CN101252206A - Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte - Google Patents
Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte Download PDFInfo
- Publication number
- CN101252206A CN101252206A CNA2008100305470A CN200810030547A CN101252206A CN 101252206 A CN101252206 A CN 101252206A CN A2008100305470 A CNA2008100305470 A CN A2008100305470A CN 200810030547 A CN200810030547 A CN 200810030547A CN 101252206 A CN101252206 A CN 101252206A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- solvent
- carbonate
- salt
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides a method for preparing cathode film forming electrolyte compound salt and a functional electrolyte of a lithium-ion cell, comprising the following steps and technology conditions: mixing a purified and dehydrated cyclic carbonic ester solvent and a linear carbonic ester solvent dually or multiply, wherein the mass ratio between the cyclic carbonic ester solvent and the linear carbonic ester solvent is between 1:1 to 1:3, the content of the carbonic ally ester is not less than ten percent. Under indoor temperature, dissolving conductive lithium salt in the solvent to make electrolyte; adding the cathode film forming electrolyte salt R4NBF4 in the electrolyte with the concentration not less than zero point one mol/L. The lithium-ion cell electrolyte prepared by the method can improve PC content in the electrolyte, restrain the embedment damage affect on a graphite cathode by the PC solvent and improve the initial reversible capacity of the cell so as to promote the compatibility between the PC-based electrolyte and the graphic anode material and the cyclic life of cells.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes, the particularly a kind of novel lithium ion battery cathode film-forming electrolyte compound salt and the preparation method of function electrolyte thereof.
Background technology
Lithium ion battery becomes the focus of new forms of energy research owing to have advantages such as operating voltage height, energy density is big, environmental pollution is little.Along with deepening continuously of the lithium-ions battery marketization, people are more and more higher to the expectation of lithium-ions battery.Present commercial lithium-ions battery has been difficult to satisfy the needs of practical application, as electric automobile, space technology, military field etc.And the formation of the ionic conductivity of electrolyte and SEI film all has confidential relation with choice of Solvent.Therefore composition, the proportioning of studying solvent in the electrolyte have crucial meaning to the high temperature performance that improves lithium-ions battery.Ethylene carbonate (EC) is the fine solvent of lithium ion battery film forming, but the EC fusing point is higher, under cryogenic conditions, its as solvent easy crystallization separate out, greatly influenced the cryogenic property of lithium battery; Propene carbonate (PC) then has very wide liquid journey scope, this makes the PC solvent have good high temperature performance, in electrolyte, add a certain amount of PC and can suppress ethylene carbonate (EC) crystallization when low temperature effectively and separate out, improve the cryogenic property of lithium ion effectively.But PC generally is not used as the component of lithium-ions battery electrolyte at present, its main cause is to be the lithium-ions battery that material with carbon element is used for negative pole at graphite, PC is total to embedding to graphite cathode together with lithium ion easily, and graphite linings is peeled off, and causes the lithium-ions battery cycle performance to descend.G.H.Wrodnigg uses ethylene sulfite (ES) to prevent that as additive the PC molecule from embedding graphite (J.Electrochem Comm.1999,1 (3～4): 148); D.L.Foster use crown ether compound prevent PC embed graphite electrode (J.Power Source2000,85:299); Also there is research to improve the compatibility of graphite cathode and PC base electrolyte by the way of adding function organic solvent (as sultones) in addition.
So far, these ways all are the ways that is conceived to improve solvent, and addition can not be too high, when PC content is higher, can produce bigger irreversible capacity in cyclic process first, cause efficient significantly to reduce, and cycle performance significantly descends.
Summary of the invention
Purpose of the present invention is exactly to be to solve the deficiency that above-mentioned way exists, and sets about from electrolytic salt, and a kind of novel lithium ion battery cathode film-forming electrolyte compound salt and the preparation method of function electrolyte thereof are provided.The concentration of this electrolyte compound salt can be higher, and this function electrolyte can improve the irreversible capacity first of graphite material significantly, improves the efficiency for charge-discharge of battery.
