CN109841903A - A kind of high voltage nonaqueous electrolytic solution of resistance to combustion - Google Patents
A kind of high voltage nonaqueous electrolytic solution of resistance to combustion Download PDFInfo
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- CN109841903A CN109841903A CN201910246978.9A CN201910246978A CN109841903A CN 109841903 A CN109841903 A CN 109841903A CN 201910246978 A CN201910246978 A CN 201910246978A CN 109841903 A CN109841903 A CN 109841903A
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- nonaqueous electrolytic
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to chemical field more particularly to a kind of high voltage nonaqueous electrolytic solutions of resistance to combustion of lithium ion battery.It include following substance according to weight fraction: 10-20 parts of electrolyte lithium salt, 70-80 parts of high pressure solvent, 5-10 parts of film for additive, 1-5 parts of functional additive.The high pressure solvent is used as solvent using at least one of two nitrile solvents, sulfone class solvent, ionic liquid, and the oxidation stability of electrolyte can be effectively improved instead of currently used carbonate solvent；Prior to solvent molecule oxidation/reduction decomposition reaction can occur for the film for additive; and one layer is formed in electrode surface, film is effectively protected; it is formed by film or even can inhibit the dissolution of positive electrode metal ion and the deposition in cathode, to significantly improve the cycle performance of electrode/electrolyte interface stability and battery.
Description
Technical field
The present invention relates to chemical field, it is related to battery electrolyte research field more particularly to a kind of lithium ion battery is high
The voltage nonaqueous electrolytic solution of resistance to combustion.
Background technique
During the exploitation of lithium ion battery and application, in terms of common carbonic ester electrolyte suffers from following two
Problem seriously hinders high-voltage anode material first, conventional carbonic ester electrolyte stability of anode is poor, oxidation resistance is not strong
The exploitation of material.In order to further enhance the energy density of lithium ion battery, it is developed with the anode compared with high working voltage
Material mainly includes high voltage LiNi0.5Mn1.5O4、LiMPO4(M=Mn, Co, V), Li2MPO4F (M=Ni, Co) and rich lithium manganese
Based solid solution xLi2MnO3(1-x) LiMeO2(Me=Ni, Co, Mn) etc., their charge cutoff voltage all in 4.7V or more,
And on the positive electrode surface of high oxidation activity irreversible oxygen occurs for conventional carbonic ester electrolyte when current potential reaches 4.5V
Change and decompose, generates CO2、H2The products such as O and poly- ethylene carbonate base (PEC) cause battery flatulence, the variation of electrode interface composition, polarization
Increase etc., the problems such as capable of obviously deteriorating so as to cause high-voltage anode material circulation.Therefore, exploitation have stability of anode it is high,
The high-voltage electrolyte of good in oxidation resistance be develop high-voltage anode material there is an urgent need to.
The low-flash and inflammability of common organic carbonic ester electrolyte are that burning, explosion accident occur for lithium ion battery
Main cause, therefore, reducing electrolyte combustibility is to improve the effective way of lithium ion battery security.Traditional electrolyte
System is in addition to containing lithium salts LiPF6, high dielectric constant cyclic carbonate vinyl acetate EC outside, further include low boiling point, low viscosity it is linear
Carbonate solvent such as DMC, DEC or EMC etc., their flash-point is usually lower, and respectively 17,33 and 23 DEG C.When battery was in
In the case where the abuses such as charging, short circuit, high thermal shock, the temperature and pressure of inside battery is very high, and carbonic ester electrolyte is easy
It is ignited, it is likely that cause battery that burning, the even danger such as explosion occurs.Therefore, the cosolvent with high-flash, development are found
Resistance to combustion electrolyte is while improving lithium ion battery voltage and energy density, to guarantee the effective way of safety.
In conclusion the research and development resistance to combustion electrolyte of high voltage is that promotion is electronic as the critical material of high capacity lithium ion battery
The urgent need of the field of new energy technologies commercial applications such as automobile, energy-accumulating power station.
Summary of the invention
The present invention is in view of the shortcomings of the prior art, provide a kind of high voltage nonaqueous electrolytic solution of resistance to combustion.In order to achieve the above object,
The technical solution of the present invention is as follows:
A kind of voltage nonaqueous electrolytic solution of resistance to combustion, includes following substance according to weight fraction:
Preferably, the electrolyte lithium salt is double fluorine sulfimide lithium (LiFSI), bis trifluoromethyl sulfimide lithium
(LiTFSI), (LiBOB), LiODFB (LiDFOB), difluorophosphate (LiPF in dioxalic acid lithium borate2O2)、4,5-
At least one of dicyano -2- trifluoromethyl imidazoles lithium (LiDTI).
Preferably, the high pressure solvent is at least one of two nitrile solvents, sulfone class solvent and ionic liquid；It is described
Two nitrile solvents be at least one of glutaronitrile, adiponitrile, pimelic dinitrile, hexamethylene dicyanide, sebacic dinitrile and dinitrile；It is described
Sulfone class solvent be at least one of sulfolane (TMS), the first and second sulfones (EMSF)；The ionic liquid is Methyl-N-propyl
(trimethyl fluoride sulfonyl) imines of piperidines two (PP13TFSI), N- methyl-N- butyl piperidine sulfonyloxy methyl imines (PP14TFSI), N-
Methyl-N- butyl pyrroles's bis trifluoromethyl sulfimide (C4Mpyr-TFSI), bis- (the trifluoromethyl sulphurs of 1- methyl-1-ethyl piperidine
At least one of acyl) imines ion liquid (EMP-TFSI).
