CN102780039A - Nonaqueous organic electrolyte of lithium ion secondary battery and preparation method of nonaqueous organic electrolyte - Google Patents
Nonaqueous organic electrolyte of lithium ion secondary battery and preparation method of nonaqueous organic electrolyte Download PDFInfo
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Abstract
An embodiment of the invention discloses nonaqueous organic electrolyte of a lithium ion secondary battery and a preparation method of the nonaqueous organic electrolyte. The nonaqueous organic electrolyte of the lithium ion secondary battery in the embodiment is composed of nonaqueous organic electrolyte solvent, lithium salt and additive, wherein the nonaqueous organic electrolyte solvent comprises gamma-butyrolactone and saturated cyclic ester compounds, and the additive comprises unsaturated cyclic ester compounds and sulfone compounds. The nonaqueous organic electrolyte has high flash point, high-voltage stability and high-temperature safety of the lithium ion secondary battery can be effectively improved while capacity loss of the lithium ion secondary battery in long-time high-temperature storage can be effectively reduced, and integral performances of the lithium ion secondary battery can be improved.
Description
Technical field
The present invention relates to nonaqueous electrolytic solution, relate in particular to non-water organic electrolyte of a kind of lithium rechargeable battery and preparation method thereof.
Background technology
At present, lithium rechargeable battery maturation be applied in the portable type electronic products such as mobile phone, camera and notebook computer.But expansion along with application; Comprise the research and development application of new in recent years high-energy positive electrode; The appearance of the application scenarios that particularly large-scale energy-accumulating power station, high temperature base station power backup etc. are new; Lithium rechargeable battery has been proposed new demand, pressed for more high-octane lithium rechargeable battery, and high energy battery need keep long-term good high-temperature storage characteristics and high security when high voltage completely charges.
The electrolyte that lithium rechargeable battery adopts mainly comprises the mixed organic solvents that cyclic carbonate and linear carbonate are formed.This mixed solvent carbonaceous material surface at negative electrode in the initial charging process of lithium rechargeable battery reacts; And product is deposited on and forms passivating film (Solid electrolyte Interphase on the cathode surface; SEI); This passivating film can stop electrolyte to continue to prevent the further deterioration of performance of lithium-ion secondary battery in the cathode surface decomposition reaction.
Because the mixed solvent of carbonic ester is the chemical stability variation at high temperature; Ester exchange reaction takes place easily; And oxidation reaction takes place on the positive electrode surface in carbonic ester mixed solvent electrochemical stability variation easily under the high voltage, on the negative material surface reduction reaction takes place.Particularly lithium rechargeable battery is under to the above high voltage of lithium current potential 4.5V; Its high-temperature storage characteristics is with variation, and especially cyclic carbonate ethylene carbonate (EC) is the reason of lithium rechargeable battery high-temperature storage performance variation in negative pole reduction, anodal oxidation easily.In addition, long-time high temperature (45 spend-60 degree) is when storing under high voltage when lithium rechargeable battery, and As time goes on the diaphragm of SEI formation is destroyed gradually; In this case; Carbonate solvent in the electrolyte and the cathode surface reaction that exposes because of the destruction of SEI cause continuous side reaction, and these side reactions constantly produce gas; Can cause that the lithium rechargeable battery internal pressure increases, lithium rechargeable battery is expanded.
In addition; The general flash-point of carbonate solvent used in the lithium rechargeable battery organic electrolyte is low; Has very high combustibility; Particularly the linear carbonate vapour pressure is lower, flash-point is lower, is easy to take place safety issue during long-time high temperature under to the above high voltage of lithium current potential 4.5V (45 degree-60 degree) storage.
In sum, how to improve the high-voltage stability and the high temperature safety of the organic electrolyte of lithium rechargeable battery, reducing the capacitance loss of lithium rechargeable battery in long-time high temperature storage is current problem demanding prompt solution.
Summary of the invention
The embodiment of the invention provides non-water organic electrolyte of a kind of lithium rechargeable battery and preparation method thereof; Be used for lithium rechargeable battery; Can effectively improve the high-voltage stability and the high temperature safety of lithium rechargeable battery; Simultaneously, can effectively reduce the capacitance loss of lithium rechargeable battery in long-time high temperature storage, improve the overall performance of lithium rechargeable battery.
The component of the non-water organic electrolyte of the lithium rechargeable battery in the embodiment of the invention comprises:
Non-water organic electrolyte solvent, lithium salts, additive;
Said non-water organic electrolyte solvent comprises: gamma-butyrolacton, saturated cyclic ester compounds;
Said additive comprises: unsaturated cyclic ester compounds, sulfone compound;
Wherein, said saturated cyclic ester compounds is at least a in the compound shown in the formula (1), and said unsaturated cyclic ester compounds is at least a, concrete in the compound shown in the formula (2):
In the formula (1); X1 is selected from carbon back, sulfenyl or phosphorus base; Y1 is selected from oxygen base, methyl or ethyl, and R1, R2, R3, R4 independently are selected from hydrogen base, halogen, cyanic acid, nitro respectively and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno;
In the formula (2), X2 is selected from carbon back, sulfenyl or phosphorus base, and Y2 is selected from oxygen base, methyl or ethyl, and R5 and R6 are independently selected from hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
The preparation method of the non-water organic electrolyte of the lithium rechargeable battery in the embodiment of the invention comprises:
Mix after purifying dewaters respectively with gamma-butyrolacton, saturated cyclic ester compounds, obtain non-water organic electrolyte solvent;
Lithium salts is dissolved in the said non-water organic electrolyte solvent, obtains matrix electrolyte;
Additive is added said matrix electrolyte, obtain non-water organic electrolyte, said additive comprises: sulfone compound and unsaturated cyclic ester compounds;
Wherein, the saturated cyclic ester compounds is at least a in the compound shown in the formula (1), at least a suc as formula in the compound shown in (2) of unsaturated cyclic ester compounds;
In the formula (1); X1 is selected from carbon back, sulfenyl or phosphorus base; Y1 is selected from oxygen base, methyl or ethyl, and R1, R2, R3, R4 independently are selected from hydrogen base, halogen, cyanic acid, nitro respectively and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno;
In the formula (2), X2 is selected from carbon back, sulfenyl or phosphorus base, and Y2 is selected from oxygen base, methyl or ethyl, and R5 and R6 are independently selected from hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
Can find out that from above technical scheme the embodiment of the invention has the following advantages:
The non-water organic electrolyte of the lithium rechargeable battery among the present invention comprises non-water organic electrolyte solvent, lithium salts and additive; Wherein non-water organic electrolyte solvent comprises gamma-butyrolacton and saturated cyclic ester compounds; Additive comprises unsaturated cyclic ester compounds and sulfone compound; Aerogenesis when this non-water organic electrolyte has higher flash-point and can suppress battery storage under decomposition and the high temperature of electrolyte solvent under the high voltage expands; Can effectively improve the high-voltage stability and the high temperature safety of lithium rechargeable battery, effectively reduce the capacitance loss of lithium rechargeable battery in long-time high temperature storage simultaneously.
Description of drawings
Fig. 1 is a sketch map of the non-water organic electrolysis liquid and preparation method thereof of lithium rechargeable battery in the embodiment of the invention.
Embodiment
The embodiment of the invention provides non-water organic electrolyte of a kind of lithium rechargeable battery and preparation method thereof, can access have higher flash point, the non-water organic electrolyte of the lithium rechargeable battery of high-temperature stability and high temperature safety, low capacity loss preferably.
In the embodiment of the invention a kind of non-water organic electrolyte of lithium rechargeable battery is provided, this non-water organic electrolyte comprises:
Non-water organic electrolyte solvent, lithium salts, additive;
Wherein, non-water organic electrolyte solvent comprises: gamma-butyrolacton, saturated cyclic ester compounds; Additive comprises: unsaturated cyclic ester compounds, sulfone compound;
Wherein, the saturated cyclic ester compounds is at least a, concrete in the compound shown in the formula (1):
In formula (1), Y1 is the oxygen base, methyl or ethyl, and when Y1 was oxygen base or methyl, this saturated cyclic ester compounds was the five-membered cyclic ester compounds, when Y1 was ethyl, this saturated cyclic ester compounds was the six-membered cyclic carboxylate.
In formula (1), X1 is carbon back, sulfenyl or phosphorus base, and R1, R2, R3, R4 independently are respectively hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
Preferably, in embodiments of the present invention, have at least one to be halogen group among R1, R2, R3, the R4.
Wherein, the unsaturated cyclic ester compounds is at least a, concrete in the compound shown in the formula (2):
In formula (2), Y2 is the oxygen base, methyl or ethyl, and when Y2 was oxygen base or methyl, this unsaturated cyclic ester compounds was the five-membered cyclic ester compounds, when Y2 was ethyl, this unsaturated cyclic ester compounds was the six-membered cyclic ester compounds.
In formula (2), X2 is carbon back or phosphorus base, and R5, R6 independently are respectively hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
In embodiments of the present invention, sulfone compound is any one or a few in the halide of ethylmethane sulfonate, sulfolane, positive fourth sulfone, methoxy sulfone, ethyl vinyl sulfone, ethyl methoxyethyl sulfone, methyl sulphonyl benzene, benzyl sulfone, tetramethylene sulfone, butadienyl sulfone, siloyl group sulfone and above-claimed cpd.
In embodiments of the present invention; Lithium salts is one or more the mixture of arbitrary proportion of compound among LiPF6, LiBF4, LiCF3SO3, Li (CF3SO2) 2N, LiBOB, the LiDFOB, and the concentration of lithium salts in non-water organic electrolyte is 0.5mol/L to 1.5mol/L.
In embodiments of the present invention, the proportion of each component of non-water organic electrolyte can for:
The volume ratio that gamma-butyrolacton accounts for non-water organic electrolyte solvent is 1% ~ 80%;
The mass ratio that sulfone compound accounts for non-water organic electrolyte solvent is 1% ~ 10%;
The mass ratio that the unsaturated cyclic ester compounds accounts for non-water organic electrolyte solvent is 1% ~ 5%.
In embodiments of the present invention; Use gamma-butyrolacton, saturated cyclic ester compounds non-water organic electrolyte solvent in the non-water organic electrolyte as it; Use sulfone compound and unsaturated cyclic ester compounds as its additive; Effectively raise the high-temperature stability and the high-voltage safety property of the non-water organic electrolyte of lithium rechargeable battery, and have higher flash-point, reduced the capacitance loss of lithium rechargeable battery.
See also Fig. 1, the embodiment for the preparation method of the non-water organic electrolyte in the embodiment of the invention comprises:
101, mix after purifying dewaters respectively with gamma-butyrolacton, saturated cyclic ester compounds, obtain non-water organic electrolyte solvent;
In embodiments of the present invention; When the non-water organic electrolyte of preparation, can gamma-butyrolacton, saturated cyclic ester compounds be mixed the purifying back that dewaters respectively, as non-water organic electrolyte solvent; Wherein, The saturated cyclic ester compounds is at least a in the compound shown in the formula (1), and wherein, the volume ratio that gamma-butyrolacton accounts for the non-water organic electrolyte solvent of preparation is 1% ~ 80%.
102, lithium salts is dissolved in the non-water organic electrolyte solvent, obtains matrix electrolyte;
In embodiments of the present invention; After obtaining non-water organic electrolyte solvent; The lithium salts solvent in this non-water organic electrolyte solvent, is obtained mixed solvent, wherein; Lithium salts is one or more the mixture of arbitrary proportion of compound among LiPF6, LiBF4, LiCF3SO3, Li (CF3SO2) 2N, LiBOB, the LiDFOB, and the concentration of lithium salts in the non-water organic electrolyte of preparation is 0.5mol/L to 1.5mol/L.
103, additive is added in matrix electrolyte, obtains non-water organic electrolyte, additive comprises sulfone compound and unsaturated cyclic ester compounds.
In embodiments of the present invention; After obtaining matrix electrolyte; Can additive be added this matrix electrolyte; Obtain non-water organic electrolyte, wherein, additive comprises sulfone compound and unsaturated cyclic ester compounds; And this unsaturated cyclic ester compounds is at least a in the compound shown in the formula (2); Sulfone compound is any one or a few in the halide of ethylmethane sulfonate, sulfolane, positive fourth sulfone, methoxy sulfone, ethyl vinyl sulfone, ethyl methoxyethyl sulfone, methyl sulphonyl benzene, benzyl sulfone, tetramethylene sulfone, butadienyl sulfone, siloyl group sulfone and above-claimed cpd, and the mass ratio that sulfone compound accounts for non-water organic electrolyte is 1% ~ 10%, and the mass ratio that the unsaturated cyclic ester compounds accounts for non-water organic electrolyte is 1% ~ 5%.
