CN101662030A - Electrolyte solution, preparation method thereof and use thereof - Google Patents
Electrolyte solution, preparation method thereof and use thereof Download PDFInfo
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Abstract
The invention provides electrolyte solution, which contains an organic solvent, a lithium salt or lithium oxide, a compound containing an electron-withdrawing group and an additive, wherein the solvent is a carbonic ester and/or ether solvent; and the additive is a compound having a molecular formula of RBC2O4Li, R in the formula may be -C2O4, -F2, -C6H2O2, alkyl or fluorine-containing substitutedalkyl, and the concentration of the additive in the electrolyte solution is 0.005 to 0.1mol/l. The invention also provides a preparation method of the electrolyte solution. The invention also provides a lithium cell, which comprises a lithium cell diaphragm soaked in the electrolyte solution. The electrolyte solution of the invention has the advantages of high transport number of lithium ions, high conductivity and wide electrochemical window. Meanwhile, the electrolyte solution has high compatibility with a carbon cathode material.
Description
Technical field
The present invention relates to the preparation method and application of a kind of electrolyte solution and this electrolyte solution, the invention further relates to a kind of lithium battery, the battery contains the barrier film that the electrolyte solution soaked.
Background technology
The concept of chargeable lithium battery is proposed from phase earlier 1970s, then since the nineties initial stage realizes its commercial applications first by Sony (SONY) company, the basic research and application of chargeable lithium battery rapidly become one of International Electrochemical study hotspot.The optimization and selection of wherein organic electrolyte solution are one of most challenging work during chargeable lithium battery is studied.The organic electrolyte solution that chargeable lithium battery is used is to be dissolved in the electrolyte solution formed in organic mixed solvent with appropriate lithium salts.As the electrolyte solution of chargeable lithium battery, it should typically meet claimed below：(1) ionic conductivity is high, should typically reach 10-3~2*10-2S/cm；(2) lithium ion transference number is high, to obtain high lithium ion conductivity；(3) electrochemical window is wide, i.e., chemical property is stable in wider potential range；(4) heat endurance is high, is not decomposed within the scope of wider temperature；(5) chemical stability is high, i.e., do not chemically reacted with electrode material such as positive pole, negative pole, collector, binding agent, conductive agent and the barrier film of battery system etc.；(6) there is relatively low interfacial migration resistance；(7) it is good with the positive and negative pole material compatibility that is currently mainly used；(8) it is nontoxic, pollution-free, use safety, it is therefore desirable to it is biodegradable；(9) low cost is easily prepared.
By the research and practice of decades, the electrolyte used at present in the chargeable lithium battery of commercialization is typically chosen lithium hexafluoro phosphate (LiPF6) as lithium salts, solvent is generally the mixed solvent that ethylene carbonate (EC) is constituted with dimethyl carbonate (DMC) or diethyl carbonate (DEC).Such system finally can large-scale use, not its indices has prominent characteristic, but its overall target can meet the requirement of existing chargeable lithium battery substantially.
《Electrochemistry magazine (J.Electrochem.Soc)》2001,148 phases, page 1100 and《Chemistry comments (Chemical Review)》2004,104 phases, page 4303 page -4417 disclosed with LiPF6Two notable weak points are there are as the electrolyte of lithium salts：
(1) thermal instability, its reason is：In the solution, anion PF6 -In the presence of a balance：LiPF6→LiF+PF5(1), and LiF belongs to strong Lewis acid, it and PF5Tend to react with organic solvent to cause balance to carry out to the right.
(2) while P-F keys are very sensitive to water, even the water of trace can also trigger following reaction：LiPF6+H2O→POF3+ LiF+2HF (2), PF5+H2O→POF3The HF that+2HF (3), formula (2) and formula (3) are produced will promote the dissolving of positive electrode, its lithium storage content is gradually decayed.
Simultaneously with LiPF6、LiClO4、LiF、LiBF4、LiCF3SO3、LiN(CF3SO2)2, LiBOB as the electrolyte solution of lithium salts, the characteristics of also generally existing lithium ion transference number is low, the lithium ion transference number of these general electrolyte is less than 0.3.In electrolyte solution, lithium ion can conduct with anion.The transport number of lithium ion refers to the electrical conductivity divided by total ionic conductivity of lithium ion.For chargeable lithium battery, the transfer of electrolyte solution effective charge is lithium ion, and non-anion.Therefore low lithium ion transference number will reduce the electrical conductivity of effective lithium ion in electrolyte solution, increase the polarization of inside battery.The reason for these electrolyte numbers are low is that lithium ion is carried out after solvation with solvent, and the radius of solvated ion is big all the better relative to anion.