The present invention is achieved through the following technical solutions:
The first step: will carry out binary or polynary mixing by purifying removal of impurities, the cyclic carbonate ester solvent and the linear carbonate solvent that remove water treatment, the quality of wherein mixing ring-type carbonate solvent and linear carbonate solvent is between 1: 1 to 1: 3 than scope, and the mass content of propene carbonate (PC) is no less than 10%;
Second step: at ambient temperature, electric conducting lithium salt is added in the above-mentioned solvent, stirring is made into electrolyte;
The 3rd step: in electrolyte, add a certain amount of film-forming electrolyte salt R
4NBF
4, its concentration is between 0.1mol/L to 0.6mol/L.
Described cyclic carbonate ester solvent is a propene carbonate, or one or both solvents that mix with propene carbonate in the ethylene carbonate, butylene.
Described linear carbonate solvent is any one or a two or more mixed solvent in Methylethyl carbonic ester, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, the ethyl propyl carbonic ester.
Described electric conducting lithium salt is LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2, any one or multiple combination among LiBOB and the LiDFOB.
In the first step, the purifying removal of impurities, remove water treatment technology and comprise one or more combination in cosolvent method, boulton process, distillation crystallisation, the molecular sieve adsorption.Can also adopt simultaneously any one the above material in active carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, non-oxidation two phosphorus, alkali metal or the alkaline-earth metal; The molecular sieve that the impurity removal process that dewaters adopts can adopt 3A, 4A and 5A, preferred 5A or 4A.
Described additive R
4NBF
4Middle R group can be any four moiety combinations in methyl, ethyl, propyl group, butyl, the methoxy ethyl.As R wherein
4N
+Can be in dimethyl diethyl ammonium, dimethyl dibutyl ammonium, dimethyl dipropylammonium, dipropyl dibutyl ammonium ammonium, tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA, monomethyl triethyl ammonium, monomethyl tributyl ammonium, an ethyl tripropyl ammonium, monomethyl trimethoxy ammonium, an ethyl trimethyl ammonium, dimethylformamide dimethyl oxygen base ammonium and the diethyl dimethoxy ammonium any one.Preferred asymmetric group.
Used film forming composite electrolyte salt R
4NBF
4Purity should be greater than 99.99%, and concentration is controlled between the 0.1mol/L to 0.6mol/L.
Described electric conducting lithium salt concentration should be controlled within 0.5mol/L to the 2.0mol/L scope, preferentially selects between 1.0～1.2mol/L.
In the lithium ion battery of Li-ion battery cathode film forming function electrolyte of the present invention, the negative electrode active material of battery comprises native graphite, electrographite, asphalt base carbon fiber, carbonaceous mesophase spherules.More excellent electrographite or the carbonaceous mesophase spherules of being chosen as.The positive active material of battery comprises LiMn2O4, cobalt acid lithium, lithium nickelate and LiFePO4, more preferably selects LiFePO4.
The present invention compared with prior art has following advantage and effect:
1. the present invention can improve the compatibility of basic electrolyte of propene carbonate (PC) and graphite cathode material significantly by solvent formula is improved, and obviously improves first charge-discharge efficiency.Improve the low temperature efficient of battery.
2. the present invention is by adding the electrolytic salt complex salt R good to the PC compatibility
4NBF
4, and can guarantee higher adding concentration, electrode surface form one deck densification, stable SEI film, reduce a large amount of consumption of first charge-discharge to lithium ion, reduced PC simultaneously and graphite embedded altogether the structural deterioration that causes.
Description of drawings
Fig. 1 is first three time cycle charge-discharge curve chart of embodiment 1, embodiment 2 and comparative example;
First three time cyclic voltammetric comparison diagram of Fig. 2 embodiment 1, embodiment 2 and comparative example
Fig. 3 AG hot pressing sample, embodiment 2 scheme with comparative example's SEI film FTIR
Table 1 is first three time cycle charge-discharge experimental data table of embodiment 1 and comparative example
Table 2 is first three time cycle charge-discharge experimental data table of embodiment 2 and comparative example
Table 3 is first three time cycle charge-discharge experimental data table of embodiment 3 and comparative example
Table 4 is first three time cycle charge-discharge experimental data table of embodiment 4 and comparative example.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.The present invention can implement by described any mode of summary of the invention.
