CN1822423A - Electrolyte for lithium secondary battery and lithium secondary battery comprising same - Google Patents
Electrolyte for lithium secondary battery and lithium secondary battery comprising same Download PDFInfo
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- CN1822423A CN1822423A CNA200510108659XA CN200510108659A CN1822423A CN 1822423 A CN1822423 A CN 1822423A CN A200510108659X A CNA200510108659X A CN A200510108659XA CN 200510108659 A CN200510108659 A CN 200510108659A CN 1822423 A CN1822423 A CN 1822423A
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- carbonate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- 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
Abstract
A non-aqueous electrolyte for a lithium secondary battery is provided. The electrolyte comprises a lithium salt, a non-aqueous solvent, and an organic compound selected from the group consisting of compounds represented by Formulae (1) to (6): wherein R1 to R12 are each independently selected from the group consisting of primary, secondary, and tertiary alkyl groups, alkenyl groups, and aryl groups; X is hydrogen or halogen; and n and m are numerical values ranging from 0 to 3.
Description
The application is to be on May 10th, 2002 applying date, and application number is 02119206.5, is entitled as the dividing an application of national applications of " electrolyte of lithium secondary battery and contain the lithium secondary battery of this electrolyte ".
The cross reference of related application
The application is based on 2001-25763 and the 2001-25764 application that propose to Korean Patent office May 11 calendar year 2001, and its content is incorporated herein by reference.
Invention field
The present invention relates to the electrolyte of lithium secondary battery, and relate to the lithium secondary battery that comprises this electrolyte, relate more specifically to a kind of electrolyte that can improve the low-temperature characteristics of lithium secondary battery, and the lithium secondary battery that comprises this electrolyte.
Background of invention
Because the high-tech electronic industrial expansion, along with electronic equipment becomes more and more littler and more and more lighter, the use of portable electric appts constantly increases.Along with increase, the research of lithium secondary battery is carried out energetically as the demand of the high energy density cells of these portable electric appts power supplys.Contain the positive electrode active materials that lithium metal oxide is used as lithium secondary battery, and the lithium metal, contain lithium alloy, crystallization and unbodied carbon, and contain the negative active core-shell material that carbon complex is used as lithium secondary battery.
The average discharge volt of lithium secondary battery is about 3.6～3.7V, and it is higher than other alkaline battery, Ni-MH battery, Ni-Cd battery etc.But, in order to produce so high driving voltage, need be in the charging/discharging voltage scope of 0～4.2V the electrolyte of electrochemical stability.Therefore, use non-aqueous carbonate ester group solvent such as ethylene carbonate, dimethyl carbonate, diethyl carbonate etc., with lithium salts such as LiPF
6, LiBF
4Or LiClO
4Mixture as electrolyte.Yet the ionic conductance of this electrolyte is markedly inferior to the aqueous electrolyte of using in Ni-MH battery or Ni-Cd battery, thereby causes the deterioration of battery performance in the charge and discharge process under the two-forty.
Charge-discharge characteristic is subjected to the influence of the ionic conductance of electrolyte, therefore preferred high ionic conductance.Because a large amount of free ions can increase ionic conductance (cause of ionic conductance is a large amount of free ion), so the viscosity of the dielectric constant height of electrolyte and electrolyte is low.In addition, this electrolyte has low solidifying point, causes free ion motion good (Makoto Ue, Solution Chemistry ofOrganic Electrolyte, Progress in Battery Materials Vol.16 (1997)).
US5639575 and 5525443 discloses a kind of solvent with high-k, its with have low viscous solvent and mix mutually, so that strengthen the electrochemical properties of lithium ion battery, more specifically, it has subzero solvent and mixes mutually with a kind of, to strengthen lithium ion battery electrochemical properties at low temperatures.Yet when lithium ion battery discharged under two-forty (1C), its flash-over characteristic worsened rapidly, because at low temperatures, particularly under-20 ℃, the animal migration of lithium ion is too low.Therefore, when lithium ion battery discharged under two-forty, in order to strengthen the flash-over characteristic under its two-forty, electrolyte must have high ionic conductance and low internal resistance.
