R in fluoroalkyl (the S-fluoroalkyl sulfimide base) sulphonamide that step in above-mentioned 4 (3) prepares
f(R
fsO
2n) SONH
2), solvent is methylene dichloride, acetonitrile, Nitromethane 99Min., methylcarbonate, diethyl carbonate.At-40～60 ℃, preferably to stir at-20～20 ℃, the reaction times is 4～24 hours, preferably 8～12 hours.After completion of the reaction, decompress filter is removed insoluble solid by product, revolves to steam to remove after organic solvent, and by stoichiometry, adding mol ratio is 1:1～1:3, the fluorination reagent of preferred 1:1～1:2, at 0～60 ℃, preferably to stir at 20～40 ℃, the reaction times is 4～24 hours, preferably 8～12 hours, after completion of the reaction, add polar aprotic solvent, comprise acetonitrile, Nitromethane 99Min., methylcarbonate etc., gradation is by 1.2～5 times, preferably 1.5～3 times to the Anhydrous potassium carbonate of group with imine moiety mole number, Carbon Dioxide caesium or Carbon Dioxide rubidium solid, join in above-mentioned organic solution, continue reaction 5～20 hours, preferably 10～12 hours, filtration under diminished pressure, corresponding product (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (difluoro phosphinylidyne) imines sylvite that obtains after elimination insolubles, ((fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (difluoro phosphinylidyne) imines cesium salt or (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (difluoro phosphinylidyne) imines rubidium salt ([(R
f(R
fsO
2n) SO) (F
2pO) N] K), described fluorination reagent can be one or more in anhydrous hydrogen fluoride, hydrogen fluoride solution, Potassium monofluoride, cesium fluoride, tetrabutyl ammonium fluoride, Sodium Fluoride, lithium fluoride, and wherein said hydrogen fluoride solution can be hydrogen fluoride-pyridine solution, hydrogen fluoride-triethylamine solution, hydrogen fluoride-diethyl ether solution or aqueous hydrogen fluoride solution.
Step (2) will two (fluoroalkyl) chlorethoxyfos (R
f2pOCl) by stoichiometry mol ratio, be fluoroalkyl (the S-fluoroalkyl sulfimide base) sulphonamide (R that 1:1～1.5:1 is added drop-wise to step in above-mentioned 4 (3) and prepares
f(R
fsO
2n) SONH
2) in, solvent is methylene dichloride, acetonitrile, Nitromethane 99Min., methylcarbonate or diethyl carbonate.At-40～60 ℃, preferably to stir at-20～20 ℃, the reaction times is 4～24 hours, preferably 8～12 hours, then decompress filter was removed solid by-product, under agitation, gradation is by 1.2～5 times, preferably 1.5～3 times to the Anhydrous potassium carbonate of group with imine moiety mole number, Carbon Dioxide caesium or Carbon Dioxide rubidium solid join in above-mentioned organic solution, continue reaction 5～20 hours, preferably 10～12 hours, filtration under diminished pressure, elimination insolubles obtains corresponding product (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl phosphinylidyne) imines sylvite, (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl phosphinylidyne) imines cesium salt, or (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl phosphinylidyne) imines rubidium salt ([(R
f(R
fsO
2n) SO
2) (R
f2pO) N] M, M=K, Rb, Cs),
(fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (difluoro phosphinylidyne) the imines potassium that step (3) is prepared above-mentioned (1) and (2) or (fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonyl) (fluoroalkyl phosphinylidyne) imines potassium are dissolved in polar aprotic solvent, with the MClO that waits mole number
4or MBF
4(M=Li, or Na) carries out metathesis exchange reaction, obtains colourless lithium salts or sodium salt, and wherein said polar aprotic solvent can be methylcarbonate, diethyl carbonate, acetonitrile or acetone.
Following general formula for ionic liquid provided by the invention (IX) represents:
C
＋Ａ
－ (Ⅸ)
In formula (IX),
C
+the positively charged ion being selected from following formula (a) to (h):
Wherein
Substituent R in formula (a) to (h)
1-R
4identical or not identical, and respectively, separately or jointly there is following implication:
Alkyl (C
1-C
12);
.-(CH
2)
ny, wherein n=1-8; Y=CN or CO
2r, R=C
1-C
4alkyl;
.-(CH
2cH
2o)
x(CH
2)
ycH
3, x=1-12 wherein; Y=0-4;
.-CH
2o (CH
2)
zcH
3, z=0-4 wherein;
.-(CH
2cH
2o)
xr
f, x=1-12 wherein, R
f=C
mf
2m+1, m=1-8;
.-(CH
2cH
2s)
xr
f, x=1-12 wherein, R
f=C
mf
2m+1, m=1-8;
A
-the negatively charged ion being selected from following formula (X), (XI) or (XII):
In formula (X)
R
f 1=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2, R
f 3can be identical or different.
In formula (XI)
R
f 1=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 4=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2, R
f 3, R
f 4can be identical or different.
In formula (XII)
R
f 5=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 6=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 7=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 8=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 5, R
f 6, R
f 7, R
f 8can be identical or different.