Under 15 ℃ of conditions of the first step, at first utilize Rotary Evaporators that cyclic carbonate ester solvent PC, EC and linear carbonate solvent DMC are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 30 ℃, 40 ℃, 30 ℃ conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EC, DMC carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EC and DMC with the micro-analysis electronic balance, and wherein three's mass ratio is 1: 1: 3, measures the 10ml mixed electrolytic solution with graduated cylinder (15ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 1.519g LiPF with the micro-analysis electronic balance in glove box under 15 ℃ of conditions
6Electrolytic salt.Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation in solution, promptly being made into concentration is 1mol/L LiPF
6/ PC+EC+DMC electrolyte;
The 3rd step took by weighing film-forming electrolyte salt Et with the micro-analysis electronic balance in glove box under 15 ℃ of conditions
4NBF
4(purity＞99.99%) 0.6513g slowly pours in the described electrolyte of step, stirs, and guarantees that its ultimate density is at 0.3mol/L.
As mentioned above, prepare Li-ion battery cathode film forming function electrolyte of the present invention.
Under 15 ℃ of conditions of the first step, at first utilize Rotary Evaporators that cyclic carbonate ester solvent PC, EC and linear carbonate solvent DMC are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 30 ℃, 40 ℃, 30 ℃ conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EC, DMC carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EC and DMC with the micro-analysis electronic balance, and wherein three's mass ratio is 1: 1: 3, measures the 10ml mixed electrolytic solution with graduated cylinder (15ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 1.519g LiPF with plum Teller micro-analysis electronic balance in glove box under 15 ℃ of conditions
6Electrolytic salt.Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation in solution, promptly being made into concentration is 1mol/L LiPF
6/ PC+EC+DMC electrolyte;
The 3rd step took by weighing film-forming electrolyte salt MeEt with plum Teller micro-analysis electronic balance in glove box under 15 ℃ of conditions
3NBF
4(purity＞99.99%) 1.0155g slowly pours in the described electrolyte of step, stirs, and guarantees that its ultimate density is at 0.5mol/L.
As mentioned above, prepare Li-ion battery cathode film forming function electrolyte of the present invention.
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that cyclic carbonate ester solvent PC, EC and linear carbonate solvent DEC are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 30 ℃, 40 ℃, 30 ℃ conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EC, DEC carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EC and DEC with the micro-analysis electronic balance, and wherein three's mass ratio is 2: 1: 2.5, measures the 10ml mixed electrolytic solution with graduated cylinder (15ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 1.125gLiBF with plum Teller micro-analysis electronic balance in glove box under 25 ℃ of conditions
4Electrolytic salt.Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation in solution, promptly being made into concentration is 1.2mol/L LiBF
4/ PC+EC+DEC electrolyte;
The 3rd step took by weighing film-forming electrolyte salt MeEt with plum Teller micro-analysis electronic balance in glove box under 25 ℃ of conditions
3NBF
4Purity＞99.99%) 0.6091g slowly pours in the described electrolyte of step, stirs, and guarantees that its ultimate density is at 0.3mol/L.
As mentioned above, prepare Li-ion battery cathode film forming function electrolyte of the present invention.