In embodiments of the present invention, use the non-water organic electrolyte of method for preparing to have higher flash-point, reach high-voltage stability and high temperature safety preferably, and have lower capacitance loss.
No matter need to prove, for lithium rechargeable battery, be rectangular cell or cylindrical battery or soft-package battery, no matter is takeup type or stacked battery also, and non-water organic electrolyte can both be obtained identical effect in the employing embodiment of the invention.
For the result of use of the non-water organic electrolyte in the embodiment of the invention better is described; Making and test with square coiled lithium ion secondary soft-package battery (model is 423450) is example below; Divide a plurality of application scenarioss that the present invention is further explained; Wherein, the anode active material of square Soft Roll 423450 batteries is selected graphite type material for use, is binding agent with Kynoar (PVDF).Active material of cathode is selected high voltage material LiCoPO4 for use, and (PVDF) is binding agent with Kynoar, and acetylene black is made conductive agent.Wherein, the component of the non-water organic electrolyte in square Soft Roll 423450 batteries is an example with following application scenarios:
Application scenarios one:
Gamma-butyrolacton, fluoro carbonic acid ethyl ester and carbonic acid propyl diester are mixed according to the volume ratio of 80:15:5; Be made into even minute water organic electrolyte solvent; Again the LiPF6 of 0.9M is dissolved in this minute water organic electrolyte solvent as the lithium salts of electrolyte; Obtain matrix electrolyte, in this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 0.5% (Wt), as the non-water organic electrolyte of application scenarios one.
Application scenarios two
Use the matrix electrolyte identical, in this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 1% (Wt), as the non-water organic electrolyte of application scenarios two with application scenarios one.
Application scenarios three
Use the matrix electrolyte identical, in this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios three with application scenarios one.
Application scenarios four
Use the matrix electrolyte identical, in this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 5% (Wt), as the non-water organic electrolyte of application scenarios four with application scenarios one.
Application scenarios five
Use the matrix electrolyte identical, in this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 10% (Wt), as the non-water organic electrolyte of application scenarios five with application scenarios one.
Application scenarios six
Use the matrix electrolyte identical, in this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of the sulfolane, 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios six with application scenarios one.
Application scenarios seven
Use the matrix electrolyte identical, in this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of the sulfolane, 2% (Wt) of 5% (Wt), as the non-water organic electrolyte of application scenarios seven with application scenarios one.
Application scenarios eight
Use the matrix electrolyte identical, in this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of the methyl sulphonyl benzene, 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios eight with application scenarios one.
Application scenarios nine
Use the matrix electrolyte identical with application scenarios one; In this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of methyl sulphonyl benzene, 2% (Wt) of the sulfolane and 3% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios nine.
Application scenarios ten
Gamma-butyrolacton, fluoro carbonic acid ethyl ester and carbonic acid propyl diester are mixed according to the volume ratio of 80:15:5; Be made into even minute water organic electrolyte solvent; Again the LiBF4 of the LiPF6 of 0.65M and 0.15M is dissolved in this minute water organic electrolyte solvent as the lithium salts of electrolyte, obtains matrix electrolyte.In this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios ten.
Application scenarios 11
Use the matrix electrolyte identical with application scenarios ten, in this matrix electrolyte, add the sulfolane of 3% (Wt), the di-oxalate lithium borate of the ethylene carbonate of 2% (Wt) and 2% (Wt) is as the non-water organic electrolyte of application scenarios 11.
Application scenarios 12
Use the matrix electrolyte identical with application scenarios ten; In this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of methyl sulphonyl benzene, 2% (Wt) of the sulfolane and 3% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios 12.
Application scenarios 13
Gamma-butyrolacton, fluoro carbonic acid ethyl ester and carbonic acid propyl diester are mixed according to the volume ratio of 85:10:5; Be made into even minute water organic electrolyte solvent; Again the LiPF6 of 0.9M is dissolved in this minute water organic electrolyte solvent as the lithium salts of electrolyte, obtains matrix electrolyte.In this matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios 13.