The preparation method of ionic liquid provided by the invention, comprises the following steps:
By the imine alkali metal salt provided by the invention of equimolar amount (be called again in present patent application: containing " S-fluoroalkyl sulfimide base ") and be dissolved in respectively in deionized water with the halogenide of sulfonium salt, ammonium salt or the microcosmic salt of following formula (a) to (h), then at 25 ℃, mix, stir after 0.5 hour, stratification, with separating funnel, separate lower floor's liquid, be dissolved in methylene dichloride, use again deionized water wash 3～5 times, decompression is removed after dichloromethane solvent, 90 ℃ of vacuum decompressions are dried 12 hours, obtain colourless or light yellow ionic liquid
Il electrolyte provided by the invention comprises ionic liquid and lithium salts, and the ionic liquid in this il electrolyte is a kind of in following (A), (B), (C):
(A) one or two or more kinds mixed system in above-mentioned ionic liquid provided by the invention;
(B) one or two or more kinds in above-mentioned ionic liquid provided by the invention and the mixed system of other ionic liquids, other described ionic liquid is by negatively charged ion TFSI
-, FSI
-, PF
6 -or BF
4 -with the ionic liquid to one or more compositions in the positively charged ion of sulfonium salt, ammonium salt, microcosmic salt and the guanidinesalt of (h) representative with following formula (a);
(C) one or two or more kinds in above-mentioned ionic liquid provided by the invention and the mixed system of organic solvent, described organic solvent comprises: cyclic carbonate, chain linear carbonate, carboxylicesters, and described cyclic carbonate can be NSC 11801 (EC) or propylene carbonate (PC); Described chain linear carbonate can be one or two or more kinds the mixture in methylcarbonate (DMC), Methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC); Described carboxylicesters can be CH
3cO
2cH
3(MA), CF
3cO
2cF
3(MA-f), CH
3cO
2cH
2cH
3(EA), CF
3cO
2cF
2cF
3(EA-f), CH
3cO
2cH
2cF
3(TFEA), CF
3cO
2cH
2cH
3(ETFA), CH
3cH
2cO
2cH
3(MP), CF
3cF
2cO
2cF
3(MP-f) mixture of one or two or more kinds in.
Nonaqueous electrolytic solution provided by the invention is comprised of electric conducting lithium salt and organic solvent, the content of electric conducting lithium salt in electrolytic solution is 0.1-3 mol/L, it is characterized in that, described electric conducting lithium salt is the lithium salts in above-mentioned imine alkali metal salt provided by the invention, described organic solvent can be one or two or more kinds the mixed solvent in cyclic carbonate, chain linear carbonate, carboxylicesters, annular lactone, and the described cyclic carbonate as organic solvent is NSC 11801 (EC) or propylene carbonate (PC); The described chain linear carbonate as organic solvent is a kind or the two kinds of above mixtures in methylcarbonate (DMC), Methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC); The described carboxylicesters as organic solvent is CH
3cO
2cH
3(MA), CF
3cO
2cF
3(MA-f), CH
3cO
2cH
2cH
3(EA), CF
3cO
2cF
2cF
3(EA-f), CH
3cO
2cH
2cF
3(TFEA), CF
3cO
2cH
2cH
3(ETFA), CH
3cH
2cO
2cH
3(MP), CF
3cF
2cO
2cF
3(MP-f) mixture of one or two or more kinds in; The described annular lactone as organic solvent is the mixture of one or two or more kinds in beta-propiolactone (BPL), beta-butyrolactone (BBL), gamma-butyrolactone (GBL), Alpha-Methyl-gamma-butyrolactone (AMGBL), γ-valerolactone (GVL), δ-valerolactone (DVL), γ-hexalactone (GCL), 6-caprolactone (ECL) specifically.
Above-mentioned nonaqueous electrolytic solution can also contain functional additive, described functional additive is solid electrolyte interface (the Solid electrolyte interface of carbon back negative material, SEI) film forming accelerating, anti-overshoot additive, fire retardant is or/and stablizer, wherein said SEI membrane-forming agent can be one or two or more kinds the mixture in following SEI membrane-forming agent: vinylene carbonate (VC), fluorinated ethylene ester (FEC), chloroethylenes ester (ClEC), propyl sulfonic acid lactone (PS), butyl sulfonic acid lactone, tetraalkyl-dialkylene siloxanes, (to vinyl benzene sulphonyl) (perfluoroalkyl sulphonyl) inferior amine salt.
Nonaqueous electrolytic solution provided by the invention can be used for preparing lithium ion battery, lithium cell and carbon back ultracapacitor.
Innovative point of the present invention is: the sulphur valence state of take reacts to prepare important intermediate fluoroalkyl (the S-fluoroalkyl sulfimide base) sulphonamide of synthetic fluoroalkyl sulfimide as+4 (fluoroalkyl sulphonyl) (fluoroalkyl sulfinyl) imines with azanol oxygen sulfonic acid, ((fluoroalkyl sulfinyl) imines is by chlorination from (fluoroalkyl sulphonyl) effectively to have shortened existing literature method, fluoridize, three steps of amination are prepared the route of fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonamide, this operation can be carried out in room temperature range, avoided under traditional low temperature and the harsh reaction conditions of liquefied ammonia.Therefore, preparation provided by the invention is brief containing the method operation steps of " S-fluoroalkyl sulfimide base " imine alkali metal salt, the easily separated purification of product, the productive rate of its product and purity are all very high, can be as the preparation of the lithium salts in ionogen, catalyzer and high-performance ionic liquid synthetic etc.Imine lithium provided by the invention has good thermostability and hydrolytic resistance, possess high specific conductivity and oxidizing potential, and the electrode materials of widespread use has good consistency in traditional carbonate solution.
Two (fluoroalkyl sulphonyl) imines ([(R with bibliographical information
fsO
2)
2n]
-) negatively charged ion compares, negatively charged ion in formula VI and (VII) is owing to further having introduced strong electron-withdrawing group " S-fluoroalkyl sulfimide base ", formed larger delocalization conjugation anion structure, the negative charge that makes negatively charged ion is high dispersing delocalization more, namely make imines negatively charged ion provided by the invention (formula VI and (VII)) present more weak coordination ability, thereby effectively raise specific conductivity, dissociation constant and transport number containing " S-fluoroalkyl sulfimide base " imine lithium electrolytic solution.On the other hand, contain respectively-SO in the anion structure in formula VI and (VII)
2-N=SO-N-SO
2-and-SO
2-N=SO-N-SO=N-SO
2-wait the molecular structure unit with good flexibility, increase flexibility and the degree of freedom of molecule, thereby made the ionic liquid that contains this two anionoid, at room temperature there is lower viscosity.
