CN101599558B - Phase variation electrolyte as well as preparation method and application thereof - Google Patents
Phase variation electrolyte as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a phase variation lithium ion electrolyte comprising the following components of lithium salts and organic compounds containing acid amide functional groups. The invention also provides a preparation method of the electrolyte, comprising the following steps: a. mixing the lithium salts and the organic compounds containing acid amide functional groups; b. heating the mixture and melting the mixture to obtain transparency liquid; and c. cooling the transparency liquid to obtain the electrolyte, wherein the steps a, b and c are operated in dry environments. The phase variation lithium ion electrolyte is applied to chargeable and dischargeable lithium batteries. In addition, the invention also provides a chargeable and dischargeable lithium battery comprising the electrolyte. The electrolyte has lower electrical conductivity and higher thermal and chemical stability when being a solid under the condition that the temperature is lower than a phase variation temperature and has higher electrical conductivity when being liquid under the condition that the temperature is higher than the phase variation temperature.
Description
Technical field
The present invention relates to a kind of phase variation electrolyte and this electrolyte preparation method and application, belong to the material technology field.
Background technology
Because numerous natural calamities makes us have higher requirement to the storing mode of the energy, the extensive snow disaster that takes place in China south at the beginning of 2008 has caused large-scale power supply shortage; And the extensive earthquake that take place in China Sichuan in May, 2008, if the destruction of causing electrical network when the electrical network cisco unity malfunction, also has the work of decentralized power supply system, and the power supply that will help under the emergency condition provides.Therefore except high-energy-density, high power density lithium ion battery, the research of long-life accumulation energy type lithium ion battery also causes concern gradually.Consider that from the clean energy resource angle current two to enjoy the new forms of energy of high praise be solar energy and wind energy, but their shortcoming be energy output all over time and fluctuation changes; " there is wind just to have; not have wind just not have " exactly, " have the sun that electricity is just arranged, do not have the sun just not have ".So solar energy and wind power generation system that can continuous firing need be equipped with " safe, long-lived, efficient, inexpensive energy-storage battery ".The lithium-ion energy storage battery conduct is one of energy-storage battery the most efficiently, and its storage battery has up to the conversion ratio that discharges and recharges more than 90%, and this is than transformation efficiency 80% height at the energy storing and electricity generating station of drawing water, and is also taller than the generating efficiency of hydrogen fuel cell 80%.Also immature at present as for the hydrogen fuel cell technology, and its cost of electricity-generating also will be very expensive.So lithium-ion energy storage battery is a direction that merits our study.
As the electrolyte that in lithium-ion energy storage battery, uses; Except the character that will satisfy general lithium ion battery electrolyte; Also need and be suitable for the characteristics that energy-storage battery uses: 1. in the process of energy storage; Electrolyte has lower conductivity, makes that the self-discharge rate of energy-storage battery is lower, and energy loss is little in the process of energy storage; Electrolyte should have higher conductivity in work, makes that battery can operate as normal; 2. electrolyte chemistry and Heat stability is good make the energy-storage battery stable performance can adapt to different environmental conditions.3. cheap, be easy to preparation, be suitable for extensive use.
At present, the liquid electrolyte that contains organic solvent used in the commercial Li-ion batteries is mainly the lithium hexafluoro phosphate that contains 1 mol, and volume ratio is 1: 1 vinyl carbonate and a diethyl carbonate.In " electrochemistry magazine (J.Electrochem.Soc) " calendar year 2001,148 phases, 1100 pages with " chemistry comment (Chemical Review) " 2004,104 phases, 4303 pages-4417 pages disclose with LiPF
6Electrolyte as lithium salts exists two remarkable weak points: (1) thermal instability, and its reason is: in solution, anion PF
6 -There is balance a: LiPF
6→ LiF+PF
5(I), and LiF belongs to strong Lewis acid, it and PF
5Thereby all tend to cause balance to be carried out to the right with organic solvent reaction; (2) the P-F key is very responsive to water simultaneously, even the water of trace also can cause following reaction: LiPF
6+ H
2O → POF
3+ LiF+2HF (II), PF
5+ H
2O → POF
3+ 2HF (III), the HF that formula (II) and formula (III) produce will promote the dissolving of positive electrode, and its lithium storage content is decayed gradually.