《Electrochemistry magazine (J.Electrochem.Soc)》Page 3825 of 143 phase in 1996 and《Electrochemistry magazine (J.Electrochem.Soc)》145 phase page 2813 in 1998, which was once reported, points out that, using boryl electrophilic compound and research of the nitrogen base electrophilic compound as the additive of electrolyte solution, such additive promotes the dissociation of some lithium salts in the solution, such as LiCF3SO3With LiF dissociation, total ionic conductivity of solution is improved.Yang Xiaoqing etc. has carried out System describe in United States Patent (USP) US5705689, US5789585, US6022643, US6120941 and US6352798 to application of such electron withdraw group compound in electrolyte solution, but contains the electrolyte solution and negative pole compatibility issue of electrophilic compound without reference to such.In our nearest researchs, during using carbonate-based solvent as bath composition, this electrolyte system and carbon negative pole material compatibility be not good, easily causes the irreversible deintercalation of graphite cathode.Referring to 2008《Energy magazine (J.PowerSources)》.Because this system can not form stable solid liquid interface film (SEI), cause carbon material, especially the graphite negative electrodes material can not the normal discharge and recharge in lithium ion battery.
Electrochemistry magazine (《J.Electrochem.Soc》) 1-5 pages of 143 phase in 1996 and 149 phase A1190-A1195 in 2002 indicate the theoretical energy density highest of lithium-air battery, up to 11, one of 000Wh/kg electrochemical energy storage system, has important application prospect in dual-use high energy density cells field.The main electrodes reaction occurred during lithium-air battery discharges is 2Li (s)+O2(g)→Li2O2(s) (4), 2Li (s)+O2(g)→Li2O(s)(5).If air is changed into pure oxygen, lithium-aeration cell is properly termed as.Lithium sky battery or lithium-oxygen battery are also referred to as lithium metal fuel cell.But lithium sky battery and lithium-oxygen battery are one-shot battery at present, discharge and recharge is unable to substantially, therefore above receive certain limitation in application.Mainly its discharge and recharge is restricted by following two factors：(1) Li-O keys are not easy to break at room temperature.(2) product Li2O、Li2O2For electronic body, and insoluble in organic solvent, with the space entered in guild's filling electrode of reaction, the diffusion of barrier gas, while significantly reducing active material Li in air electrode2O、Li2O2With the electrical contact of collector, charge and discharge electrical property have impact on.With in recent years can the lithium battery of discharge and recharge further develop to high-energy-density, high power density, long-life direction, in the urgent need to exploitation in some aspects, the more excellent electrolyte solution of performance.
The content of the invention
A purpose of the invention provides a kind of electrolyte solution, and this electrolyte solution has higher ionic conductivity and lithium ion transference number.And the carbon negative pole material compatibility of this electrolyte solution and battery is good, the negative material of battery remains able to normal discharge and recharge.
Another object of the present invention provides a kind of method for preparing electrolyte solution.
Still a further object of the present invention provide the electrolyte solution for prepare can be in the lithium battery of discharge and recharge application.
Still a further object of the present invention, which is provided, contains described electrolyte solution in a kind of lithium battery, the battery.
Term " compound containing electron withdraw group " in the present invention refers to " containing electron withdraw group in the compound; this make it that the central atom in the compound becomes positively charged lotus; group or atomic interaction that it can be with the having electronic in other compounds beyond the compound; cause the ionic bond in compound to be broken, so as to form new electrolyte solution.”
One aspect of the present invention provides a kind of electrolyte solution, the electrolyte solution includes organic solvent, the oxide of lithium salts or lithium, the compound containing electron withdraw group and additive, described organic solvent is carbonic ester and/or ether organic solvent, and described additive is the compound with following molecular formula：
RBC2O4Li,
R is-C in formula2O4、-F2、-C6H4O2, alkyl or fluorine-containing substitution alkyl, and concentration of the additive in the electrolyte solution is 0.005-0.1mol/l.
Preferably, concentration of the described additive in the electrolyte solution is 0.01-0.05mol/l.
Preferably, described lithium salts is LiF, LiBr, LiCl, LiI, Li2S、Li3N、Li2CO3、Li2C2O4、Li2SO4、LiBF4、LiPF6、LiAsF6、LiClO4、LiN(SO2CF3)2、LiN(SO2F)2、LiSO3CF3、LiC2O4BC2O4And LiBFa[(C6Fx(CnFmH(2n+1-m))yH(5-x-y))](4-a), a=0,1,2,3, x=0,1,2,3,4,5, y=0,1,2,3,4,5 and x+y≤5；N, m are the integer more than or equal to zero, and concentration of the lithium salts in the electrolyte solution is 0.2mol/l-2mol/l.