Application scenarios 14
Use the matrix electrolyte identical, in this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of the sulfolane, 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios 14 with application scenarios 13.
Application scenarios 15
Gamma-butyrolacton, fluoro carbonic acid ethyl ester and carbonic acid propyl diester are mixed according to the volume ratio of 85:10:5; Be made into even minute water organic electrolyte solvent; Again the LiBF4 of the LiPF6 of 0.65M and 0.15M is dissolved in this minute water organic electrolyte solvent as the lithium salts of electrolyte, obtains matrix electrolyte.In matrix electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios 15.
Application scenarios 16
Use the matrix electrolyte identical, in this matrix electrolyte, add the di-oxalate lithium borate of ethylene carbonate and 2% (Wt) of the sulfolane, 2% (Wt) of 3% (Wt), as the non-water organic electrolyte of application scenarios 16 with application scenarios 15.
For with above-mentioned 16 application scenarioss in the experimental data of non-water organic electrolyte compare, will be configured to following four kinds of non-water organic electrolytes of the prior art down, be respectively:
Comparative Examples one
Use traditional electrolyte: carbonic acid ethyl ester, methyl ethyl carbonate, dimethyl carbonate are mixed according to the volume ratio of 1:1:1; In this tradition electrolyte, again the LiPF6 of 0.9M is dissolved in the mixed solution as the lithium salts of electrolyte, obtains the electrolyte in the Comparative Examples one.
Comparative Examples two
Use traditional electrolyte: carbonic acid ethyl ester, methyl ethyl carbonate, dimethyl carbonate are mixed according to the volume ratio of 1:1:1, in this tradition electrolyte, add the ethylene carbonate of 2% (Wt), obtain the electrolyte in the Comparative Examples two.
Comparative Examples three
Use traditional electrolyte: carbonic acid ethyl ester, methyl ethyl carbonate, dimethyl carbonate are mixed according to the volume ratio of 1:1:1, in this tradition electrolyte, add the ethylene carbonate of the sulfolane and 2% (Wt) of 3% (Wt), obtain the electrolyte in the Comparative Examples three.
Comparative Examples four
Gamma-butyrolacton, fluoro carbonic acid ethyl ester and carbonic acid propyl diester are mixed according to the volume ratio of 80:15:5, be made into homogeneous mixture solotion, again the LiPF6 of 0.9M is dissolved in the mixed solution as the lithium salts of electrolyte, obtain the electrolyte in the Comparative Examples four.
Need to prove; At above-mentioned application scenarios one to application scenarios 16; And in Comparative Examples one to the Comparative Examples four; The percentage number average that relates to is meant mass percent, is meant that specifically each ingredients constitute does not comprise the mass percent of the basic electrolyte of lithium salts, and the amount that adds lithium salts is refered in particular to the molal quantity that adds in the 1L electrolyte.
When actual tests, will reach the electrolyte that obtains in Comparative Examples one to the Comparative Examples four and inject 423450 batteries respectively at above-mentioned application scenarios one to application scenarios 16, battery is carried out performance test, obtain test data as shown in the table:
In above-mentioned experiment; Respectively with the 1C constant current charge, the charging upper limit is to 5V, with 5V constant voltage charging 2 hours with battery; Shelved under the room temperature then 1 hour; Cross battery with 1C and be charged to 10V, phenomenons such as whether recording cell occurs in the overcharge process is smoldered, on fire, burning, blast, the result of record are the 1C-10V test result in the table; The battery of room temperature being shelved 1 hour full electric attitude 5V places the outside to have on the wire netting of protective device; Directly battery is heated with liquefied gas flame below; Phenomenons such as whether recording cell smolder in burning test process, on fire, burning, blast, the result of record is the baked wheaten cake test result in showing.
In last table; High temperature storage varied in thickness and high temperature storage capacity restoration rate are the test of high-temperature storage characteristics; Specifically be the battery that room temperature is shelved 1 hour full electric attitude 5V to be put into 60 degree high temperature cabinets placed 10 days; At the thickness of storage fore-and-aft survey battery, calculate the thickness growth rate that cell thickness is compared before the cell thickness and high temperature storage after the high temperature storage, result of calculation is the high temperature storage thickness change in showing.In addition, the battery of high temperature storage after 10 days shelved 5 hours under 35 degree constant temperature, the 1C constant-current discharge is to 3.0V then; The 1C constant current charge is to 5V again; Last 1C constant current is discharged to 3.0V again, calculates the high temperature storage capacity restoration rate of battery, and result of calculation is the high temperature storage capacity restoration rate in the table; Wherein, high temperature storage capacity restoration rate is refered in particular to the ratio that the discharge capacity before the discharge capacity of battery after high temperature storage and the high temperature storage is compared.
In the high temperature storage test, Comparative Examples one, Comparative Examples two and Comparative Examples three batteries use traditional electrolyte, and the high voltage that can't satisfy battery charges and discharge, and battery capacity worsens serious, and it is very poor that battery high-temperature memory capacity is recovered.Embodiment one aerogenesis is serious, can't form firm compact protective film on the negative material surface, under high voltage, during high temperature storage, can not stop the decomposition of solvent, and generating a large amount of gas has increased inner pressure of battery, and it is serious to cause battery capacity to worsen; Embodiment two-phase comparing embodiment one has added film forming solvent VC, can form layer protecting film in negative terminal surface; Reduce solvent and further decompose, but under high potential, the oxidation of solvent still exists at negative pole; Aerogenesis is still serious, and the high temperature storage capacity worsens still serious; In embodiment three, added sulphones, improved the high voltage capability of traditional electrolyte, the high temperature storage recovery capacity obviously improves.The comparative example four, adopt the weak solvent of oxidizability, show good high voltage capability, satisfy the demand of high energy battery to high voltage electrolyte, and thickness swelling is not obvious, but the recovery rate of high temperature storage capacity are low.
Can know last table analysis: the present invention provides the non-water organic electrolyte in application scenarios one to the application scenarios 16 to compare traditional electrolyte in high voltage overshoot test with burn in the test and have good security and stability.Contain a large amount of straight chain solvent dimethyl carbonate and methyl ethyl carbonate in the Comparative Examples electrolyte; The flash-point of dimethyl carbonate and methyl ethyl carbonate is lower; Combustion explosion takes place easily in overcharge test and baked wheaten cake test; And non-water organic electrolyte provided by the invention all has very high flash-point; Overcharging test and burn in the test and show good stability, and the non-water organic electrolyte that provides in the embodiment of the invention has high-temperature storage characteristics preferably, and its high temperature storage thickness change is little and high temperature storage capacity restoration rate is bigger.
One of ordinary skill in the art will appreciate that all or part of step that realizes in the foregoing description method is to instruct relevant hardware to accomplish through program; Described program can be stored in a kind of computer-readable recording medium; The above-mentioned storage medium of mentioning can be a read-only memory, disk or CD etc.
More than non-water organic electrolyte of a kind of lithium rechargeable battery provided by the present invention and preparation method thereof has been carried out detailed introduction; For one of ordinary skill in the art; Thought according to the embodiment of the invention; The part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1. the non-water organic electrolyte of a lithium rechargeable battery is characterized in that component comprises:
Non-water organic electrolyte solvent, lithium salts, additive;
Said non-water organic electrolyte solvent comprises: gamma-butyrolacton, saturated cyclic ester compounds;
Said additive comprises: unsaturated cyclic ester compounds, sulfone compound;
Wherein, said saturated cyclic ester compounds is at least a in the compound shown in the formula (1), and said unsaturated cyclic ester compounds is at least a, concrete in the compound shown in the formula (2):
In the formula (1); X1 is selected from carbon back, sulfenyl or phosphorus base; Y1 is selected from oxygen base, methyl or ethyl, and R1, R2, R3, R4 independently are selected from hydrogen base, halogen, cyanic acid, nitro respectively and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno;
In the formula (2), X2 is selected from carbon back, sulfenyl or phosphorus base, and Y2 is selected from oxygen base, methyl or ethyl, and R5 and R6 are independently selected from hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
2. non-water organic electrolyte according to claim 1 is characterized in that, has at least one to be halogen group among said R1, R2, R3, the R4.
