CN102786443B - Binary or ternary fluorine-containing sulfimide alkali metal salt and ionic liquid and applications thereof - Google Patents
Binary or ternary fluorine-containing sulfimide alkali metal salt and ionic liquid and applications thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing binary or ternary fluorine-containing sulfimide alkali metal salts, a method for preparing ionic liquid by the binary or ternary fluorine-containing sulfimide alkali metal salts, and applications of the alkali metal salts and ionic liquid as electrolytes in carbon-based super capacitors, secondary lithium (ion) batteries, and the like. The method for preparing the binary or ternary fluorine-containing sulfimide alkali metal salts provided by the invention is short in operation steps, easy for product separation and purification, and high in product yield and purity; the binary or ternary fluorine-containing sulfimide lithium provided by the invention has good thermal stability and hydrolysis resistance; a nonaqueous electrolytic solution of the binary or ternary fluorine-containing sulfimide lithium has high conductivity and lithium ion transference number, and also exhibits good oxidation resistance and good compatibility with widely-used electrode materials; meanwhile, the ionic liquid containing the binary or ternary fluorine-containing sulfimide anions exhibits the properties of low viscosity and high conductivity, and has a wide electrochemical window.
Description
Technical field
The invention belongs to organic fluorine chemistry, novel material and advanced power technique fields, be specifically related to an alkali metal salt of a kind of binary or the fluorine-containing sulfimide of ternary and the preparation method of ionic liquid, and an alkali metal salt and ionic liquid are as the application of electrolyte in lithium (ion) battery and Carbon-based supercapacitor.
Background technology
Fluorine-containing sulfimide and an alkali metal salt thereof and ionic liquid, particularly lithium salts are important fluorine-containing organic ionic compounds.They are in the clean energy device fields such as high-performance nonaqueous electrolyte material and efficient catalyst such as secondary lithium (ion) battery, ultracapacitor and aluminium electrolutic capacitors, all have important commercial application and are worth.Therefore, people are being devoted to the Synthesis and application research carrying out novel fluorine sulfimide and derivative thereof always.
At present, about the research of fluorine-containing sulfimide mainly concentrate on the fluorine-containing sulfimide of unitary (namely in molecule only containing a sulfonylimino group-SO
2-N-SO
2-) (Coord.Chem.Rev., 1997,158,413), as per-fluoroalkyl sulfonyl 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), that representative is two (trimethyl fluoride sulfonyl) imine lithium (Li [(CF
3sO
2)
2n], be called for short LiTFSI) and two (fluorine sulphonyl) imine lithium (Li [(FSO
2)
2n], be called for short LiFSI) etc.Applicant in preparation and the Application Areas thereof of fluorine-containing sulfimide and an alkali metal salt thereof, also develops some new Method and Technology (CN101654229, CN101747242, CN101747242, Chem.Lett., 2010,39,472) recently.
Research report about polynary sulfimide and metal-salt thereof is less.Argropoulos etc. adopt two (chlorine sulphonyl) imines (H [(ClSO
2)
2n]) obtain the ternary sulfimide of corresponding arylamine to arylamine condensation, and carried out characterizing (J.Appli.Poly.Sci., 1981,26,3073) to its structure.Nie Jin etc. utilize two (chlorine sulphonyl) imines (H [(ClSO
2)
2n]) and perfluorinated alkyl sulfonamide (R
fsO
2nH
2) reaction; the ternary sulfimide and an alkali metal salt thereof and transition metal salt that contain two (perfluoroalkyl group sulfonyl) are obtained; and report their application (CN1450052 in ionogen and catalyzer; CN1450053; J.Fluorine Chem.; 2004; 125; 27); but its work is only limitted to the ternary sulfonyl imide compounds containing perfluoroalkyl, do not comprise preparation method and the application of ternary sulfimide, an alkali metal salt and other derivative that substituted radical is fluorine atom.DesMarteau etc. report a kind of with the binary sulfimide lithium salts of the fluorine-containing long-chain connection of aliphatics and per-fluoroalkyl sulfonyl imines lithium salts polymkeric substance, and have studied conductivity (the Solid State Ionics of the polymer solid electrolyte of these lithium salts and polyethers (PEO) blended formation, 2002,148,173).But the synthesis step of this kind of binary that DesMarteau etc. report and polymkeric substance fluorine-containing sulfimide lithium salts is loaded down with trivial details, and owing to being failed by fluoroalkyl interval between sulfimide moiety to form conjugation extended system on molecular structure.In addition, Zhang etc. utilize urea and sulfuryl chloride (SO
2cl
2) or two (chlorine sulphonyl) imines (H [(ClSO
2)
2n]) reaction, or utilize thionamic acid (NH
2sO
3h) with phosphorus pentachloride (PCl
5) reaction, obtain oligomer and the polymkeric substance of phosphinylidyne sulfimide and sulfimide respectively.The oligomer of gained phosphinylidyne sulfimide or sulfimide and polymkeric substance react with lithium hydride further; obtain corresponding lithium salts oligomer and polymkeric substance, and determine chemical property (Electrochim.Acta, 2000 of these lithium salts as polymer dielectric; 45,1229).
About the report of the fluorine-containing sulfimide of binary is few.Roesky etc. utilize (Cl
3p=N)
2sO
2with fluosulfonic acid (FSO
3h) react, prepared two (fluorine sulphonyl) sulphonyl diimine (H
2[(FSO
2n)
2sO
2]) (Chem.Ber., 1968,101,162.).But this synthetic route is not only attended by two fluorine sulfimide (HN (SO
2f)
2) by product generation, cause product separation purification difficult, and Fluoride for Raw Material sulfonic acid (FSO
3h) toxicity is comparatively large, is not easy to operation.Jan etc. report and utilize trimethyl fluoride sulfonyl trichlorine phosphonitrile (CF
3sO
2n=PCl
3) and fluosulfonic acid (FSO
3h) two (trimethyl fluoride sulfonyl) sulphonyl diimine (H of reaction preparation
2[(CF
3sO
2n)
2sO
2]), and characterize the crystalline structure (Acta Crystallographica, Section C:Crystal Structure Communs., 2004, C60, O79.) of this compound.The method is equally owing to using the fluosulfonic acid acid (FSO that toxicity is larger
3h) be reaction raw materials, be unfavorable for experimental implementation and scale operation.