Preferably, the compound containing electron withdraw group is the compound (CH with following molecular formula3O)3B(No.1)、(CF3CH2O)3B(No.2)、(C3F7CH2O)3B(No.3)、[(CF3)2CHO]3B(No.4)、[(CF3)3CO]3B(No.5)、[(CF3)2C(C6H5)O]3B(No.6)、(C6H5O)3B(No.7)、(FC6H4O)3B(No.8)、(F2C6H3O)3B(No.9)、(F4C6HO)3B(No.10)、(C6F5O)3B(No.11)、(CF3C6H4O)3B(No.12)、[(CF3)2C6H3O]3B(No.13)、(C6F5)3B(No.14)、(C6F5)3OB(No.15)、(C6F4)(C6F5)O2B(No.16)、[(CF3)2C]2O2B(C6F5)(No.17)、(C6H3F)(C6H3F2)O2B(No.18)、(C6H3F)(C6H4CF3)O2B(No.19)、(C6H3F)[C6H3(CF3)2]O2B(No.20)、(C6F4)(C6H4F)O2B(No.21)、(C6F4)(C6H3F2)O2B(No.22)、(C6F4)(C6H4CF3)O2B(No.23)、(C6F4)[C6H4(CF3)2]O2B(No.24)、[(CF3)2C]2O2B(C6H5)(No.25)、[(CF3)2C]2O2B(C6H3F2)(No.26)、[(CF3)2CH]2O2B(C6H5)(No.27)、[(CF3)2CH]2O2B(C6H3F2)(No.28)、[(CF3)2CH]2O2B(C6F5)(No.29)、[(CF3SO2)(CH3)N(CH2)]2(No.30)、[(CF3SO2)2N(CH2)]2(No.31)、[(CF3SO2)2N(CH2)2]2N(CF3SO2)(No.32)、[(CF3SO2)2N(CH2)2N(CF3SO2)CH2]2(No.33)、[(CF3SO2)2N(CH2)2N(CF3SO2)(CH2)2N(CF3SO2)CH2]2(No.34)、[(CF3SO2)CH2NCH2]6(No.35)、[(CF3SO2)CH2N(CH2)3NCH2(CF3SO2)]2(No.36)、[NH(CH3C6H5SO2)(CH2)3N(CH3C6H5SO2)CH2]2(No.37)、[(CH3SO2)O(CH2)2]2N(CH3C6H5SO2)(No.38)、[(CH3SO2)O(CH2)2N(CH3C6H5SO2)CH2]2(No.39)、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2]2CH2(No.40)、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2]2N(CH3C6H5SO2)(No.41)、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2N(CH3C6H5SO2)CH2]2(No.42)、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2N(CH3C6H5SO2)CH2]2N(CH3C6H5SO2)(No.43)、[CH2NH(CH2)3NH(CH2)2]2CH2(No.44)、[CH2NH(CH2)3NH(CH2)2]2NH(No.45)、[CH2NH(CH2)3NH(CH2)2NHCH2]2(No.46)、[CH2NH(CH2)3NH(CH2)2NHCH2]2NH(No.47)、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2]2CH2(No.48)、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2]2N(CF3SO2)(No.49)、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2(CF3SO2)NCH2]2Or [CH (No.50)2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2NCH2]2N(CF3SO2)(No.51)。
Preferably, described carbonate based organic solvent is ring-type and/or linear carbonate class organic solvent.
Preferably, described cyclic carbonates organic solvent is selected from the one or more in ethylene carbonate (English abbreviation EC), propene carbonate (English abbreviation PC), gamma-butyrolacton (English abbreviation GBL) and ethylene carbonate (English abbreviation BC) organic solvent, and described linear carbonate class organic solvent is the carbonate organic solvent that straight or branched aliphatic monool that carbon number is 3-8 is synthesized with carbonic acid.
Preferably, described linear carbonate class organic solvent is selected from the one or more in dimethyl carbonate (English abbreviation DMC), diethyl carbonate (English abbreviation DEC), dipropyl carbonate (English abbreviation DPC) and methyl ethyl ester (English abbreviation EMC) organic solvent.
Preferably, described ether organic solvent is selected from tetrahydrofuran (English abbreviation THF), 2- methyltetrahydrofurans (2-Methyl-THF), 1, one or more in 3- dioxolanes (English abbreviation DOL), dimethoxymethane (English abbreviation DMM), 1,2- dimethoxies (English abbreviation DME) and diethylene glycol dimethyl ether (dimethyl carbitol) organic solvent.
Another aspect of the present invention provides a kind of method for preparing the electrolyte solution, and this method comprises the following steps：In the organic solvent that the oxide of lithium salts or lithium, the compound containing electron withdraw group and additive are added to carbonic ester and/or ethers, stirring obtains uniform mixture, the operation is carried out in the dry environment full of inert gas.
Further aspect of the present invention provide the electrolyte solution for prepare can be in the lithium battery of discharge and recharge application.
Preferably, it is described can the lithium battery of discharge and recharge be Li/ air or Li/ aeration cells.
Further aspect of the present invention provides a kind of lithium battery, including anode, negative electrode, flow collection sheet, and the battery includes the lithium battery diaphragm that described electrolyte solution soaked.