Embodiment 4
Under 25 ℃ of conditions of the first step, at first utilize Rotary Evaporators that cyclic carbonate ester solvent PC, EC and linear carbonate solvent DEC are distilled purification respectively, remove the minor amount of water of the inside, utilize the 4A molecular sieve under 30 ℃, 40 ℃, 30 ℃ conditions, to carry out degree of depth adsorb traces water respectively then.Such operation is carried out three times repeatedly, until impurity, moisture＜0.005%.PC, EC, DEC carry out the ternary solvent mixing subsequently, respectively take by weighing a certain amount of PC, EC and DEC with the micro-analysis electronic balance, and wherein three's mass ratio is 2: 1: 2.5, measures the 10ml mixed electrolytic solution with graduated cylinder (15ml) and pours port grinding bottle into.All processes of the preparation of electrolyte are all carried out in being full of the glove box of high-purity argon gas;
Second step took by weighing 1.125gLiBF with plum Teller micro-analysis electronic balance in glove box under 25 ℃ of conditions
4Electrolytic salt.Then it is added on (in the port grinding bottle) in the above-mentioned ternary mixed solvent, stirs, clarification, no post precipitation in solution, promptly being made into concentration is 1.2mol/L LiBF
4/ PC+EC+DEC electrolyte;
The 3rd step took by weighing film-forming electrolyte salt MeOMe with plum Teller micro-analysis electronic balance in glove box under 25 ℃ of conditions
3NBF
4(purity＞99.99%) 0.9255g slowly pours in the described electrolyte of step, stirs, and guarantees that its ultimate density is at 0.5mol/L.
As mentioned above, prepare Li-ion battery cathode film forming function electrolyte of the present invention.
The comparative example 1
Prepare contrast comparative example electrolyte by first, second one step process among the embodiment 1, get then that the electrolyte of preparing compares test among the embodiment 1.At first electrolyte is tested: water content is measured with moisture teller, and the water content of electrolyte＜5ppm acid content is measured acid content＜2ppm with karl Fischer potentiometric titrimeter 798 GPT Titrino.Experimentize then:
(1) constant current charge-discharge experiment
Electrolyte is for as mentioned above during experiment.Adopt three electrode simulated batteries, work electrode is for to mix after hot pressing forms in 94: 6 ratio (dry weight) with PTFE with artificial graphite sample, and barrier film is a microporous polypropylene membrane.In the glove box that is full of high-purity Ar gas, assemble battery, take out the back and carry out constant current charge and discharge experiment with blue electricity (LAND) series battery test macro, the charge and discharge current density is 15.00mA/g, and end of charge voltage is 0.000V, and final discharging voltage is 2.000V.
First three time charging and discharging curve and efficient and capacity are shown in Fig. 1, table 1 in embodiment 1 and the comparative example's electrolyte, and wherein a is the charging and discharging curve that does not add comparative example's electrolyte of film-forming electrolyte salt.B is the charging and discharging curve of embodiment 1 function electrolyte.
(2) cyclic voltammetry experiment
Electrolyte is for as mentioned above during experiment.Cyclic voltammetry experiment adopts three-electrode system, work electrode is that (electrode is made: with mass ratio is that 94: 6 graphite and PVDF is dissolved in the N-methyl pyrrolidone to carbon electrode, stir and coat on the Copper Foil, 120 ℃ of dry 14h of vacuum), large-area metal lithium sheet is as reference electrode with to electrode.Used instrument be U.S. PE company the electrochemistry integrated test system (PerkinElmerinstrument, USA).Potential value in the literary composition is all with respect to Li/Li+.
Cyclic voltammetry curve figure as shown in Figure 2.Wherein a is the charging and discharging curve that does not add comparative example's electrolyte of film-forming electrolyte salt.B is the charging and discharging curve of embodiment 1. Subscript 1,2,3 represent first, second, third circulation respectively.
The comparative example 2
Prepare comparative example's electrolyte by first, second one step process among the embodiment 2, get then that the electrolyte of preparing compares test among the embodiment 2.At first electrolyte is tested: water content is measured with plum Teller-Tuo benefit karl Fischer (Karl Fisher) moisture teller DL32, the water content of electrolyte＜5ppm acid content is measured acid content＜2ppm with karl Fischer (Karl Fisher) potentiometric titrimeter 798 GPT Titrino.Experimentize then:
(1) constant current charge-discharge experiment
Be that embodiment 2 and comparative example are described with electrolyte during experiment.Adopt three electrode simulated batteries, work electrode is for to mix after hot pressing forms in 94: 6 ratio (dry weight) with PTFE with artificial graphite sample, and barrier film is a microporous polypropylene membrane.In the glove box that is full of high-purity Ar gas, assemble battery, take out the back and carry out constant current charge and discharge experiment with blue electricity (LAND) series battery test macro, the charge and discharge current density is 15.00mA/g, and end of charge voltage is 0.000V, and final discharging voltage is 2.000V.
