CN101882696A - Nonaqueous electrolyte material of fluorosulfonylimide lithium and application thereof - Google Patents
Nonaqueous electrolyte material of fluorosulfonylimide lithium and application thereof Download PDFInfo
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- CN101882696A CN101882696A CN2009100834534A CN200910083453A CN101882696A CN 101882696 A CN101882696 A CN 101882696A CN 2009100834534 A CN2009100834534 A CN 2009100834534A CN 200910083453 A CN200910083453 A CN 200910083453A CN 101882696 A CN101882696 A CN 101882696A
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Abstract
The invention provides a nonaqueous electrolyte material, which consists of fluorosulfonylimide lithium and organic solvent with dielectric constant less than 30, and the organic solvent is selected from one or more of chain-like carbonate solvent, phosphate solvent, siloxane solvent, boroxane solvent, acetate solvent, propionate solvent, butyrate solvent, CF3OCH2CH2OCF3 solvent, C2H5OCH2CH2OCH3 solvent, C2F5OCH2CH2OCF3 solvent, 1,3-dioxolane solvent and aliphatic nitrile solvent with more than two carbon atoms. The ionic conductivity of the nonaqueous electrolyte material is 0.01mS/cm to 18mS/cm, the lithium ion transference number is tLi plus equal to 0.2 to 0.8, and the applicable temperature range is 80DEG C below zero to 60DEG C below zero. The invention also provides an application of the nonaqueous electrolyte material in the preparation of lithium batteries and super capacitors. Furthermore, the invention provides a lithium battery and a super capacitor which contain the nonaqueous electrolyte material of fluorosulfonylimide lithium.
Description
Technical field
The present invention relates to the advanced energy and material technology field.Particularly, the present invention relates to a kind of nonaqueous electrolyte material and the application in lithium battery, ultracapacitor thereof of the fluorine-containing sulfimide base lithium salts as conducting salt.
Background technology
The notion of chargeable lithium battery was proposed from phase earlier 1970s, since at first realizing its commercial applications by company of Sony (SONY) to the nineties initial stage, can discharge and recharge the basic research of lithium battery and industry and use and become the advanced energy, material, and multi-disciplinary research focus such as electrochemistry rapidly.Nonaqueous electrolyte is one of critical material of lithium battery, and its combination property (as chemistry and electrochemical stability, high temperature performance etc.) directly influences the use of serondary lithium battery.At present, commercialization serondary lithium battery electrolyte (mainly is LiPF by organic carbonate (as dimethyl carbonate (DMC), diethyl carbonate (DEC), vinyl carbonate (EC) etc.) and conducting salt mainly
6) form.The optimization of organic carbonate non-aqueous electrolytic solution and selection are to improve to discharge and recharge one of important research direction of lithium (ion) battery combination property.Be applied to discharge and recharge the non-aqueous electrolytic solution of lithium (ion) battery, generally should satisfy following requirement: (1) ionic conductivity height generally should reach 10
-3S/cm; (2) lithium ion transference number height is to obtain high lithium ion conductivity; (3) electrochemical window is wide, promptly satisfy lithium ion in the reversible embedding of positive and negative electrode with deviate from, and chemistry or electrochemical decomposition does not take place electrolyte; Chemistry or electrochemical decomposition do not take place in (4) thermal stability height in the operating temperature range of broad; (5) chemical stability height, promptly chemical reaction does not take place as positive pole, negative pole, collector, binding agent, conductive agent and barrier film etc. in the electrode material with battery system; (6) has lower interfacial migration resistance; (7) with at present the main positive and negative pole material compatibility of using is good; (8) nontoxic, pollution-free, safe in utilization, preferably can biodegradation; (9) preparation easily, cost is low.
Through research and the practice of decades, the nonaqueous electrolytic solution that is applied to the commercialization serondary lithium battery is at present generally selected lithium hexafluoro phosphate (LiPF
6) as conducting salt, the mixed solvent that the ethylene carbonate (EC), propene carbonate (PC) that solvent mostly is high viscosity, high-k and dimethyl carbonate (DMC), diethyl carbonate (DEC) or the Methylethyl carbonic ester (EMC) of low viscosity, low-k constitute.This type of system finally can be used on a large scale, is not that its every index has outstanding characteristic, but its overall target can satisfy the industry application requirements of existing serondary lithium battery substantially.
Although with LiPF
6Nonaqueous electrolytic solution as conducting salt has obtained immense success on the lithium ion battery industry, but LiPF
6The drawbacks limit that self is intrinsic the application (as extremely low temperature) of its electrolyte under maximum conditions.This mainly is because PF
6 -Anion symmetry height, its lithium salts LiPF
6Lattice energy is big, the fusing point height.Because compound solubility in organic solvent that lattice energy is big, fusing point is high is little, thereby, LiPF
6Conducting salt at low temperatures easily from organic electrolyte crystallization separate out.In addition, adopted dystectic cyclic carbonate ester solvent (as EC, mp37 ℃) in its electrolyte, this class organic solvent self is also easily crystallization at low temperatures.So, with LiPF
6For conducting salt and contain the general solidifying point of electrolyte of EC higher (-20 to 0 ℃ approximately).Why must use EC in the electrolyte, be because LiPF
6Have at DMC (dielectric constant is 3), DEC (dielectric constant is 3) etc. and to have lower solubility in low-k, the low viscous linear carbonate, therefore must add a certain proportion of have high-k, full-bodied EC (dielectric constant is 90), PC cyclic carbonates such as (dielectric constant are 65), to promote LiPF
6Dissociate.A kind of like this by mixing the method for high-k, full-bodied annular lipid solvent and low-k, low viscous chain lipid solvent, be to prepare the modal way of the commercial electrolyte of serondary lithium battery at present, referring to " Chemical Review " 2004,104 phases, 4303 to 4417 pages of summaries that go up about nonaqueous electrolyte.
In sum, adopt LiPF
6For the serondary lithium battery cryogenic property of conducting salt is difficult to satisfy actual needs.When ambient temperature is low to moderate 40 degrees below zero, even when lower, battery can't discharge its all told fully, even can't operate as normal, thereby has limited the application of serondary lithium battery under extreme temperature conditions.When temperature reduces, at present with LiPF
6Partial crystallization or curing can take place in the commercial electrolyte solution part as conducting salt, and viscosity increases, and conductivity sharply descends, and the interface impedance of electrolyte and electrode increases greatly, causes battery performance sharply to descend, even causes battery not work.