The beneficial effects of the present invention are electrolyte solution for preparing the application in chargeable lithium battery, it is preferable that it is described can the lithium battery of discharge and recharge be Li/ air or Li/ aeration cells.Due to the compound containing electron withdraw group in the electrolyte solution in the present invention, the electrolyte solution has lithium ion transference number high, electrical conductivity is high, the wide advantage of electrochemical window, so various positive electrodes can obtain good circulating effect using such electrolyte solution.In addition, due to adding the additive in a certain amount of additive, i.e., electrolyte solution of the present invention in such electrolyte solution, so being conducive to forming stable solid liquid interface film on carbon material negative pole surface.Which improve the compatibility of the compatibility of such electrolyte solution and carbon negative pole material, particularly graphite-like electrode material so that the reversible removal lithium embedded of graphite cathode can be normally carried out.
Beneficial effects of the present invention are also resided in：Lithium-air battery can be additionally used in based on the electrolyte solution containing electron withdraw group compound, instant invention overcomes the defect that the lithium/air having been generally acknowledged that or lithium/aeration cell can not be used in charge and discharge battery.It has been generally acknowledged that lithium/air or lithium/aeration cell be although theoretical energy density highest battery, but be due to that (1) Li-O keys are not easy to break at room temperature, (2) product Li2O、Li2O2For electronic body, and insoluble in organic solvent, so can not be used in the battery of discharge and recharge.But the researcher of the present invention has found：In the electrophilic compound or nitrogenous electrophilic compound of boracic, due to the electron-withdrawing power of side group, positive charge is carried on the boron or nitrogen-atoms in electrophilic compound, with electrophilic ability, in the presence of the positive electricity subcenter centered on B or N atoms, it can directly and Li2O or Li2O2In O interaction, promote Li2O or Li2O2The fracture of middle Li-O keys, therefore form new electrolyte solution.Although Li2O or Li2O2In the organic solvent that carbonates or ethers can not be dissolved in, but after it with the addition of the electrophilic organic compound of boracic or nitrogenous electrophilic organic compound, Li2O or Li2O2Solubility greatly increase, obtained organic electrolyte solution has higher room temperature and low-temperature ion electrical conductivity.Study and find simultaneously, the organic electrolyte solution of compound containing electrophilic, the oxide of lithium based on the present invention, lithium ion transference number is generally higher than 0.6, is significantly higher than existing organic electrolyte solution.Therefore the electrolyte solution of the present invention can also be in lithium-air battery or lithium-aeration cell as electrolyte solution application, while so that lithium-air battery or lithium-aeration cell have the property of discharge and recharge.Using electrolyte solution proposed by the present invention, high with lithium ion conductivity, lithium ion transference number is high, and security is good, electrochemical stability waits well remarkable advantage, can effectively improve using life-span of chargeable lithium battery of existing electrolyte, security, charge/discharge rate property.Because electrolyte solution in the inventive solutions is no longer completely dependent on LiPF6, manufacturing cost is also greatly reduced.Small with polarizing when being applied using the electrolyte solution of the present invention in lithium-air battery or lithium-aeration cell, capacity is high, the remarkable advantage such as reversible discharge and recharge of energy.
Brief description of the drawings
Hereinafter, embodiments of the invention are described in detail with reference to accompanying drawing, wherein：
Fig. 1 represents the schematic diagram of lithium battery of the present invention.Wherein：1 it is anode tap, 2 be stainless steel sealing nut (and negative electrode connection), 3 be polytetrafluoroethylene (PTFE) nut, 4 be stainless steel steel column, 5 be polytetrafluoroethyllining lining, 6 be stainless steel cylinder (and anode connection), 7,8 be lithium piece (negative electrode), 9 be barrier film of the dipping containing electron withdraw group compound electrolyte solution, 10 be anode, 11 be copper foil current collector, 12 is cathode leg.
Fig. 2 represents all charging and discharging curve contrasts of the head of embodiment 1, wherein figure a represents all charging and discharging curves of head for being prepared from battery as electrolyte solution using organic solvent, the oxide of lithium salts or lithium, the compound for containing electron withdraw group, and figure b represents all charging and discharging curves of head for being prepared from battery as electrolyte solution using organic solvent, the oxide of lithium salts or lithium, the compound for containing electron withdraw group and additive.
Fig. 3 represents the electrochemical window of according to embodiments of the present invention 1 organic bath prepared.
Fig. 4 represents that first five week of the chargeable lithium battery prepared by embodiment 1 is charged and discharged curve, and interior list of illustrations therein shows the enlarged drawing of top discharge curve.
Embodiment
Component A in the examples below represents lithium salts, and component B represents the compound containing electron withdraw group, and component C represents additive, and component D represents carbonates and/or ether organic solvent.