In the initial charge process of lithium secondary battery, move to the carbon negative pole by the lithium ion that contains lithium metal oxide release of anode, embed in carbon at this this ion.Because its high response, lithium and carbon negative reaction produce Li
2CO
3, LiO, LiOH etc., thus on the surface of negative pole, form film.This film is called solid electrolyte interface (SEI) film.The SEI film that forms in the initial charge process not only stops the reaction between the lithium ion and carbon negative pole or other material in charging and the discharge process, and plays the effect of ion tunnel, only allows lithium ion to pass through.Disintegrating of the anti-blocking negative pole structure of this ion tunnel, this organic solvent that causes having HMW in the electrolyte of disintegrating forms the lithium ion solvate, and this solvent and lithium ion solvate are embedded in the carbon negative pole jointly.
In case formed the SEI film, lithium ion just no longer reacts with carbon electrode or other material, causes the amount of lithium ion to be kept.That is to say, in the initial charge process,, form passivation layer thus from the carbon and the electrolyte reaction of negative pole, SEI film as forming on negative terminal surface causes electrolyte solution no longer to decompose, and can keep constant charge and discharge (J.Power Sources, 51 (1994), 79-104).As a result, in lithium secondary battery, do not exist irreversible passivation layer to form reaction, and can after the initial charge reaction, keep stable cycle life.
Because the characteristic of this SEI film is subjected to the influence of the type of solvent of employed electrolyte and additive, and they influence the motion of ion and the migration of electric charge, and may change battery efficiency, so they play conclusive effect (Shoichiro Mori to battery efficiency, Chemical Properties of VariousOrganic Electrolytes for Lithium Rechargeable Batteries, J.Power Sources, 68 (1997)).
In order to strengthen the characteristic of this SEI film, proposed in electrolyte, to add additive.For example, publication number is that the Japan Patent of 95-176323 discloses a kind of CO that added
2Electrolyte, and publication number is that the Japan Patent of 95-320779 discloses a kind of electrolyte with sulfide based compound additive, to prevent electrolyte decomposition.
Summary of the invention
The purpose of this invention is to provide a kind of electrolyte that has the lithium secondary battery of improved electrochemical properties at low temperatures.
Another object of the present invention provides a kind of lithium secondary battery that has improved electrochemical properties at low temperatures.
In order to realize these purposes, the invention provides a kind of electrolyte of lithium secondary battery.This electrolyte comprises lithium salts; Non-aqueous organic solvent; And at least aly be selected from the organic compound shown in following general formula (1)～(6):
R
9-SO
3-Si(C
mH
2m+1)
3 (3)
C
nX
2n+1-SO
3-Si(C
mH
2m+1)
3 (4)
R wherein
1～R
12Be selected from independently of one another: the primary, the second month in a season and tertiary alkyl, thiazolinyl, and aryl; X is hydrogen or halogen atom; And n and m are respectively 0～3 numerical value.Preferred R
1～R
12Be selected from C independently of one another
1～C
11Alkyl, C
2～C
11Thiazolinyl, and C
6～C
14Aryl.In a preferred embodiment of the invention, R
1～R
12Be selected from independently of one another: vinyl, benzyl and phenyl.
The present invention also provides a kind of lithium secondary battery that contains this electrolyte.
The accompanying drawing summary
The more complete description of the present invention and advantage thereof become with reference in conjunction with the accompanying drawings following detailed description to be easier to understand, wherein:
Fig. 1 is the curve chart of the battery cycle life of the explanation embodiment of the invention 1～3 and Comparative Examples 1;
Fig. 2 is the curve chart of the battery cycle life of the explanation embodiment of the invention 4～6 and Comparative Examples 1;
Fig. 3 is the curve chart of the battery cycle life of the explanation embodiment of the invention 15～18 and Comparative Examples 1.
Detailed Description Of The Invention
In the following detailed description, only illustrate and illustrated the preferred embodiment of the invention, illustrate by the optimal mode of making the present inventor's proposition simply.It should be noted that the present invention can make improvements aspect tangible various, all these all do not break away from the present invention.Therefore, drawing and description are interpreted as illustrative, rather than restrictive.
Electrolyte of the present invention comprises lithium salts, non-aqueous organic solvent and at least aly is selected from the compound shown in general formula (1)～(6).
The lithium salts that is used as the solute of electrolyte comprises at least a being selected from: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, Li (CF
3SO
2)
2N, LiC
4F
9SO
3, LiSbF
6, LiAlO
4, LiAlCl
4, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) (wherein, x and y are natural numbers), LiCl, LiI and composition thereof.
The concentration of lithium salts is preferably 0.7～2.0M.When the concentration of lithium salts is lower than 0.7M, make the mis-behave of electrolyte owing to its ionic conductance.When the concentration of lithium salts is higher than 2.0M, because the rising of electrolyte viscosity, and the mobility of lithium ion is descended.Lithium salts plays the effect of lithium ion source of supply in battery, make the basic operation of lithium secondary battery become possibility.
Non-aqueous organic solvent can comprise cyclic carbonate, linear carbonate or its mixture.Exemplary cyclic carbonate comprises: ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).Exemplary linear carbonate comprises: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid first propyl ester (MPC), ethyl propyl carbonic acid ester (EPC) and methyl ethyl carbonate (MEC).
In the present invention, cyclic carbonate and linear carbonate preferably mix with 1: 1～1: 9 volume ratio.When cyclic carbonate and linear carbonate are mixed with 1: 1～1: 9 volume ratio and with this mixture during as electrolyte, the performance of this electrolyte can strengthen.
In addition, electrolyte of the present invention also can comprise the mixture of carbonate group solvent and aromatic solvent.Exemplary aromatic solvent comprises: benzene, fluorobenzene, toluene, benzotrifluoride, dimethylbenzene and composition thereof.Carbonate group solvent and aromatic hydrocarbons preferably mix with 1: 1～10: 1 volume ratio.When carbonate group solvent and aromatic solvent mix with above-mentioned volume ratio and with this mixture during as electrolyte, the performance of this electrolyte can strengthen.
Organic compound shown in general formula (1)～(6) is added in the non-aqueous organic solvent, to prepare electrolyte of the present invention.
Exemplary organic compound can comprise: two (trimethyl silyl) sulfuric ester, di-t-butyl silicyl two (trifluoromethayl sulfonic acid ester), the trimethyl silyl methane sulfonate, the trimethyl silyl benzene sulfonate, trimethyl silyl trifluoromethayl sulfonic acid ester, triethylsilyl trifluoromethayl sulfonic acid ester, methyl mesylate, right-the toluenesulfonic acid methyl esters, benzene sulfonyl fluorine, and right-tosyl fluorine.
With the amount of organic compound with 0.1～10 weight %, preferably the amount with 0.1～5 weight % joins in the non-aqueous organic solvent, by the total weight of electrolyte.When the consumption of organic compound was lower than 0.1 weight %, electrolyte was not worked.When the consumption of organic compound was higher than 10 weight %, the cycle life characteristics of electrolyte may worsen.
In the discharge process under two-forty low temperature, this organic compound decomposes earlier than the organic solvent of electrolyte, so that react with lithium ion, the result forms the SEI film on negative terminal surface, thereby the organic solvent that has prevented electrolyte decomposes.This SEI film helps lithium ion easily to be embedded on the negative terminal surface, and internal resistance is reduced.Therefore, lithium secondary battery can have improved electrochemical properties.
Usually, electrolyte of the present invention is stable in-20～60 ℃ temperature range, even therefore also can make battery keep stable properties under the voltage of 4V.This electrolyte can be used in all types of lithium secondary batteries, as lithium ion battery and lithium polymer battery.
Lithium secondary battery of the present invention uses can reversibly embed/deviate from the material of lithium ion as positive pole and negative active core-shell material.This positive electrode active materials comprises lithium-containing compound, as lithium transition-metal oxide, as LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2O
4Or LiNi
1-x-yCo
xM
yO
2(wherein 0≤x≤1,0≤y≤1,0≤x+y≤1, and M is a metal, as Al, Sr, Mg, La etc.); Perhaps can reversibly embed/deviate from the lithium chalcogenide of lithium ion.This negative active core-shell material comprises amorphous or crystalline carbon, the compound of carbon containing, lithium metal or contain the alloy of lithium.
Lithium secondary battery prepares by following method: active material is applied on the collector body thin plate with suitable thickness and length, or the coating film forming of active material own is prepared the electrode group; The electrode group is placed in tank body or the similar container; The nonaqueous electrolytic solution that will contain organic compound then injects this tank body or container.Subsequently, the material or the film of coating are reeled or lamination with the insulating barrier of porous.Resin molding, as polyethylene, polypropylene etc. can be used as this dividing plate.
The following examples further describe the present invention, but not as limitation of the scope of the invention.
Embodiment and Comparative Examples
The electrolyte of embodiment 1～18 prepares according to following method: with the LiPF of 1M
6Join in the non-aqueous organic solvent, contain the ethylene carbonate (EC) and the dimethyl carbonate (DMC) that mix at 1: 1 with volume ratio in this non-aqueous organic solvent, then the organic compound shown in the table 1 is added in the solvent.
Table 1
| Organic compound | Addition (weight %) | |
| | Two (trimethyl silyl) | 1 |
| Embodiment 2 | Two (trimethyl silyl) sulfuric ester | 2 |
| Embodiment 3 | Two (trimethyl silyl) sulfuric ester | 5 |
| Embodiment 4 | Di-t-butyl silicyl two (trifluoromethayl sulfonic acid ester) | 1 |
| Embodiment 5 | Di-t-butyl silicyl two (trifluoromethayl sulfonic acid ester) | 2 |
| Embodiment 6 | Di-t-butyl silicyl two (trifluoromethayl sulfonic acid ester) | 5 |
| Embodiment 7 | The trimethyl silyl methane sulfonate | 2 |
| Embodiment 8 | The trimethyl silyl benzene sulfonate | 2 |
| Embodiment 9 | Trimethyl silyl trifluoromethayl sulfonic acid ester | 2 |
| Embodiment 10 | Triethylsilyl trifluoromethayl sulfonic acid ester | 2 |
| Embodiment 11 | Methyl mesylate | 2 |
| Embodiment 12 | Methyl mesylate | 5 |
| Embodiment 13 | Right-the toluenesulfonic acid methyl esters | 2 |
| Embodiment 14 | Right-the toluenesulfonic acid methyl esters | 5 |
| Embodiment 15 | The tosyl fluorine | 2 |
| Embodiment 16 | The tosyl fluorine | 5 |
| Embodiment 17 | Right-the tosyl fluorine | 2 |
| Embodiment 18 | Right-the tosyl fluorine | 5 |
Comparative Examples 1
Prepare electrolyte according to the method identical with embodiment 1～18, different is, not to the LiPF of non-aqueous organic solvent and 1M
6Mixture in be added with organic compounds.
The measurement of decomposition voltage
By cyclic voltammetry, measure embodiment 2,5,7～11,13,15 and 17, and the decomposition voltage of the electrolyte of Comparative Examples 1.Its result is shown in following table 2.
Table 2
| Decomposition voltage (V) | |
| Embodiment 2 | 0.85 |
| Embodiment 5 | 1.05 |
| Embodiment 7 | 0.92 |
| Embodiment 8 | 0.83 |
| Embodiment 9 | 0.75 |
| Embodiment 10 | 0.65 |
| Embodiment 11 | 0.54 |
| Embodiment 13 | 1.05 |
| Embodiment 15 | 0.90 |
| Embodiment 17 | 1.33 |
| Comparative Examples 1 | 0.5 |
The measuring condition of decomposition voltage is as follows:
Work electrode: mesocarbon fiber (MCF); Reference electrode: Li-metal; Counterelectrode: Li-metal; Voltage range: 3V～0V; Sweep speed: 0.1mV/s.
The decomposition voltage of electrolyte that has wherein added the embodiment of organic compound is higher than the decomposition voltage of the electrolyte of the Comparative Examples 1 that does not wherein add organic compound.Therefore, in the initial charge process, the electrolyte among the embodiment is than the first decomposition of carbonate group organic solvent, and forms the SEI film under decomposition voltage on negative pole.
The manufacturing of lithium ion battery
Will be as the LiCoO of positive electrode active materials
2,, and after mixing with 92: 4: 4 weight ratio as the carbon of conductive agent, prepare anode sizing agent by this mixture is distributed in the N-N-methyl-2-2-pyrrolidone N-(NMP) as the polyvinylidene fluoride (PVdF) of binding agent.Thickness with 20 μ m is coated on this slurry on the aluminium foil, and dry and compacting makes positive pole thus.After will mixing with 92: 8 weight ratio,, this mixture prepares cathode size among the NMP by being distributed to as the crystallization Delanium of negative active core-shell material with as the PVdF of binding agent.Thickness with 15 μ m is applied to this slurry on the Copper Foil, and dry and compacting makes negative pole thus.With prepared electrode with the thick polyethylene separator of 25 μ m through reeling and compacting, place the prismatic tank body that is of a size of 30mm * 48mm * 6mm then.Every kind of electrolyte of embodiment 1～18 and Comparative Examples 1 is injected other tank body of branch, finished the manufacturing of lithium ion battery thus.
The measurement of the discharge capacity retention rate of lithium ion battery
The lithium ion battery that makes by the electrolyte that injects embodiment 1～18 and Comparative Examples 1 under constant current and constant voltage (CC-CV) with the current charges of 160mA charging voltage to 4.2V.Then, battery was left standstill 1 hour, and under 2.5V with the current discharge of 160mA, and left standstill again 1 hour.After repeating this process 3 times, battery was charged to the voltage of 4.2V with the electric current of 800mA in 2 hours 30 minutes.After the charging, battery is placed in-20 ℃ the condenser, left standstill 16 hours.Then, be 2.75V with battery with current discharge to the voltage of 160mA, to measure the discharge capacity of battery.The discharge capacity retention rate of battery is listed in the table 3.
Table 3
| Discharge capacity retention rate (%) | |
| | 72.4 |
| Embodiment 2 | 75.5 |
| Embodiment 3 | 70.0 |
| Embodiment 4 | 73.0 |
| Embodiment 5 | 77.3 |
| Embodiment 6 | 75.8 |
| Embodiment 7 | 73.5 |
| Embodiment 8 | 75.9 |
| Embodiment 9 | 74.3 |
| Embodiment 10 | 76.2 |
| Embodiment 11 | 75.4 |
| Embodiment 12 | 71.9 |
| Embodiment 13 | 73.3 |
| Embodiment 14 | 69.8 |
| Embodiment 15 | 71.0 |
| Embodiment 16 | 75.3 |
| Embodiment 17 | 76.8 |
| Embodiment 18 | 73.5 |
| Comparative Examples 1 | 69.5 |
With battery current charges to voltage with 160mA under CC-CV is 4.2V, and they were left standstill in-20 ℃ condenser 5 hours.Is 2.75V with battery with current discharge to the voltage of 800mA.Discharge capacity retention rate corresponding to the cycle-index of battery is listed in the table 4.
Table 4
| Initial discharge voltage (V) | Discharge capacity retention rate (%) | |
| | 3.55 | 24.4 |
| Embodiment 2 | 3.61 | 39.5 |
| Embodiment 3 | 3.41 | 18.2 |
| Embodiment 4 | 3.35 | 10.4 |
| Embodiment 5 | 3.52 | 21.1 |
| Embodiment 6 | 3.55 | 16.6 |
| Embodiment 7 | 3.25 | 3.5 |
| Embodiment 8 | 3.31 | 17.9 |
| Embodiment 9 | 3.25 | 9.2 |
| Embodiment 10 | 3.46 | 21.9 |
| Embodiment 11 | 3.55 | 24.4 |
| Embodiment 12 | 3.35 | 11.9 |
| Embodiment 13 | 3.25 | 18.2 |
| Embodiment 14 | 3.20 | 7.9 |
| Embodiment 15 | 3.52 | 12.4 |
| Embodiment 16 | 3.55 | 17.5 |
| Embodiment 17 | 3.25 | 26.8 |
| Embodiment 18 | 3.31 | 18.9 |
| Comparative Examples 1 | 3.11 | 2 |
As shown in table 4, the battery of electrolyte that contains the embodiment of the invention 1～18 is compared with the electrolyte of Comparative Examples 1 of the present invention under-20 ℃ low temperature, has the cycle life characteristics that more improves.
The flash-over characteristic that comprises the lithium ion battery of the present invention of the electrolyte that contains organic compound has improved 2～5% under low rate (0.2C), and has improved greater than 20% under two-forty (1C).
Under room temperature and CC-CV condition, battery is 4.2V with current charges to the voltage of 800mA.The battery of charging is 2.75V with current discharge to the voltage of 800mA.Battery to the electrolyte that contains embodiment 1～3 carries out charge and discharge cycles 300 times, and cycle life characteristics is shown among Fig. 1.Also the battery to the electrolyte that contains embodiment 4～6 has carried out charge and discharge cycles 300 times, and cycle life characteristics is shown among Fig. 2.Equally, the battery of the electrolyte that contains embodiment 15～18 has been carried out charge and discharge cycles 300 times, and cycle life characteristics is shown among Fig. 3.For the cycle life characteristics of the battery of comparing embodiment, also be painted with the cycle life characteristics of the battery of the electrolyte that contains Comparative Examples 1 on each figure.
Shown in Fig. 1～3, the battery that comprises the electrolyte of the organic compound that contains embodiment is better than containing the battery of the electrolyte of Comparative Examples 1 aspect cycle life characteristics.
In the discharge process under two-forty and low temperature, this organic compound decomposes prior to the organic solvent of electrolysis, so that react with lithium ion, the result forms the SEI film on the surface of negative pole, has therefore prevented the decomposition of carbonate group organic solvent.This SEI film helps lithium ion easily to be embedded on the surface of electrode, and reduces internal resistance.Therefore, lithium ion battery can have improved electrochemical properties.Lithium ion battery of the present invention has the excellent charging and discharging characteristic, and improved cycle life and flash-over characteristic under two-forty and low temperature.
The present invention is described with reference to embodiment preferred, and the skilled person in those this areas should be understood that and can make various improvement and replacement, and do not depart from the spirit and scope of the present invention that limit in the appending claims.
Claims (22)
1, a kind of nonaqueous electrolytic solution of lithium secondary battery comprises:
A kind of lithium salts;
A kind of non-aqueous organic solvent; And
At least a organic compound that is selected from following general formula (1)～(6):
R
9-SO
3-Si(C
mH
2m+1)
3 (3)
C
nX
2n+1-SO
3-Si(C
mH
2m+1)
3 (4)
R wherein
7～R
9Independently be selected from separately: the primary, the second month in a season and tertiary alkyl, thiazolinyl, and aryl; X is a hydrogen or halogen; And n and m are respectively 0～3 numerical value.
2, according to the electrolyte of the lithium secondary battery of claim 1, wherein this lithium salts is selected from: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, Li (CF
3SO
2)
2N, LiC
4F
9SO
3, LiSbF
6, LiAlO
4, LiAlCl
4, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) (wherein, x and y are natural numbers), LiCl, LiI and composition thereof.
3, according to the electrolyte of the lithium secondary battery of claim 2, wherein the concentration of this lithium salts is in 0.7～2.0M scope.
4, according to the electrolyte of the lithium secondary battery of claim 1, wherein this non-aqueous organic solvent is selected from: cyclic carbonate, linear carbonate and composition thereof.
5, according to the electrolyte of the lithium secondary battery of claim 4, wherein this non-aqueous organic solvent contains the cyclic carbonate and the linear carbonate of mixing in 1: 1～1: 9 with volume ratio.
6, according to the electrolyte of the lithium secondary battery of claim 4, wherein this non-aqueous organic solvent comprises and is selected from ethylene carbonate (EC), propylene carbonate (PC), the cyclic carbonate of butylene carbonate (BC) and composition thereof.
7, according to the electrolyte of the lithium secondary battery of claim 4, wherein this non-aqueous organic solvent comprises and is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid first propyl ester (MPC), ethyl propyl carbonic acid ester (EPC), the linear carbonate of methyl ethyl carbonate (MEC) and composition thereof.
8, according to the electrolyte of the lithium secondary battery of claim 1, wherein this non-aqueous organic solvent comprises the mixture of carbonate group solvent and aromatic solvent.
9, the electrolyte of lithium secondary battery according to Claim 8, wherein this aromatic solvent is selected from benzene, fluorobenzene, toluene, benzotrifluoride, dimethylbenzene and composition thereof.
10, the electrolyte of lithium secondary battery according to Claim 8, wherein this carbonate group solvent and aromatic solvent mixed with volume ratio in 1: 1～10: 1.
11, according to the electrolyte of the lithium secondary battery of claim 1, wherein this organic compound is selected from di-t-butyl silicyl two (trifluoromethayl sulfonic acid ester), the trimethyl silyl methane sulfonate, the trimethyl silyl benzene sulfonate, trimethyl silyl trifluoromethayl sulfonic acid ester, and triethylsilyl trifluoromethayl sulfonic acid ester.
12, according to the electrolyte of the lithium secondary battery of claim 1, wherein this organic compound exists with the weight ratio of 0.1～10 weight %.
13, according to the electrolyte of the lithium secondary battery of claim 1, wherein this organic compound exists with the weight ratio of 0.1～5 weight %.
14, the electrolyte of lithium secondary battery comprises:
A kind of lithium salts;
A kind of non-aqueous organic solvent; And
Organic compound shown in the general formula (4) below a kind of:
C
nX
2n+1-SO
3-Si(C
mH
2m+1)
3 (4)
Wherein X is a hydrogen or halogen; And n and m are 0～3 numerical value.
15, according to the electrolyte of the lithium secondary battery of claim 14, wherein this lithium salts is selected from: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, Li (CF
3SO
2)
2N, LiC
4F
9SO
3, LiSbF
6, LiAlO
4, LiAlCl
4, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) (wherein, x and y are natural numbers), LiCl, LiI and composition thereof.
16, according to the electrolyte of the lithium secondary battery of claim 15, wherein the concentration of this lithium salts is in the scope of 0.7～2.0M.
17, according to the electrolyte of the lithium secondary battery of claim 14, wherein this non-aqueous organic solvent comprises the mixture of carbonate group solvent and aromatic solvent.
18, according to the electrolyte of the lithium secondary battery of claim 17, wherein this aromatic solvent is selected from benzene, fluorobenzene, toluene, benzotrifluoride, dimethylbenzene and composition thereof.
19, according to the electrolyte of the lithium secondary battery of claim 14, wherein this organic compound is a trimethyl silyl trifluoromethayl sulfonic acid ester.
20, according to the electrolyte of the lithium secondary battery of claim 14, wherein:
This lithium salts is LiPF
6
This non-aqueous organic solvent comprises ethylene carbonate (EC) and dimethyl carbonate (DMC); And
This organic compound is a trimethyl silyl trifluoromethayl sulfonic acid ester.
21, a kind of lithium secondary battery comprises:
According to each electrolyte in the aforementioned claim;
Positive pole, this positive pole comprises the positive electrode active materials that can reversibly embed/deviate from lithium ion; And
Negative pole, this negative pole comprises the negative active core-shell material that can reversibly embed/deviate from lithium ion.
22, according to the lithium secondary battery of claim 21, wherein this lithium secondary battery is lithium ion battery or lithium polymer battery.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0025763A KR100412522B1 (en) | 2001-05-11 | 2001-05-11 | A non-aqueous electrolyte and a lithium secondary battery comprising the same |
| KR0025763/01 | 2001-05-11 | ||
| KR0025764/01 | 2001-05-11 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021192065A Division CN1269254C (en) | 2001-05-11 | 2002-05-10 | Electrolytic solution for lithium secondary cell and lithium cell containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1822423A true CN1822423A (en) | 2006-08-23 |
| CN100433444C CN100433444C (en) | 2008-11-12 |
Family
ID=36923562
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510108659XA Expired - Fee Related CN100433444C (en) | 2001-05-11 | 2002-05-10 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100412522B1 (en) |
| CN (1) | CN100433444C (en) |
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| CN103560270A (en) * | 2013-10-30 | 2014-02-05 | 河南师范大学 | Electrolyte for lithium ion battery |
| CN104393242A (en) * | 2007-06-11 | 2015-03-04 | 株式会社Lg化学 | Non-aqueous electrolyte and secondary battery comprising the same |
| CN106159321A (en) * | 2015-03-31 | 2016-11-23 | 比亚迪股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN107403956A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
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| CN110429336A (en) * | 2019-07-24 | 2019-11-08 | 江苏国泰超威新材料有限公司 | A kind of nonaqueous electrolytic solution and lithium ion battery |
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| CN111554976A (en) * | 2019-02-12 | 2020-08-18 | 三星电子株式会社 | Lithium battery |
| CN112567558A (en) * | 2018-08-07 | 2021-03-26 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
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| KR20160099133A (en) * | 2015-02-11 | 2016-08-22 | 전자부품연구원 | Electrolyte for lithium-ion battery and lithium-ion battery having the same |
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| KR20220124870A (en) | 2021-03-04 | 2022-09-14 | 동화일렉트로라이트 주식회사 | Electrolyte Solution for Secondary Battery and Secondary Battery Comprising the Same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07101611B2 (en) * | 1987-12-01 | 1995-11-01 | 日立マクセル株式会社 | Inorganic non-aqueous electrolyte battery |
| JP3428910B2 (en) * | 1997-09-25 | 2003-07-22 | キヤノン株式会社 | Method for producing electrolyte and method for producing secondary battery |
-
2001
- 2001-05-11 KR KR10-2001-0025763A patent/KR100412522B1/en active IP Right Grant
-
2002
- 2002-05-10 CN CNB200510108659XA patent/CN100433444C/en not_active Expired - Fee Related
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| CN103560270B (en) * | 2013-10-30 | 2015-11-18 | 河南师范大学 | A kind of electrolyte for lithium ion battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100433444C (en) | 2008-11-12 |
| KR100412522B1 (en) | 2003-12-31 |
| KR20020086068A (en) | 2002-11-18 |
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