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 primarily of organic carbonate as methylcarbonate, diethyl carbonate, vinyl carbonate etc., and ionogen conducting salt (mainly LiPF
6) composition.In this system, the inflammable and easy volatile of organic carbonate is major security risk (as burning, blast, leaks) (J.Electrochem.Soc., 2001,148,1100 of current lithium ion battery; Chem.Rev., 2004,104,4303).Meanwhile, traditional electrolyte matter conducting salt LiPF
6due to its chemical instability (comprising thermally labile and easily hydrolysis), make to use LiPF
6(secondary) lithium ion battery when working under high temperature (> 55 DEG C), cycle performance and work-ing life greatly reduce (Electrochem.Communs, 2005,7,669).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 is the performance deficiency of different aspect respectively, as LiClO
4there is potential explosivity, LiBF
4specific conductivity is too low, Li [SO
3cF
3] and LiTFSI positive current collector material aluminium foil is corrosive, LiBOB solubleness in carbonic ether is low, makes these lithium salts fail to obtain in lithium ion battery to widely use.Therefore, research and development chemical stability (as thermostability, water stability, etc.) are high, and chemical property is (as high conductivity, wide electrochemical window, does not have corrodibility etc. to aluminium foil) excellent novel conductive lithium salts electrolyte replaces traditional lithium salts LiPF
6it is the important research direction of exploitation large-sized power battery and large-scale energy storage electron device.
Up to the present, about an alkali metal salt (particularly lithium salts) of the fluorine-containing sulfimide of binary and the preparation of ionic liquid, and they as the research that electrolyte is applied in lithium ion battery, there is not been reported.
Summary of the invention
Task of the present invention is to provide an alkali metal salt of a kind of binary or the fluorine-containing sulfimide of ternary and such binary or the fluorine-containing sulfimide of ternary and preparation method thereof.
Another task of the present invention be to provide a kind of containing above-mentioned binary or ternary fluorine-containing sulfimide anion ion liquid and preparation method thereof with its in lithium cell, lithium ion battery and Carbon-based supercapacitor as electrolytical application.
Another task of the present invention is to provide binary or ternary containing the purposes of fluorine-based sulfimide lithium, namely in lithium cell, lithium ion battery and Carbon-based supercapacitor as electrolytical application.
Realizing technical scheme of the present invention is:
The fluorine-containing sulfimide of binary provided by the invention has with structure following formula (I) Suo Shi,
In formula (I):
R
f 1c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 2c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 1and R
f 2can be identical or different.
Binary fluorine-containing sulfimide alkali metal salt provided by the invention has structure shown in formula (II),
In formula (II):
M=Li, Na, K, Rb or Cs;
R
f 1c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 2c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 1and R
f 2can be identical or different.
Ternary fluorine sulfimide provided by the invention has structure shown in formula (III),
Ternary fluorine sulfimide alkali metal salt provided by the invention has structure shown in formula IV,
In formula (IV):
M=Li, Na, K, Rb or Cs;
The preparation method of the fluorine-containing sulfimide of binary provided by the invention and an alkali metal salt and the fluorine-containing sulfimide of ternary and an alkali metal salt thereof, comprises the following steps:
Step one: by sulphamide (NH
2sO
2nH
2) or two (amido sulphonyl) imines (NH
2sO
2nHSO
2nH
2), thionyl chloride stoichiometrically mol ratio be 1: 1 ~ 1: 5, preferably 1: 1 ~ 1: 3 mixing are placed in reaction flask, adding with sulphamide (or two (amido sulphonyl) imines) nonstoichiometric molar ratio is 1: 1 ~ 1: 3, the preferably chlorsulfonic acid (ClSO of 1: 1 ~ 1: 2
3or perfluoro alkyl sulfonic acid (R H)
fsO
3h), at 60 ~ 150 DEG C, preferably stir at 100 ~ 120 DEG C, the reaction times is 4 ~ 24 hours, preferably 8 ~ 12 hours, and after completion of the reaction, underpressure distillation obtains two (chlorine sulphonyl) sulphonyl diimine (H accordingly
2[(ClSO
2n)
2sO
2]) or two (per-fluoroalkyl sulfonyl) sulphonyl diimine (H
2[(R
fsO
2n)
2sO
2]) or two (chlorine sulphonyl)-bis-(sulphonyl) three imines (H
3{ (ClSO
2n)
2[(SO
2)
2n] });
Step 2: two (chlorine sulphonyl) sulphonyl diimine (H obtained to above-mentioned steps one
2[(ClSO
2n)
2sO
2]), or two (chlorine sulphonyl)-bis-(sulphonyl) three imines (H
3{ (ClSO
2n)
2[(SO
2)
2n] }) in, stoichiometrically adding mol ratio is 1: 1 ~ 1: 3, preferably antimony trifluoride (the SbF of 1: 1 ~ 1: 2
3), at 0 ~ 60 DEG C, preferably stir at 20 ~ 40 DEG C, the reaction times is 4 ~ 24 hours, preferably 8 ~ 12 hours, and after completion of the reaction, underpressure distillation obtains two (fluorine sulphonyl) sulphonyl diimine (H respectively
2[(FSO
2n)
2sO
2]) or two (fluorine sulphonyl)-bis-(sulphonyl) three imines (H
3{ (FSO
2n)
2[(SO
2)
2n] });
Step 3: to two (per-fluoroalkyl sulfonyl) sulphonyl diimine (H prepared by step one
2[(R
fsO
2n)
2sO
2]) or two (fluorine sulphonyl) sulphonyl diimine (H prepared by step 2
2[(FSO
2n)
2sO
2]) or two (fluorine sulphonyl)-bis-(sulphonyl) three imines (H
3{ (FSO
2n)
2[(SO
2)
2n] }) compound adds polar aprotic solvent, gradation is by nonstoichiometric molar ratio 1.2 ~ 5 times, preferably 1.5 ~ 3 times of Anhydrous potassium carbonates to group with imine moiety mole number or 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 obtained an alkali metal salt ([(R of the fluorine-containing sulfimide of binary
fsO
2n)
2sO
2] M, M=K, Rb or Cs) or an alkali metal salt ([(FSO of the fluorine-containing sulfimide of ternary
2n)
2sO
2] M, M=K, Rb or Cs).