Accompanying drawing explanation
Fig. 1: press the lithium ion battery that embodiment 25 makes, when 25 ℃ of cycle charge-discharges, the graph of a relation of specific discharge capacity to cycle index; Filled symbols represents specific discharge capacity, and open symbols represents coulombic efficiency.
Fig. 2: press the lithium ion battery that embodiment 26 makes, when 25 ℃ of cycle charge-discharges, the graph of a relation of specific discharge capacity to cycle index; Filled symbols represents specific discharge capacity, and open symbols represents coulombic efficiency.
Fig. 3: (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li, LiSTFSI)
19f NMR spectrum.
Fig. 4: (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li, LiSTFSI) DSC-TGA thermal analysis curve.
Fig. 5: aluminium foil (working electrode) is at 1M(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li, LiSTFSI)-EC/EMC(3:7, v/v) cyclic voltammetry curve of electrolytic solution.
Fig. 6: the temperature variant graph of a relation of specific conductivity in several frequently seen lithium salts conducting salt non-aqueous solution electrolysis liquid system; Electrolytic solution forms: 1M lithium salts; Solvent: EC/EMC(3:7, v/v).
Embodiment
Enumerate part of compounds preparation involved in the present invention below, so that the present invention is further detailed explanation, but the preparation method of embodiment is not restricted to the preparation of cited compound.
Embodiment 1-9 relates to the preparation containing " S-fluoroalkyl sulfimide base " imine alkali metal salt
Embodiment 1:(trimethyl fluoride sulfonyl) (trifluoromethyl sulphinyl) imines potassium ([(CF
3sO
2) (SOCF
3) N] K) preparation building-up reactions route as follows:
In 250mL there-necked flask, add Sodium trifluoromethanesulfinate (CF
3sO
2na) (65.5g, 0.42mol), 100mL chlorobenzene.Mechanical stirring, is heated to 30 ℃, slowly drips SOCl
2(59.5g, 0.5mol), dropwises rear continuation and stirs 2 hours.Air distillation, collects the cut of 30 ℃.Obtain 55g trimethyl fluoride sulfonyl chlorine (light brown liquid), productive rate 87%.
In 250mL eggplant type bottle, add trimethyl fluoride sulfonyl amine (CF
3sO
2nH
2) (29.8g, 0.2mol), acetonitrile (80mL), pyridine (31.6g, 0.4mol) is done acid binding agent, and stirring and dissolving drips trifluoromethyl sulphinyl chlorine (CF under ice bath
3sOCl) (35g, 0.23mol), dropwises recession deicing and bathes, and continues to stir after 24h under room temperature, and decompression backspin steams except desolventizing and the complete CF of unreacted
3sOCl, obtains yellow thick solid, adds 20mL water stirring and dissolving, slowly adds K in batches
2cO
3(40g, 0.29mol), moisture is removed in decompression after completion of the reaction, and gained solid is dissolved in acetone, and filtration under diminished pressure, collects filtrate, revolves to steam to remove after organic solvent, obtains tawny solid, and acetone/methylene dichloride recrystallization obtains white solid.Output 44g, productive rate 76%.
Embodiment 2: trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (CF
3(CF
3sO
2n) SONH
2) preparation
By (trimethyl fluoride sulfonyl) (trifluoromethyl sulphinyl) imines potassium ([(CF
3sO
2) (SOCF
3) N] K) (66.7g, 0.22mol) be dissolved in 200mL distilled water, successively adds hydroxylamine acid (NH under mechanical stirring
2oSO
3h) (38.2g, 0.34mol) and sodium acetate (CH
3cO
2na) (27.9g, 0.34mol), stirred after 8 hours, by extracted with diethyl ether (50mLx3), merged organic phase.After adding anhydrous magnesium sulfate drying, filter, collect filtrate, revolve to steam and remove ether, obtain white plates solid.Output 34.8g, productive rate 60%.
Embodiment 3:(fluoroalkyl sulphonyl) preparation of (fluoroalkyl sulfinyl) imines potassium and fluoro-alkyl (S-fluoroalkyl sulfimide base) sulphonamide
The experiment condition of table 1 preparation (fluoroalkyl sulphonyl) (fluoroalkyl sulfinyl) imines potassium and fluoro-alkyl (S-fluoroalkyl sulfimide base) sulphonamide: experiment 1-6 is the preparation of fluoroalkyl sulphinyl chlorine; Experiment 6-14 is (fluoroalkyl sulphonyl) (fluoroalkyl sulfinyl)
The preparation of imines potassium; Experiment 15-20 is the preparation of fluoroalkyl (S-fluoroalkyl sulfimide base) sulphonamide.
Embodiment 4:(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imines potassium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2n)] preparation K)
In 100mL eggplant type bottle, add trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (CF
3(CF
3sO
2n) SONH
2) (28g, 0.1mol), 50mL acetonitrile, diisopropyl ethyl amine (DIPEA) (27.6g, 0.24mol) is done acid binding agent, and stirring and dissolving drips trimethyl fluoride sulfonyl chlorine (CF under ice bath
3sO
2cl) (18.5g, 0.11mol), after reaction 2h, removes ice bath, stirring at room 12h.Suction filtration is removed solid by-product.Revolve after solvent is removed in steaming and obtain yellow thick solid, add 5mL water stirring and dissolving, slowly add K in batches
2cO
3(34.5g, 0.25mol), stirs under room temperature 6 hours.Drying under reduced pressure 4h.Gained solid is dissolved in dry acetone, and filtration under diminished pressure, collects filtrate, revolves to steam and removes acetone, obtains yellow solid.With acetone and methylene dichloride recrystallization, obtain white solid.Output 41g, productive rate 91%.