At other energy storage devices, as ultracapacitor etc., used nonaqueous electrolyte performance at low temperatures equally also is difficult to satisfy actual needs.
In addition, in electrochemistry magazine (" (J.Electrochem.Soc ") calendar year 2001,148 phases, the 1100th page and chemistry comment that (" Chemical Review " 2004,104 phases have openly set forth with LiPF for 4303 to 4417 pages
6Electrolyte as lithium salts exists two remarkable weak points:
(1) thermal instability, its reason is: in solution, anion PF
6There is balance a: LiPF
6→ LiF+PF
5(1), this mainly is because Li
+Be hard acid, F
-Be hard base, tend to form LiF and cause LiPF
6Decompose, thereby cause balance to be carried out to the right.
(2) in by organic carbonate isopolarity aprotic solvent (dipolar aprotic solvent) electrolyte system, LiPF
6Conducting salt is in height solvation state, and PF
6 -The solvation degree is extremely low, the reactivity height; Minor amount of water is as nucleopilic reagent in the electrolyte, and as substrate PF
6 -Nucleophilic substitution: LiPF takes place
6+ H
2O → POF
3+ LiF+2HF (2), PF
5+ H
2O → POF
3+ 2HF (3).The P-F key that this reaction just it has often been said is to the very responsive basic reason of water place.The HF that formula (2) that even more serious is and formula (3) produce is very harmful to positive electrode, with promoting the dissolving of positive electrode, its lithium storage content is decayed gradually.
In addition, with LiPF
6, LiClO
4, LiF, LiBF
4, Li[CF
3SO
3], Li[N (CF
3SO
2)
2], Li[BOB] two (oxalyl) borate) etc. (BOB: common lithium salts is gone back the low shortcoming of ubiquity lithium ion transference number as the electrolyte solution of conducting salt, and generally these electrolytical lithium ion transference numbers are less than 0.3.In electrolyte solution, lithium ion and anion all can conduct.The transport number of lithium ion is meant that the conductivity of lithium ion is divided by total ionic conductivity.For serondary lithium battery, in the electrolyte solution, can realize that the active ion that effective charge shifts is a lithium ion, but not anion.Therefore low lithium ion transference number will reduce the conductivity of effective lithium ion in the electrolyte solution, increase the polarization of inside battery.After the reason that these electrolyte numbers are low was lithium ion generation solvation, the radius of solvation ion was big all the better with respect to anion.
1994, scientists such as the Christophe Michot of Canadian Hydro-Quebec company and Michel Armand proposed to comprise that general formula is [R
1SO
2NSO
2R
2] salt of M, wherein R
1, R
2Comprise F, CF
3, C
2F
5, C
3F
7Deng group, M comprises Li, Na, K etc. for example with [FSO
2NSO
2F] H and LiF reaction, generate [FSO
2NSO
2F] Li salt (LiFSI).In this series invention, this lithium salts or as the lithium salts of polymer dielectric, perhaps as the lithium salts that contains the polymer dielectric of PC, perhaps in containing nonaqueous solventss such as cyclic carbonate, use, be used for serondary lithium battery, referring to FR94/03276, the patent of invention of WO95/26056, US5916475, US6254797B1, US6682855B2.Wherein patent US6682855B2 mutual-through type is Li[(ZSO
2)
2N] the compound application patent of invention, Z comprises F and fluoridizes organo-functional group.In these patents of invention, as embodiment, the concentration of LiFSI and LiTFSI is 1M ,-40 ℃ of conductivity less than 1 * 10
-4S/cm.2003, the Kumiko Mie of Japan etc. has applied for adopting the patent of invention (referring to US2004106047A1) that LiFSI is dissolved in the electrolytical lithium ion battery of butyrolactone (BL) (dielectric constant is 39) formation, in this patent of invention, can also comprise second kind of lithium salts, as LiPF
6, LiAsF
6, LiBF
4And the additive VEC that is used for negative pole SEI film film forming, and in butyrolactone, mix ring-type carbonate solvent such as PC, EC.In this patent, the minimum temperature of battery testing is 0 ℃, for the data of conductivity are provided.
2004, the Karim Zaghib of Hydro-Quebec company etc. has applied for the patent of invention (referring to US20070111105A1, WO2004/068610A2) of chargeable lithium battery, in this patent, adopt lithium metal as negative pole, this battery can be in-20-60 ℃ work, the electrolyte polymer dielectric of plasticizer-containing preferably in this battery.Wherein lithium salts comprises LiFSI and LiTFSI salt, and the plasticizer solvent is preferably butyrolactone, and mixes the butyrolactone that contains PC, EC, and in this patent of invention, salt is 0.2-2.5M. in the concentration of polymer dielectric
2005, the Christophe Michot of Hydro-Quebec company further disclosed the preparation method of LiFSI in patent of invention CA2527802A1.
On March 10th, 2006, U.S. Hammami Ama etc. has applied for [R
1SO
2NSO
2R
2]
-For the patent of invention of anion ion liquid, referring to WO2007/104144A1.Such ion liquid fusing point is more than 0 ℃.The Ishiko Eriko that on November 12nd, 2006 is Japanese etc. has applied for adopting and has comprised FSI
-The patent of invention of ion liquid lithium ion battery.This patent is not reported the cryogenic property of battery.Referring to EP1995817A1.On July 18th, 2007, the Kashima Mari of Japan etc. has applied for adopting and has comprised FSI
-The patent of invention of ion liquid lithium ion battery, referring to WO2009/011249A1.The purpose of this invention is the fail safe that utilizes ion liquid flame retardancy, low volatility to improve lithium ion battery.