Embodiment 1
1.3g LiF are weighed to be placed in beaker as component B as component A and 25.6g TPFPB, 25 milliliters of propylene carbonates (PC) are added after drying and are used as component D as component D and 25 milliliters of dimethyl carbonates (DMC), then by magnetic stirrer 1 hour, as transparent electrolyte solution.0.485 gram of LiBOB is weighed as component C, in the electrolyte solution prepared before addition, by magnetic stirrer 1 hour.Prepare stand-by.Aforesaid operations are operated in the environment full of argon gas.
The electrolyte is added drop-wise into two end electrodes to be in the glass conductance cell of platinum electrode, its electrical conductivity is measured in the range of 5Hz-13MHz using HP4192 impedance spectrometers, 25 DEG C of electrical conductivity are measured for 3.2ms/cm.It is combined with GDW6005 types high-low temperature test chamber, the electrical conductivity under sample different temperatures is measured.CHI627C electrochemical workstations are used, with the method for cyclic voltammetric, its electrochemical window are measured.It is copper sheet with working electrode, to electrode, the glass three-electrode electro Chemical cell that reference electrode is metal lithium sheet, it is 0.1mV/s to sweep speed, and measurement range is 0-3V vs Li/Li+.What Fig. 3 was represented is the electrochemical window of the organic electrolyte solution prepared according to the above method.As can be seen from the figure the electrolyte solution containing additive prepared as stated above peak point current (figure b in cyclic voltammetry：0.008mA) it is significantly less than electrolyte solution (the figure a without additive：1.0mA), illustrate that electrochemical stability is significantly improved after addition additive.
Above-mentioned electrolyte solution is directly used in an experiment lithium battery and measures its matching with electrode.
The assembling for testing lithium battery is as follows：
By MCMB (15 μm of granularity) and the N of Kynoar (PVDF), N dimethyl pyrrolidones (NMP) solution mixing system is into homogeneous composite mortar, and then even application is on the Copper Foil (20 μm of thickness) as collector.2-20 μm of gained film thickness, is dried at 160 DEG C, is compressed under 1MPa pressure, continues to dry 12 hours at 160 DEG C.In pole piece after drying, MCMB accounts for the 94wt% of total coating, and Kynoar (PVDF) accounts for 6wt%.Then gained pole piece is cut into area for 1cm2Disk is used as anode.
Dried pole piece is moved into argon gas glove box, PVDF-HFP perforated membranes are put between a cathode and an anode, the electrolyte solution being prepared from using above method is added dropwise, is submerged anode pole piece, cathode sheet and perforated membrane, is assembled into the experimental cell shown in accompanying drawing 1.Experimental cell carries out charge and discharge cycles test on micro-processor controlled auto charge and discharge instrument.Current density 0.1mA/cm2, charge cutoff voltage 2.5V, discharge cut-off voltage 0V, temperature are 25 DEG C.The battery capacity measured is 94% of the battery capacity according to active material calculated mass.First week charging and discharging curve is referring to Fig. 2, and first five week charging and discharging curve is referring to Fig. 4, and from the figure a in accompanying drawing 2 it can be seen that not adding additive, the voltage of battery maintains 0.8V, is PC embedded caused altogether, it is impossible to carry out normal discharge and recharge；Figure b is the charging and discharging curve that battery is prepared using electrolyte solution of the present invention, and as can be seen from the figure battery can normally discharge and recharge.From Fig. 4 it can also be seen that first five week Capacity fading of battery is seldom.Therefore it is visible it is of the invention containing electrolyte of the present invention can discharge and recharge the electrolyte of battery and the compatibility of GND increased, from related data referring to subordinate list 1.
1.3g LiF are weighed to be placed in beaker as component B as component A and 25.6g TPFPB, 25 milliliters of vinyl carbonates (EC) are added after drying and are used as component D as component D and 25 milliliters of diethyl carbonates (DEC), then by magnetic stirrer 1 hour, as transparent electrolyte solution.0.388 gram of LiBOB is weighed as component C, in the electrolyte solution prepared before addition, by magnetic stirrer 1 hour.Prepare stand-by.Aforesaid operations are operated in the environment full of argon gas.
The electrolyte is added drop-wise into two end electrodes to be in the glass conductance cell of platinum electrode, its electrical conductivity is measured in the range of 5Hz-13MHz using HP4192 impedance spectrometers, 25 DEG C of electrical conductivity are measured for 3.1ms/cm.It is combined with GDW6005 types high-low temperature test chamber, the electrical conductivity under sample different temperatures is measured.CHI627C electrochemical workstations are used, with the method for cyclic voltammetric, its electrochemical window are measured.It is copper sheet with working electrode, to electrode, the glass three-electrode electro Chemical cell that reference electrode is metal lithium sheet, it is 0.1mV/s to sweep speed, and measurement range is 0-3V vs Li/Li+.What Fig. 3 was represented is the electrochemical window of the organic electrolyte solution prepared according to the above method.