Embodiment 5:(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (fluorine sulphonyl) imines potassium ([(CF
3(CF
3sO
2n) SO) (FSO
2) N] K) preparation
Under nitrogen protection, by trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (CF
3(CF
3sO
2n) SONH
2) (28g, 0.1mol), thionyl chloride (SOCl
2) (17.8g, 0.15mol), chlorsulfonic acid (ClSO
3h) (11.6g, 0.1mol) joins in 100mL reaction flask successively, and 130 ℃ of stirring reactions 24 hours, excessive lower boiling reactant was removed in air distillation, then carries out underpressure distillation, collects the cut of 136-138 ℃/2mmHg, under room temperature, obtains [(CF
3(CF
3sO
2n) SO) (ClSO
2) N] 31.1 grams of H colourless crystallizations, productive rate 82%.
Under stirring and nitrogen protection, by [(CF
3(CF
3sO
2n) SO) (ClSO
2) N] H(37.9g, 0.1mol), and anhydrous antimony trifluoride (SbF
3) (9g, 0.05mol) be placed in the there-necked flask of 100mL, stirs lower reaction after 12 hours under room temperature, carries out underpressure distillation, collects the cut of 116-118 ℃/2mmHg, obtains [(CF
3(CF
3sO
2n) SO) (FSO
2) N] 31.1 grams of H colourless liquids, productive rate 86%.
Under agitation, to [(CF
3(CF
3sO
2n) SO) (FSO
2) N] H(36.2g, 0.1mol) in add the acetonitrile of 100mL.Under ice-water bath and stirring, Anhydrous potassium carbonate solid (20.7g, 0.15mol) is added in reaction flask, adds rear continuation reaction 4 hours.Then, the pH value of the hydrochloric acid regulation system of use 2M is to neutral.Filtration under diminished pressure is removed solid insoluble, and filtrate is concentrated, adds isopyknic CH
2cl
2carry out recrystallization.Filter, wash, be dried, obtain [(CF
3(CF
3sO
2n) SO) (FSO
2) N] 36.8 grams of the colourless crystallization solids of K, productive rate 92%.
Embodiment 6:(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li) preparation
In vacuum glove box, by [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] anhydrous acetonitrile of K (45g, 0.1mol), 100mL joins in the there-necked flask of 500mL successively, after stirring and dissolving, slowly splashes into lithium perchlorate (LiClO under room temperature
4) acetonitrile solution 50mL(contain 10.6g, the LiClO of 0.1mol
4), under room temperature, stirring reaction is 24 hours, static spending the night, and filtration under diminished pressure, removes insolubles potassium perchlorate (KClO
4), after filtrate is concentrated, add isopyknic CH
2cl
2carry out recrystallization.Filtration, CH
2cl
2washing, vacuum-drying, obtain 41.8g(0.1mol) white solid powder [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li.
Embodiment 7:(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imines sodium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Na) preparation
In vacuum glove box, by [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] K(45g, 0.1mol), the anhydrous acetonitrile of 100mL joins in the there-necked flask of 500mL successively, after stirring and dissolving, slowly splashes into sodium perchlorate (NaClO under room temperature
4) acetonitrile solution 50mL(contain 12.2g, the NaClO of 0.1mol
4), under room temperature, stirring reaction is 24 hours, static spending the night, and filtration under diminished pressure, removes insolubles potassium perchlorate (KClO
4), after filtrate is concentrated, add isopyknic CH
2cl
2carry out recrystallization.Filtration, CH
2cl
2washing, vacuum-drying, obtain 43.4g(0.1mol) white solid powder [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Na.
Embodiment 8: containing the preparation of " S-fluoroalkyl sulfimide base " imine alkali metal salt
Table 2 preparation contains the experiment condition of " S-fluoroalkyl sulfimide base " imine alkali metal salt: 4 preparations of experiment 1-5 reference example; 5 preparations of experiment 6-11 reference example.
Embodiment 9:(trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (difluoro phosphinylidyne) imines potassium ([(CF
3(CF
3sO
2n) SO) (F
2pO) N] K) preparation
In 100mL flask, add trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonamide (CF
3(CF
3sO
2n) SONH
2) (28g, 0.1mol), pyridine (15.8g, 0.2mol), 50mL Nitromethane 99Min., under room temperature, drip phosphorus oxychloride (POCl
3) (15.3g, 0.1mol), after dropwising, under room temperature, stir 10 hours.Reaction system is proceeded in 500mL PFA bottle, add the hydrogen fluoride solution (C of triethylamine
2h
5)
3n. (HF)
4(18.1g, 0.1mol), at room temperature, stirs 4h, stopped reaction.At 50 ℃, with dry nitrogen air-flow, remove the volatile constituents such as hydrogenchloride of excessive residual, at-30 ℃, under stirring, add saturated potassium carbonate solid, in solution without CO
2γ-ray emission, adds diethyl carbonate extraction extraction three times, and each 100mL, collects diethyl carbonate phase, after adding 25g salt of wormwood dry, filter, collect filtrate, pressure reducing and steaming solvent, obtain faint yellow solid, after ethyl alcohol recrystallization, obtain white solid, output 33g, yield 82%.
The experiment condition of table 3 preparation (fluoro-alkyl (S-fluoro-alkyl sulfimide base) sulphonyl) (fluoro-alkyl phosphinylidyne) imine alkali metal salt.9 preparations of experiment 1-6 reference example.