In the paper of publishing, the relevant work of LiFSI has also obtained corresponding report, and brief description is as follows.2005, Karim Zaghib etc. reported native graphite, LiFePO on Journal of Power Sources 134 (2004) 124-129
4At 1.5M LiFSI-EC/GBL or LiFSI-EC/PC/DMC or contain the electrochemical behavior of room temperature in the polymer dielectric of PEO.They continued to have reported LiFePO at Journal of Power Sources 146 (2005) 380-385 in 2005
4At 1.5M LiFSI-EC/GBL or LiFSI-EC/PC/DMC or contain in the polymer dielectric of PEO 20 ℃ electrochemical behavior.2006, graphite cathode electrochemical behavior under the room temperature in the EMI-FSI ionic liquid reported in the articles on contributing and be published in Journal of Power Sources 162 (2006) 658-662 on February 13rd, 2006 such as Ishiko Eriko of Japan.After this, with FSI is that anion ion liquid is respectively at Electrochimica Acta 52 (2007) 6346-6352, J.Phys.Chem.B 2007,111,12829-12833, Journal of Molecular Liquids 143 (2008) 64-69, J.Phys.Chem.B 2008,112,13577-13580, Journal of Power Sources 185 (2008) 1585-1588, Journal of Power Sources 183 (2008) 436-440, Journal of Power Sources 175 (2008) 866-873 are reported by different authors.At present about FSI
-The research of base mainly focuses on ionic liquid, and these ionic liquids are owing to have high melt point, and viscosity all is not suitable for using in the low temperature serondary lithium battery.
Use in the nonaqueous electrolyte at lithium battery of publishing at present or ultracapacitor, generally based on the carbonic ester mixed solvent, usually comprise the cyclic carbonate ester solvent (general dielectric constant is greater than 30) of a high viscosity, high-k,, be mainly used in promotion as LiPF as EC, PC, BL
6, LiBF
4Deng dissociating of lithium salts, also comprise the linear carbonate solvent of one or more low viscosities, low-k, as DEC, DMC, EMC etc.Referring to " Chemical Review " 2004,104 phases, 4303 to 4417 pages of summaries about nonaqueous electrolyte.Because the existence of high viscosity solvent, generally this electrolytelike scope of application is at-20 to 55 ℃.
In the lithium battery and ultracapacitor that use nonaqueous electrolyte,, also add each based flame retardant usually, as phosphate, siloxanes etc. in order to improve fail safe.In nonaqueous electrolyte, add the patent of invention of phosphate referring to CN97194924.7, ZL98119237.8, ZL03827181.8, CN200580039032.1, ZL200580023980.6, CN200710129716.1; In nonaqueous electrolyte, add the patent of invention of siloxanes referring to CN01121452.x, ZL200410034171.2,, CN200610004543.6, CN200610172944.2, CN200610151899.2, CN200710005782.8, CN200710147198.6).In nonaqueous electrolyte, add the patent of invention of boroxane referring to ZL02142463.2, JP10223258A, JP11121033A.Because the solubility of existing most of lithium salts in the additive of these low-ks is lower, general phosphate, siloxanes and boroxane all are added in the non-aqueous organic solvent as additive, particularly comprise cyclic carbonate and linear carbonate and the organic solvent deposited in.When the battery practical application, the fail safe that can improve battery to a certain extent as the existence of the fire retardant of additive, but because existence inflammable, volatile organic solvent, fire-retardant effect is unsatisfactory.
Summary of the invention
One object of the present invention is to provide a kind of novel nonaqueous electrolyte material, this nonaqueous electrolyte material adopts novel fluorine sulfimide lithium salts as conducting salt, replace present extensive use, but the lithium hexafluoro phosphate (as thermal stability and poor chemical stability, the low-temperature conductive rate is low) that has many shortcomings.This lithium salts is low owing to having its anion symmetry, thereby have lower fusing point and a binding energy, the present invention finds, this class lithium salts can dissolve higher concentration (as DMC in the solvent that only contains low-k, dielectric constant 3, lithium salts solubility can reach 5M), this discovery has changed present lithium salts class nonaqueous electrolyte and must be dissolved in and contain in the electrolyte with high dielectric constant solvent or the present situation in the ionic liquid.Usually has lower fusing point owing to have linear carbonate class, phosphoric acid ester, type siloxane or the boroxane kind solvent of low-k, being difficult for crystallization solidifies, therefore, the electrolyte of this type of low melting point solvent of employing of the present invention preparation has higher ionic conductivity at low temperature, is particularly suitable for energy storage device such as lithium battery, ultracapacitor uses at low temperature.The present invention also finds, novel fluorine sulfimide lithium salts as conducting salt also can be in the past mainly as the solvent of flame-retardant additive, in phosphate, siloxanes, have higher solubility (1-2M), having changed the past fire retardant can not be as the present situation of primary solvent.Therefore, can produce a class new based on the former flame retardant additives that is used as, and in the present invention as the novel electrolytes of primary solvent, such electrolyte had both had the advantage of high safety, also was applicable to wide temperature range.Adopt this fluorine-containing sulfimide lithium as conducting salt, be dissolved in the electrolyte solution that only contains specific organic solvent preparation, in-80 ℃ to 60 ℃ temperature range, can realize high ionic conductivity and lithium ion transference number by certain molar concentration.Thereby, make this class adopt fluorine-containing sulfimide lithium can in very wide temperature range, use, and have higher fail safe as the electrolyte solution of conducting salt.Simultaneously, the present invention finds that also the non-aqueous electrolytic solution that the present invention proposes is at energy storage device, as having good electrode matching in lithium battery, the ultracapacitor.
Another object of the present invention is to provide the application of nonaqueous electrolyte material of the present invention in preparation lithium battery and/or ultracapacitor.
Another purpose of the present invention is to provide a kind of lithium battery that comprises nonaqueous electrolyte material of the present invention.
A further object of the present invention is to provide a kind of ultracapacitor (also being called as electrochemical double layer capacitor) that comprises nonaqueous electrolyte material of the present invention.
On the one hand, the invention provides a kind of nonaqueous electrolyte material, described nonaqueous electrolyte material comprises as the fluorine-containing sulfimide lithium salts of conducting salt and dielectric constant less than 30 organic solvent, and this organic solvent is selected from linear carbonate class, phosphoric acid ester, type siloxane, boroxane class, acetate esters, propionic acid ester, butyric acid ester, CF
3OCH
2CH
2OCF
3, C
2H
5OCH
2CH
2OCH
3, C
2F
5OCH
2CH
2OCF
3, 1,3-dioxolanes and carbon number are greater than in 2 the fatty nitrile organic solvent one or more.