For present lithium-ion energy storage battery, use the liquid organic electrolyte simultaneously, in the process of storage power, have certain self-discharge rate, cause energy loss easily.
Summary of the invention
One object of the present invention is to provide a kind of phase variation electrolyte, it than present liquid electrolyte safer and be more suitable for being applied in the lithium-ion energy storage battery.
Another object of the present invention provides this electrolyte preparation method.
A purpose more of the present invention provides this electrolytical purposes.
A purpose more of the present invention provides a kind of battery, and it contains electrolyte of the present invention.
Term among the present invention " phase variation electrolyte " refers to the electrolyte that under a certain temperature, has phase transition property, and this electrolyte has great raising from the solid-state liquid state while electrolytic conductivity that becomes under this temperature, and this temperature is called " phase transition temperature ".
One aspect of the present invention provides a kind of lithium-ion electrolyte that changes mutually, and this electrolyte comprises following composition: the organic compound of lithium salts and amide containing functional group, described lithium salts is selected from LiBO
2(C
6H
4)
2, LiBO
2(C
6H
3F)
2, LiBO
2(C
6H
4F
4)
2, LiBO
2(C
10H
16)
2, LiBO
2(C
12H
20)
2, LiB (C
7H
10O
3)
2, LiB (C
2O
4)
2, LiB (C
3O
4)
2, LiB (C
6F
12O
2)
2, LiB (C
8H
12O
3)
2, LiB (C
7H
8O
3Cl
2)
2, LiB (C
7H
7O
3Cl
3)
2, LiBO
2(C
5H
3N)
2, LiPO
2(C
6H
4)
3, LiPO
2(C
7H
6)
3, LiPO
2(C
6H
3F)
3, LiPF
3(CF
2CF
3)
3, LiN (SO
2C
4F
9) (SO
2CF
3) and LiN (SO
2C
6H
4NO
2)
2In one or more.LiBO
2(C
6H
4)
2English abbreviate LBBB, LiBO as
2(C
6H
3F)
2English abbreviates 3-FLBBB, LiBO as
2(C
6H
4F
4)
2English abbreviates TFLBBB, LiBO as
2(C
10H
16)
2English abbreviates LBNB, LiBO as
2(C
12H
20)
2English abbreviates LBBPB, LiB (C as
7H
10O
3)
2English abbreviates LBSB, LiB (C as
2O
4)
2English abbreviates LBOB, LiB (C as
3O
4)
2English abbreviates LBMB, LiB (C as
6F
12O
2)
2English abbreviates LBPFPB, LiB (C as
8H
12O
3)
2English abbreviates 3-MLBSB, LiB (C as
7H
8O
3Cl
2)
2English abbreviates DCLBSB, LiB (C as
7H
7O
3Cl
3)
2English abbreviates TCLBSB, LiBO as
2(C
5H
3N)
2English abbreviates LBPB, LiPO as
2(C
6H
4)
3English abbreviates LTBP, LiPO as
2(C
7H
6)
3English abbreviates 4-MLTBP, LiPO as
2(C
6H
3F)
3English abbreviates 3-FLTBP, LiPF as
3(CF
2CF
3)
3English abbreviates LFAP, LiN (SO as
2C
4F
9) (SO
2CF
3) English abbreviates LiTNSI, LiN (SO as
2C
6H
4NO
2)
2English abbreviates LiNPSI as.
Preferably, this electrolyte also comprises inorganic oxide and polymer.
Preferably, wherein this electrolytical phase transition point temperature is 25-90 ℃.
Preferably, this electrolytical phase transition point temperature is 45-65 ℃.
More preferably, this electrolytical phase transition point temperature is 45-55 ℃.
Preferably, the organic compound of said amide containing functional group is selected from following formula: compound
In one or more, substituent R
1, R
2, R
3, R
4, R
5Be selected from H, methyl, ethyl, phenyl or trifluoromethyl independently of each other.
Preferably, the organic compound of said amide containing functional group is selected from one or more in dimethyl formamide, urea, acetamide, trifluoroacetamide dimethyl urea, tetramethylurea, AAA, N-methylacetamide, trifluoroacetyl aniline, caprolactam and the pyrrolidones.