Embodiment 10-24 relates to the preparation containing the ionic liquid of " S-fluoroalkyl sulfimide base " sulphur/phosphorimide
The general preparation method of the ionic liquid that following examples are cited is as follows: by equimolar an alkali metal salt, and the halogenide of sulfonium salt, ammonium salt or microcosmic salt is dissolved in respectively in appropriate amount of deionized water and (is generally 20mmol salt and is dissolved in 10mL deionized water), then mixed at room temperature, induction stirring was reacted after 30 minutes, stratification.With separating funnel, separate lower floor's liquid, be dissolved in 20～30mL methylene dichloride, then use deionized water wash 3 times, each deionized water consumption is 5mL, and decompression is removed after dichloromethane solvent, and 90 ℃ of vacuum decompressions are dried 12 hours, obtain colourless or light yellow ionic liquid.Referring to specific embodiment, the present invention is described, it will be appreciated by those skilled in the art that these examples are only for illustrating object of the present invention, the scope that it does not limit the present invention in any way.Take embodiment 37 as example, and other embodiment intermediate ion liquid are by similar approach preparation.
Embodiment 10: ionic liquid [(CH
3cH
2)
3s] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [(CH
3cH
2)
3s] I and K[N (CF
3(CF
3sO
2n) SO) (CF
3sO
2)] reaction preparation.Concrete operations are as follows: by 7.5g (20mmol) [(CH
3cH
2)
3s] I and 9.0g(20mmol) [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] K, be dissolved in respectively in 10mL deionized water, after two solution mix, stirring reaction 30 minutes, stratification, lower floor is dissolved in 20mL methylene dichloride, deionized water wash 3 times (3 * 5mL), decompression is removed after dichloromethane solvent, and 90 ℃ of vacuum decompressions are dried 12 hours, obtain 9.5 grams of colorless oil, productive rate 90%.
Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.56 (t, 3 * 3H), 3.55ppm (q, 3 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.7 (s, 6F) ， – 80.1 (s, 3F).Ultimate analysis: theoretical value C
9h
15f
9n
2o
5s
4: C, 20.38; H, 2.85; N, 5.28; Experimental value C, 20.30; H, 2.88; N, 5.24.
Embodiment 11: ionic liquid [(CH
3)
2sCH
2cH
2oCH
3] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [(CH
3)
2sCH
2cH
2oCH
3] I and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.16 (s, 2 * 3H), 3.42 (s, 3H), 3.78 (m, 2H), 3.98ppm (m, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.7 (s, 6F) ， – 80.1 (s, 3F).Ultimate analysis: theoretical value C
8h
13f
9n
2o
6s
4: C, 18.05; H, 2.46; N, 5.26; Experimental value C, 18.00; H, 2.48; N, 5.23.
Embodiment 12: ionic liquid [(CH
3) (CH
3cH
2)
2nCH
2cH
2cH
3] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [(CH
3) (CH
3cH
2)
2nCH
2cH
2cH
3] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 95%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.01 (t, 3H), 1.42 (t, 2 * 3H), 1.87 (m, 2H) .3.13 (s, 3H), 3.38 (m, 2H), 3.53ppm (q, 2 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.8 (s, 6F) ， – 80.1 (s, 3F).Ultimate analysis: theoretical value C
11h
20f
9n
3o
5s
3: C, 24.40; H, 3.72; N, 7.76; Experimental value C, 34.36; H, 3.70; N, 7.80.
Embodiment 13: ionic liquid [(CH
3) (CH
3cH
2)
2nCH
2cH
2oCH
3] [N (CF
3(CF
3sO
2n) SO) (CF
3sO
2)]
By [(CH
3) (CH
3cH
2)
2nCH
2cH
2oCH
3] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 87%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.40 (t, 2 * 3H), 3.21 (s, 3H), 3.38 (s, 3H), 3.60 (q, 2 * 2H), 3.68 (t, 2H), 3.90ppm (s, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.8 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
11h
20f
2n
3o
6s
3: C, 23.70; H, 3.62; N, 7.54; Experimental value C, 23.654; H, 3.65; N, 7.50.
Embodiment 14: ionic liquid [(CH
3oCH
2cH
2)
4n] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [(CH
3oCH
2cH
2)
4n] I and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, 90%.Nuclear magnetic resonance data: (acetone-d
6, TMS, 400MHz): δ=3.35 (br s, 4 * 3H), 3.93-3.88 (m, 8 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
15h
28f
9n
3o
9s
3: C, 27.23; H, 4.27; N, 6.35; Experimental value C, 27.20; H, 64.30; N, 6.28.
Embodiment 15: ionic liquid [(CH
3)
3nCH
2cH
2cN] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [(CH
3)
3nCH
2cH
2cN] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 63%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.33 (t, 2H), 3.42 (s, 3 * 3H), 3.98ppm (t, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
9h
13f
9n
4o
5s
3: C, 20.61; H, 2.50; N, 10.68; Experimental value C, 20.54; H, 2.42; N, 10.65.
Embodiment 16: ionic liquid [Py (CH
3) (CH
2cH
2cH
3)] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [Py (CH
3) (CH
2cH
2cH
3)] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 96%.Nuclear magnetic resonance data:
1h NMR(acetone-d
6, TMS, 400MHz): δ=1.00 (t, 3H), 1.32 (t, 3 * 2H), 1.67-1.81 (m, 2H), 2.91 (s, 3H), 3.09-3.14 (m, 2H), 3.29ppm (q, 2 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
11h
18f
9n
3o
5s
3: C, 24.49; H, 3.36; N, 7.79; Experimental value C, 24.41; H, 3.40; N, 7.72.
Embodiment 17: ionic liquid [P
y(CH
3) (CH
2cH
2cN)] [N (CF
3(CF
3sO
2n) SO) (CF
3sO
2)]
By [Py (CH
3) (CH
2cH
2cN)] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 78%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=2.39 (br, 2 * 2H), 3.37 (t, 2H), 3.39 (s, 3H), 3.84-3.90 (m, 2 * 2H), 4.03ppm (t, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
11h
15f
9n
4o
5s
3: C, 24.00; H, 2.75; N, 10.18; Experimental value C, 23.92; H, 2.70; N, 10.12.