Preferably, described fluorine-containing sulfimide lithium salts is one or more in the compound shown in the chemical formula (I):
Wherein, substituent R
1, R
2Be selected from halogen, carbon number independently of one another and be 1 to 6 saturated or unsaturated alkyl, carbon number and be the aryl that alkyl, halogen that 1 to 6 saturated or undersaturated halogen partly replaces or replace entirely partly replace or replace entirely, described halogen is selected from F, Cl, Br and I; Preferably, substituent R
1=R
2=F, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F)
2] (be abbreviated as Li[FSI]); Or preferably, substituent R
1=R
2=CF
3, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2CF
3)
2] (be abbreviated as Li[TFSI]); Or preferably, substituent R
1=F, R
2=CF
3, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2CF
3)] (be abbreviated as Li[FTFSI]); Or preferably, substituent R
1=F, R
2=C
2F
5, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
2F
5)] (be abbreviated as Li[FEFSI]); Or preferably, substituent R
1=F, R
2=C
3F
7, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
3F
7)] (be abbreviated as Li[FPFSI]); Or preferably, substituent R
1=F, R
2=C
5F
6, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
5F
6)] (be abbreviated as Li[FPHFSI]).
Preferably, the molar concentration of described fluorine sulfimide lithium salts in this nonaqueous electrolyte material is 0.1-5mol/L.
Preferably, described linear carbonate class organic solvent has structure shown in the chemical formula (II):
Wherein, substituent R
3, R
4Be selected from halogen, carbon number independently of one another and be 1 to 10 saturated or unsaturated alkyl, carbon number and be aryl, carbon number that alkyl, halogen that 1 to 10 saturated or unsaturated halogen partly replaces or replace entirely partly replace or replace entirely and be 1 to 10 saturated or undersaturated alkoxyl, described halogen is selected from F, Cl, Br and I.Preferably, described linear carbonate class organic solvent is selected from CH
3OCO
2CH
3(being abbreviated as DMC), CF
3OCO
2CF
3(being abbreviated as DMC-f), CH
3OCO
2CH
2CH
3(being abbreviated as EMC), CF
3OCO
2CF
2CF
3(being abbreviated as EMC-f), CH
3CH
2OCO
2CH
2CH
3(being abbreviated as DEC), CF
3CF
2OCO
2CF
2CF
3(being abbreviated as DEC-f), and composition thereof.
Preferably, described phosphoric acid ester organic solvent have chemical formula (III), (IV) or (V) shown in structure:
Wherein, substituent R
5, R
6, R
7Be selected from independently of one another: carbon number is that 1 to 10 saturated or unsaturated alkyl, carbon number are that 1 to 10 saturated or undersaturated halogen partly replaces or full substituted alkyl, and aryl, the carbon number that halogen partly replaces or replaces entirely is 1 to 10 saturated or undersaturated alkoxyl.Substituent R
5, R
6Also but cyclisation constitutes the annular phosphate that contains 2 to 5 carbon.Substituent X
1, X
2Be halogen independently of one another, described halogen is selected from F, Cl, Br and I.Preferably, described phosphoric acid ester organic solvent is the phosphoric acid ester shown in the formula (III), as trimethyl phosphate ((CH
3O)
3PO is abbreviated as TMP), triethyl phosphate ((C
2H
5O)
3PO is abbreviated as TEP), tricresyl phosphate n-butyl, trioctyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, p diethylaminobenzoic acid one methyl esters, di(2-ethylhexyl)phosphate fourth one methyl esters, tricresyl phosphate fluoro ethyl dimethyl esters, tricresyl phosphate (trifluoromethyl) ester, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (tribromo neopentyl) ester, di(2-ethylhexyl)phosphate methyl formate, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (2,6-3,5-dimethylphenyl) ester, p diethylaminobenzoic acid one propyl ester, tricresyl phosphate (trifluoroethyl) ester, phosphoric acid dipropyl one ethyl ester, fluoro dimethyl phosphate ((CH
3O)
2FPO is abbreviated as f-TMP), difluorophosphoric acid methyl esters ((CH
3O) F
2PO is abbreviated as 2f-TMP), or its mixture.
Preferably, described type siloxane organic solvent has structure shown in the chemical formula (VI):
Wherein, substituent R
8, R
9, R
10, R
11Identical or different, be selected from H, carbon number independently of one another and be 1 to 10 saturated or unsaturated alkyl and OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
mWith the polymeric groups based on ethyoxyl, wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero; Perhaps, substituent R
8, R
9, R
10, R
11Can be identical or different, be can be independently of one another by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aryl, described aryl is phenyl and/or naphthyl, or is can be by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aromatic heterocyclic radical, described aromatic heterocyclic radical is pyridine radicals, pyrazolyl and/or pyrimidine radicals, and wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero.Preferably, described type siloxane organic solvent is the type siloxane shown in the formula (VI), as tetramethoxy-silicane ((CH
3O)
4Si), ethyl triethoxy silicane oxygen alkane ((CH
3CH
2O)
3SiC
2H
5), ethyl triacetyl oxygen radical siloxane ((CH
3COO)
3SiC
2H
5), diphenyl methoxy radical siloxane ((CH
3O)
2Si (C
5H
6)
2), silicohetane oxyalkyl fluomethane sulfonate ((C
2H
5)
3SiCH
2SO
3CF
3), or its mixture.
Preferably, described boroxane class organic solvent have chemical formula (VII) or (VIII) shown in structure:
Wherein, substituent R
12, R
13, R
14Identical or different, be that H, carbon number are 1 to 10 saturated or undersaturated alkyl and OC independently of one another
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2CnF
2n+1-mH
mWith the polymeric groups based on ethyoxyl, wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero; Perhaps, substituent R
8, R
9, R
10, R
11Can be identical or different, be can be independently of one another by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2CnF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aryl, described aryl is phenyl and/or naphthyl, or is can be by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aromatic heterocyclic radical, described aromatic heterocyclic radical is pyridine radicals, pyrazolyl and/or pyrimidine radicals.Preferably, described boroxane class organic solvent is selected from triethoxy boroxane (TEOBX), perfluor replaces triethoxy borine (PFTEOBX), trivinyl boroxane (TEBX), three propargyl boroxanes (TABX), boron triethyl acid esters (TEB), perfluor replacement boron triethyl acid esters (PFTEB), and composition thereof.