The assembling of experiment lithium battery, test mode are same as Example 1.The composition and test data of the present embodiment are referring to table 1.
1.3g LiF are weighed to be placed in beaker as component B as component A and 25.6g TPFPB, 25 milliliters of propylene carbonates (PC) are added after drying and are used as component D as component D and 25 milliliters of vinyl carbonates (EC), then by magnetic stirrer 1 hour, as transparent electrolyte solution.0.243 gram of LiBOB is weighed as component C, in the electrolyte solution prepared before addition, by magnetic stirrer 1 hour.Prepare stand-by.Aforesaid operations are operated in the environment full of argon gas.
The electrolyte is added drop-wise into two end electrodes to be in the glass conductance cell of platinum electrode, its electrical conductivity is measured in the range of 5Hz-13MHz using HP4192 impedance spectrometers, 25 DEG C of electrical conductivity are measured for 3.1ms/cm.It is combined with GDW6005 types high-low temperature test chamber, the electrical conductivity under sample different temperatures is measured.CHI627C electrochemical workstations are used, with the method for cyclic voltammetric, its electrochemical window are measured.It is copper sheet with working electrode, to electrode, the glass three-electrode electro Chemical cell that reference electrode is metal lithium sheet, it is 0.1mV/s to sweep speed, and measurement range is 0-3V vs Li/Li+。
This above-mentioned electrolyte solution is directly used in an experiment lithium battery and measures its compatibility with electrode.The assembling of experiment lithium battery, test mode are same as Example 1.The composition and test data of the present embodiment are referring to table 1.
Embodiment 4
1.3g LiF are weighed to be placed in beaker as component B as component A and 25.6g TPFPB, 25 milliliters of vinyl carbonates (EC) are added after drying and are used as component D as component D and 25 milliliters of methyl ethyl carbonates (EMC), then by magnetic stirrer 1 hour, as transparent electrolyte solution.0.097 gram of LiBOB is weighed as component C, in the electrolyte solution prepared before addition, by magnetic stirrer 1 hour.Prepare stand-by.Aforesaid operations are operated in the environment full of argon gas.
The electrolyte is added drop-wise into two end electrodes to be in the glass conductance cell of platinum electrode, its electrical conductivity is measured in the range of 5Hz-13MHz using HP4192 impedance spectrometers, 25 DEG C of electrical conductivity are measured for 3.0ms/cm.It is combined with GDW6005 types high-low temperature test chamber, the electrical conductivity under sample different temperatures is measured.CHI627C electrochemical workstations are used, with the method for cyclic voltammetric, its electrochemical window are measured.It is copper sheet with working electrode, to electrode, the glass three-electrode electro Chemical cell that reference electrode is metal lithium sheet, it is 0.1mV/s to sweep speed, and measurement range is 0-3V vs Li/Li+。
This be directly used in containing electron withdraw group compound electrolyte in an experiment lithium battery is measured into its compatibility with electrode.The assembling of experiment lithium battery, test mode are same as Example 1.The composition and test data of the present embodiment are referring to table 1.
Embodiment 5
Weigh 1.3g LiF as component A and 25.6g TPFPB as component B in beaker, 13.3 milliliters of propylene carbonates (PC) are added after drying and are used as component D as component D, 13.3 milliliters of dimethyl carbonates (DMC) and 13.3 milliliters of vinyl carbonates (EC), then by magnetic stirrer 1 hour, as transparent electrolyte solution.0.049 gram of LiBOB is weighed as component C, in the electrolyte solution prepared before addition, by magnetic stirrer 1 hour.Prepare stand-by.Aforesaid operations are operated in the environment full of argon gas.
The electrolyte is added drop-wise into two end electrodes to be in the glass conductance cell of platinum electrode, its electrical conductivity is measured in the range of 5Hz-13MHz using HP4192 impedance spectrometers, 25 DEG C of electrical conductivity are measured for 3.0ms/cm.It is combined with GDW6005 types high-low temperature test chamber, the electrical conductivity under sample different temperatures is measured.CHI627C electrochemical workstations are used, with the method for cyclic voltammetric, its electrochemical window are measured.It is copper sheet with working electrode, to electrode, the glass three-electrode electro Chemical cell that reference electrode is metal lithium sheet, it is 0.1mV/s to sweep speed, and measurement range is 0-3V vs Li/Li+。
This be directly used in containing above-mentioned electrolyte solution in an experiment lithium battery is measured into its compatibility with electrode.The assembling of experiment lithium battery, test mode are same as Example 1.The composition and test data of the present embodiment are referring to table 1.
Embodiment 6-10：Be the same as Example 1, simply changes component A lithium salts LiF into LiBF that concentration is 1M3(C6F5), D solvents composition also has change.The composition and test data of the present embodiment are referring to table 1.