Embodiment 18: ionic liquid [Py (CH
3) (CH
2cH
2oCH
3)] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [Py (CH
3) (CH
2oCH
3)] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=2.29 (m, 2 * 2H), 3.24 (s, 3H), 3.61 (m, 2H), 3.70 (m, 5H), 4.78ppm (s, 2H).
19F NMR(acetone-d
6,CCl
3F，376.5MHz)：δ=-79.9(s,6F),–80.0(s,3F)。Ultimate analysis: theoretical value C
11h
18f
9n
3o
6s
3: C, 23.79; H, 3.27; N, 7.56; Experimental value C, 23.70; H, 3.20; N, 7.51.
Embodiment 19: ionic liquid [Pi (CH
3) (CH
2cH
2cH
2cH
3)] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [Pi (CH
3) (CH
2cH
2cH
2cH
3)] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 88%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=0.99 (t, 3H), 1.44 (m, 2H), 1.74 (m, 2H), 1.87 (br s, 2H), 1.99 (br s, 2 * 2H), 3.23 (s, 3H), 3.52ppm (m, 3 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
13h
22f
9n
3o
5s
3: C, 27.51; H, 3.91; N, 7.40; Experimental value C, 27.45; H, 3.83; N, 7.35.
Embodiment 20: ionic liquid [Im (CH
3) (CH
2cH
3)] [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N]
By [Im (CH
3) (CH
2cH
3)] Br and [(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 94%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.56 (t, 3H), 4.03 (s, 3H), 4.38 (q, 2H), 7.67 (s, 1H), 7.74 (s, 1H), 8.94ppm (s, 1H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=-79.9 (s, 6F) ， – 80.0 (s, 3F).Ultimate analysis: theoretical value C
9h
11f
9n
4o
5s
3: C, 20.69; H, 2.12; N, 10.73; Experimental value C, 20.60; H, 2.05; N, 10.68.
Embodiment 21: ionic liquid [(CH
3cH
2)
3s] [(F (FSO
2n) SO) (FSO
2) N]
By [(CH
3cH
2)
3s] I and [(F (FSO
2n) SO) (FSO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 90%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.56 (t, 3 * 3H), 3.55ppm (q, 3 * 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.8 (s, 2F), 51.3 (s, F).Ultimate analysis: theoretical value C
6h
15f
3n
2o
5s
4: C, 18.94; H, 3.97; N, 7.36; Experimental value C, 19.01; H, 3.90; N, 7.30.
Embodiment 22: ionic liquid [(CH
3)
2sCH
2cH
2oCH
3] [(F (FSO
2n) SO) (FSO
2) N]
By [(CH
3)
2sCH
2cH
2oCH
3] I and [(F (FSO
2n) SO) (FSO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.16 (s, 2 * 3H), 3.42 (s, 3H), 3.78 (m, 2H), 3.98ppm (m, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.8 (s, 2F), 51.3 (s, F).Ultimate analysis: theoretical value C
5h
13f
3n
2o
6s
4: C, 15.70; H, 3.43; N, 7.33; Experimental value C, 15.65; H, 3.40; N, 7.38.
Embodiment 23: ionic liquid [Im (CH
3) (CH
2cH
3)] [(CF
3(CF
3sO
2n) SO) (FSO
2) N]
By [Im (CH
3) (CH
2cH
3)] Br and [(CF
3(CF
3sO
2n) SO) (FSO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 94%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.55 (t, 3H), 4.03 (s, 3H), 4.38 (q, 2H), 7.69 (s, 1H), 7.74 (s, 1H), 8.92ppm (s, 1H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.7 (s, F) ,-79.8 (s, 3F) ， – 80.1 (s, 3F).Ultimate analysis: theoretical value C
8h
11f
7n
4o
5s
3: C, 20.34; H, 2.35; N, 11.86; Experimental value C, 20.28; H, 2.30; N, 10.80.
Embodiment 24: ionic liquid [Py (CH
3) (CH
2cH
2oCH
3)] [(CF
3(CF
3sO
2n) SO) (FSO
2) N]
By [Py (CH
3) (CH
2cH
2oCH
3)] Br and [(CF
3(CF
3sO
2n) SO) (FSO
2) N] preparation of K room temperature reaction.
Colourless liquid, productive rate 88%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=2.28 (m, 2 * 2H), 3.23 (s, 3H), 3.61 (m, 2H), 3.70 (m, 5H), 4.79ppm (s, 2H).
19F NMR(acetone-d
6,CCl
3F，376.5MHz)：δ=51.7(s,F),-79.8(s,3F),–80.1(s,3F)。Ultimate analysis: theoretical value C
10h
18f
7n
3o
6s
3: C, 23.76; H, 3.59; N, 8.31; Experimental value C, 23.70; H, 3.54; N, 8.32.
Embodiment 25 application of low viscosity ionic liquid in ultracapacitor
Adopt 2032(diameter 2.0cm, height 0.32cm) button electric capacity, activated carbon is positive and negative electrode material (diameter 1.0cm, thickness 0.6mm), polypropylene diaphragm, and the ionic liquid in table 4 and common organic electrolyte are assembled electrical condenser in vacuum glove box.Ultracapacitor impulse electricity test condition is: voltage V=0 to 2.8V, electric current 5mA.At 25 ℃, the electrical capacity of mensuration is as shown in table 4.
Table 4 ionic liquid and the electrolytical carbon back ultracapacitor of common organic electrolyte electrical capacity (25 ℃)
The application of embodiment 26 ionic liquid electrolytes in serondary lithium battery
(1) anodal making
With LiCoO
2positive electrode material is example: by anodal LiCoO
2powder, carbon black (granularity is 1000nm), poly(vinylidene fluoride) (PVDF) and N, N-dimethyl pyrrolidone (NMP) is mixed and made into the slurry of homogeneous, and slurry is evenly coated on aluminium foil (15 μ m) collector, is then dried, and rolling, obtains LiCoO
2positive electrode material.At 120 ℃, dry 12 hours, in dried pole piece, LiCoO
2account for 94% of total painting application, binding agent accounts for 4%, and carbon black accounts for 2%.Then gained pole piece being cut into diameter is that 8mm disk is as positive pole.Other positive electrode material LiMn
2o
4, LiFePO
4preparation in the same way.
(2) making of negative pole
Take artificial plumbago negative pole material as example: by synthetic graphite, poly(vinylidene fluoride) (PVDF) and N, N '-dimethyl pyrrolidone (NMP) is mixed and made into the slurry of homogeneous, slurry is evenly coated on Copper Foil (15 μ m) collector, then be dried, rolling, obtains carbon negative pole material.At 120 ℃, dry 12 hours, in dried pole piece, graphite accounts for 96.4% of total painting application, and binding agent accounts for 3.6%, and then gained pole piece being cut into diameter is that 9mm disk is as positive pole.Other negative material Li
4ti
5o
12preparation in the same way.
(3) preparation of electrolytic solution
Conducting salt is proceeded to glove box containing after the imine lithium vacuum-drying of " S-fluoroalkyl sulfimide base ", weigh a certain amount of lithium salts, organic solvent EC/EMC (the 3:7 that slowly adds ionic liquid or prepare in advance, v/v), be mixed with the electrolytic solution that concentration is respectively 1M and 0.7M, seal stand-by.
(4) composition of CR2032 fastening lithium ionic cell and performance evaluation
Polyethylene porous membrane is placed between above-mentioned steps (1) and (2) prepared positive/negative plate, drips the electrolytic solution that above-mentioned steps (3) prepares, pole piece is flooded, be assembled into the button cell of CR2032.Upper at micro-processor controlled automatic inflatable instrument (Land, CT2001A), carry out cycle performance of battery test.Test condition: rate of charge is 0.5C, discharge-rate is 0.2C, graphite/LiCoO
2electrode system: 3.0～4.2V; Metallic lithium/LiCoO
2electrode system: 3.0～4.2V; Graphite/LiFePO
4electrode system: 2.75～3.9V; Metallic lithium/LiFePO
4electrode system: 2.75～3.9V; Li
4ti
5o
12/ LiCoO
2electrode system: 1.0～2.6V; Li
4ti
5o
12/ LiFePO
4electrode system: 1.0～2.6V, probe temperature: 25 ℃.The test data of the present embodiment is referring to table 5.The recycle ratio capacity of battery and coulombic efficiency are as shown in Figure 1.
The performance of secondary lithium (ion) battery of table 5 based on lithium salts/ionic liquid electrolyte
Embodiment 27 is combined into the application of electrolytic solution in secondary lithium (ion) battery containing imine lithium and the carbonate solvent of " S-fluoroalkyl sulfimide base ".
Change the ion liquid solvent in embodiment 26 into carbonic ether, other implementation conditions are consistent with embodiment 26 with evaluation method.The test data of the present embodiment is in Table 6.
The performance of table 6 based on the electrolytical serondary lithium battery of lithium salts/carbonic ether
Embodiment 28 is combined into the mensuration of electrolytic solution electrochemical properties containing the imine lithium of " S-fluoroalkyl sulfimide base " and ionic liquid or carbonate solvent.
(1) thermal stability determination: differential scanning calorimetry and thermogravimetric analysis are carried out on NETSCH STA449CDSC-TGA analyser.In glove box, take 5mg[(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li(is called for short LiSTFSI), be sealed in an aluminium sample crucible, in sample crucible, open an aperture, the gas of sample thermolysis and volatile products can be overflowed.Be determined under argon atmosphere and carry out, heat-up rate is 10 ℃ of min
-1.[(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] and Li DSC-TGA collection of illustrative plates as shown in Figure 4.[(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] fusing point of Li solid is 111 ℃, heat decomposition temperature is 323 ℃.
(2) corrosion measurement of aluminium foil in electrolytic solution: on Autolab electrochemical workstation, adopt 3 electrode systems, aluminium foil (S=0.30cm
2) be working electrode, metallic lithium is to electrode and reference electrode, at open circuit voltage (OCV), measures the vs.Li to 5.0V
+between/Li, measure volt-ampere curve, sweep velocity is 0.1mV s
-1.The present invention is with (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li, LiSTFSI-EC/EMC (3:7, v/v) electrolytic solution is example, the volt-ampere curve of front 3 circulations is as shown in Figure 5.
(3) mensuration of specific conductivity: use the platinum black conductance electrode of DJS-10, Julabo type temperature controller, Autolab electrochemical workstation is measured electrolytic solution prepared by embodiment 1 step (3) specific conductivity (seeing accompanying drawing 6) between-20 to 60 ℃.
A kind of method of preparing containing the imine alkali metal salt of " S-fluoroalkyl sulfimide base " disclosed by the invention, easy and simple to handle, products collection efficiency and purity are all very high, are suitable for suitability for industrialized production.Prepared ionic liquid or carbonic ester electrolyte all possess quite high purity, meet the application requiring in field of electronic devices.
As shown in drawings, (trifluoromethyl (S-trifluoromethanesulp-onyl-onyl imide base) sulphonyl) (trimethyl fluoride sulfonyl) imine lithium ([(CF
3(CF
3sO
2n) SO) (CF
3sO
2) N] Li) at EC/EMC(3:7, v/v) in solution, aluminum foil current collector is shown to good passivation effect, this is different from traditional fluorine sulfimide salt, two (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) for example, two (pentafluoroethyl group sulphonyl) imine lithiums (LiBETI), (trimethyl fluoride sulfonyl) (perfluoro butyl sulphonyl) imine lithium etc.These lithium salts all show serious corrodibility at noble potential (3-5V) to aluminium foil.
Embodiment 25 shows that the imine lithium containing " S-fluoroalkyl sulfimide base " provided by the invention and the electrolytic solution that ionic liquid is combined into show good cycle performance on lithium ion battery.
Embodiment 26 shows the imine lithium containing " S-fluoroalkyl sulfimide base " provided by the invention and the electrolytic solution that carbonic ether is combined into, and the lithium ion battery becoming with current widely used electrode material combinations, compared with conventional conductive lithium salts LiPF
6show better cycle performance and Capacitance reserve power.
Claims (6)
1. there is the ionic liquid shown in following general formula (IX),
C
＋Ａ
－ (Ⅸ)
In formula (IX),
C
+the positively charged ion being selected from following formula (a) to (h):
Wherein
Substituent R in formula (a) to (h)
1-R
4identical or not identical, and respectively, separately or jointly there is following implication:
Alkyl (C
1-C
12);
.-(CH
2)
ny, wherein n=1-8; Y=CN or CO
2r, R=C
1-C
4alkyl;
.-(CH
2cH
2o)
x(CH2)
ycH
3, x=1-12 wherein; Y=0-4;
.-CH
2o (CH
2)
zcH
3, z=0-4 wherein;
.-(CH
2cH
2o)
xr
f, x=1-12 wherein, R
f=C
mf
2m+1, m=1-8;
.-(CH
2cH
2s)
xr
f, x=1-12 wherein, R
f=C
mf
2m+1, m=1-8;
A
-the negatively charged ion being selected from following formula (X), (XI) or (XII):
In formula (X)
R
f 1=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2, R
f 3can be identical or different;
In formula (XI)
R
f 1=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 2=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 3=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 4=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 1, R
f 2, R
f 3, R
f 4can be identical or different.
In formula (XII)
R
f 5=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 6=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 7=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 8=C
mf
2m+1, m=1-8 or H (CF
2cF
2o)
ncF
2cF
2or F (CF
2cF
2o)
ncF
2cF
2, n=1,2,3,4,5 or 6;
R
f 5, R
f 6, R
f 7, R
f 8can be identical or different.
2. the preparation method of ionic liquid claimed in claim 1, comprise the following steps: the halogenide containing the imine alkali metal salt of " S-fluoroalkyl sulfimide base " and sulfonium salt, ammonium salt or the microcosmic salt of formula (a) to (h) of equimolar amount is dissolved in respectively in deionized water, then at 25 ℃, mix, stir after 0.5 hour, stratification, with separating funnel, separate lower floor's liquid, be dissolved in methylene dichloride, use again deionized water wash 3～5 times, decompression is removed after dichloromethane solvent, 90 ℃ of vacuum decompressions are dried 12 hours, obtain colourless or light yellow ionic liquid
3. an il electrolyte, comprises ionic liquid and lithium salts, it is characterized in that, the ionic liquid in this il electrolyte is a kind of in following (A), (B), (C):
(A) one or two or more kinds mixed system in ionic liquid claimed in claim 1;
(B) one or two or more kinds in ionic liquid claimed in claim 1 and the mixed system of other ionic liquids, other described ionic liquid is by negatively charged ion TFSI
-, FSI
-, PF
6 -or BF
4 -with the ionic liquid to one or more compositions in the positively charged ion of sulfonium salt, ammonium salt, microcosmic salt and the guanidinesalt of (h) representative with following formula (a);
(C) one or two or more kinds in ionic liquid claimed in claim 1 and the mixed system of organic solvent, described organic solvent comprises: cyclic carbonate, chain linear carbonate, carboxylicesters.
4. il electrolyte according to claim 3, is characterized in that, described cyclic carbonate can be NSC 11801 (EC) or propylene carbonate (PC); Described chain linear carbonate can be one or two or more kinds the mixture in methylcarbonate (DMC), Methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC); Described carboxylicesters can be CH
3cO
2cH
3(MA), CF
3cO
2cF
3(MA-f), CH
3cO
2cH
2cH
3(EA), CF
3cO
2cF
2cF
3(EA-f), CH
3cO
2cH
2cF
3(TFEA), CF
3cO
2cH
2cH
3(ETFA), CH
3cH
2cO
2cH
3(MP), CF
3cF
2cO
2cF
3(MP-f) mixture of one or two or more kinds in.
5. lithium ion battery or a lithium cell, is characterized in that, contains the il electrolyte described in claim 3 or 4.
6. the application of the il electrolyte described in claim 3 or 4 in preparing lithium ion battery or lithium cell or carbon back ultracapacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105304353A (en) * | 2015-11-26 | 2016-02-03 | 渤海大学 | Ternary mixed ionic liquid electrolyte and preparation method and application thereof |
| CN109535045A (en) * | 2018-11-15 | 2019-03-29 | 华中科技大学 | A kind of preparation method of fluoroalkyl (S-oroalkane sulfonyl imido grpup) sulfonamide |
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| US6340716B1 (en) * | 1997-07-25 | 2002-01-22 | Acep Inc. | Ionic compounds with delocalized anionic charge, and their use as ion conducting components or as catalysts |
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| US6340716B1 (en) * | 1997-07-25 | 2002-01-22 | Acep Inc. | Ionic compounds with delocalized anionic charge, and their use as ion conducting components or as catalysts |
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| ROMUTE YU GARLYAUSKAYTE，ET AL: "Synthesis of new organic super acids-N-(trifluoromethylsulfonyl)-imino derivatives of trifluoromethanesulfonic acid and bis(trifluoromethylsulfonyl)imide", 《ORG. BIOMOL. CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105304353A (en) * | 2015-11-26 | 2016-02-03 | 渤海大学 | Ternary mixed ionic liquid electrolyte and preparation method and application thereof |
| CN109535045A (en) * | 2018-11-15 | 2019-03-29 | 华中科技大学 | A kind of preparation method of fluoroalkyl (S-oroalkane sulfonyl imido grpup) sulfonamide |
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