Preferably, described inorganic oxide is selected from SiO
2, Al
2O
3, TiO
2With in the MgO particle one or more.
Sphere or length that preferred particle is particle diameter 10-100nm are the aciculiform of 10-100nm.
More preferably, the quality of said inorganic oxide said electrolyte gross mass 50% in.
Preferably, wherein said polymer is selected from one or more in polyacrylonitrile, PEO, Kynoar, polyethylene and the polypropylene.
Preferably, the quality of described polymer said electrolyte gross mass 50% in.
Another aspect of the present invention also provides a kind of preparation electrolytical method, and this method may further comprise the steps:
A. the organic compound with lithium salts and amide containing functional group mixes;
B. add hot mixt, obtain transparency liquid;
C. with described transparency liquid cooling, obtain described electrolyte, operating in the dry environment of step a, b and c carried out.This electrolytical being formulated in the preferred glove box of the dry environment that is full of argon gas is carried out.
Preferably, in described step a with organic compound, inorganic oxide and the said mixed with polymers of described lithium salts, amide containing functional group.
One side more of the present invention provides the described application of lithium-ion electrolyte in chargeable lithium battery that change mutually.
One side more of the present invention also provides a kind of lithium battery that discharges and recharges, and contains described electrolyte in this battery.
It is safer and be more suitable for being applied to the phase variation electrolyte in the lithium-ion energy storage battery to the invention provides the present liquid electrolyte of a kind of ratio.This phase variation electrolyte makes after being mixed by organic compound and lithium salts, and can add inorganic additive and polymer improves performance, and the electrolyte after making is a solid when temperature is lower than phase transition temperature, and conductivity is 10
-5-10
-4MS/cm, self-discharge rate is low at this moment to use the lithium battery of this electrolyte assembling; This electrolyte is liquid when temperature is higher than phase transition temperature, and conductivity is 0.1-10mS/cm, and the battery of using this electrolyte assembling can operate as normal.
Because phase variation electrolyte of the present invention is a solid when temperature is lower than phase transition temperature, self-discharge rate is low, so have good chemistry and electrochemical stability.This phase variation electrolyte is a liquid when temperature is higher than phase transition temperature in addition, has certain viscosity and flowability, and its ionic conductivity is than higher; Owing to have flowability; Can be filled into the micropore of barrier film, between the space of barrier film and electrode interface and the powder particle of electrode active material, make between barrier film and electrode, the active material to contact with electrolyte is complete; Thereby reduced the impedance and the internal resistance of cell of electrolyte and electrode interface, helped discharging and recharging.Selected organic compound is not only nonflammable simultaneously, and has anti-flammability.The lithium addition compound that forms is not volatile.And such preparation of electrolyte technology is simple, can with present lithium ion battery, contain the capacitor of organic bath, transducer and electrochromic device compatibility are particularly suitable for lithium-ion energy storage battery.
Beneficial effect of the present invention is: the present invention has overcome in the general lithium ion battery thermal energy storage process shortcoming of unstable and self discharge loss of energy.What general lithium ion battery used is to contain LiPF
6The liquid organic electrolyte solution, this electrolyte is unstable on the one hand, decomposes easily; On the other hand, use battery self-discharge rate in thermal energy storage process of this electrolyte high, loss of energy is many.And researcher of the present invention finds; Phase variation electrolyte has at 25-90 ℃, and preferred 45-65 ℃, more preferably 45-55 ℃ transformation temperature; Below the phase transformation temperature points is solid; Conductivity is lower, and has higher calorifics and chemical stability, uses the battery of its assembling at room temperature to have lower self-discharge rate; This phase variation electrolyte is a liquid when temperature is higher than phase transition temperature, and conductivity is higher, and the battery that uses its to assemble at high temperature can operate as normal.According to this character, use the battery of phase variation electrolyte assembling, satisfied storage power safety, requirement that energy loss is low, be that a kind of very promising lithium-ion energy storage battery is used electrolyte therefore.
Can find out that from above description electrolyte solution of the present invention can use as electrolyte solution in the energy storage lithium ion battery.Because phase variation electrolyte proposed by the invention has transformation temperature, very big through the transformation temperature conductivity variations, so use this electrolytical energy storage lithium ion battery internal resistance very big at normal temperatures, can not work; And when high temperature, use this electrolytical energy storage lithium ion battery can operate as normal.So both solved the problem of energy storage lithium ion battery self discharge, obtained again can operate as normal the energy storage lithium ion battery.Simultaneously because the electrolyte solution in technical scheme of the present invention relies on LiPF no longer fully
6, manufacturing cost also descends greatly.
Description of drawings
What Fig. 1 represented is the temperature variant relation of electrolytic conductivity of embodiment 1.
What Fig. 2 represented is the electrochemical window by the organic bath of the embodiment of the invention 1 preparation.
Fig. 3 representes is by the chargeable lithium battery of the embodiment 1 preparation charging and discharging curve 60 ℃ the time.
Fig. 4 representes to use the sketch map of phase variation electrolyte simulated battery of the present invention, wherein: barrier film, 10-active material of positive electrode, 11-Copper Foil, the 12-cathode leg of 1-anode tap, 2-stainless steel sealing nut, 3-polytetrafluoroethylene nut, 4-stainless steel steel column, 5-polytetrafluoroethyllining lining, 6-stainless steel cylinder, 7-aluminium foil, 8-active material of cathode, 9-dipping phase variation electrolyte.
Embodiment
Following examples are used to explain the present invention, and are not used in restriction the present invention.The structural formula of lithium salts is following among the present invention:
LiBO
2(C
6H
4)
2 LiBO
2(C
6H
3F)
2 LiBO
2(C
6H
4F
4)
2 ?LiBO
2(C
10H
16)
2
LiBO
2(C
12H
20)
2 LiB(C
7H
10O
3)
2 ?LiB(C
2O
4)
2 ?LiB(C
3O
4)
2
LiB(C
6F
12O
2)
2 LiB(C
8H
12O
3)
2 LiB(C
7H
8O
3Cl
2)
2 LiB(C
7H
7O
3Cl
3)
2
LiBO
2(C
5H
3N)
2 LiPO
2(C
6H
4)
3 ?LiPO
2(C
7H
6)
3 ?LiPO
2(C
6H
3F)
3
LiN(SO
2C
6H
4NO
2)
2
Embodiment 1
With putting into glove box after dry beaker LBOB and the acetamide drying; The content of water is less than 1ppm, and weighing 20g LBOB and 80g acetamide slowly are heated to 80 ℃ in beaker; Make it fusing; Through magnetic stirrer 1-5 hour, become transparent liquid then, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with thermogravimetric analyzer NETSCHSTA 449C, fusing point is 50 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 5 * 10
-5Ms/cm, conductivity has reached 4.1mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.3V, to occur oxidation peak.
This phase variation electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.
The assembling of experiment lithium battery is following:
With LiFePO
4Dimethyl formamide (DMF) solution of powder, carbon black (granularity 1000nm), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF Copolymer) mixes; Process the composite mortar of homogeneous at normal temperatures and pressures; Slurry evenly is coated on the aluminium foil (thickness 15um) as collector; 160 ℃ of oven dry down, the gained film thickness is at 5-40um, at 1MPa * 1cm then
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%.Then the gained pole piece being cut into area is 1cm
2Disk is as negative electrode.
With MCMB, granularity 15um becomes the composite mortar of homogeneous with dimethyl formamide (DMF) solution mixing system of Kynoar (PVDF), evenly be coated in then on the Copper Foil (thickness 20um) as collector.Gained film thickness 2-20um is 160 ℃ of oven dry down, 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, MCMB accounts for the 94wt% that always is coated with application, and Kynoar (PVDF) accounts for 6wt%.Then the gained pole piece being cut into area is 1cm
2Disk is as anode.
Dried pole piece is moved in the argon gas glove box, with the PVDF-HFP perforated membrane be immersed in after the heat fused phase variation electrolyte in after 4 hours, take out barrier film, be placed between negative electrode and the anode, further drip phase variation electrolyte again, electrode slice is submerged.Shown in accompanying drawing 1, be assembled into Experimental cell.LiFePO on cathode sheets and the anode strip in the battery of assembling
4With the weight ratio of MCMB be 2.4-2.5: 1.