Embodiment 11-15：Be the same as Example 1, simply changes component A lithium salts LiF into the LiBF of various concentrations2(C6F5)2.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 16-20：Be the same as Example 1, changes component A lithium salts LiF into Li that concentration is 0.2M2O2.The composition and test data of the present embodiment are referring to table 1.
Embodiment 21-23：Be the same as Example 1, simply changes component A lithium salts LiF into the LiCl of same concentration, contains electron withdraw group compound 1,2,3 by what component B electron withdraw groups compound 14 changed same concentration into successively.The composition and test data of the present embodiment are referring to table 1.
Embodiment 24-26：Be the same as Example 1, simply changes component A lithium salts LiF into the LiBr of same concentration, contains electron withdraw group compound 4,5,6 by what component B contained that electron withdraw group compound 14 changes same concentration into successively.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 27-29：Be the same as Example 24, simply changes component A lithium salts LiBr into the LiI of same concentration, contains electron withdraw group compound 7,8,9 by what component B contained that electron withdraw group compound 14 changes same concentration into successively.The composition and test data of the present embodiment are referring to table 1.
Embodiment 30-32：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration2O；By component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 10,11,12；Component C additives LiBOB is changed into the LiMOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 33-35：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration2S, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 13,15,16.The composition and test data of the present embodiment are referring to table 1.
Embodiment 36-38：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration3N, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 17,18,19.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 39-41：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration2CO3, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 20,21,22.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 42-44：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration2C2O4；By component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 23,24,25；Component C additives LiBOB is changed into the LiMOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 45-47：Be the same as Example 1, simply changes component A lithium salts LiF into the Li of same concentration2SO4, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 26,27,28；Component C additives LiBOB is changed into the C of same concentrations6H4O2BC2O4Li additives.The composition and test data of the present embodiment are referring to table 1.
Embodiment 48-50：Be the same as Example 1, simply changes component A lithium salts LiF into the LiBF of same concentration4, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 29,30,31.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 51-53：Be the same as Example 1, simply changes component A lithium salts LiF into the LiPF of same concentration6, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 32,33,34.Component C additives LiBOB is changed into the LiDFOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 54-56：Be the same as Example 1, simply changes component A lithium salts LiF into the LiTFSI of same concentration；By component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 35,36,37；Component C additives LiBOB is changed into the LiMOB additives of same concentrations.The composition and test data of the present embodiment are referring to table 1.
Embodiment 57-59：Be the same as Example 1, simply changes component A lithium salts LiF into the LiFSI of same concentration, contains electron withdraw group compound 38,39,40 by what component B contained that electron withdraw group compound 14 changes same concentration into successively；Component C additives LiBOB is changed into the CH of same concentrations3C2F5BC2O4The composition and test data of Li additive the present embodiment are referring to table 1.
Embodiment 60-62：Be the same as Example 11, simply changes component A lithium salts LiF into the LiBOB of same concentration, contains electron withdraw group compound 41,42,43 by what component B contained that electron withdraw group compound 14 changes same concentration into successively.The composition and test data of the present embodiment are referring to table 1.
Embodiment 63-65：Be the same as Example 6, simply changes component A lithium salts LiF into the LiPF of same concentration6, by component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 44,45,46.The composition and test data of the present embodiment are referring to table 1.
Embodiment 66-68：Be the same as Example 1, simply changes component A lithium salts LiF into the LiAsF of same concentration6；By component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 47,48,49.The composition and test data of the present embodiment are referring to table 1.
Embodiment 69-70：Be the same as Example 1, simply changes component A lithium salts LiF into the LiSO of same concentration3CF3；By component B contain electron withdraw group compound 14 change into successively same concentration contain electron withdraw group compound 50,51.The composition and test data of the present embodiment are referring to table 1.
Embodiment 71-74：The composition and test data of the present embodiment are referring to table 1.
Component of the table 1 containing electron withdraw group compound electrolyte solution and electrochemical properties
Claims (10)
1. a kind of electrolyte solution, the electrolyte solution includes organic solvent, the oxide of lithium salts or lithium, the compound containing electron withdraw group and additive, described organic solvent is carbonic ester and/or ether organic solvent, and described additive is the compound with following molecular formula：
RBC2O4Li,
R is-C in formula2O4、-F2、-C6H4O2, alkyl or fluorine-containing substitution alkyl, and concentration of the additive in the electrolyte solution is 0.005-0.1mol/l, preferably 0.01-0.05mol/l.
2. electrolyte solution according to claim 1, wherein described lithium salts is LiF, LiBr, LiCl, LiI, Li2S、Li3N、Li2CO3、Li2C2O4、Li2SO4、LiBF4、LiPF6、LiAsF6、LiClO4、LiN(SO2CF3)2、LiN(SO2F)2、LiSO3CF3、LiC2O4BC2O4Or LiBFa[(C6Fx(CnFmH(2n+1-m))yH(5-x-y))](4-a), a=0,1,2,3, x=0,1,2,3,4,5, y=0,1,2,3,4,5 and x+y≤5；N, m are the integer more than or equal to zero, and concentration of the lithium salts in the electrolyte solution is 0.2mol/l-2mol/l.
3. electrolyte solution according to claim 1 or 2, wherein the compound containing electron withdraw group is the compound (CH with following molecular formula3O)3B、(CF3CH2O)3B、(C3F7CH2O)3B、[(CF3)2CHO]3B、[(CF3)3CO]3B、[(CF3)2C(C6H5)O]3B、(C6H5O)3B、(FC6H4O)3B、(F2C6H3O)3B、(F4C6HO)3B、(C6F5O)3B、(CF3C6H4O)3B、[(CF3)2C6H3O]3B、(C6F5)3B、(C6F5)3OB、(C6F4)(C6F5)O2B、[(CF3)2C]2O2B(C6F5)、(C6H3F)(C6H3F2)O2B、(C6H3F)(C6H4CF3)O2B、(C6H3F)[C6H3(CF3)2]O2B、(C6F4)(C6H4F)O2B、(C6F4)(C6H3F2)O2B、(C6F4)(C6H4CF3)O2B、(C6F4)[C6H4(CF3)2]O2B、[(CF3)2C]2O2B(C6H5)、[(CF3)2C]2O2B(C6H3F2)、[(CF3)2CH]2O2B(C6H5)、[(CF3)2CH]2O2B(C6H3F2)、[(CF3)2CH]2O2B(C6F5)、[(CF3SO2)(CH3)N(CH2)]2、[(CF3SO2)2N(CH2)]2、[(CF3SO2)2N(CH2)2]2N(CF3SO2)、[(CF3SO2)2N(CH2)2N(CF3SO2)CH2]2、[(CF3SO2)2N(CH2)2N(CF3SO2)(CH2)2N(CF3SO2)CH2]2、[(CF3SO2)CH2NCH2]6、[(CF3SO2)CH2N(CH2)3NCH2(CF3SO2)]2、[NH(CH3C6H5SO2)(CH2)3N(CH3C6H5SO2)CH2]2、[(CH3SO2)O(CH2)2]2N(CH3C6H5SO2)、[(CH3SO2)O(CH2)2N(CH3C6H5SO2)CH2]2、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2]2CH2、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2]2N(CH3C6H5SO2)、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2N(CH3C6H5SO2)CH2]2、[CH2(CH3C6H5SO2)N(CH2)3(CH3C6H5SO2)N(CH2)2N(CH3C6H5SO2)CH2]2N(CH3C6H5SO2)、[CH2NH(CH2)3NH(CH2)2]2CH2、[CH2NH(CH2)3NH(CH2)2]2NH、[CH2NH(CH2)3NH(CH2)2NHCH2]2、[CH2NH(CH2)3NH(CH2)2NHCH2]2NH、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2]2CH2、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2]2N(CF3SO2)、[CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2(CF3SO2)NCH2]2Or [CH2(CF3SO2)N(CH2)3(CF3SO2)N(CH2)2NCH2]2N(CF3SO2)。
4. the electrolyte solution according to any one of claim 1-3, wherein described carbonate based organic solvent is ring-type and/or linear carbonate class organic solvent.
5. electrolyte solution according to claim 4, one or more of the wherein described cyclic carbonates organic solvent in ethylene carbonate, propene carbonate, gamma-butyrolacton chain and ethylene carbonate organic solvent, and described linear carbonate class organic solvent is the carbonate organic solvent that straight or branched aliphatic monool that carbon number is 3-8 is synthesized with carbonic acid.
6. the electrolyte solution according to claim 4 or 5, wherein one or more of the described linear carbonate class organic solvent in dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl ester organic solvent.
7. the electrolyte solution according to any one of claim 1-6, wherein described ether organic solvent is selected from tetrahydrofuran, 2- methyltetrahydrofurans, 1, one or more in 3- dioxolanes, dimethoxymethane, 1,2- dimethoxies and diethylene glycol dimethyl ether organic solvent.
8. a kind of method for preparing electrolyte solution any one of claim 1-7, this method comprises the following steps：In the organic solvent that the oxide of lithium salts or lithium, the compound containing electron withdraw group and additive are added to carbonic ester and/or ethers, stirring obtains uniform mixture, the operation is carried out in the dry environment full of inert gas.
9. electrolyte solution any one of claim 1-7 for prepare can be in the lithium battery of discharge and recharge application, it is preferable that it is described can the lithium battery of discharge and recharge be Li/ air or Li/ aeration cells.
10. a kind of lithium battery, including anode, negative electrode, flow collection sheet, it is characterised in that the battery also includes the lithium battery diaphragm soaked with the electrolyte solution any one of claim 1-7.
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