Preferably, described acetate esters organic solvent is selected from CH
3CO
2CH
3(being abbreviated as MA), CF
3CO
2CF
3(being abbreviated as MA-f), CH
3CO
2CH
2CH
3(being abbreviated as EA), CF
3CO
2CF
2CF
3(being abbreviated as EA-f), CH
3CO
2CH
2CF
3(being abbreviated as TFEA), CF
3CO
2CH
2CH
3(being abbreviated as ETFA) and composition thereof; Described propionic acid ester organic solvent is selected from CH
3CH
2CO
2CH
3(being abbreviated as MP), CF
3CF
2CO
2CF
3(being abbreviated as MP-f), CH
3CH
2CO
2CH
2CH
3(being abbreviated as EP), CF
3CF
2CO
2CF
2CF
3(being abbreviated as EP-f), CF
3CF
2CO
2CH
3(being abbreviated as MPFP), and composition thereof; Described butyric acid ester organic solvent is selected from CH
3CH
2CH
2CO
2CH
3(being abbreviated as MB), CF
3CF
2CF
2CO
2CF
3(being abbreviated as MB-f), CH
3CH
2CH
2CO
2CH
2CH
3(being abbreviated as EB), CF
3CF
2CF
2CO
2CF
2CF
3(being abbreviated as EB-f), CH
3CH
2CH
2CO
2CH
2CH
2CH
3(being abbreviated as PB), CF
3CF
2CF
2CO
2CF
2CF
2CF
3(being abbreviated as PB-f), CH
3CH
2CH
2CO
2CH
2CH
2CH
2CH
3(being abbreviated as BB), CF
3CF
2CF
2CO
2CF
2CF
2CF
2CF
3(being abbreviated as BB-f), CH
3CH
2CH
2CO
2CH
2CF
3(being abbreviated as TFEB), and composition thereof.
Preferably, described carbon number is selected from propionitrile (C greater than 2 fatty nitrile organic solvent
2H
5CN is abbreviated as PN), malononitrile (NCCH
2CN is abbreviated as PDN), methoxyacetonitrile (CH
3OCH
2CN is abbreviated as MAN), 3-methoxypropionitrile (CH
3OCH
2CH
2CN is abbreviated as 3-MPN), and composition thereof.
The conductivity at room temperature of nonaqueous electrolyte material of the present invention is 0.01-18mS/cm, and the lithium ion transference number in the described nonaqueous electrolyte material is t
Li+=0.2-0.8.
The temperature range that nonaqueous electrolyte material of the present invention is suitable for is-80 ℃-60 ℃.
On the other hand, the invention provides the application of nonaqueous electrolyte material of the present invention in preparation lithium battery and/or ultracapacitor.
Another aspect the invention provides a kind of lithium battery, comprises anode, negative electrode and flow collection sheet, and described lithium battery also comprises the nonaqueous electrolyte material of fluorine-containing sulfimide base lithium of the present invention or the lithium battery diaphragm that soaked with this nonaqueous electrolyte material.
On the one hand, the invention provides a kind of ultracapacitor again, comprise anode, negative electrode and flow collection sheet, described ultracapacitor also comprises the nonaqueous electrolyte material of fluorine-containing sulphur imido grpup lithium of the present invention or the lithium battery diaphragm that soaked with this nonaqueous electrolyte material.
Compared with prior art, advantage of the present invention is:
(1) find novel fluorine sulfimide base lithium salts as conducting salt, solubility is big in the organic solvent of low-k, and low temperature is difficult for crystallization.The novel lithium salts of this class is because anion has the low-symmetry and the good degree of freedom, and its fusing point compares LiPF
6, LiBF
4, LiClO
4Low etc. common lithium salts, thereby, with the non-aqueous electrolytic solution of the novel lithium salts of this class as conducting salt, has very wide Applicable temperature scope, can in-80 ℃ to 60 ℃ scopes, use, in this Applicable temperature scope, have very high ionic conductivity, lithium ion transference number;
(2) be that the nonaqueous electrolyte of conducting salt is applied to energy storage device with such lithium salts,, have very wide temperature applicable range, can in-80 ℃ to 60 ℃ scopes, use, have good electrode matching as lithium battery.This type of electrolyte can obviously be widened the low temperature serviceability temperature of existing energy storage system, significantly improves energy storage device, as lithium battery, and the cryogenic property of capacitor;
(3) such nonaqueous electrolyte can directly adopt fire retardant as solvent, has safe remarkable advantage, adopts these electrolytical lithium batteries, ultracapacitor to have higher fail safe.
Description of drawings
Below, describe embodiments of the invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 is the schematic diagram of the simulated battery of the nonaqueous electrolyte of the fluorine-containing sulfimide lithium salts of use; Wherein: 1 is anode tap, 2 is stainless steel sealing nut (being connected with negative electrode), 3 is the polytetrafluoroethylene nut, and 4 is the stainless steel steel column, and 5 is polytetrafluoroethyllining lining, 6 is stainless steel cylinder (being connected with anode), 7,8 is the lithium sheet, and 9 for flooding the barrier film that contains electron withdraw group compound electrolyte solution, and 10 is active material of positive electrode, 11 is Copper Foil, and 12 is cathode leg;
Fig. 2 is the temperature variant figure of conductivity of nonaqueous electrolyte material among embodiment 1-3 and the embodiment 76-78;
Fig. 3 is the first all charging and discharging curves in the nonaqueous electrolyte material of negative material graphitization mesocarbon bead (MCMB) in embodiment 1-2; With
Fig. 4 first week charges and discharge curve in the nonaqueous electrolyte material for LiFePO 4 of anode material in embodiment 1-2.
Embodiment
Followingly the present invention is described with reference to specific embodiment.It will be appreciated by those skilled in the art that these embodiment only are used to illustrate purpose of the present invention, the scope that it does not limit the present invention in any way.
Electrolyte solution preparation:, put into vacuum glove box (water content is less than 1ppm) after the dimethyl carbonate of organic solvent B component (DMC) drying with two (fluorine sulphonyl) imines lithiums of conducting salt component A (Li[FSI]) vacuumize.Weighing 18.7g Li[FSI] in beaker, under magnetic agitation, slowly add DMC several times, be mixed with the electrolyte solution that molar concentration is 1.0M, sealing is preserved stand-by.
