CN109818064A - A kind of high temperature high voltage nonaqueous electrolytic solution and the lithium ion battery containing the nonaqueous electrolytic solution - Google Patents
A kind of high temperature high voltage nonaqueous electrolytic solution and the lithium ion battery containing the nonaqueous electrolytic solution Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion, and in particular to a kind of high temperature high voltage nonaqueous electrolytic solution and the lithium ion battery containing the nonaqueous electrolytic solution.High temperature high voltage nonaqueous electrolytic solution of the invention includes lithium salts, nonaqueous solvents, additive, it wherein, include first kind borate additive, the nitrogenous class lithium carbonate of the second class, third eka-silicon nitrogen base class additive and the 4th class sulphonic acid ester and sulfuric acid ester additive package in the additive.Various additives of the present invention are after suitably matching, respective advantage can be played but also mutually inhibit respective disadvantage, pass through their mutual synergistic effects, improve the high-temperature storage performance of battery, the high temperature cyclic performance for improving battery, application prospect is good under high temperature high voltage condition.
Description
Technical field
The present invention relates to technical field of lithium ion, it is specifically related to a kind of high temperature high voltage nonaqueous electrolytic solution and containing should
The lithium ion battery of nonaqueous electrolytic solution.
Background technique
In lithium ion battery, high voltage tertiary cathode material due to energy density it is high, it is environmental-friendly, have extended cycle life
Advantage is widely used in the portable electronic devices such as mobile phone, laptop and electric vehicle, large-scale energy storage device,
It is higher and higher to the energy density requirement of battery, so that commercial tertiary cathode material lithium ion battery (operating voltage 4.2V) is difficult to
It meets the requirements.
Currently, research shows that promoted ternary electrode material energy densities effective way first is that improve battery work electricity
Pressure, this is the trend of battery development and the inevitable requirement of new-energy automobile development.However ternary power battery operating voltage mentions
Gao Hou, the performances such as charge and discharge cycles of battery but decline.Reason may be: on the one hand be that positive electrode is not steady enough under high voltages
It is fixed, it is on the other hand the bad with the matching of material of electrolyte, common electrolyte can aoxidize point under conditions of high voltage
Solution, so as to cause battery high-temperature storge quality is poor, high temperature cyclic performance is poor, low temperature performance is poor and safety is poor.
Chinese invention patent application (publication number CN103579676A) proposes to solve using fluorinated solvents (FEC, TFPC etc.)
The not high pressure resistant problem of electrolyte, still, fluorinated solvents constantly restore in graphite cathode and generate HF, and HF reacts generation with electrolyte
LiF is deposited on graphite cathode, and SEI film thickness is caused to increase, and influences charge-discharge performance, while the moisture brought into during testing
It can make LiPF6It decomposes and generates HF, so that SEI film thickness is continuously increased, occur producing gas phenomenon.Therefore, it researches and develops and is suitble to high voltage three
The lithium-ion battery electrolytes of first material system are extremely urgent.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of above-mentioned background technique, a kind of high temperature high voltage non-aqueous solution electrolysis is provided
Liquid and lithium ion battery containing the nonaqueous electrolytic solution, high temperature high voltage nonaqueous electrolytic solution of the invention have used first kind addition
Agent, the second class additive, third class additive, the 4th class additive and electrolyte lithium salt, non-aqueous organic solvent cooperation, in electrode
The SEI film generated on material has good compactness, ionic conductance forthright, is conducive to the migration of lithium ion, improves battery
High-temperature storage performance simultaneously inhibits to produce gas, improves cycle performance of the battery under high temperature high voltage condition, improves the electrochemistry of battery
Performance.