First three time charging and discharging curve and efficient and capacity are shown in Fig. 1, table 2 in embodiment 2 and the comparative example's electrolyte, and wherein a is the charging and discharging curve that does not add comparative example's electrolyte of film-forming electrolyte salt.B is the charging and discharging curve of embodiment 2 function electrolytes.
(2) cyclic voltammetry experiment
Be that embodiment 2 and comparative example are described with electrolyte during experiment.Cyclic voltammetry experiment adopts three-electrode system, work electrode is that (electrode is made: with mass ratio is that 94: 6 graphite and PVDF is dissolved in the N-methyl pyrrolidone to carbon electrode, stir and coat on the Copper Foil, 120 ℃ of dry 14h of vacuum), large-area metal lithium sheet is as reference electrode with to electrode.Used instrument be used instrument be U.S. PE company the electrochemistry integrated test system (PerkinElmer instrument, USA).Potential value in the literary composition is all with respect to Li/Li+.
Cyclic voltammetry curve figure as shown in Figure 2.Wherein a is the charging and discharging curve that does not add comparative example's electrolyte of film-forming electrolyte salt.C is the charging and discharging curve of embodiment 2. Subscript 1,2,3 represent first, second, third circulation respectively.
(3) FTIR of SEI film analyzes
Be that embodiment 2 and comparative example are described with electrolyte during experiment.The three electrode simulated batteries that install graphite sample are carried out constant current (15.00mA/g) charging, stop charging during to 0.3V.Placed three hours, and in the glove box that is full of high-purity Ar gas battery was taken apart, take out carbon membrane, the electrolyte with DMC solvent clean carbon membrane remained on surface carries out drying then in vacuum drying chamber, remove DMC.Scrape SEI film powder from dried carbon membrane surface, with itself and dried spectroscopic pure KBr powder by 100: 1 mass ratio mix, fine ground, with tablet press machine at 19kg/cm
2Condition under be pressed into sheet.The AVATAR-360 Fourier transform infrared spectroscopy of producing with U.S. Nicolet company (Fourier transform infrared spectrometer is called for short FTIR) is measured the composition and the content of SEI film then.
FTIR figure as shown in Figure 3.Wherein a, b, c represent that respectively the SEI film FTIR of AG hot pressing sample, comparative example and embodiment 2 schemes among the figure.
The comparative example 3
Prepare comparative example's electrolyte by first, second one step process among the embodiment 3, get then that the electrolyte of preparing compares test among the embodiment 3.At first electrolyte is tested: water content is measured with plum Teller-Tuo benefit karl Fischer (Karl Fisher) moisture teller DL32, the water content of electrolyte＜5ppm acid content is measured acid content＜2ppm with karl Fischer (Karl Fisher) potentiometric titrimeter 798 GPT Titrino.Experimentize then:
(1) constant current charge-discharge experiment
Be that embodiment 3 and comparative example are described with electrolyte during experiment.Adopt three electrode simulated batteries, work electrode is for to mix after hot pressing forms in 95: 5 ratio (dry weight) with PVDF with the carbonaceous mesophase spherules sample, and barrier film is a microporous polypropylene membrane.In the glove box that is full of high-purity Ar gas, assemble battery, take out the back and carry out constant current charge and discharge experiment with blue electricity (LAND) series battery test macro, the charge and discharge current density is 15.00mA/g, and end of charge voltage is 0.000V, and final discharging voltage is 2.000V.
It is as shown in table 3 that first three time discharges and recharges data in embodiment 3 and the comparative example's electrolyte, and wherein a discharges and recharges data for first three time of comparative example's electrolyte of not adding film-forming electrolyte salt.B discharges and recharges data for first three time of embodiment 3 function electrolytes.Subscript 1,2,3 represent first, second, third circulation respectively.