Step 4: binary step 3 prepared or the fluorine-containing sulfimide potassium of ternary are dissolved in polar aprotic solvent, with the MClO of the mole numbers such as stoichiometry
4or MBF
4, M=Li, or Na, carry out metathesis exchange reaction, obtains lithium salts or the sodium salt ([(R of the fluorine-containing sulfimide of colourless binary
fsO
2n)
2sO
2] M, M=Li or Na) or the lithium salts of the fluorine-containing sulfimide of ternary or sodium salt ([(FSO
2n)
2sO
2] M, M=Li or Na), described polar aprotic solvent can be methylcarbonate, diethyl carbonate, acetonitrile, acetone or Nitromethane 99Min..
The method of preparation provided by the invention (fluorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine and its an alkali metal salt, comprises the following steps:
Step (1) under agitation, by (per-fluoroalkyl sulfonyl) (aminosulfonyl) imines (R
fsO
2nHSO
2nH
2) and thionyl chloride (SOCl
2), chlorsulfonic acid (ClSO
3h) after mixing by mole ratio 1: 1.2: 1, at 80 ~ 150 DEG C, preferably back flow reaction 8 ~ 40 hours at 110 ~ 130 DEG C, preferably 12 ~ 24 hours, after underpressure distillation, obtain (chlorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine (H
2[(ClSO
2n) (R
fsO
2n) SO
2]);
(chlorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine (H that step (2) obtains to above-mentioned steps (1)
2[(ClSO
2n) (R
fsO
2n) SO
2]) in, add nonstoichiometric molar ratio 1 ~ 4 times, preferably antimony trifluoride (the SbF of 1.5 ~ 2 times amount
3), after room temperature reaction 10-20 hour, underpressure distillation can obtain (fluorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine (H
2[(FSO
2n) (R
fsO
2n) SO
2]), the polar aprotic solvent adding diimine volume 4 ~ 10 times is prepared into imide liquor; The preferred acetonitrile of aprotic, polar, Nitromethane 99Min., tetrahydrofuran (THF), methylcarbonate, Methyl ethyl carbonate, diethyl carbonate, Nitromethane 99Min., tetrahydrofuran (THF);
Step (3) is to (fluorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine (H prepared by step (2)
2[(FSO
2n) (R
fsO
2n) SO
2]) solution in add nonstoichiometric molar ratio 1 ~ 5 times, preferably the alkaline carbonate of 1.5 ~ 2 times amount reacts, after completion of the reaction, suction filtration, revolve an alkali metal salt namely obtaining (fluorine sulphonyl) (per-fluoroalkyl sulfonyl) sulphonyl diimine after solvent is removed in steaming.
Ionic liquid provided by the invention represents with following logical formula V,
C
+A
-(V)
In formula (V): C
+be selected from the positively charged ion with following formula (a) to (j):
With the substituent R in above formula (a) to (j)
1-R
4identical or not identical, and respectively, separately or jointly there is following implication:
-C
mh
2m+1, wherein m=1-12;
-(CH
2)
ny, wherein n=1-8, Y=CN;
-CO
2r, wherein R=C
1-C
4alkyl;
-(CH
2cH
2o)
x(CH
2)
ycH
3, wherein x=1-12; Y=0-4;
-CH
2o (CH
2)
zcH
3, wherein z=0-4;
-(CH
2cH
2o)
xr
f, wherein x=1-12, R
f=C
mf
2m+1, m=1-8;
-(CH
2cH
2s)
xr
f, wherein x=1-12, R
f=C
mf
2m+1, m=1-8);
And
A
-the negatively charged ion being selected from following formula VI or formula (VII):
In formula VI:
R
f 1c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 2c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 1and R
f 2can be identical or different.
The preparation method of above-mentioned ionic liquid provided by the invention, comprise the following steps: by stoichiometry equimolar amount have with an alkali metal salt of the fluorine-containing sulfimide of binary of structure following formula (II) Suo Shi or have structure shown in following formula IV the fluorine-containing sulfimide of ternary an alkali metal salt with the sulfonium salt representated by following formula (a) to (j), the halogenide of ammonium salt microcosmic salt or guanidinesalt is dissolved in deionized water respectively, be generally 20mmol salt and be dissolved in 10mL deionized water, then at room temperature mix, stir about is after 0.5 hour, stratification, lower floor's liquid is separated with separating funnel, be dissolved in methylene dichloride, use deionized water wash again 3 ~ 5 times, after decompression removing dichloromethane solvent, dry 12 hours of 90 DEG C of vacuum decompressions, obtain colourless or light yellow ionic liquid.
In formula (II):
M=Li, Na, K, Rb or Cs;
R
f 1c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 2c
mf
2m+1, wherein m=0-8, (CF
3)
2cHO, CF
3cH
2o, HCF
2cH
2o or H (CF
2cF
2o)
ncF
2cF
2, wherein n=1-6;
R
f 1and R
f 2can be identical or different;
In formula IV:
M=Li, Na, K, Rb or Cs;
One or two or more kinds mixed system in the invention described above ionic liquid and lithium salts can form il electrolyte.
Mixed system and the lithium salts of one or two or more kinds and other ionic liquids in the invention described above ionic liquid also can form il electrolyte, and other described ionic liquids are by negatively charged ion TFSI
-, FSI
-, PF
6 -, BF
4 -in any one with the sulfonium salt representated by following formula (a) to (j), ammonium salt, in the positively charged ion of microcosmic salt, guanidinesalt any one composition.
Mixture and the lithium salts of one or two or more kinds and organic solvent in the invention described above ionic liquid also can form il electrolyte, described organic solvent can be cyclic carbonate, chain linear carbonate or carboxylicesters, and described cyclic carbonate can be NSC 11801 (EC) or propylene carbonate (PC); Described chain linear carbonate can be the mixture of one or two or more kinds 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 made up of electric conducting lithium salt and organic solvent, electric conducting lithium salt content is in organic solvent 0.1-3 mol/L, described electric conducting lithium salt is the fluorine-containing sulfimide lithium of binary or ternary, described organic solvent is the mixed solvent of one or two or more kinds 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 the mixture of one or two or more kinds 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; One or two or more kinds the mixture of the described annular lactone as organic solvent specifically 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).