3. non-water organic electrolyte according to claim 1 is characterized in that,
Said sulfone compound is any one or a few in the halide of ethylmethane sulfonate, sulfolane, positive fourth sulfone, methoxy sulfone, ethyl vinyl sulfone, ethyl methoxyethyl sulfone, methyl sulphonyl benzene, benzyl sulfone, tetramethylene sulfone, butadienyl sulfone, siloyl group sulfone and above-claimed cpd.
4. non-water organic electrolyte according to claim 1 is characterized in that,
Said lithium salts is one or more the mixture of arbitrary proportion of compound among LiPF6, LiBF4, LiCF3SO3, Li (CF3SO2) 2N, LiBOB, the LiDFOB.
5. non-water organic electrolyte according to claim 4 is characterized in that, the concentration of said lithium salts in said non-water organic electrolyte is 0.5mol/L to 1.5mol/L.
6. according to each described non-water organic electrolyte of claim 1 to 5, it is characterized in that the volume ratio that said saturated cyclic ester compounds accounts for said non-water organic electrolyte solvent is 5% ~ 50%.
7. according to each described non-water organic electrolyte of claim 1 to 5, it is characterized in that the volume ratio that said gamma-butyrolacton accounts for said non-water organic electrolyte solvent is 1% ~ 80%.
8. according to each described non-water organic electrolyte of claim 1 to 5, it is characterized in that the mass ratio that said sulfone compound accounts for said non-water organic electrolyte solvent is 1% ~ 10%.
9. according to each described non-water organic electrolyte of claim 1 to 5, it is characterized in that the mass ratio that said unsaturated cyclic ester compounds accounts for said non-water organic electrolyte solvent is 1% ~ 5%.
10. the preparation method of the non-water organic electrolyte of a lithium rechargeable battery is characterized in that, comprising:
Mix after purifying dewaters respectively with gamma-butyrolacton, saturated cyclic ester compounds, obtain non-water organic electrolyte solvent;
Lithium salts is dissolved in the said non-water organic electrolyte solvent, obtains matrix electrolyte;
Additive is added said matrix electrolyte, obtain non-water organic electrolyte, said additive comprises: sulfone compound and unsaturated cyclic ester compounds;
Wherein, the saturated cyclic ester compounds is at least a in the compound shown in the formula (1), at least a suc as formula in the compound shown in (2) of unsaturated cyclic ester compounds;
In the formula (1); X1 is selected from carbon back, sulfenyl or phosphorus base; Y1 is selected from oxygen base, methyl or ethyl, and R1, R2, R3, R4 independently are selected from hydrogen base, halogen, cyanic acid, nitro respectively and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno;
In the formula (2), X2 is selected from carbon back, sulfenyl or phosphorus base, and Y2 is selected from oxygen base, methyl or ethyl, and R5 and R6 are independently selected from hydrogen base, halogen, cyanic acid, nitro and have the part halo of carbon to six carbon or the carbochain or the ethers group of perhalogeno.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105680097A (en) * | 2016-01-25 | 2016-06-15 | 山东玉皇新能源科技有限公司 | High-safety lithium-ion battery electrolyte solution |
| CN105895957A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Battery fluid and lithium ion battery |
| CN105895958A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
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| CN1612383A (en) * | 2003-10-29 | 2005-05-04 | 三星Sdi株式会社 | Lithium battery having effective performance |
| CN101621139A (en) * | 2008-01-31 | 2010-01-06 | 索尼株式会社 | Non-aqueous electrolytic solution battery and non-aqueous electrolytic solution composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1612383A (en) * | 2003-10-29 | 2005-05-04 | 三星Sdi株式会社 | Lithium battery having effective performance |
| CN101621139A (en) * | 2008-01-31 | 2010-01-06 | 索尼株式会社 | Non-aqueous electrolytic solution battery and non-aqueous electrolytic solution composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105680097A (en) * | 2016-01-25 | 2016-06-15 | 山东玉皇新能源科技有限公司 | High-safety lithium-ion battery electrolyte solution |
| CN105895957A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Battery fluid and lithium ion battery |
| CN105895958A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN105895957B (en) * | 2016-06-29 | 2019-04-02 | 宁德时代新能源科技股份有限公司 | Battery fluid and lithium ion battery |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
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