The comparative example 4
Prepare comparative example's electrolyte by first, second one step process among the embodiment 4, get then that the electrolyte of preparing compares test among the embodiment 4.At first electrolyte is tested: water content is measured with plum Teller-Tuo benefit karl Fischer (Karl Fisher) moisture teller DL32, the water content of electrolyte＜5ppm acid content is measured acid content＜2ppm with karl Fischer (Karl Fisher) potentiometric titrimeter 798 GPT Titrino.Experimentize then:
(1) constant current charge-discharge experiment
Be that embodiment 4 and comparative example are described with electrolyte during experiment.Adopt three electrode simulated batteries, work electrode is for to mix after hot pressing forms in 95: 5 ratio (dry weight) with PVDF with the carbonaceous mesophase spherules sample, and barrier film is a microporous polypropylene membrane.In the glove box that is full of high-purity Ar gas, assemble battery, take out the back and carry out constant current charge and discharge experiment with blue electricity (LAND) series battery test macro, the charge and discharge current density is 15.00mA/g, and end of charge voltage is 0.000V, and final discharging voltage is 2.000V.
It is as shown in table 4 that first three time discharges and recharges data in embodiment 4 and the comparative example's electrolyte, and wherein a discharges and recharges data for first three time of comparative example's electrolyte of not adding film-forming electrolyte salt.B discharges and recharges data for first three time of embodiment 4 function electrolytes.Subscript 1,2,3 represent first, second, third circulation respectively.
Table 1
| No | Lithium battery electrolytes | Circulation for the first time | Circulation for the second time | Circulation for the third time | ||||||
| C 1 mAh/g | D 1 mAh/g | η 1 ％ | C 2 mAh/g | D 2 mAh/g | η 2 (％) | C 3 mAh/g | D 3 mAh/g | η 3 ％ | ||
| a | 1M LiPF 6/EC+PC+DMC(1∶1∶ 3) | 526.2 | 264.9 | 50.4 | 284.6 | 265.6 | 93.3 | 274.6 | 264.6 | 96.4 |
| b | 1M LiPF6 +0.3M Et 4NBF 4/EC+PC+DMC (1∶1∶3) | 368.7 | 280.1 | 76.0 | 298.8 | 289.1 | 96.7 | 306.3 | 299.8 | 97.9 |
Table 2
| No | Lithium battery electrolytes | Circulation for the first time | Circulation for the second time | Circulation for the third time | ||||||
| C 1 mAh/g | D 1 mAh/g | η 1 ％ | C 2 mAh/g | D 2 mAh/g | η 2 (％) | C 3 mAh/g | D 3 mAh/g | η 3 ％ | ||
| a | 1M LiPF 6/EC+PC+DMC(1∶1∶ 3) | 526.2 | 264.9 | 50.4 | 284.6 | 265.6 | 93.3 | 274.6 | 264.6 | 96.4 |
| b | 1M LiPF6 +0.5M Me 1Et 3NBF 4/EC+PC+ DMC(1∶1∶3) | 344.7 | 281.3 | 81.6 | 317.5 | 308.2 | 97.1 | 318.6 | 312.5 | 98.1 |
Table 3
| No | Lithium battery electrolytes | Circulation for the first time | Circulation for the second time | Circulation for the third time | ||||||
| C 1 mAh/g | D 1 mAh/g | η 1 ％ | C 2 mAh/g | D 2 mAh/g | η 2 (％) | C 3 mAh/g | D 3 mAh/g | η 3 ％ | ||
| a | 1M LiBF 4/EC+PC+DEC(2∶1∶ 2.5) | 723.4 | 370.1 | 51.2 | 398.9 | 374.9 | 94.1 | 388.2 | 375.7 | 96.8 |
| b | 1.2M LiBF 4+0.3M Me 1Et 3NBF 4 /EC+PC+DEC(2∶1∶2.5) | 560.2 | 398.6 | 71.1 | 403.6 | 384.6 | 95.3 | 396.7 | 388.4 | 97.9 |
Table 4
| No | Lithium battery electrolytes | Circulation for the first time | Circulation for the second time | Circulation for the third time | ||||||
| C 1 mAh/g | D 1 mAh/g | η 1 ％ | C 2 mAh/g | D 2 mAh/g | η 2 (％) | C 3 mAh/g | D 3 mAh/g | η 3 ％ | ||
| a | 1M LiBF 4/EC+PC+DEC(2∶1∶ 2.5) | 723.4 | 370.1 | 51.2 | 398.9 | 374.9 | 94.1 | 388.2 | 375.7 | 96.8 |
| b | 1.2M LiBF 4+0.5M MeO 1Me 3NBF 4/EC+PC+DEC (2∶1∶2.5) | 540.1 | 410.3 | 75.9 | 420.9 | 402.4 | 95.6 | 411.3 | 404.7 | 98.4 |
Claims (8)
1. one kind is used for lithium ion battery cathode film-forming electrolyte compound salt and function electrolyte preparation method thereof, it is characterized in that comprising the steps and process conditions:
(1) at first, will carry out binary or polynary mixing by purifying removal of impurities, the cyclic carbonate ester solvent and the linear carbonate solvent that remove water treatment; The quality of wherein mixing ring-type carbonate solvent and linear carbonate solvent is between 1: 1 to 1: 3 than scope, and contains propene carbonate in the cyclic carbonate, and its mass content is no less than 10%;
(2) then, at ambient temperature, electric conducting lithium salt is added in the above-mentioned solvent, stirring is made into electrolyte;
(3) last, in electrolyte, add a certain amount of cathode film formation electrolytic salt R
4NBF
4, its concentration is between 0.1mol/L to 0.6mol/L, and stirring promptly prepares film forming function electrolyte.
2. preparation method according to claim 1 is characterized in that: additive R
4NBF
4Middle R group is any four moiety combinations in methyl, ethyl, propyl group, butyl, the methoxy ethyl.
3. preparation method according to claim 1 is characterized in that: described cyclic carbonate ester solvent is a propene carbonate, or one or both solvents that mix with propene carbonate in the ethylene carbonate, butylene.
4. preparation method according to claim 1 is characterized in that: described linear carbonate solvent is any one or a two or more mixed solvent in Methylethyl carbonic ester, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, the ethyl propyl carbonic ester.
5. preparation method according to claim 1 is characterized in that: described electric conducting lithium salt is LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
3)
2, at least a among LiBOB and the LiDFOB.
6. preparation method according to claim 1 or 5, it is characterized in that: electric conducting lithium salt concentration is between the 0.5mol/L to 2.0mol/L.
7. preparation method according to claim 1 is characterized in that: the described impurity removal process that dewaters comprises one or more the combination in cosolvent method, boulton process, distillation crystallisation, the molecular sieve adsorption.
8. preparation method according to claim 1 is characterized in that: lithium ion battery cathode film-forming electrolyte compound salt is at least a and film forming salt R in the electric conducting lithium salt
4NBF
4In at least a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100305470A CN101252206B (en) | 2008-01-25 | 2008-01-25 | Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100305470A CN101252206B (en) | 2008-01-25 | 2008-01-25 | Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101252206A true CN101252206A (en) | 2008-08-27 |
| CN101252206B CN101252206B (en) | 2011-04-13 |
Family
ID=39955465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100305470A Expired - Fee Related CN101252206B (en) | 2008-01-25 | 2008-01-25 | Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101252206B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214839A (en) * | 2010-04-07 | 2011-10-12 | 深圳市比克电池有限公司 | Liquid-state soft package lithium battery and preparation method thereof |
| CN103682420A (en) * | 2013-11-28 | 2014-03-26 | 华南师范大学 | High voltage lithium ion battery functional electrolyte and preparation method and application |
| CN105161765A (en) * | 2015-07-06 | 2015-12-16 | 东莞市天丰电源材料有限公司 | Electrolyte of lithium ion power battery |
| CN106129472A (en) * | 2016-07-01 | 2016-11-16 | 东风商用车有限公司 | A kind of ferric phosphate lithium cell low-temperature electrolyte |
| CN107860810A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of sign formation of SEI films and the electrochemical method of decomposable process and system |
| CN110994031A (en) * | 2019-12-19 | 2020-04-10 | 湖南美尼科技有限公司 | Fast-charging high-temperature-resistant electrolyte and preparation method thereof |
| CN111600076A (en) * | 2020-05-02 | 2020-08-28 | 安徽五行动力新能源有限公司 | Lithium battery lamination processing technology |
-
2008
- 2008-01-25 CN CN2008100305470A patent/CN101252206B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214839A (en) * | 2010-04-07 | 2011-10-12 | 深圳市比克电池有限公司 | Liquid-state soft package lithium battery and preparation method thereof |