Conductance measurement: above-mentioned electrolyte solution is added drop-wise in the glass conductance cell that two end electrodes is platinum electrode, use GDW6005 type high-low temperature test chamber temperature control, HP4192 impedance spectrometer is measured impedance spectrum (5Hz-13MHz), obtains temperature range and is-80 ℃ to 60 ℃ conductivity.Conductivity when recording-80 ℃ is 0.2mS/cm, and the conductivity in the time of 25 ℃ is 9.2mS/cm, and the conductivity in the time of 60 ℃ is 14.6mS/cm.The temperature variant rule of the conductivity of the electrolyte solution that obtains as shown in Figure 2.
Prototype lithium battery assembling and performance measurement: with above-mentioned Li[FSI] be directly used in a prototype lithium battery as the non-aqueous electrolytic solution of conducting salt, measure the compatibility and the battery performance of itself and positive and negative electrode material.
The number of assembling steps of prototype lithium battery is as follows:
With MCMB, the N of granularity 15 μ m and Kynoar (PVDF), N-dimethyl pyrrolidone (NMP) solution mixing system becomes the composite mortar of homogeneous, evenly is coated in then as on the copper foil of affluxion body (thickness 20 μ m).Gained film thickness 2-20 μ m 160 ℃ of oven dry down, compresses under 1MPa pressure, continues to dry by the fire 12 hours down at 160 ℃.In the pole piece after the oven dry, MCMB accounts for the 94wt% that always is coated with application, and Kynoar (PVDF) accounts for 6wt%.The gained pole piece being cut into area then is 1cm
2Disk is as anode.
With LiFePO
4The N of powder, carbon black (granularity 1000nm), Kynoar (PVDF), N-dimethyl pyrrolidone (NMP) solution mixing system becomes the composite mortar of homogeneous, slurry evenly is coated on the aluminium foil (thickness 15 μ m) as collector, then 160 ℃ of oven dry down, the gained film thickness is at 5-40 μ m, at 1MPa * 1cm
2Compress under the pressure, continue to dry by the fire 12 hours down at 160 ℃.In the pole piece after the oven dry, LiFePO
4Account for the 85wt% that always is coated with application, copolymer comprised 5wt%, carbon black accounts for 10wt%.The gained pole piece being cut into area then is 1cm
2Disk is as negative electrode.
Dried pole piece is moved in the argon gas glove box, the PVDF perforated membrane is placed on MCMB pole piece (perhaps LiFePO
4Pole piece) and between the metal lithium sheet, drip the above-mentioned Li[FSI for preparing] as the electrolyte solution of conducting salt, electrode slice is submerged.Shown in accompanying drawing 1, be assembled into Experimental cell.Experimental cell carries out the charge and discharge cycles test on micro-processor controlled auto charge and discharge instrument.Current density 0.1mA/cm
2, charging cut-ff voltage 2.5V, discharge cut-off voltage 0V, probe temperature are-80 ℃ ,-40 ℃, 0 ℃, 25 ℃ and 60 ℃.Recording battery capacity respectively is according to active material Mass Calculation value 31%, 45%, 63%, 94% and 89%.Related data is referring to subordinate list 1.MCMB and the LiFePO4 pole piece charging and discharging curve in the prepared nonaqueous electrolyte material of embodiment 1 is shown in Fig. 3 (A) and Fig. 4 (A).
Electrolyte solution preparation: with two (fluorine sulphonyl) imines lithiums of conducting salt component A (Li[FSI]) vacuumize, the DMC of organic solvent B component and ethyl triethoxy silicane oxygen alkane ((CH
3CH
2O)
3SiC
2H
5) put into vacuum glove box (water content is less than 1ppm) after (abbreviating silane as) drying.Weighing 18.7g Li[FSI] in beaker, under magnetic agitation, slowly add several times in the mixed solvent of DMC and sliane (DMC: silane=1: 4, volume ratio), being mixed with the electrolyte solution that molar concentration is 1M, sealing is preserved stand-by.
Conductance measurement: above-mentioned electrolyte solution is added drop-wise in the glass conductance cell that two end electrodes is platinum electrode, use GDW6005 type high-low temperature test chamber temperature control, HP4192 impedance spectrometer is measured impedance spectrum (5Hz-13MHz), obtains temperature range and is-80 ℃ to 60 ℃ conductivity.Conductivity when recording-80 ℃ is 0.03mS/cm, and the conductivity in the time of 25 ℃ is 2.4mS/cm, and the conductivity in the time of 60 ℃ is 7.6mS/cm, and the temperature variant rule of the conductivity of the electrolyte solution that obtains as shown in Figure 2.
Prototype lithium battery assembling and performance measurement: with above-mentioned Li[FSI] be directly used in a prototype lithium battery as the non-aqueous electrolytic solution of conducting salt, measure itself and MCMB and LiFePO
4The compatibility of electrode material and battery performance.Experiment lithium battery assembling, test mode are identical with embodiment 1.The composition of present embodiment and test data are referring to table 1.MCMB and LiFePO
4Pole piece at the charging and discharging curve in this electrolyte shown in Fig. 3 (B) and Fig. 4 (B).
The preparation of electrolyte solution: with two (fluorine sulphonyl) imines lithiums of conducting salt component A (Li[FSI]) vacuumize, the DMC of organic solvent B component, and put into vacuum glove box (water content is less than 1ppm) after trimethyl phosphate (TMP) drying.Weighing 18.7g Li[FSI] in beaker, under magnetic agitation, slowly add several times in the mixed solvent of dimethyl carbonate (DMC) and TMP (DMC: TMP=1: 1, volume ratio), being mixed with the electrolyte solution that molar concentration is 1.0M, sealing is preserved stand-by.
Conductance measurement: above-mentioned electrolyte solution is added drop-wise in the glass conductance cell that two end electrodes is platinum electrode, use GDW6005 type high-low temperature test chamber temperature control, HP4192 impedance spectrometer is measured impedance spectrum (5Hz-13MHz), obtains temperature range and is-80 ℃ to 60 ℃ conductivity.Conductivity when recording-80 ℃ is 0.1mS/cm, and the conductivity in the time of 25 ℃ is 8.7mS/cm, and the conductivity in the time of 60 ℃ is 16.8mS/cm, and the temperature variant rule of the conductivity of the electrolyte solution that obtains as shown in Figure 2.
Prototype lithium battery assembling and performance measurement: with above-mentioned Li[FSI] be directly used in a prototype lithium battery as the electrolyte solution of conducting salt, measure the compatibility and the battery performance of itself and positive and negative electrode material.Experiment lithium battery assembling, test mode are identical with embodiment 1.The composition of present embodiment and test data are referring to table 1.
Embodiment 4-embodiment 235
The method of operation of embodiment 4-embodiment 235 is identical with embodiment 1-3.The composition of component A and B component and test data are referring to table 1 and 2 among this embodiment.
The comparative example 236
The preparation of electrolyte solution:, in vacuum glove box, be dissolved in the organic solvent propene carbonate (PC) (water content is less than 1ppm) with two (fluorine sulphonyl) imines lithiums of conducting salt component A (Li[FSI]) vacuumize.Weighing 18.7g Li[FSI] in beaker, under magnetic agitation, slowly add PC several times, be mixed with the electrolyte solution that molar concentration is 1.0M, sealing is preserved stand-by.Prepare 1.0M[(CH with similar approach
3CH
2)
3] NCH
3] [BF
4The general electrolyte solution of]/propene carbonate (PC).
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 Li[FSI of above-mentioned 1.0M] and [(CH
3CH
2)
3] NCH
3] [BF
4]/propene carbonate (PC) electrolyte is assembled capacitor in vacuum glove box.Ultracapacitor impulse electricity test condition is: voltage V=0 to 2.8V, electric current 5mA.Under 25 ℃, the capacitance of mensuration is respectively 14.7,13.4F/cm
3Under-25 ℃, capacity is respectively 9.3, and 12.7F/cm
3Therefore, under the low temperature, adopt Li[FSI] as the capacity of super capacitor height of conducting salt.
Conductance measurement: above-mentioned electrolyte solution is added drop-wise in the glass conductance cell that two end electrodes is platinum electrode, use GDW6005 type high-low temperature test chamber temperature control, HP4192 impedance spectrometer is measured impedance spectrum (5Hz-13MHz), test this electrolyte solution conductivity under the temperature of-40 ℃ and 60 ℃, it is as follows to obtain the result: conductivity value is 0.1mS/cm in the time of-40 ℃, and the conductivity 60 ℃ the time is 10mS/cm.
Because there is solid-liquid phase change in the PC solvent about-40 ℃, at-40 ℃ or more under the low temperature, system can change into solid-state, and conductivity sharply drops to and can't measure, and battery can't normally discharge and recharge.
Comparative example 237-256
The method of operation of comparative example 237-256 is identical with embodiment 1-3.Component A is selected from LiPF among this embodiment
6, LiFSI and/or LiBF
4B component is selected from following solvent: diethyl ether, dimethoxy-ethane, oxolane, dimethyl-tetrahydrofuran, dioxane, toluic acid ester, ethyl ester, propylene carbonate, vinyl carbonate, butyrolactone, acetonitrile, propionitrile, nitromethane, nitrobenzene, dimethyl formamide, diethylformamide, N-methyl pyrrolidone, methyl-sulfoxide, tetramethylene sulfone and/or tetraethyl sulfanilamide (SN).These systems all can't operate as normal under-80 degree.
The fluorine-containing sulfimide base of table 1 lithium salts is as the component and the electrochemical properties thereof of the nonaqueous electrolyte of conducting salt
Annotate: in conductivity and the capability retention data unquote is temperature, and no specified otherwise then is 25 ℃ of room temperatures.Embodiment 237-256 is-80 degrees of data.
Table 2 lithium ion transference number relatively
Described the present invention in detail with reference to embodiment, to those skilled in the art, should be understood that, above-mentioned embodiment should not be understood that to limit scope of the present invention.Therefore, can make various changes and improvements to embodiment of the present invention without departing from the spirit and scope of the present invention.
Claims (12)
1. nonaqueous electrolyte material, it is characterized in that, described nonaqueous electrolyte material comprises as the fluorine-containing sulfimide lithium salts of conducting salt and dielectric constant less than 30 organic solvent, and this organic solvent is selected from linear carbonate class, phosphoric acid ester, type siloxane, boroxane class, acetate esters, propionic acid ester, butyric acid ester, CF
3OCH
2CH
2OCF
3, C
2H
5OCH
2CH
2OCH
3, C
2F
5OCH
2CH
2OCF
3, 1,3-dioxolanes and carbon number are greater than in 2 the fatty nitrile organic solvent one or more.
2. nonaqueous electrolyte material according to claim 1 is characterized in that, described fluorine-containing sulfimide lithium salts is one or more in the compound shown in the chemical formula (I):
Wherein, substituent R
1, R
2Be selected from halogen, carbon number independently of one another and be 1 to 6 saturated or unsaturated alkyl, carbon number and be the aryl that alkyl, halogen that 1 to 6 saturated or undersaturated halogen partly replaces or replace entirely partly replace or replace entirely, described halogen is selected from F, Cl, Br and I; Preferably, substituent R
1=R
2=F, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F)
2]; Or preferably, substituent R
1=R
2=CF
3, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2CF
3)
2]; Or preferably, R
1=F, R
2=CF
3, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2CF
3)]; Or preferably, R
1=F, R
2=C
2F
5, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
2F
5)]; Or preferably, R
1=F, R
2=C
3F
7, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
3F
7)]; Or preferably, R
1=F, R
2=C
5F
6, this moment, described fluorine-containing sulfimide lithium salts was Li[N (SO
2F) (SO
2C
5F
6)].
3. nonaqueous electrolyte material according to claim 1 and 2 is characterized in that, the molar concentration of described fluorine sulfimide lithium salts in this nonaqueous electrolyte material is 0.1-5mol/L.
4. according to each described nonaqueous electrolyte material among the claim 1-3, it is characterized in that described linear carbonate class organic solvent has structure shown in the chemical formula (II):
Wherein, substituent R
3, R
4Be selected from halogen, carbon number independently of one another and be 1 to 10 saturated or unsaturated alkyl, carbon number and be aryl, carbon number that alkyl, halogen that 1 to 10 saturated or unsaturated halogen partly replaces or replace entirely partly replace or replace entirely and be 1 to 10 saturated or undersaturated alkoxyl, described halogen is selected from F, Cl, Br and I; Preferably, described linear carbonate class organic solvent is selected from CH
3OCO
2CH
3, CF
3OCO
2CF
3, CH
3OCO
2CH
2CH
3, CF
3OCO
2CF
2CF
3, CH
3CH
2OCO
2CH
2CH
3, CF
3CF
2OCO
2CF
2CF
3, and composition thereof.
5. according to each described nonaqueous electrolyte material among the claim 1-4, it is characterized in that, described phosphoric acid ester organic solvent have chemical formula (III), (IV) or (V) shown in structure:
Wherein, substituent R
5, R
6, R
7Be selected from carbon number independently of one another and be 1 to 10 saturated or unsaturated alkyl, carbon number and be that 1 to 10 saturated or undersaturated halogen partly replaces or full substituted alkyl, halogen partly replaces or the aryl, the carbon number that replace entirely are 1 to 10 saturated or undersaturated alkoxyl; Preferably, substituent R
5, R
6Cyclisation constitutes the annular phosphate that contains 2 to 5 carbon atoms;
Substituent X
1, X
2Be halogen independently of one another, described halogen is selected from F, Cl, Br and I;
Preferably, described phosphoric acid ester organic solvent is selected from trimethyl phosphate, triethyl phosphate, the tricresyl phosphate n-butyl, trioctyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, p diethylaminobenzoic acid one methyl esters, di(2-ethylhexyl)phosphate fourth one methyl esters, tricresyl phosphate fluoro ethyl dimethyl esters, tricresyl phosphate (trifluoromethyl) ester, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (tribromo neopentyl) ester, the di(2-ethylhexyl)phosphate methyl formate, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (2, the 6-3,5-dimethylphenyl) ester, p diethylaminobenzoic acid one propyl ester, tricresyl phosphate (trifluoroethyl) ester, phosphoric acid dipropyl one ethyl ester, the fluoro dimethyl phosphate, the difluorophosphoric acid methyl esters, and composition thereof.
6. according to each described nonaqueous electrolyte material among the claim 1-5, it is characterized in that described type siloxane organic solvent has structure shown in the chemical formula (VI):
Wherein, substituent R
8, R
9, R
10, R
11Identical or different, be selected from H, carbon number independently of one another and be 1 to 10 saturated or unsaturated alkyl and OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
mWith the polymeric groups based on ethyoxyl, wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero; Perhaps, substituent R
8, R
9, R
10, R
11Identical or different, be by F, C independently of one another
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aryl, described aryl is phenyl and/or naphthyl, or is by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aromatic heterocyclic radical, described aromatic heterocyclic radical is pyridine radicals, pyrazolyl and/or pyrimidine radicals, and wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero; Preferably, described type siloxane organic solvent is selected from tetramethoxy-silicane, ethyl triethoxy silicane oxygen alkane, ethyl triacetyl oxygen radical siloxane, diphenyl methoxy radical siloxane, silicohetane oxyalkyl fluomethane sulfonate, and composition thereof.
7. according to each described nonaqueous electrolyte material among the claim 1-6, it is characterized in that, described boroxane class organic solvent have chemical formula (VII) or (VIII) shown in structure:
Wherein, substituent R
12, R
13, R
14Identical or different, be that H, carbon number are 1 to 10 saturated or undersaturated alkyl and OC independently of one another
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2CnF
2n+1-mH
mWith the polymeric groups based on ethyoxyl, wherein, n is 1 to 10 integer, and m is the integer greater than zero, and 2n+1-m is more than or equal to zero; Perhaps, substituent R
8, R
9, R
10, R
11Identical or different, be by F, C independently of one another
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2CnF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aryl, described aryl is phenyl and/or naphthyl, or is by F, C
nF
2n+1-mH
m, OC
nF
2n+1-mH
m, OCOC
nF
2n+1-mH
m, OSO
2C
nF
2n+1-mH
m, N (C
nF
2n+1-mH
m)
2Do not replace or single the replacement or polysubstituted aromatic heterocyclic radical, described aromatic heterocyclic radical is pyridine radicals, pyrazolyl and/or pyrimidine radicals; Preferably, described boroxane class organic solvent is selected from the triethoxy boroxane, perfluor replaces triethoxy borine, trivinyl boroxane, three propargyl boroxanes, boron triethyl acid esters, perfluor replacement boron triethyl acid esters, and composition thereof.
8. according to each described nonaqueous electrolyte material among the claim 1-7, it is characterized in that described acetate esters organic solvent is selected from CH
3CO
2CH
3, CF
3CO
2CF
3, CH
3CO
2CH
2CH
3, CF
3CO
2CF
2CF
3, CH
3CO
2CH
2CF
3, CF
3CO
2CH
2CH
3, and composition thereof; Described propionic acid ester organic solvent is selected from CH
3CH
2CO
2CH
3, CF
3CF
2CO
2CF
3, CH
3CH
2CO
2CH
2CH
3, CF
3CF
2CO
2CF
2CF
3, CF
3CF
2CO
2CH
3, and composition thereof; Described butyric acid ester organic solvent is selected from CH
3CH
2CH
2CO
2CH
3, CF
3CF
2CF
2CO
2CF
3, CH
3CH
2CH
2CO
2CH
2CH
3, CF
3CF
2CF
2CO
2CF
2CF
3, CH
3CH
2CH
2CO
2CH
2CH
2CH
3, CF
3CF
2CF
2CO
2CF
2CF
2CF
3, CH
3CH
2CH
2CO
2CH
2CH
2CH
2CH
3, CF
3CF
2CF
2CO
2CF
2CF
2CF
2CF
3, CH
3CH
2CH
2CO
2CH
2CF
3, and composition thereof.
9. according to each described nonaqueous electrolyte material among the claim 1-8, it is characterized in that described carbon number is selected from propionitrile, malononitrile, methoxyacetonitrile, 3-methoxypropionitrile greater than 2 fatty nitrile organic solvent, and composition thereof.
10. the application of each described nonaqueous electrolyte material in preparation lithium battery and/or ultracapacitor among the claim 1-9.
11. lithium battery, comprise anode, negative electrode and flow collection sheet, it is characterized in that described lithium battery also comprises the nonaqueous electrolyte material of each described fluorine-containing sulfimide base lithium among the claim 1-9 or the lithium battery diaphragm that soaked with this nonaqueous electrolyte material.
12. ultracapacitor, comprise anode, negative electrode and flow collection sheet, it is characterized in that described ultracapacitor also comprises the nonaqueous electrolyte material of each described fluorine-containing sulfimide base lithium among the claim 1-9 or the lithium battery diaphragm that soaked with this nonaqueous electrolyte material.
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