Experimental cell carries out the charge and discharge cycles test on micro-processor controlled auto charge and discharge appearance.Current density 0.1mA/cm
2, charging cut-ff voltage 4.2V, discharge cut-off voltage 2.5V, temperature is 60 ℃.Recording battery capacity is according to 84% of active material Mass Calculation value.Related data is referring to subordinate list 1.
With putting into glove box (content of water is less than 1ppm) after LBOB and the urea drying; Weighing 10gLiBOB and 90g urea are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 89 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 7 * 10
-5Ms/cm has reached 2.2mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With LBOB, dimethyl formamide, SiO
2And put into glove box (content of water is less than 1ppm), weighing 10g LiBOB, 60g dimethyl formamide, 10g SiO after polyacrylonitrile (PAN) drying
2With 20g PAN in beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 54 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 4 * 10
-5Ms/cm has reached 1.0mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.3V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With 3-FLBBB, dimethyl urea, Al
2O
3And put into glove box (content of water is less than 1ppm), weighing 20g 3-FLBBB, 60g dimethyl urea, 10g Al after PEO (PEO) drying
2O
3With 10g PEO in beaker, slowly be heated to 100 ℃, make it the fusing; Pass through magnetic agitation and 10g PEO then in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 78 ℃.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in 5Hz-1 3MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 3 * 10
-5Ms/cm has reached 0.5mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.2V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With TFLBBB, tetramethylurea, TiO
2And put into glove box (content of water is less than 1ppm), weighing 10g TFLBBB, 70g tetramethylurea, 10g TiO after Kynoar (PVDF) drying
2With 10g PVDF urea in beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 55 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 7 * 10
-5MS/cm has reached 5.2mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.3V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
(content of water is less than 1ppm); Weighing 30g LBNB, 50g AAA, 10g MgO and 10g PE are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 67 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 6 * 10
-5Ms/cm has reached 7.1mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.2V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With LBBPB, N-methylacetamide, Al
2O
3With put into glove box (content of water is less than 1ppm), weighing 10g LBBPB, 50g N-methylacetamide, 20gAl after polypropylene (PP) drying
2O
3With 20g PP in beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 45 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 2 * 10
-5Ms/cm has reached 0.2mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.3V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With putting into glove box after LBSB and the trifluoroacetyl aniline drying; The content of water is less than 1ppm, and weighing 50g LBSB and 50g trifluoroacetyl aniline slowly are heated to 100 ℃ in beaker; Make it fusing; Through magnetic stirrer 1-5 hour, become transparent liquid then, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 43 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 4 * 10
-5Ms/cm has reached 6.1ms/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5Vvs Li/Li
+, find when being higher than 4.1V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 9
With putting into glove box (content of water is less than 1ppm) after LBMB and the caprolactam drying; Weighing 40g LBMB and 60g caprolactam are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 45 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 2 * 10
-5MS/cm has reached 0.9mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 10
With LBPFPB, pyrrole network alkane ketone and TiO
2Put into glove box (content of water is less than 1ppm) after the drying, weighing 10g LBPFPB, 50g pyrrole network alkane ketone and 40g TiO
2In beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 25 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 8 * 10
-5Ms/cm has reached 4.6mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.3V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 11
With 3-MLBSB, acetamide and SiO
2Put into glove box (content of water is less than 1ppm) after the drying, weighing 10g 3-MLBSB, 40g acetamide and 50g SiO
2In beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 57 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 1 * 10
-5Ms/cm has reached 0.4mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.2V, to occur oxidation peak.
Test the assembling such as the embodiment 1 of lithium battery, discharge and recharge data and list in table 1.
Embodiment 12
With DCLBSB, acetamide and SiO
2Put into glove box (content of water is less than 1ppm) after the drying, weighing 10g DCLBSB, 80g acetamide and 10g SiO
2In beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCHSTA 449C thermogravimetric analyzer, fusing point is 44 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 4 * 10
-5Ms/cm has reached 3.8mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.4V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 13
With TCLBSB, acetamide and SiO
2Put into glove box (content of water is less than 1ppm) after the drying, weighing 30g TCLBSB, 30g acetamide and 40g SiO
2In beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCHSTA 449C thermogravimetric analyzer, fusing point is 33 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 7 * 10
-5Ms/cm has reached 5.8mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 14
With LBPB, acetamide and SiO
2Put into glove box (content of water is less than 1ppm) after the drying, weighing 10g LBPB, 60g acetamide and 30g SiO
2In beaker, slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour, become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 47 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 6 * 10
-5Ms/cm has reached 3.3mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.4V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 15
With putting into glove box (content of water is less than 1ppm) after LTBP and the acetamide drying; Weighing 80g LTBP and 20g acetamide are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 44 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 7 * 10
-5Ms/cm has reached 4.1mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.2V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 16
With putting into glove box (content of water is less than 1ppm) after 4-MLTBP and the acetamide drying; Weighing 90g 4-MLTBP and 10g acetamide are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 53 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 1 * 10
-5Ms/cm has reached 3.1mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.1V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 17
With putting into glove box (content of water is less than 1ppm) after 3-FLTBP and the trifluoroacetamide drying; Weighing 10g 3-FLTBP and 90g trifluoroacetamide are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 37 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 6 * 10
-5Ms/cm has reached 4.1mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 18
With putting into glove box (content of water is less than 1ppm) after LFAP and the trifluoroacetyl aniline drying; Weighing 30g LFAP and 70g trifluoroacetyl aniline are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 46 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 3 * 10
-5Ms/cm has reached 3.7mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 19
With putting into glove box (content of water is less than 1ppm) after LiTNSI, N-methylacetamide and the PAN drying; Weighing 20g LiTNSI, 30g N-methylacetamide and 50gPAN are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA449C thermogravimetric analyzer, fusing point is 37 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 4 * 10
-5Ms/cm has reached 0.8mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
With putting into glove box (content of water is less than 1ppm) after LiNPSI and the urea drying; Weighing 10gLiNPSI and 90g urea are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 55 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 2 * 10
-5Ms/cm has reached 0.9mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.4V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 21
With putting into glove box (content of water is less than 1ppm) after LBOB and the ethyl acetamide drying; Weighing 10g LiBOB and 90g ethyl acetamide are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 45 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 3 * 10
-5Ms/cm has reached 3.3mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
Embodiment 22
With putting into glove box (content of water is less than 1ppm) after LBOB and the trifluoroacetamide dimethyl urea drying; Weighing 10g LiBOB and 90g trifluoroacetamide dimethyl urea are in beaker; Slowly be heated to 100 ℃, make it fusing, then through magnetic stirrer 1-5 hour; Become transparent liquid, become behind the natural cooling that the white wax shape is solid-state promptly to obtain required phase variation electrolyte.Measure its thermal property with NETSCH STA 449C thermogravimetric analyzer, fusing point is 56 ℃, and fusing point is the phase transition temperature point.
Be in the stainless glass conductance cell putting into two end electrodes behind this electrolyte melting, use HP4192 impedance spectrometer in the 5Hz-13MHz scope, to measure its conductivity, recording 25 ℃ of conductivity is 2 * 10
-5Ms/cm has reached 4.6mS/cm in the time of 60 ℃.With the coupling of GDW6005 type high-low temperature test chamber, the conductivity under the sample different temperatures is measured.Use the CHI627C electrochemical workstation,, measure its electrochemical window with the method for cyclic voltammetric.Using work electrode to be the Pt sheet, is the glass three-electrode electro Chemical cell of metal lithium sheet to electrode, reference electrode, sweeps speed and is 0.5mV/s, and measuring range is 1-5V vs Li/Li
+, find when being higher than 4.5V, to occur oxidation peak.
This electrolyte directly is used for the matching that an experiment lithium battery is measured itself and electrode.The assembling such as the embodiment 1 of experiment lithium battery discharge and recharge data and list in table 1.
The component of table 1 phase variation electrolyte and physical property
| Lithium salts (mass percent %) | Organic compound (mass percent %) | Nanometer additive (mass percent %) | Polymer (mass percent %) | Fusing point ℃ | Conductivity (mS/c m) (25 ℃) | Conductivity (ms/c m) (60 ℃) | Electrochemical window (V) | Battery capacity percentage (%) | Embodiment |
| LBOB(20％) | Acetamide (80%) | - | - | 50 | 5×10 -5 | 4.1 | 4.3 | 84 | 1 |
| LBOB(10％) | Urea (90%) | - | - | 89 | 7×10 -5 | 2.2 | 4.5 | 77 | 2 |
| LBBB(10％) | Dimethyl formamide (60%) | SiO 2(10％) | PAN(20％) | 54 | 4×10 -5 | 1.0 | 4.3 | 67 | 3 |
| 3-FLBBB (20％) | Dimethyl urea (60%) | Al 2O 3(10％) | PE0(10％) | 48 | 3×10 -5 | 0.5 | 4.2 | 69 | 4 |
| TFLBBB (10％) | Tetramethylurea (70%) | TiO 2(10％) | PVDF(10％) | 55 | 7×10 -5 | 5.2 | 4.3 | 79 | 5 |
| LBNB(30％) | AAA (50%) | MgO(10％) | PE(10％) | 56 | 6×10 -5 | 7.1 | 4.2 | 56 | 6 |
| LBBPB(10％) | N-methylacetamide (50%) | Al 2O 3(20％) | PP(20％) | 45 | 2×10 -5 | 0.2 | 4.3 | 59 | 7 |
| LBSB(50％) | Trifluoroacetyl aniline (50%) | - | - | 43 | 4×10 -5 | 6.1 | 4.1 | 77 | 8 |
| LBMB(40％) | Caprolactam (60%) | - | - | 45 | 2×10 -5 | 0.9 | 4.2 | 66 | 9 |
| LBPFPB (10％) | Pyrrole network alkane ketone (50%) | TiO 2(40％) | - | 25 | 8×10 -5 | 4.6 | 4.3 | 72 | 10 |
| 3-MLBSB (10％) | Acetamide (40%) | SiO 2(50％) | - | 57 | 1×10 -5 | 0.4 | 4.2 | 59 | 11 |
| DCLBSB | Acetamide (80%) | SiO 2(10％) | - | 44 | 4×10 -5 | 3.8 | 4.4 | 66 | 12 |
| (10％) | |||||||||
| TCLBSB (30％) | Acetamide (30%) | SiO 2(40％) | - | 33 | 7×10 -5 | 5.8 | 4.5 | 77 | 13 |
| LBPB(10％) | Acetamide (60%) | SiO 2(30％) | - | 47 | 6×10 -5 | 3.3 | 4.4 | 68 | 14 |
| LTBP(80％) | Acetamide (20%) | - | - | 55 | 7×10 -5 | 4.1 | 4.2 | 78 | 15 |
| 4-MLTBP (90％) | Acetamide (10%) | - | - | 53 | 1×10 -5 | 3.1 | 4.1 | 56 | 16 |
| 3-FLTBP (10％) | Trifluoroacetamide (90%) | - | - | 37 | 6×10 -5 | 4.1 | 4.5 | 77 | 17 |
| LFAP(30％) | Trifluoroacetyl aniline (70%) | - | - | 46 | 3×10 -5 | 3.7 | 4.5 | 79 | 18 |
| LiTNSI(20％) | N-methylacetamide (30%) | - | PAN(50％) | 37 | 4×10 -5 | 0.8 | 4.5 | 66 | 19 |
| LiNPSI(10％) | Urea (90%) | - | - | 55 | 2×10 -5 | 0.9 | 4.4 | 75 | 20 |
| LBOB(10％) | Ethyl acetamide (90%) | - | - | 45 | 3×10 -5 | 3.3 | 4.5 | 78 | 21 |
| LBOB(10％) | Trifluoroacetamide dimethyl urea (90%) | - | - | 56 | 2×10 -5 | 4.6 | 4.5 | 77 | 22 |
Claims (10)
1. one kind changes lithium-ion electrolyte mutually, and this electrolyte comprises following composition: the organic compound of lithium salts and amide containing functional group, described lithium salts is selected from LiBO
2(C
6H
4)
2, LiBO
2(C
6H
3F)
2, LiBO
2(C
6H
4F
4)
2, LiBO
2(C
10H
16)
2, LiBO
2(C
12H
20)
2, LiB (C
7H
10O
3)
2, LiB (C
2O
4)
2, LiB (C
3O
4)
2, LiB (C
6F
12O
2)
2, LiB (C
8H
12O
3)
2, LiB (C
7H
8O
3C
L2)
2, LiB (C
7H
7O
3Cl
3)
2, LiBO
2(C
5H
3N)
2, LiPO
2(C
6H
4)
3, LiPO
2(C
7H
6)
3, LiPO
2(C
6H
3F)
3, LiPF
3(CF
2CF
3)
3, LiN (SO
2C
4F
9) (SO
2CF
3) and LiN (SO
2C
6H
4NO
2)
2In one or more; The organic compound of said amide containing functional group is selected from following formula: compound:
In one or more, substituent R
1, R
2, R
3, R
4, R
5Be H, methyl, ethyl, phenyl or trifluoromethyl independently of each other; Said electrolytical phase transition point temperature is 25-90 ℃, said changing into mutually from the solid-state liquid state that becomes.