Above-mentioned nonaqueous electrolytic solution provided by the invention, functional additive can also be contained, described functional additive is solid electrolyte interface (the Solid electrolyte interface of carbon based negative electrodes material, SEI) film forming accelerating, anti-overshoot additive, fire retardant is or/and stablizer, wherein said SEI membrane-forming agent can be the mixture of one or two or more kinds 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) (per-fluoroalkyl sulfonyl) inferior amine salt.
Nonaqueous electrolytic solution provided by the invention can be used for the preparation of lithium ion battery and lithium cell and Carbon-based supercapacitor.
Adopt containing above-mentioned binary or the fluorine-containing sulfimide lithium of ternary as in lithium (ion) battery of conducting salt, comprising can the positive electrode active materials of reversible doff lithium, and can be, but not limited to is the oxidate for lithium of single transition metal oxidate for lithium or multiple hybrid transition metal.Described single transition metal oxidate for lithium is cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2) or the LiMn of spinel type
2o
4; The oxidate for lithium of described multiple hybrid transition metal is ternary material LiNi
xa
yb
(1-x-y)o
2, wherein A, B are the one in Co, Al, Mn, and A, not identical with B, 0 < x < 1,0 < y < 1, or the LiMPO of olivine-type
4, wherein M is one or more the mixture in Co, Ni, Fe, Mn, or Li
1-x(A
yb
zc
1-y-z) O
2, wherein 0≤x < 1,0≤y < 1,0≤z < 1, A, B, C is one or more the mixture in Co, Ni, Fe, Mn.
Adopt containing above-mentioned binary or the fluorine-containing sulfimide lithium of ternary as in lithium (ion) battery of conducting salt, comprise and can the negative active core-shell material of reversible doff lithium can be, but not limited to be metallic lithium, or under be listed in < 2V versus Li/Li
+below can embed one or more the mixture in the material of metallic lithium: natural graphite, synthetic graphite, mesophase spherule micro-carbon ball (MCMB), hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO
2, spinel structure lithiumation TiO
2-Li
4ti
5o
12, Li-Al alloy.
The method operation steps preparing binary or ternary fluorine-containing sulfimide alkali metal salt provided by the invention is brief, the easily separated purification of product, the productive rate of its product and purity are all very high, can be used as (to comprise liquid state in ionogen, gel, solid-state) lithium salts conducting salt, the preparation of catalyzer and the synthesis etc. of high-performance ionic liquid.
Innovative point of the present invention is in prepared binary or the fluorine-containing sulfimide negatively charged ion of ternary, due to its SO
2-N-SO
2the conjugated structure of group, make this anionoid have negative charge dispersion, structural flexibility is good, and-the SO at two ends
2-group also effectively can shield the negative charge in atom N.So this kind of imines negatively charged ion presents the performance of weak coordination, thus effectively raise the specific conductivity of binary or ternary fluorine-containing sulfimide lithium electrolytic solution, dissociation constant and cationic transport number thereof, show good oxidation resistance, thermostability and hydrolytic resistance simultaneously.Make can show low viscosity, the character of high conductivity containing binary or the fluorine-containing sulfimide anion ion liquid of ternary, and there is wide electrochemical window, when being applied to field of electronic devices, effectively can improve the high rate performance etc. of lithium ion battery.
Accompanying drawing explanation
Fig. 1: the lithium ion battery (lithium salts adopts two (fluorine sulphonyl) sulphonyl diimine lithium and lithium hexafluoro phosphate to compare) made by embodiment 29, at 25 DEG C of circulation times, the graph of a relation of specific discharge capacity and cycle index; Filled symbols represents specific discharge capacity, and open symbols represents coulombic efficiency.
Fig. 2: the lithium ion battery (lithium salts adopts two (fluorine sulphonyl) sulphonyl diimine lithium) made by embodiment 29, at 25 DEG C of circulation times, respectively at the 1st week, the 3rd week, the 30th week and the charging and discharging specific storage of the 100th week and the curve of current potential.
Fig. 3: two (fluorine sulphonyl) sulfimide lithium (LiFSDI's)
19f NMR composes.
Fig. 4: aluminium foil (working electrode) is at two (fluorine sulphonyl) the sulphonyl diimine lithium (H of 1M
2[(FSO
2n)
2sO
2]), LiFSDI) cyclic voltammetry curve of-EC/EMC (3: 7, v/v) electrolytic solution.
Two (fluorine sulphonyl) the sulphonyl diimine lithium (H of Figure 51 M
2[(FSO
2n)
2sO
2]), LiFSDI) specific conductivity of corresponding electrolytic solution of-EC/EMC (3: 7, v/v) electrolytic solution and several frequently seen lithium salts varies with temperature curve comparison figure.
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 1-10 relates to the preparation of binary fluorine-containing sulfimide alkali metal salt and ternary fluorine-containing sulfimide alkali metal salt.
Embodiment 1: two (chlorine sulphonyl) sulphonyl diimine (H
2[(ClSO
2n)
2sO
2]) preparation
Building-up reactions route is as follows:
NH
2SO
2NH
2+SOCl
2+ClSO
3H→H
2[(ClSO
2N)
2SO
2]+SO
2+HCl
Sulphamide (NH is added in 500mL there-necked flask
2sO
2nH
2) (48g, 0.5mol), SOCl
2(167g, 1.4mol), ClSO
3h (116g, 1mol).Magnetic agitation, be heated to 120 DEG C of backflows after 24 hours, underpressure distillation, collects the cut of 112-114 DEG C/1-2mm Hg.Obtain 135g colourless liquid, yield 92%.
Embodiment 2:(chlorine sulphonyl) (perfluoro butyl sulphonyl) sulphonyl diimine (H
2[(ClSO
2n) (C
4f
9sO
2n) SO
2]) preparation
Prepared C is added in 250mL flask
4f
9sO
2nHSO
2nH
2(37.8g, 0.1mol), SOCl
2(16.7g, 0.14mol), ClSO
3h (11.6g, 0.1mol).Be heated to 120 DEG C under stirring, reflux underpressure distillation after 24 hours, collects the cut of 141-143 DEG C/1-2mm Hg.Obtain 40g product, yield 84%.
Embodiment 3: the preparation of the fluorine-containing sulfimide of binary and the fluorine-containing sulfimide of ternary
Preparation condition, the experimental result of the fluorine-containing sulfimide of part binary and the fluorine-containing sulfimide of ternary are listed in table 1.