To achieve the object of the present invention, high temperature high voltage nonaqueous electrolytic solution of the invention includes lithium salts, nonaqueous solvents, addition
Agent, wherein include first kind borate additive, the nitrogenous class lithium carbonate of the second class, third eka-silicon nitrogen in the additive
Base class additive and the 4th class sulphonic acid ester and sulfuric acid ester additive package, and the third eka-silicon nitrogen base class additive such as general formula
(1) or shown in (2):
Wherein, R1-R3Separately indicate C1-C61-2 hydrogen atom is by C in alkyl, vinyl, amino or amino1-C4
The hydrocarbon amino that alkyl replaces；R4-R6Separately indicate C1-C61-2 hydrogen atom quilt in alkyl, vinyl, amino or amino
C1-C4The hydrocarbon amino that alkyl replaces；R7-R8Separately indicate hydrogen atom, C1-C61- in alkyl, vinyl, amino or amino
2 hydrogen atoms are by C1-C4The hydrocarbon amino or there is group described in structure (3) that alkyl replaces；
In structure (3), R9-R11Separately indicate C1-C61-2 hydrogen in alkyl, phenyl, vinyl, amino or amino
Atom is by C1-C4The hydrocarbon amino that alkyl replaces.
In the present invention, it is preferable that the first kind borate additive is selected from difluorine oxalic acid boracic acid lithium (LiDBOF), two grass
Sour lithium borate (LiBOB), LiBF4 (LiBF4), bis- (2- methyl -2- fluorine malonic acid) lithium borates (LiBMFMB), ten difluoros
Two lithium (Li of boric acid2B12F12) one of or it is a variety of.
Preferably, the nitrogenous class lithium carbonate of second class is selected from double fluorine sulfimide lithiums (LiFSI), bis trifluoromethyl
One of sulfonic acid Asia amide lithium (LiTFSI), fluorine sulphonyl (trimethyl fluoride sulfonyl) imine lithium (LiFTFSI) are a variety of.
Preferably, the third eka-silicon nitrogen base class additive is selected from 1- (trimethyl silicon substrate) imidazoles (TMSI), 1- (triethyl group
Silicon substrate) imidazoles, 1,1- dimethyl -1- ethyl silicon substrate imidazoles, N, N- dimethylamino trimethyl silane, N, N- diethylamino three
One of methyl-monosilane, two silicon nitrogen base of 1,3- dibutyl -1,1,3,3- tetramethyl are a variety of.
It is highly preferred that the first kind borate additive is difluorine oxalic acid boracic acid lithium (LiDBOF), second class contains
Nitrogen class lithium carbonate is double fluorine sulfimide lithiums (LiFSI), and the third eka-silicon nitrogen base class additive is 1- (trimethyl silicane
Base) imidazoles (TMSI) or 1,1- dimethyl -1- ethyl silicon substrate imidazoles, the 4th class sulphonic acid ester and sulfuric acid ester additive package
For the mixture of sulfuric acid vinyl ester (DTD) and propene sultone (PST).
It is further preferred that the additive amount of the first kind borate additive is the 0.5-10% of electrolyte gross mass,
Such as 1%；The additive amount of the nitrogenous class lithium carbonate of second class is the 0.1-5% of electrolyte gross mass, such as 1-3%；
The additive amount of the third eka-silicon nitrogen base class additive is the 0.01-0.7% of electrolyte gross mass, such as 0.1-0.5%；It is described
The additive amount of sulfonic acid esters additive is the 0.1- of electrolyte gross mass in 4th class sulphonic acid ester and sulfuric acid ester additive package
1%, the additive amount of sulfuric acid ester additive is the 1-2% of electrolyte gross mass.
It is further preferred that including the difluorine oxalic acid boracic acid lithium of electrolyte gross mass 1%, electrolyte in the additive
Double fluorine sulfimide lithiums of gross mass 1-3%, 1- (trimethyl silicon substrate) imidazoles (TMSI) of electrolyte gross mass 0.1-0.5% or
The 0.5% of 1,1- dimethyl -1- ethyl silicon substrate imidazoles, the sulfuric acid vinyl ester of electrolyte gross mass 1-2% and electrolyte gross mass
Propene sultone.
Preferably, the lithium salts includes lithium hexafluoro phosphate (LiPF6), and its additive amount is the 0.5- of electrolyte gross mass
20%, such as 12.5%.
In the present invention, the nonaqueous solvents is organic carbonate solvents, it is preferable that the organic carbonate solvents choosing
From ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first third
It is one or more among ester, it is highly preferred that including ethylene carbonate, methyl ethyl carbonate and carbonic acid diethyl in the nonaqueous solvents
Ester；It is further preferred that the ethylene carbonate, methyl ethyl carbonate, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1.
The present invention also provides a kind of lithium ion battery for matching above-mentioned electrolyte, which includes positive pole
Piece, cathode pole piece and high temperature high voltage nonaqueous electrolytic solution of the present invention, the anode pole piece include plus plate current-collecting body and just
The positive diaphragm of pole collection liquid surface, the cathode pole piece include the cathode membrane of negative current collector and negative current collector surface；
The anode diaphragm includes positive active material, conductive agent and binder, and the cathode membrane includes negative electrode active material, conduction
Agent and binder；The positive active material is LiNi1-x-y-zCoxMnyAlzO2, in which: 0≤x≤1,0≤y≤1,0≤z≤1
And 0≤x+y+z≤1；The negative electrode active material is nano-silicon or SiOxThe silicon-carbon cathode material being combined with graphite.
Preferably, the positive active material is at least one of ternary system NCM622, NCM811, NCA, described negative
Pole active material is artificial graphite.
Compared with prior art, high temperature high voltage nonaqueous electrolytic solution provided by the invention and lithium containing the nonaqueous electrolytic solution from
Sub- battery has the advantage that
(1) it in nonaqueous electrolytic solution of the invention, by adding first kind borate additive, can be formed on positive and negative anodes
The SEI film of good ionic conductivity, improves the cycle performance and high-temperature storage performance of battery；Add the nitrogenous class lithium salts of the second class
Additive is able to ascend the cycle performance of battery under high voltages；Third eka-silicon nitrogen base class additive is added, can be effectively improved
The high temperature performance of battery, and the additive can inhibit the decomposition of LiPF6, a small amount of decomposition product passes through electrostatic in graphite surface
Effect forms good SEI film, improves cycle performance and inhibits to produce gas simultaneously；
(2) of the invention by silicon nitrogen based additive and solvent, lithium salts and nitrogen class lithium carbonate, borate, sulfonic acid esters
With sulfuric acid ester additive package after suitably matching, respective advantage can be played but also mutually inhibit respective scarce
Point, by their mutual synergistic effects, so that electrolyte of the present invention application prospect under high temperature high voltage condition is good.
(3) in electrolyte of the invention, the characteristic of the Si-N key in additive 1- (trimethyl silicon substrate) imidazoles is effective clear
In addition to the moisture in electrolyte, it is suppressed that LiFP6Decomposition, and decomposition product graphite surface pass through electrostatic interaction reduce resistance
Anti-, the SEI film of formation has good ionic conductivity, improves the high-temperature storage performance of battery, improves the high temperature of battery
Cycle performance.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " containing " or its any other deformation, it is intended that covering non-exclusionism
Include.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those elements, but
It may include not expressly listed other elements or such composition, step, method, product or the intrinsic element of device.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and the 1- of electrolyte gross mass 0.1% is added into mixed liquor
(trimethyl silicon substrate) imidazoles (TMSI) and the sulfuric acid vinyl ester (DTD) of electrolyte gross mass 1%, electrolyte gross mass 0.5%
The lithium hexafluoro phosphate of electrolyte gross mass 12.5% is then added in 1,3- propene sultone (PST) into mixed liquor respectively
(LiPF6) and double fluorine sulfimide lithiums (LiFSI) of electrolyte gross mass 1%, electrolyte gross mass 1% difluoro oxalate boric acid
Lithium (LiDFOB), stirring makes it completely dissolved, and obtains the electrolyte of embodiment 1.
The electrolyte solution prepared is injected by NCM622 as positive electrode, Soft Roll lithium of the graphite cathode as cathode
Be packaged in ion battery, after the completion of fluid injection shelve, be melted into, aging, secondary encapsulation, the processes such as partial volume, obtain NCM622/ stone
Black battery.
Embodiment 2
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.2% is added into mixed liquor
Electrolysis is then added in the PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5% into mixed liquor respectively
The LiPF of liquid gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 1%, electrolyte gross mass 1%, stirring makes
It is completely dissolved, and in addition to this, operates similarly to Example 1, prepares lithium ion battery.
Embodiment 3
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.5% is added into mixed liquor
Electrolysis is then added in the PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5% into mixed liquor respectively
The LiPF of liquid gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 1%, electrolyte gross mass 1%, stirring makes
It is completely dissolved, and in addition to this, operates similarly to Example 1, prepares lithium ion battery.
Embodiment 4
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.7% is added into mixed liquor
The PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 1%, are then added electrolyte into mixed liquor respectively
The LiPF of gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 1%, electrolyte gross mass 1%, stirring makes it
It is completely dissolved, in addition to this, operates similarly to Example 1, prepare lithium ion battery.
Embodiment 5
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.3% is added into mixed liquor
Electrolysis is then added in the PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5% into mixed liquor respectively
The LiPF of liquid gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 2%, electrolyte gross mass 1%, stirring makes
It is completely dissolved, and in addition to this, operates similarly to Example 1, prepares lithium ion battery.
Embodiment 6
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.3% is added into mixed liquor
Electrolysis is then added in the PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5% into mixed liquor respectively
The LiPF of liquid gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 3%, electrolyte gross mass 1%, stirring makes
It is completely dissolved, and in addition to this, operates similarly to Example 1, prepares lithium ion battery.
Embodiment 7
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and the 1 of electrolyte gross mass 0.3% is added into mixed liquor,
The PST of 1- dimethyl -1- ethyl silicon substrate imidazoles and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5%, then respectively
The LiPF of electrolyte gross mass 12.5% is added into mixed liquor6LiFSI, electrolyte gross mass with electrolyte gross mass 1%
1% LiDFOB, stirring make it completely dissolved, and in addition to this, operate similarly to Example 1, prepare lithium ion battery.
Embodiment 8
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and the 1 of electrolyte gross mass 0.3% is added into mixed liquor,
The PST of 1- dimethyl -1- ethyl silicon substrate imidazoles and the DTD of electrolyte gross mass 2%, electrolyte gross mass 0.1%, then respectively
The LiPF of electrolyte gross mass 12.5% is added into mixed liquor6LiFSI, electrolyte gross mass with electrolyte gross mass 1%
1% LiDFOB, stirring make it completely dissolved, and in addition to this, operate similarly to Example 1, prepare lithium ion battery.
Embodiment 9
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and the N of electrolyte gross mass 0.3% is added into mixed liquor,
The PST of N- dimethylamino trimethyl silane and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5%, then respectively
The LiPF of electrolyte gross mass 12.5% is added into mixed liquor6LiFSI, electrolyte gross mass with electrolyte gross mass 1%
1% LiDFOB, stirring make it completely dissolved, and in addition to this, operate similarly to Example 1, prepare lithium ion battery.
Embodiment 10
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.3% is added into mixed liquor
Electrolysis is then added in the PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 0.5% into mixed liquor respectively
The LiPF of liquid gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 7%, electrolyte gross mass 10%, stirring makes
It is completely dissolved, and in addition to this, operates similarly to Example 1, prepares lithium ion battery.
Embodiment 11
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.3% is added into mixed liquor
The PST of TMSI and the DTD of electrolyte gross mass 1%, electrolyte gross mass 5%, are then added electrolyte into mixed liquor respectively
The LiPF of gross mass 12.5%6With the LiDFOB of the LiFSI of electrolyte gross mass 1%, electrolyte gross mass 1%, stirring makes it
It is completely dissolved, in addition to this, operates similarly to Example 1, prepare lithium ion battery.
Comparative example 1
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 12.5% is separately added into mixed solution
LiPF6With the LiDFOB of electrolyte gross mass 1%, stirring is made it completely dissolved, and obtains the electrolyte of comparative example 1.
The electrolyte solution prepared is injected by NCM622 as positive electrode, Soft Roll lithium of the graphite cathode as cathode
Be packaged in ion battery, after the completion of fluid injection shelve, be melted into, aging, secondary encapsulation, the processes such as partial volume, obtain NCM622/ stone
Black battery.
Comparative example 2
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass is then added into mixed liquor respectively
12.5% LiPF6With the LiDFOB of electrolyte gross mass 3%, stirring is made it completely dissolved, in addition to this, same with comparative example 1
Sample operation, prepares lithium ion battery.
Comparative example 3
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass is then added into mixed liquor respectively
12.5% LiPF6With the LiDFOB of electrolyte gross mass 15%, stirring is made it completely dissolved, in addition to this, same with comparative example 1
Sample operation, prepares lithium ion battery.
Comparative example 4
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass is then added into mixed liquor respectively
12.5% LiPF6With the LiFSI of electrolyte gross mass 1%, stirring is made it completely dissolved, in addition to this, same as comparative example 1
Operation, prepares lithium ion battery.
Comparative example 5
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass is then added into mixed liquor respectively
12.5% LiPF6With the LiFSI of electrolyte gross mass 10%, stirring is made it completely dissolved, in addition to this, same with comparative example 1
Sample operation, prepares lithium ion battery.
Comparative example 6
It is being full of argon gas, and in oxygen content≤1ppm, water content≤1ppm glove box, by ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1, and electrolyte gross mass 0.5% is added into mixed liquor
The LiPF of electrolyte gross mass 12.5% is then added in DTD into mixed liquor respectively6Made it completely dissolved with stirring, except this with
Outside, it is equally operated with comparative example 1, prepares lithium ion battery.
Electrochemical property test
(1) normal-temperature circulating performance is tested: at 25 DEG C, extremely by 1C constant-current constant-voltage charging by the lithium ion battery after chemical conversion
4.35V, cut-off current 0.02C, then by 1C constant-current discharge to 3.0V.The 500th cycle is calculated after charge/discharge 500 times circulations to follow
Ring capacity retention ratio (is referred to as 25 DEG C of capacity %) in table 1.Calculation formula are as follows:
All cyclic discharge capacity × 100% of 500th week capacity retention ratio=500th week cyclic discharge capacity/head.
(2) 60 DEG C of high-temperature storage performances: by battery, by 0.5C charge and discharge, primary, cut-off current 0.02C, record are first at room temperature
Beginning capacity, then be full of by 0.5C constant current constant voltage, test initial battery thickness, and the internal resistance of use internal resistance test device test battery,
Voltage；Full electric battery is placed in 60 DEG C of isoperibol and is stored 7 days, tests the hot thickness of battery, and calculate hot expansion (table 1
In referred to as hot thickness %)；Cold thickness is tested after battery is cooled to room temperature 6h, with the internal resistance of internal resistance test device test battery, note
Record data simultaneously calculate internal resistance change rate (internal resistance % is referred to as in table 1), after the completion of test, are discharged to 3.0V, record electricity by 0.5C
Pond residual capacity；It presses 0.5C charge and discharge cycles 3 times again, records the maximum capacity in 3 circulations, i.e. battery recovery capacity, calculate
Battery capacity surplus ratio (residue % is referred to as in table 1) and capacity resuming rate (referred to as restoring % in table 1).Calculation formula
Are as follows:
The hot expansion rate of battery (%'s)=(hot thickness-original depth)/original depth × 100%；
Internal resistance of cell change rate (%'s)=(internal resistance-initial internal resistance after storage)/initial internal resistance × 100%；
Battery capacity surplus ratio (%'s)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%'s)=recovery capacity/initial capacity × 100%.
(3) 60 DEG C of cycle performance tests: the lithium ion battery after chemical conversion is placed in 60 DEG C of environment and is filled by 1C constant current constant voltage
Electricity is to 4.35V, cut-off current 0.02C, then by 1C constant-current discharge to 3.0V.It is calculated the 500th week after charge/discharge 500 times circulations
Secondary circulation volume conservation rate (60 DEG C of capacity % are referred to as in table 1).Calculation formula are as follows:
All cyclic discharge capacity × 100% of 500th week capacity retention ratio=500th week cyclic discharge capacity/head.
1 battery performance test result of table
Table 1 the results showed that in LiFSI+DTD+LiDFOB+PST system, silazane base is added, can be in stone
Black cathode forms stable SEI film, and the Si-N bond energy in additive enough effectively inhibits in electrolyte minor amount of water to LiPF6's
It decomposes, and decomposition product reduces impedance by electrostatic interaction in graphite surface, improves cycle performance, the high temperature storage of battery
It can and improve high temperature cyclic performance.
The comparison of the experimental result of comparative example 1-6 and each embodiment shows in table 1: in electrolyte of the invention, by silicon nitrogen base
Additive and solvent, lithium salts and nitrogen class lithium carbonate, borate, sulfonic acid esters and sulfuric acid ester additive package are by closing
After suitable proportion, respective advantage can be played but also mutually inhibit respective disadvantage, made by their mutual collaborations
With so that electrolyte of the present invention application prospect under high temperature high voltage condition is good.
As it will be easily appreciated by one skilled in the art that the foregoing is merely few examples of the invention, not to limit
The system present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in
Within protection scope of the present invention.
Claims (10)
1. a kind of high temperature high voltage nonaqueous electrolytic solution, which is characterized in that the high temperature high voltage nonaqueous electrolytic solution includes lithium salts, non-aqueous
Solvent, additive, wherein include first kind borate additive, the nitrogenous class lithium carbonate of the second class, the in the additive
Three eka-silicon nitrogen base class additives and the 4th class sulphonic acid ester and sulfuric acid ester additive package, and the third eka-silicon nitrogen base class adds
Shown in agent such as general formula (1) or (2):
Wherein, R1-R3Separately indicate C1-C61-2 hydrogen atom is by C in alkyl, vinyl, amino or amino1-C4Alkyl
Substituted hydrocarbon amino；R4-R6Separately indicate C1-C61-2 hydrogen atom is by C in alkyl, vinyl, amino or amino1-C4
The hydrocarbon amino that alkyl replaces；R7-R8Separately indicate hydrogen atom, C1-C61-2 in alkyl, vinyl, amino or amino
Hydrogen atom is by C1-C4The hydrocarbon amino or there is group described in structure (3) that alkyl replaces；
In structure (3), R9-R11Separately indicate C1-C61-2 hydrogen atom in alkyl, phenyl, vinyl, amino or amino
By C1-C4The hydrocarbon amino that alkyl replaces.
2. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the first kind borate addition
Agent is selected from difluorine oxalic acid boracic acid lithium, dioxalic acid lithium borate, LiBF4, bis- (2- methyl -2- fluorine malonic acid) lithium borates, 12
One of two lithium of fluoboric acid is a variety of.
3. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the nitrogenous class lithium salts of the second class
Additive is in double fluorine sulfimide lithiums, bis trifluoromethyl sulfonic acid Asia amide lithium, fluorine sulphonyl (trimethyl fluoride sulfonyl) imine lithium
It is one or more.
4. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the third eka-silicon nitrogen base class adds
Agent is added to be selected from 1- (trimethyl silicon substrate) imidazoles, 1- (triethyl group silicon substrate) imidazoles, 1,1- dimethyl -1- ethyl silicon substrate imidazoles, N, N-
Dimethylamino trimethyl silane, N, N- diethylamino trimethyl silane, two silicon nitrogen of 1,3- dibutyl -1,1,3,3- tetramethyl
One of base is a variety of.
5. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the first kind borate addition
Agent is difluorine oxalic acid boracic acid lithium, and the nitrogenous class lithium carbonate of the second class is double fluorine sulfimide lithiums, the third eka-silicon nitrogen
Base class additive be 1- (trimethyl silicon substrate) imidazoles or 1,1- dimethyl -1- ethyl silicon substrate imidazoles, the 4th class sulphonic acid ester and
Sulfuric acid ester additive package is the mixture of sulfuric acid vinyl ester and propene sultone；Preferably, the first kind borate
The additive amount of additive is the 0.5-10% of electrolyte gross mass, such as 1%；The nitrogenous class lithium carbonate of second class adds
Dosage is the 0.1-5% of electrolyte gross mass, such as 1-3%；The additive amount of the third eka-silicon nitrogen base class additive is electrolysis
The 0.01-0.7% of liquid gross mass, such as 0.1-0.5%；Sulfonic acid in the 4th class sulphonic acid ester and sulfuric acid ester additive package
The additive amount of esters additive is the 0.1-1% of electrolyte gross mass, and the additive amount of sulfuric acid ester additive is the total matter of electrolyte
The 1-2% of amount.
6. high temperature high voltage nonaqueous electrolytic solution according to claim 5, which is characterized in that include electrolysis in the additive
The difluorine oxalic acid boracic acid lithium of liquid gross mass 1%, double fluorine sulfimide lithiums of electrolyte gross mass 1-3%, electrolyte gross mass
1- (trimethyl silicon substrate) imidazoles (TMSI) of 0.1-0.5% or 1,1- dimethyl -1- ethyl silicon substrate imidazoles, electrolyte gross mass 1-
2% sulfuric acid vinyl ester and 0.5% propene sultone of electrolyte gross mass.
7. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the lithium salts includes hexafluorophosphoric acid
Lithium, and its additive amount is the 0.5-20% of electrolyte gross mass, such as 12.5%.
8. high temperature high voltage nonaqueous electrolytic solution according to claim 1, which is characterized in that the nonaqueous solvents is organic carbon
Esters of gallic acid solvent；Preferably, the organic carbonate solvents are selected from ethylene carbonate, propene carbonate, butylene, carbon
It is dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate, one or more among methyl propyl carbonate；It is highly preferred that described non-aqueous
It include ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in agent；It is further preferred that the ethylene carbonate, carbonic acid first
Ethyl ester, diethyl carbonate are uniformly mixed with the mass ratio of 1:1:1.
9. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode pole piece, cathode pole piece and claim 1-
8 described in any item high temperature high voltage nonaqueous electrolytic solutions, the anode pole piece include plus plate current-collecting body and plus plate current-collecting body surface
Positive diaphragm, the cathode pole piece includes the cathode membrane of negative current collector and negative current collector surface；The anode diaphragm
Including positive active material, conductive agent and binder, the cathode membrane includes negative electrode active material, conductive agent and binder；
The positive active material is LiNi1-x-y-zCoxMnyAlzO2, in which: 0≤x≤1,0≤y≤1,0≤z≤1 and 0≤x+y+z≤
1；The negative electrode active material is nano-silicon or SiOxThe silicon-carbon cathode material being combined with graphite.
10. lithium ion battery according to claim 9, which is characterized in that the positive active material is ternary system
At least one of NCM622, NCM811, NCA, the negative electrode active material are artificial graphite.
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