2. electrolyte according to claim 1, wherein this electrolyte also comprises inorganic oxide and polymer, and wherein, described inorganic oxide is selected from SiO
2, Al
2O
3, TiO
2With in the MgO particle one or more, it is that particle diameter is that sphere or the length of 10-100nm is the aciculiform of 10-100nm, the percentage that the quality of said inorganic oxide accounts for said electrolyte gross mass for greater than 0 less than 50%; Described polymer is selected from one or more in polyacrylonitrile, PEO, Kynoar, polyethylene and the polypropylene, and the percentage that the quality of said polymer accounts for said electrolyte gross mass is less than 50% greater than 0.
3. electrolyte according to claim 1 and 2, wherein this electrolytical phase transition point temperature is 45-65 ℃.
4. electrolyte according to claim 1 and 2, wherein this electrolytical phase transition point temperature is 45-55 ℃.
5. electrolyte according to claim 1 and 2, the organic compound of wherein said amide containing functional group is selected from one or more in dimethyl formamide, urea, acetamide, AAA, N-methylacetamide, trifluoroacetyl aniline, caprolactam and the pyrrolidones.
6. electrolyte according to claim 5, wherein said urea are one or both in trifluoroacetamide dimethyl urea and the tetramethylurea.
7. one kind prepares the said electrolytical method of claim 1, and this method may further comprise the steps:
A. the organic compound with lithium salts and amide containing functional group mixes;
B. add hot mixt, obtain transparency liquid;
C. with described transparency liquid cooling, obtain described electrolyte, operating in the dry environment of step a, b and c carried out.
8. one kind prepares the said electrolytical method of claim 2, and this method may further comprise the steps:
A. with organic compound, inorganic oxide and the mixed with polymers of lithium salts, amide containing functional group;
B. add hot mixt, obtain transparency liquid;
C. with described transparency liquid cooling, obtain described electrolyte, operating in the dry environment of step a, b and c carried out.
9. each describedly changes the application of lithium-ion electrolyte in chargeable lithium battery mutually among the claim 1-6.
10. the lithium battery that can discharge and recharge contains each described electrolyte among the claim 1-6 in this battery.
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| CN102832409B (en) * | 2012-08-13 | 2015-05-13 | 中航锂电（洛阳）有限公司 | Low temperature lithium ion battery electrolyte and its preparation method |
| WO2017106563A1 (en) * | 2015-12-15 | 2017-06-22 | Sila Nanotechnologies Inc. | Solid state electrolytes for safe metal and metal-ion batteries |
| JP6786231B2 (en) * | 2016-03-16 | 2020-11-18 | 株式会社東芝 | Laminates for lithium-ion secondary batteries, lithium-ion secondary batteries, battery packs and vehicles |
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| CN113258144B (en) * | 2021-04-16 | 2023-05-02 | 北京航空航天大学 | Aqueous phase-change electrolyte and application thereof |
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| CN1371141A (en) * | 2001-02-27 | 2002-09-25 | 中国科学院物理研究所 | Lithium ion electrolyte containing lithium addition compound |
| CN1487618A (en) * | 2003-07-04 | 2004-04-07 | 华中科技大学 | Molecular gel electrolyte and its prepn |
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| CN101599558A (en) | 2009-12-09 |
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