| CN103682420A (en) * | 2013-11-28 | 2014-03-26 | 华南师范大学 | High voltage lithium ion battery functional electrolyte and preparation method and application |
| CN105161765A (en) * | 2015-07-06 | 2015-12-16 | 东莞市天丰电源材料有限公司 | Electrolyte of lithium ion power battery |
| CN105161765B (en) * | 2015-07-06 | 2018-09-28 | 东莞市天丰电源材料有限公司 | A kind of lithium ion power battery electrolyte |
| CN106129472A (en) * | 2016-07-01 | 2016-11-16 | 东风商用车有限公司 | A kind of ferric phosphate lithium cell low-temperature electrolyte |
| CN107860810A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of sign formation of SEI films and the electrochemical method of decomposable process and system |
| CN110994031A (en) * | 2019-12-19 | 2020-04-10 | 湖南美尼科技有限公司 | Fast-charging high-temperature-resistant electrolyte and preparation method thereof |
| CN111600076A (en) * | 2020-05-02 | 2020-08-28 | 安徽五行动力新能源有限公司 | Lithium battery lamination processing technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101252206B (en) | 2011-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101682080B (en) | Non-aqueous electrolyte and electrochemical device having the same | |
| CN107069093B (en) | High-concentration ester electrolyte for lithium-sulfur battery | |
| CN100365863C (en) | Li-ion battery cathode film forming function electrolyte and its preparing process | |
| CN110911740B (en) | Gel electrolyte battery and preparation method thereof | |
| CN101252206B (en) | Lithium ion battery cathode film-forming electrolyte compound salt and method for preparing function electrolyte | |
| CN110112465B (en) | Electrolyte for battery with lithium-rich manganese-based positive electrode material system and lithium ion battery | |
| CN1290974A (en) | Non-aqeous electrolytic sotution and lithium accumulator using said non-aqeous electrolytic solution | |
| CN102637903A (en) | Formation method of lithium ion battery | |
| CN101645521A (en) | Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof | |
| CN105390742A (en) | High-voltage lithium-ion battery electrolyte as well as preparation method and application thereof | |
| CN101587970A (en) | Electrolyte for high multiplying power lithium ion battery and preparation method thereof | |
| CN101702447A (en) | Nonaqueous electrolytic solution for high-voltage lithium ion batteries and preparation method and application thereof | |
| WO2014114068A1 (en) | Non-aqueous organic electrolyte, preparation method therefor and lithium ion secondary battery | |
| CN102231441A (en) | Sulfur-containing electrolyte with film forming function for lithium ion battery as well as preparation method and application thereof | |
| CN108258317A (en) | A kind of lithium-sulfur cell | |
| CN110190330B (en) | Lithium battery, electrolyte thereof and preparation method of electrolyte | |
| KR20010068820A (en) | New electrolytes and lithium ion battery using the same | |
| CN105390747A (en) | Trimethyl borate additive-containing electrolyte solution, preparation method therefor and application thereof | |
| CN111116651B (en) | Phosphite ester compound containing thienyl and application thereof | |
| CN110372736B (en) | High-voltage electrolyte additive, high-voltage electrolyte containing high-voltage electrolyte additive and lithium ion battery | |
| JP3815180B2 (en) | Nonaqueous electrolyte and lithium secondary battery using the same | |
| CN105355976A (en) | An electrolyte containing a tripropylborate additive, a preparing method thereof and applications of the electrolyte | |
| CN105742711A (en) | Electrolyte and lithium ion battery | |
| CN111342133B (en) | Novel non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN109309253A (en) | Electrolyte and electrochemical energy storage device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110413 Termination date: 20170125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |