CN101394008A - Lithium ion secondary battery using lithium iron phosphate as anode material with overall consideration of high and low temperature performance - Google Patents
Lithium ion secondary battery using lithium iron phosphate as anode material with overall consideration of high and low temperature performance Download PDFInfo
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- CN101394008A CN101394008A CNA2008102188109A CN200810218810A CN101394008A CN 101394008 A CN101394008 A CN 101394008A CN A2008102188109 A CNA2008102188109 A CN A2008102188109A CN 200810218810 A CN200810218810 A CN 200810218810A CN 101394008 A CN101394008 A CN 101394008A
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Abstract
The invention discloses an aqueous electrolyte solution of a secondary lithium ion battery with ferric phosphate considering as the positive material and with both the high temperature performance and the low temperature performance. The aqueous electrolyte solution comprises LiPF6 lithium salt, an organic solvent and a film-forming additive, and is characterized in that the electrolyte solution further comprises high temperature additive; the organic solvent is composed of one or a plurality of carbonic esters and one or more carboxylic esters with low melting point and high boiling point. The carboxylic esters with low melting point and high boiling point are selected from one or a combination of methyl butyrate, ethyl butyrate, propyl butyrate and butyl acetate. The high temperature additive is 1, 3- propane sultone and 1, 4- butane sultone. The electrolyte solution is used for maintaining both the circulation performance in a high temperature state and the low temperature laying performance of the secondary lithium ion battery with the ferric phosphate lithium as the positive material.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery nonaqueous electrolytic solution, relating in particular to the LiFePO4 that a kind of high and low temperature performance takes into account is the lithium rechargeable battery nonaqueous electrolytic solution of positive electrode.
Background technology
Serious day by day along with the progressively exhausted and vehicle exhaust environmental pollution of whole world petroleum resources, electric motor car (EV) and hybrid vehicle (HEV) and corresponding electrical source of power are developed rapidly.At present; EV and HEV mainly use plumbic acid and Ni-MH battery as driving power; but their life-span is short; and cause environmental pollution easily; appearance along with energy crisis in the global range; lithium ion battery becomes the main developing direction of 21 century energy field as the energy green, sustainable development.Lithium rechargeable battery becomes the research focus of present new energy field because energy density is big, operating voltage is high, have extended cycle life, environmental pollution is little etc. plurality of advantages.Along with the swift and violent increase of lithium ion battery consumption and electric automobile demand to high capacity lithium ion battery, press for development and have high security, high-energy-density, high power, long circulation, environmental protection and inexpensive lithium ion battery, need for this reason to develop that environmental friendliness, raw material resources are abundant, the lithium ion battery positive and negative electrode material and the electrolyte of excellent performance.LiFePO4 (LiFePO
4) with its excellent performance, cheap price becomes the positive electrode of power lithium-ion battery first-selection.
Electrolyte is as the important component part of battery, between both positive and negative polarity, play a part transmission lithium ion and conduction current, selecting suitable electrolyte also is the key that obtains the good lithium rechargeable battery of high-energy-density, long circulation life and fail safe, therefore in further investigation lithium iron phosphate positive material production technology, the electrolyte that exploitation is applicable to LiFePO4 is very important also.At present at high temperature capacitance loss is rapid for LiFePO 4, and cycle performance is poor, and very low and high-rate discharge ability battery of discharge capacity also is difficult to reach the requirement of electrokinetic cell at low temperatures.For satisfying the demand, in the exploitation of electrolyte, tend to optimize the composition of organic electrolyte gradually with some new solvents and additive, this is the conductivity that improves organic electrolyte, reduces polarization, is to improve one of most important approach of battery performance.By optimizing the composition of organic solvent, can make electrolyte obtain high as far as possible conductivity.Use the difficult requirement that reaches electrolyte of single solvent in lithium ion battery, present commercial liquid lithium ionic cell all is to adopt mixed solvent system.
In order to satisfy lithium ion battery high voltage (〉 4V) performance demands, should have following characteristic as the organic electrolyte of lithium ion battery practicality:
(1) with Li
+The ionic conductivity of conduction is high as much as possible;
(2) potential range of electrochemical stability is wide as far as possible;
(3) good thermal stability, the temperature range of use is wide as far as possible;
(4) good chemical stability does not react with collector and active material in the battery;
(5) good fail safe and alap toxicity preferably can biodegradation;
(6) price is low.
It is a lot of as the factor of lithium ion battery electrolyte solvent to influence an organic solvent, but determines that the greatest factor of its commercial applications is its fail safe, long-term stability and reaction rate.Fail safe mainly is to consider flash-point, volatility, toxicity and the battery of the organic solvent problems such as reaction with other battery material under the abuse state.Because lithium ion battery has higher voltage, this just requires electrolyte should have enough oxidation stabilities, and the electrolyte that development can be applied to battery and have thermodynamics and kinetics stability is the most challenging in a Study on Li-ion batteries using job.Because ether electrolyte is when voltage is above above 4V, oxidation reaction will take place, make organic solvent generation polymerization, if in the organic solvent molecule, introduce for example cyano group of certain electronegativity group, carbonate or ester group, will increase the resistance to oxidation stability of organic solvent, even under higher voltage, also be difficult to oxidized as acetonitrile, but acetonitrile is to the lithium instability, can in lithium ion battery, be applied and be still waiting further research, organic carbonate class such as EC, PC and DMC etc. have obtained application with its good electrochemical stability in lithium ion battery, Sony company has just used mixed solvent as lithium-ion battery electrolytes in its commercial the earliest battery.
Long-term stability is exactly to require electrolyte to have inherent stability, and the active electrode material with battery does not react, and perhaps can form the extraordinary film of ion permeability in the electrode surface reaction, and this just requires Li
+Have higher mobility and its transport number near 1, yet when lithium salts was dissolved in organic solvent, the contained oxygen atom of solvent molecule, nitrogen-atoms nearly all can form the solvent complex thing with lithium generation coordination, thereby the transport number that makes lithium ion is less than 0.5.Therefore the polarity effect that reduces lithium ion is a major criterion of selective solvent to the influence of lithium ion transference number and the conductivity of raising electrolyte.The conductivity that improves organic electrolyte is to improve the reaction rate of electrode, realize the prerequisite of battery high current charge-discharge under reversible capacity, optimize the composition of organic electrolyte, improve the conductivity of organic electrolyte, improving the performance of SEI film, is one of most important approach that improves electrode reaction speed.
To lithium ion battery, the compatible coupling of organic electrolyte and electrode is the key factor of the performance characteristics such as high voltage, high-energy-density and long cycle efficieny of restriction lithium ion battery.The interaction mechanism of research organic electrolyte and electrode is the important channel of improving the lithium ion battery performance.The interaction mechanism of generally accepted organic electrolyte of people and electrode is now: the polar non-solute as lithium ion battery in battery first charge-discharge process all will react on the boundary of electrode and electrolyte inevitably, formation covers the passivation thin layer-solid electrolyte phase boundary facial mask on the electrode surface, the formation of SEI film has consumed lithium ion limited in the battery on the one hand, also increased the interface resistance of electrode/electrolyte on the other hand, caused certain voltage delay, but good SEI film has the insoluble of organic solvent, allow lithium ion more freely to pass in and out electrode and solvent molecule can't pass through, thereby stoped slotting altogether the destruction of solvent molecule, improved the cycle life of battery greatly electrode.Thereby, how to optimize the electrode fine structure, improve state of interface, how to select suitable electrolyte, guarantee that it is the key factor that realizes the electrode/electrolyte compatibility that each component of electrolyte forms the SEI film good, stable performance, that lithium ion can be led at the electrode/electrolyte boundary.
Carbonic ester mainly comprises cyclic carbonate and linear carbonate two classes.The carbonates solvent has electrochemical stability preferably, higher flash-point and lower fusing point and is widely used in lithium ion battery, all adopts the solvent of carbonic ester as electrolyte in business-like lithium ion battery basically.Cyclic carbonate commonly used in the lithium ion battery mainly comprises vinyl carbonate (EC), propylene carbonate (PC) and butylene (BC) etc., and PC is a research the longest historical solvent.EC has bigger dielectric constant, thereby has obtained to use more widely in lithium ion battery.Linear carbonate mainly comprises dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) etc., this kind solvent all has lower viscosity and lower dielectric constant, and they usually are used for lithium ion battery with cyclic carbonate composition mixed solvent.
Carboxylate equally also comprises cyclic carboxylic esters and chain carboxylate two classes.Topmost organic solvent is gamma-butyrolacton and its some derivatives in the cyclic carboxylic esters.The dielectric constant of gamma-butyrolacton, once was used widely in disposable lithium-battery so its electrical conductivity of solution is lower than PC less than PC.Chain carboxylate R
1COOR
2(R wherein
1And R
2Be that carbon number is at the alkyl below 5) wherein mainly contain methyl formate (MF), Ethyl formate (EF), methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), ethyl butyrate (EB) etc.These materials have low viscosity and wide advantages such as molten boiling temperature scope, so it is expected to be applied in secondary lithium battery electrolyte field.
Film for additive mainly comprises vinylene carbonate (VC), ethylene sulfite (ES), di-oxalate lithium borate (LiBOB), 1,3-propane sultone (PS), LiBF4 (LiBF
4) etc., mainly be that adding by film for additive makes after the battery preliminary filling and to form a kind of densification, stable, the low SEI film of impedance on the negative material surface.
Chinese patent 01116314.3 discloses a kind of nonaqueous electrolytic solution, it comprises at least a in carbonic ester and the carboxylate, form film by adding carbonic acid (divinyl) ethylidene ester at negative pole, improve the shelving performance under the high-temperature charging state of this nonaqueous electrolytic solution, but the battery that injects the nonaqueous electrolytic solution of this invention is difficult to take into account cycle performance and the low temperature shelving performance under the condition of high temperature.
Summary of the invention
It is the lithium rechargeable battery nonaqueous electrolytic solution of positive electrode that technical problem to be solved by this invention provides the LiFePO4 that a kind of high and low temperature performance takes into account, and this used for electrolyte is that the lithium rechargeable battery of positive electrode can be taken into account cycle performance and the low temperature shelving performance under the condition of high temperature at LiFePO4.
The present invention solves the technical scheme that its technical problem adopts:
The lithium rechargeable battery nonaqueous electrolytic solution that a kind of high and low temperature performance is taken into account, it comprises: LiPF
6Lithium salts, organic solvent, the inferior ethene film for additive of carbonic acid, high temperature additive; Described organic solvent is made up of one or more carbonic esters and one or more low melting points, high boiling carboxylate.
Described low melting point, high boiling carboxylate are selected from the one or more combination in methyl butyrate, ethyl butyrate, propyl butyrate or the butyl acetate.
Described low melting point, high boiling carboxylate are selected from the one or more combination in methyl butyrate, ethyl butyrate, the propyl butyrate.Described high temperature additive is 1,3-propane sultone or 1,4-butane sultone.
The addition of described high temperature additive be non-hydrolysis electrolyte total amount percentage by weight 3%～4%.
In described nonaqueous electrolytic solution, add anti-overcharge additive biphenyl or cyclohexyl benzene.
Advantage of the present invention: solvent of the present invention is made up of one or more carbonic esters and one or more low melting points, high boiling carboxylate.The present invention filters out methyl butyrate, ethyl butyrate, propyl butyrate, butyl acetate by experiment from a large amount of carboxylates, their fusing point, boiling point are respectively-97 ℃, 102.3 ℃;-98 ℃, 121.6 ℃;-95.2 ℃, 142.7 ℃;-77.9 ℃, 121.6 ℃; They all are low melting point, high boiling carboxylate.Adopt low melting point and high boiling carboxylic acid esters solvent, especially methyl butyrate, ethyl butyrate, propyl butyrate series, its temperature range is wideer.Make electrolyte have wide serviceability temperature scope, guarantee that electrolyte is highly stable when high temperature, do not decompose, battery is inflatable not.Because ratio of viscosities is lower under this kind solvent normal temperature, so under cryogenic conditions, can make electrolyte have certain conductivity, guarantee the performance of capacity under the low temperature condition, so can take into account the high and low temperature performance of electrolyte to a certain extent, and lithium iron phosphate positive material be had compatible preferably.
The advantage that adds film for additive mainly is to obtain constitutionally stable SEI film in the formation of negative material surface by solvent and lithium salts reduction in battery preliminary filling process; good SEI film can play the effect of protection carbon negative pole, can improve the stability of carbon negative pole in the electrochemistry cyclic process.Vinylene carbonate is a film for additive relatively more commonly used at present.But some other film for additive also shows reasonable filming performance.
Adding high temperature additive mainly is by the SEI film being modified and reinforced, make it keep Stability Analysis of Structures in the high temperature circulation process, can improving the high temperature circulation stability of battery like this.
Because power lithium-ion battery is more and more higher to the requirement of fail safe, the adding of anti-overcharge additive can improve the over-charging of battery effectively in the electrolyte, guarantees that it under the 3C10V situation, does not explode, and is not on fire, is able to the purpose of practical application.
Description of drawings
Fig. 1 is the curve of the high temperature circulation discharge performance of battery liquid in battery of embodiment 1-12, Comparative Examples 1-4.
The corresponding embodiment 1-12 of 1-12 difference in the abscissa among the figure, the corresponding Comparative Examples 1-4 of 13-16 difference in the abscissa.Ordinate represents to inject the capability retention of ferric phosphate lithium cell after 200 weeks of circulation under 60 ℃ of embodiment 1-12 and Comparative Examples 1-4 among the figure.
Embodiment
The electrolyte quota method of embodiments of the invention and Comparative Examples:
With the carbonates solvent with carboxylic acid esters is molten mixes by required quality proportioning, in this solvent, add LiPF then
6, average mark adds for three times, each time interval 1.5-2 hour of adding, fully shake up the back after the adding and add additive, whole electrolyte is all operated in glove box in process for preparation, and glove box is an ar gas environment, temperature in the case is controlled in 25 ℃, and moisture is below 1ppm.This electrolyte is injected in the battery, tests.
Comparative Examples 1: with ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) mixes, and makes three's mass ratio reach 30:30:40, dissolves lithium salts LiPF by the ratio with 1M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, and modulated nonaqueous electrolytic solution.
Comparative Examples 2: with ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and ethyl butyrate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 1M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, and modulated nonaqueous electrolytic solution.
Comparative Examples 3: with ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and propyl butyrate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 1M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, and modulated nonaqueous electrolytic solution.
Comparative Examples 4: with ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and methyl butyrate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 1M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, and modulated nonaqueous electrolytic solution.
Embodiment 1: on the basis of Comparative Examples 2, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and 3-propane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 2: on the basis of Comparative Examples 2, add the high temperature additive 1 that accounts for electrolyte total weight 4%, and 3-propane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 3: on the basis of Comparative Examples 2, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and the 4-butane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 4: on the basis of Comparative Examples 2, add the high temperature additive 1 that accounts for electrolyte total weight 4%, and the 4-butane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 5: on the basis of Comparative Examples 3, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and 3-propane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 6: on the basis of Comparative Examples 3, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and the 4-butane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 7: on the basis of Comparative Examples 4, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and 3-propane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 8: on the basis of Comparative Examples 4, add the high temperature additive 1 that accounts for electrolyte total weight 3%, and the 4-butane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 9: on the basis of Comparative Examples 2 with the fluoroethylene carbonic ester (FEC) that accounts for electrolyte total weight 2% as film for additive, add and account for 1 of electrolyte total weight 3%, 3-propane sultone is as high temperature additive, and modulated nonaqueous electrolytic solution.
Embodiment 10: on the basis of Comparative Examples 3 with the fluoroethylene carbonic ester (FEC) that accounts for electrolyte total weight 2% as film for additive, add and account for 1 of electrolyte total weight 3%, 3-propane sultone is as high temperature additive, and modulated nonaqueous electrolytic solution.
Embodiment 11: on the basis of Comparative Examples 4 with the fluoroethylene carbonic ester (FEC) that accounts for electrolyte total weight 2% as film for additive, add and account for 1 of electrolyte total weight 3%, 3-propane sultone is as high temperature additive, and modulated nonaqueous electrolytic solution.
Embodiment 12: with ethylene carbonate (EC), and dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and butyl acetate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 1M in this solvent
6With film for additive vinylene carbonate that accounts for electrolyte total weight 2% and the high temperature additive 1 that accounts for total electrolyte total weight 3%, 3-propane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 13: on the basis of Comparative Examples 2, add the high temperature additive 1 account for electrolyte total weight 3%, and 3-propane sultone and account for the overcharging additive biphenyl (BP) of electrolyte total weight 5%, and modulated nonaqueous electrolytic solution.
Embodiment 14: on the basis of Comparative Examples 2, add the high temperature additive 1 account for electrolyte total weight 3%, and 3-propane sultone and account for the overcharging additive cyclohexyl benzene (CHB) of electrolyte total weight 5%, and modulated nonaqueous electrolytic solution.
Embodiment 15: with ethylene carbonate (EC), and dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and ethyl butyrate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 1.5M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, add the high temperature additive 1 that accounts for electrolyte total weight 3.5%, the 4-butane sultone, and modulated nonaqueous electrolytic solution.
Embodiment 16: with ethylene carbonate (EC), and dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and propyl butyrate mix, and make the mass ratio of above-mentioned solvent reach 30:30:20:20, dissolve lithium salts LiPF by the ratio with 0.8M in this solvent
6With the film for additive vinylene carbonate that accounts for electrolyte total weight 2%, add the high temperature additive 1 that accounts for electrolyte total weight 3.5%, 3-propane sultone, and modulated nonaqueous electrolytic solution.
The performance test of embodiment and Comparative Examples and explanation
Employed battery is:
Anodal preparation: active material LiFePO
4 Content 90%, carbon black 5%, binding agent PVDF5%, aluminium foil is as collector, pole piece width 4.0cm, thickness 150 μ m.
The preparation of negative pole: the content 95.2% of active material Delanium, conductive agent 1.8%, the content 2.0% of binding agent, dispersant 1.0%, Copper Foil are collector, the wide 4.1cm of pole piece, thickness 110 μ m.
Barrier film is PE/PP/PE three strata compound films, barrier film width 4.3cm, the design capacity 400mAh of battery.
Detection method: respectively embodiment 1-12 or Comparative Examples 1-4 gained electrolyte are respectively annotated 6 batteries, after battery changes into, the on average irreversible capacity first of counting cell, wherein three batteries carry out 60 ℃ of loop tests of high temperature, and three batteries are done-20 ℃ and are placed test in 4 hours.
The detection method of battery high-temperature test: the 1C loop test that under 60 ℃, carries out battery by the volume test cabinet of secondary cell.
The detection method of battery low-temperature test: under the normal temperature, in the secondary cell Performance Detection cashier's office in a shop with 0.5C electric current constant voltage charge to 3.85V, cut-off current is 10mA, shelves after the 5min, carries out constant-current discharge to 2.0V with the 0.5C electric current, shelves capacity under the 5min postscript.After placing 4h under-20 ℃, repeat the top step that charges and discharge then, record battery discharge capacity at low temperatures.
With the moisture in the coulomb Ka Shi method mensuration electrolyte, the acidity of acid base titration test electrolyte, measure the conductivity of electrolyte with DJS-307 type electric conductivity instrument.
The irreversible capacity loss of table 1 embodiment 1-12 and Comparative Examples 1-4 and low temperature performance
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| Irreversible capacity loss | 15.2 | 13.9 | 13.7 | 15.1 | 14.3 | 15.1 | 11.8 | 15.3 | 13.8 |
| Discharge rate ①/％ | 55.9 | 53.5 | 52.7 | 53.0 | 53.3 | 54.4 | 53.8 | 53.3 | 54.2 |
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Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |||
| Irreversible capacity loss | 12.9 | 13.6 | 14.3 | 15.8 | 15.6 | 14.8 | 15.5 | ||
| Discharge rate ①/％ | 56.3 | 55.5 | 51.7 | 48.9 | 55.4 | 56.8 | 53.2 |
1. discharge rate=-20 ℃ are placed 0.5C discharge capacity under 0.5C discharge capacity/normal temperature behind the 4h down
Table 1 for embodiment 1-12 and Comparative Examples-20 ℃ of low temperature discharge data of shelving 4h, as can be seen from the table, the adding of carboxylate solvent can improve the cryogenic property of battery, from the low temperature discharge data of embodiment 1-8 as can be seen, after adding high temperature additive, the cryogenic property of electrolyte is affected, may be because the increase of SEI membrane impedance causes.The cryogenic property of finding ethyl butyrate simultaneously is relatively good, has reached the purpose that high temperature performance is taken into account.The cryogenic property that changes over the embodiment 9-11 behind the film additive is fine, may be because the SEI membrane impedance that this kind film for additive forms is less.Embodiment 12 has adopted this carboxylate solvent of butyl acetate, data find out that cryogenic property does not have the cryogenic property of butyrate series good from table, so think, the adding of carboxylate solvent can improve the cryogenic property of electrolyte, and the adding of high temperature additive can improve its high-temperature behavior when guaranteeing the cryogenic property performance, reach the purpose that high temperature performance is taken into account, and low melting point and high boiling butyrate series have better performance at the high low temperature of ferric phosphate lithium cell aspect taking into account in carboxylate series, thereby widened the serviceability temperature scope of ferric phosphate lithium cell.
Embodiment 1-8 compares discovery to two kinds of high temperature additive at the high-temperature behavior of different carboxylic acids ester solvent as can be seen from Figure 1, the adding high temperature additive can improve the high-temperature behavior of battery significantly, and account for the high temperature additive 1 of electrolyte total weight 3%, the electrolyte high temperature cyclic performance of 3-propane sultone is best, finds that simultaneously ethyl butyrate can improve the high temperature cyclic performance of battery effectively.Changed the film for additive in the Comparative Examples among the embodiment 9-11, high-temperature behavior has good performance equally.
Claims (6)
1, the LiFePO4 taken into account of a kind of high and low temperature performance is the lithium rechargeable battery nonaqueous electrolytic solution of positive electrode, and it comprises: LiPF
6Lithium salts, organic solvent, film for additive; It is characterized in that: it also contains high temperature additive; Described organic solvent is made up of one or more carbonic esters and one or more low melting points, high boiling carboxylate.
2, lithium rechargeable battery nonaqueous electrolytic solution according to claim 1 is characterized in that: described low melting point, high boiling carboxylate are selected from the one or more combination in methyl butyrate, ethyl butyrate, propyl butyrate or the butyl acetate.
3, lithium rechargeable battery nonaqueous electrolytic solution according to claim 2 is characterized in that: described low melting point, high boiling carboxylate are selected from the one or more combination in methyl butyrate, ethyl butyrate, the propyl butyrate.
4, lithium rechargeable battery nonaqueous electrolytic solution according to claim 1 is characterized in that: described high temperature additive is 1,3-propane sultone or 1,4-butane sultone.
5, lithium rechargeable battery nonaqueous electrolytic solution according to claim 1 is characterized in that: the addition of described high temperature additive be non-hydrolysis electrolyte total amount percentage by weight 3%～4%.
6, according to the described lithium rechargeable battery nonaqueous electrolytic solution of claim 1-5, it is characterized in that: in described nonaqueous electrolytic solution, add anti-overcharge additive biphenyl or cyclohexyl benzene.
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