The experimental result of binary and the fluorine-containing sulfimide of ternary prepared by table 1
Embodiment 4: two (fluorine sulphonyl) sulphonyl diimine (H
2[(FSO
2n)
2sO
2]) preparation
Building-up reactions route is as follows:
3H
2[(ClSO
2N)
2SO
2]+2SbF
3→3H
2[(FSO
2N)
2SO
2]+2SbCl
3
Under stirring and nitrogen protection, by the H of 117g (0.4mol)
2[(ClSO
2n)
2sO
2], and the anhydrous antimony trifluoride of 48g (0.27mol) is placed in the there-necked flask of 250mL, reacts after 12 hours, carry out underpressure distillation under stirred at ambient temperature, collects the cut of 102-104 DEG C/1-2mmHg, obtains H
2[(FSO
2n)
2sO
2] colourless liquid 92g, yield 88%.
Embodiment 5: fluoridizing of the chloride sulfimide of binary and the chloride sulfimide of ternary
Fluorination conditions, the experimental result of the chloride sulfimide of part binary and the chloride sulfimide of ternary are listed in table 2.
Table 2 binary and the chloride sulfimide of ternary fluoridize result
Embodiment 6: two (fluorine sulphonyl) sulphonyl diimine potassium (K
2[(FSO
2n)
2sO
2]) preparation
Building-up reactions route is as follows:
H
2[(FSO
2N)
2SO
2]+K
2CO
3→K
2[(FSO
2N)
2SO
2]+CO
2+H
2O
In 250mL flask, add the H of 65g (0.25mol)
2[(FSO
2n)
2sO
2], 100mL anhydrous acetonitrile, slowly adds the potash solid of 34.5g (0.25mol) in batches under stirring, continue stirring reaction after 2 hours, then to add a small amount of salt of wormwood regulation system be pH6 ~ 7.Leave standstill and filter, obtain white solid after filtrate being spin-dried for, recrystallization in acetone/methylene dichloride, obtain 78g white crystal, yield 93%.
Embodiment 7: the preparation of binary fluorine-containing sulfimide alkali metal salt and ternary fluorine-containing sulfimide alkali metal salt
Preparation condition, the experimental result of part binary fluorine-containing sulfimide alkali metal salt and ternary fluorine-containing sulfimide alkali metal salt are listed in table 3.
The experimental result of table 3 binary and ternary fluorine-containing sulfimide alkali metal salt
Embodiment 8: two (fluorine sulphonyl) sulphonyl diimine lithium (Li
2[(FSO
2n)
2sO
2]) preparation
Building-up reactions route is as follows:
K
2[(FSO
2N)
2SO
2]+2LiBF
4→Li
2[(FSO
2N)
2SO
2]+2KBF
4
In vacuum glove box, by 84.1g (0.25mol) K
2[(FSO
2n)
2sO
2], the methylcarbonate of 200mL joins in the there-necked flask of 500mL successively, after stirring and dissolving, slowly instillation is dissolved with the LiBF4 (LiBF of 46.8g (0.50mol)
4) methylcarbonate solution, stirred at ambient temperature reacts 12 hours, filtration under diminished pressure, removes undissolved potassium tetrafluoroborate.Filtrate is concentrated into 50mL continuation pressurization and pumps solvent, add methylene dichloride recrystallization, obtain the Li of 66.6g
2[(FSO
2n)
2sO
2] (LiFSDI) white solid, yield 98%.Its
19f NMR composes as shown in Figure 3.
Embodiment 9: two (fluorine sulphonyl) sulphonyl diimine sodium (Na
2[(FSO
2n)
2sO
2]) preparation
Building-up reactions route is as follows:
K
2[(FSO
2N)
2SO
2]+2NaBF
4→Na
2[(FSO
2N)
2SO
2]+2KBF
4
In vacuum glove box, by 84.1g (0.25mol) K
2[(FSO
2n)
2sO
2], the methylcarbonate of 200mL joins in the there-necked flask of 500mL successively, after stirring and dissolving, slowly instillation is dissolved with the sodium tetrafluoroborate (NaBF of 54.9g (0.50mol)
4) methylcarbonate solution, stirred at ambient temperature reacts 12 hours, filtration under diminished pressure, removes undissolved potassium tetrafluoroborate.Filtrate is concentrated into 50mL continuation pressurization and pumps solvent, add methylene dichloride recrystallization, obtain the Na of 73.8g
2[(FSO
2n)
2sO
2] white solid, yield 97%.
Embodiment 10: the preparation of binary sulfimide lithium and sodium salt, ternary sulfimide lithium and sodium salt
Preparation condition, the experimental result of part binary sulfimide lithium and sodium salt, ternary sulfimide lithium and sodium salt are listed in table 4.
The experimental result of binary and ternary sulfimide lithium and sodium prepared by table 4
Embodiment 11-26 relates to the preparation of the ionic liquid of binary or the fluorine-containing sulfimide of ternary
The general preparative methods of the ionic liquid cited by following examples is as follows: by equimolar an alkali metal salt, and the halogenide of sulfonium salt, ammonium salt, microcosmic salt or guanidinesalt 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, stirring reaction is after 30 minutes, stratification.Separate lower floor's liquid with separating funnel, be dissolved in 20 ~ 30mL methylene dichloride, then use deionized water wash 3 times, each deionized water consumption is 5mL, and after decompression removing dichloromethane solvent, dry 12 hours of 90 DEG C of vacuum decompressions, 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 only for illustration of object of the present invention, its scope do not limited the present invention in any way.For embodiment 13, other embodiment intermediate ion liquid is by similar approach preparation.
Embodiment 11: ionic liquid [(CH
3cH
2)
3s]
2[(FSO
2n)
2sO
2]
By [(CH
3cH
2)
3s] I and K
2[(FSO
2n)
2sO
2] reaction preparation.Concrete operations are as follows: by 7.5g (20mmol) [(CH
3cH
2)
3s] I and 3.4g (10mmol) K
2[(FSO
2n)
2sO
2], be dissolved in 10mL deionized water respectively, after two solution mixing mixing, induction stirring reacts 30 minutes, stratification, lower floor is dissolved in 20mL methylene dichloride, deionized water wash 3 times (3 × 5mL), after decompression removing dichloromethane solvent, dry 12 hours of 90 DEG C of vacuum decompressions, obtain 9.5 grams of colorless oil, productive rate 92%.
Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.55 (t, 3 × 3H), 3.55ppm (q, 3 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.5 (s, 2F).Ultimate analysis: theoretical value C
12h
30f
2n
2o
6s
5: C, 29.02; H, 6.09; N, 5.64; Experimental value C, 28.95; H, 6.05; N, 5.60.
Embodiment 12: ionic liquid [(CH
3)
2sCH
2cH
2oCH
3]
2[(FSO
2n)
2sO
2]
By [(CH
3)
2sCH
2cH
2oCH
3] I and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.16 (s, 2 × 3H), 3.41 (s, 3H), 3.78 (m, 2H), 3.97ppm (m, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.6 (s, 2F).Ultimate analysis: theoretical value C
10h
26f
2n
2o
8s
5: C, 23.99; H, 5.23; N, 5.60; Experimental value C, 23.95; H, 5.20; N, 5.55.
Embodiment 13: ionic liquid [(CH
3) (CH
3cH
2)
2nCH
2cH
2cH
3]
2[(FSO
2n)
2sO
2]
By [(CH
3) (CH
3cH
2)
2nCH
2cH
2cH
3] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 95%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.00 (t, 3H), 1.42 (t, 2 × 3H), 1.88 (m, 2H) .3.13 (s, 3H), 3.38 (m, 2H), 3.51ppm (q, 2 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.6 (s, 2F).Ultimate analysis: theoretical value C
16h
40f
2n
4o
6s
3: C, 37.05; H, 7.77; N, 10.80; Experimental value C, 37.00; H, 7.75; N, 10.75.
Embodiment 14: ionic liquid [(CH
3) (CH
3cH
2)
2nCH
2cH
2oCH
3]
2[(FSO
2n)
2sO
2]
By [(CH
3) (CH
3cH
2)
2nCH
2cH
2oCH
3] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 87%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.41 (t, 2 × 3H), 3.21 (s, 3H), 3.36 (s, 3H), 3.60 (q, 2 × 2H), 3.67 (t, 2H), 3.90ppm (s, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.6 (s, 2F).Ultimate analysis: theoretical value C
16h
40f
2n
4o
8s
3: C, 34.90; H, 7.32; N, 10.17; Experimental value C, 34.88; H, 7.28; N, 10.15.
Embodiment 15: ionic liquid [(CH
3oCH
2cH
2)
4n]
2[(FSO
2n)
2sO
2]
By [(CH
3oCH
2cH
2)
4n] I and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, 91%.Nuclear magnetic resonance data: (acetone-d
6, TMS, 400MHz): δ=3.34 (br s, 4 × 3H), 3.93-3.86 (m, 8 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.4 (s, 2F).Ultimate analysis: theoretical value C
24h
56f
2n
4o
14s
3: C, 37.98; H, 7.44; N, 7.38; Experimental value C, 37.95; H, 7.42; N, 7.36.
Embodiment 16: ionic liquid [(CH
3)
3nCH
2cH
2cN]
2[(FSO
2n)
2sO
2]
By [(CH
3)
3nCH
2cH
2cN] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 64%.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=51.5 (s, 2F).Ultimate analysis: theoretical value C
12h
26f
2n
6o
6s
3: C, 29.74; H, 5.41; N, 17.34; Experimental value C, 29.70; H, 5.40; N, 17.28.
Embodiment 17: ionic liquid [Py (CH
3) (CH
2cH
2cH
3)]
2[(FSO
2n)
2sO
2]
By [Py (CH
3) (CH
2cH
2cH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 91%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.00 (t, 3H), 1.30 (t, 3 × 2H), 1.67-1.81 (m, 2H), 2.92 (s, 3H), 3.09-3.14 (m, 2H), 3.29ppm (q, 2 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.5 (s, 2F).Ultimate analysis: theoretical value C
16h
36f
2n
4o
6s
3: C, 37.34; H, 7.05; N, 10.89; Experimental value C, 37.30; H, 7.02N, 10.85.
Embodiment 18: ionic liquid [Py (CH
3) (CH
2cH
2cN)]
2[(FSO
2n)
2sO
2]
By [Py (CH
3) (CH
2cH
2cN)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 75%.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=51.6 (s, 2F).Ultimate analysis: theoretical value C
16h
30f
2n
6o
6s
3: C, 35.81; H, 5.63; N, 15.66; Experimental value C, 35.75; H, 5.60; N, 15.62.
Embodiment 19: ionic liquid [Py (CH
3) (CH
2cH
2oCH
3)]
2[(FSO
2n)
2sO
2]
By [Py (CH
3) (CH
2oCH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=2.28 (m, 2 × 2H), 3.24 (s, 3H), 3.62 (m, 2H), 3.70 (m, 5H), 4.78ppm (s, 2H).
19F NMR(acetone-d
6，CCl
3F，376.5MHz)：δ＝51.7(s，2F)。Ultimate analysis: theoretical value C
16h
36f
2n
4o
8s
3: C, 35.15; H, 6.64; N, 10.25; Experimental value C, 35.13; H, 6.60; N, 10.22.
Embodiment 20: ionic liquid [Pi (CH
3) (CH
2cH
2cH
2cH
3)]
2[(FSO
2n)
2sO
2]
By [Pi (CH
3) (CH
2cH
2cH
2cH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 85%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=0.98 (t, 3H), 1.45 (m, 2H), 1.74 (m, 2H), 1.87 (br s, 2H), 1.97 (br s, 2 × 2H), 3.23 (s, 3H), 3.52ppm (m, 3 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.5 (s, 2F).Ultimate analysis: theoretical value C
20h
44f
2n
4o
6s
3: C, 42.09; H, 7.77; N, 9.82; Experimental value C, 42.04; H, 7.75; N, 9.85.
Embodiment 21: ionic liquid [Im (CH
3) (CH
2cH
3)]
2[(FSO
2n)
2sO
2]
By [Im (CH
3) (CH
2cH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 95%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.55 (t, 3H), 4.03 (s, 3H), 4.36 (q, 2H), 7.67 (s, 1H), 7.74 (s, 1H), 8.94ppm (s, 1H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.5 (s, 2F).Ultimate analysis: theoretical value C
12h
22f
2n
4o
6s
3: C, 31.85; H, 4.90; N, 12.38; Experimental value C, 31.82; H, 4.88; N, 10.35.
Embodiment 22: ionic liquid [G (CH
3)
4(CH
3) (CH
2cH
2oCH
3)]
2[(FSO
2n)
2sO
2]
By [G (CH
3)
4(CH
3) (CH
2cH
2oCH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 84%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.13-3.55 (m, 7H), 2.85-2.88 (t, 15H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.5 (s, 2F).Ultimate analysis: theoretical value C
18h
44f
2n
8o
8s
3: C, 34.06; H, 6.99; N, 17.65; Experimental value C, 34.02; H, 6.95; N, 17.62.
Embodiment 23: ionic liquid [CG (CH
2cH
2) (CH
3)
2(CH
2cH
3) (CH
2cH
2oCH
3)]
2[(FSO
2n)
2sO
2]
By [CG (CH
2cH
2) (CH
3)
2(CH
2cH
3) (CH
2cH
2oCH
3)] Br and K
2[(FSO
2n)
2sO
2] room temperature reaction preparation.
Colourless liquid, productive rate 86%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.14 (t, 3H), 2.91 (s, 6H), 226-3.31 (m, 5H), 3.35 (t, 2H), 3.42 (t, 2H), 3.70 (s, 4H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.6 (s, 2F).Ultimate analysis: theoretical value C
20h
44f
2n
8o
8s
3: C, 36.46; H, 6.73; N, 17.01; Experimental value C, 36.41; H, 6.70; N, 16.95.
Embodiment 24: ionic liquid [(CH
3cH
2)
3s]
3[(FSO
2n)
2(SO
2)
2n]
By [(CH
3cH
2)
3s] I and K
3[(FSO
2n)
2(SO
2)
2n] room temperature reaction preparation.
Colourless liquid, productive rate 90%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=1.56 (t, 3 × 3H), 3.54ppm (q, 3 × 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.3 (s, 2F).Ultimate analysis: theoretical value C
18h
45f
2n
3o
8s
7: C, 31.15; H, 6.54; N, 6.05; Experimental value C, 31.12; H, 6.52; N, 6.00.
Embodiment 25: ionic liquid [(CH
3)
2sCH
2cH
2oCH
3]
3[(FSO
2n)
2(SO
2)
2n]
By [(CH
3)
2sCH
2cH
2oCH
3] I and K
3[(FSO
2n)
2(SO
2)
2n] room temperature reaction preparation.
Colourless liquid, productive rate 84%.Nuclear magnetic resonance data:
1h NMR (acetone-d
6, TMS, 400MHz): δ=3.15 (s, 2 × 3H), 3.42 (s, 3H), 3.78 (m, 2H), 3.97ppm (m, 2H);
19f NMR (acetone-d
6, CCl
3f, 376.5MHz): δ=51.4 (s, F).Ultimate analysis: theoretical value C
15h
39f
2n
3o
11s
7: C, 25.74; H, 5.62; N, 6.00; Experimental value C, 25.72; H, 5.58; N, 5.96.
Embodiment 26: the ionic liquid of the fluorine-containing sulfimide of binary and the ionic liquid of the fluorine-containing sulfimide of ternary, referred to as: the ionic liquid of binary or the fluorine-containing sulfimide of ternary.
Prepared part binary and the experimental result of ternary sulfimide ionic liquid are listed in table 5.
The experimental result of binary and the fluorine-containing sulfimide ionic liquid of ternary prepared by table 5
Embodiment 27-30 is the application example of low viscosity ionic liquid in ultracapacitor and serondary lithium battery
The application of embodiment 27 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 ionic liquid in table 5 and common organic electrolyte, assemble electrical condenser in vacuum glove box.Ultracapacitor impulse electricity test condition is: voltage V=0 to 2.8V, electric current 5mA.At 25 DEG C, the electrical capacity of mensuration is as shown in table 6.
Table 6 ionic liquid and the electrolytical Carbon-based supercapacitor electrical capacity of common organic electrolyte (25 DEG C)
The application of embodiment 28 ionic liquid electrolyte in serondary lithium battery
(1) making of positive pole
With LiCoO
2positive electrode material is example: by positive pole LiCoO
2powder, carbon black (granularity is 1000nm), poly(vinylidene fluoride) (PVDF) and N, N-dimethyl pyrrolidone (NMP) is mixed and made into homogeneous slurry, by slurry even application on aluminium foil (15 μm) collector, then drying is carried out, rolling, obtains LiCoO
2positive electrode material.Dry 12 hours at 120 DEG C, in dried pole piece, LiCoO
2account for 94% of total coating, 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
4, Li (CoNiMn)
1/3o
2prepare in the same way.
(2) making of negative pole
For artificial plumbago negative pole material: by synthetic graphite, poly(vinylidene fluoride) (PVDF) and N, N-dimethyl pyrrolidone (NMP) is mixed and made into homogeneous slurry, by slurry even application on Copper Foil (15 μm) collector, then drying is carried out, rolling, obtains carbon negative pole material.Dry 12 hours at 120 DEG C, in dried pole piece, graphite accounts for 96.4% of total coating, 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
12prepare in the same way.
(3) preparation of electrolytic solution
Glove box is proceeded to by after conducting salt binary fluorine sulfimide lithium and the vacuum-drying of ternary fluorine sulfimide lithium, weigh a certain amount of lithium salts, the organic solvent EC/EMC (3: 7 slowly adding ionic liquid or prepare in advance, v/v), be mixed with the electrolytic solution that concentration is respectively 0.7M and 1M, 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 the positive/negative plate prepared by (2), drips the electrolytic solution that above-mentioned steps (3) prepares, pole piece is flooded, is assembled into the button cell of CR2032.On micro-processor controlled auto charge and discharge 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 DEG C.The test data of the present embodiment is see table 7.As shown in Figure 1, charging and discharging curve as shown in Figure 2 for the recycle ratio capacity of battery and coulombic efficiency.
Table 7 is based on the performance of the serondary lithium battery of lithium salts/ionic liquid electrolyte
Embodiment 29 binary and the fluorine-containing sulfimide lithium carbonate solvent of ternary are combined into the application of electrolytic solution in serondary lithium battery
Change the ion liquid solvent in embodiment 28 into carbonic ether, other implementation conditions are consistent with embodiment 28 with evaluation method.The test data of the present embodiment is in table 8.
Table 8 is based on the performance of secondary lithium (ion) battery of lithium salts/carbonate electrolyte
Embodiment 30 binary and the fluorine-containing sulfimide lithium of ternary and ionic liquid or carbonate solvent are combined into the mensuration of electrolyte electrochemical character
(1) aluminium foil corrosion measurement in the 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, measures to 5.0V vs.Li at open circuit voltage (OCV)
+between/Li, measure volt-ampere curve, sweep velocity is 0.1mVs
-1.The present invention is with difluoro sulphonyl diimine lithium-EC/EMC (3: 7, v/v) electrolytic solution for example, and the volt-ampere curve of front 5 circulations as shown in Figure 4.
(2) mensuration of specific conductivity: the platinum black conductance electrode using DJS-10, Julabo type temperature controller, Autolab electrochemical workstation measures the specific conductivity of electrolytic solution between-20 to 60 DEG C prepared by embodiment 28 step (3), and result as shown in Figure 5.
Claims (1)
1. there is the binary fluorine-containing sulfimide alkali metal salt of structure shown in formula (II),
(II) in formula:
M=Li, Na, K, Rb or Cs;
R
F 1、R
F 2
C respectively
mf
2m+1, and m=0-8, R
f 1and R
f 2can be identical or different.
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| CN201310559805.5A CN103641751B (en) | 2011-05-20 | 2011-05-20 | An alkali metal salt of binary or the fluorine-containing sulfimide of ternary and ionic liquid and application thereof |
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| CN201410354413.XA Division CN104193655A (en) | 2011-05-20 | 2011-05-20 | Binary fluorine-containing sulfimide and preparation method of alkali metal salt of binary fluorine-containing sulfimide |
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| CN103553948A (en) * | 2013-10-31 | 2014-02-05 | 东莞市凯欣电池材料有限公司 | Ionic liquid containing ester-based functional group as well as preparation method and application thereof |
| CN104495767B (en) * | 2014-11-21 | 2017-01-04 | 湖南博氟新材料科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| CN104549507B (en) * | 2014-12-15 | 2017-05-17 | 浙江大学 | Preparation method of iron-based catalyst for alkylation reaction |
| WO2017015996A1 (en) * | 2015-07-28 | 2017-02-02 | 东莞市凯欣电池材料有限公司 | Phosphonitrile fluoroalkyl sulfimide alkali metal salt and electrolyte solution containing the metal salt |
| CN107887604B (en) * | 2016-09-29 | 2020-11-20 | 比亚迪股份有限公司 | Battery electrode binder, electrode and lithium ion battery |
| CN107887641A (en) * | 2016-09-29 | 2018-04-06 | 比亚迪股份有限公司 | A kind of solid polyelectrolyte and solid state battery |
| CN107887639B (en) * | 2016-09-29 | 2020-02-04 | 比亚迪股份有限公司 | Composite solid electrolyte and solid battery |
| CN110870125A (en) * | 2017-01-31 | 2020-03-06 | 塞斯欧化学制品有限公司 | Method for producing hygroscopic alkali metal salt electrolyte solution |
| US10707530B2 (en) * | 2017-08-15 | 2020-07-07 | GM Global Technology Operations LLC | Carbonate-based electrolyte system improving or supporting efficiency of electrochemical cells having lithium-containing anodes |
| CN109428038B (en) * | 2017-08-31 | 2020-08-25 | 比亚迪股份有限公司 | Battery diaphragm, preparation method thereof and lithium ion battery |
| CN108912335A (en) * | 2018-05-04 | 2018-11-30 | 惠州市大道新材料科技有限公司 | Application in phosphonitrile polyanion alkali metal salt and preparation method thereof and nonaqueous electrolytic solution |
| CN109003834A (en) * | 2018-07-20 | 2018-12-14 | 安徽旭峰电容器有限公司 | A kind of supercapacitor high-voltage electrolyte |
| KR102135218B1 (en) * | 2018-08-09 | 2020-07-17 | 건국대학교 글로컬산학협력단 | Electrolyte for aqueous rechargeable lithium ion battery, and aqueous rechargeable lithium ion battery comprising the same |
| CN109456484B (en) * | 2018-09-05 | 2020-11-17 | 宁波嘉玛材料科技有限公司 | Novel fluorine-containing sulfimide single-ion conductor polymer with conjugated structure and preparation method and application thereof |
| CN110247116B (en) * | 2019-06-24 | 2022-04-05 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same |
| CN110745795B (en) * | 2019-11-07 | 2022-08-26 | 兰州大学 | Method for synthesizing lithium bis (fluorosulfonyl) imide by using electrochemistry |
| WO2022220474A1 (en) * | 2021-04-12 | 2022-10-20 | 삼성에스디아이 주식회사 | Additive, electrolyte comprising same for rechargeable lithium battery, and rechargeable lithium battery |
| CN114105907A (en) * | 2021-12-14 | 2022-03-01 | 河北工业大学 | Pyrrolidine ionic liquid and preparation method and application thereof |
| WO2023119949A1 (en) * | 2021-12-24 | 2023-06-29 | 株式会社村田製作所 | Secondary battery |
| CN114400379A (en) * | 2022-01-20 | 2022-04-26 | 湖南科技大学 | Preparation method of high-safety high-voltage electrolyte containing nitrile compounds |
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| JP2004175668A (en) * | 2002-11-22 | 2004-06-24 | Tokuyama Corp | Onium salt |
| CN1227221C (en) * | 2003-04-30 | 2005-11-16 | 华中科技大学 | Ternary sulfonimine alkali salt and synthesis method thereof |
| US20090286163A1 (en) * | 2008-02-29 | 2009-11-19 | The Regents Of The University Of California | Electrolyte mixtures useful for li-ion batteries |
| CN101747243A (en) * | 2008-11-28 | 2010-06-23 | 华中科技大学 | Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt |
| CN101747244B (en) * | 2008-12-05 | 2013-10-30 | 华中科技大学 | Method for synthesizing perfluoroalkyl sulfimide alkali metal salt and ionic liquid synthesized by same |
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