Preferably, the film for additive is trimethyl phosphate (TMP), (1,1,1,3,3,3- hexafluoro isopropyl) phosphorus
Acid esters (HFiP), three (trimethyl silicane) phosphates (TMSP), 1- propyl phosphoric acid cyclic anhydride (PACA), 1,3- propane sultone (PS)
At least one of.
Preferably, the functional additive is vinylene carbonate, methane-disulfonic acid methylene ester, 1,3-(1- propylene) sulphur
At least one of lactone, cyclohexyl benzene and fluorosulfonyl methyl difluoroacetate.
Preferably, the nonaqueous electrolytic solution is applied in lithium secondary battery.
Compared with prior art, the advantages and positive effects of the present invention are, using two nitrile solvents, sulfone class solvent, from
At least one of sub- liquid is used as solvent, and the novel dissolvent of high-voltage stability replaces currently used carbonate solvent really can
Effectively improve the oxidation stability of electrolyte；And most novel organic solvent have the advantages that it is flammable low, be expected to from
Fundamentally improve the security performance of lithium ion battery；Prior to solvent molecule oxidation/reduction can occur for the film for additive
Decomposition reaction, and electrode surface formed one layer film is effectively protected, be formed by film in addition can inhibit positive electrode metal from
Sub dissolution and the deposition in cathode, to significantly improve the cycle performance of electrode/electrolyte interface stability and battery.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing, subordinate list is briefly described, it should be apparent that, drawings in the following description are some embodiments of the invention, right
For those of ordinary skill in the art, without any creative labor, it can also be obtained according to these attached drawings
Other attached drawings, subordinate list.
Fig. 1 is embodiment 1-5 and comparative example 1LSV test result figure.
Table 1 is the high-temperature storage experimental data of embodiment 5 Yu comparative example 1.
Fig. 2 is embodiment 5 and high temperature circulation test curve of the comparative example 1 at 55 DEG C.
Specific embodiment
To better understand the objects, features and advantages of the present invention, right combined with specific embodiments below
The present invention is described further.It should be noted that in the absence of conflict, the spy in embodiments herein and embodiment
Sign can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other modes described herein are different from, therefore, the present invention is not limited to the specific of specification is described below
The limitation of embodiment.
Embodiment 1, the present embodiment provides a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, each component and its content are as follows: lithium salts
For double 10 parts of fluorine sulfimide lithiums (LiFSI), solvent is adiponitrile: the first and second sulfones (EMSF): N- methyl-N- butyl piperidine methyl sulphur
Acid imide (PP14TFSI)=1:1:1(volume ratio) 70 parts, film for additive is (1,1,1,3,3,3- hexafluoro isopropyl) phosphate
(HFiP) 5 parts, functional additive is 1 part of vinylene carbonate.
Embodiment 2, the present embodiment provides a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, each component and its content are as follows: lithium salts
For 20 parts of bis trifluoromethyl sulfimide lithium (LiTFSI), solvent is glutaronitrile: sulfolane (TMS): Methyl-N-propyl piperidines two
(trimethyl fluoride sulfonyl) imines (PP13TFSI)=1:1:1(volume ratio) 70 parts, film for additive is trimethyl phosphate (TMP) 10
Part, functional additive is 5 parts of methane-disulfonic acid methylene ester.
Embodiment 3, the present embodiment provides a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, each component and its content are as follows: lithium salts
For (LiBOB) in dioxalic acid lithium borate: LiODFB (LiDFOB)=1:1(mass ratio) 10 parts, solvent is glutaronitrile:
Sulfolane (TMS): (trimethyl fluoride sulfonyl) imines of Methyl-N-propyl piperidines two (PP13TFSI)=1:1:1(volume ratio) 80 parts, at
Film additive is three 5 parts of (trimethyl silicane) phosphates (TMSP), functional additive 1,3-(1- propylene) 5 parts of sultone.
Embodiment 4, the present embodiment provides a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, each component and its content are as follows: lithium salts
For difluorophosphate (LiPF2O2) 10 parts, solvent is pimelic dinitrile: hexamethylene dicyanide: N- methyl-N- butyl pyrroles's bis trifluoromethyl sulphonyl
Imines (C4Mpyr-TFSI)=1:1:1(volume ratio) 80 parts, film for additive is 1 part of 1- propyl phosphoric acid cyclic anhydride (PACA), function
Additive is 5 parts of cyclohexyl benzene.
Embodiment 5, the present embodiment provides a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, each component and its content are as follows: lithium salts
For 15 parts of 4,5- dicyano-2- trifluoromethyl imidazoles lithium (LiDTI), solvent is sebacic dinitrile: dinitrile: 1- methyl-1-second
Bis- (trimethyl fluoride sulfonyl) imines ion liquid (the EMP-TFSI)=1:1:1(volume ratios of phenylpiperidines) 75 parts, film for additive 1,
7 parts of 3- propane sultone (PS), functional additive are 3 parts of fluorosulfonyl methyl difluoroacetate.
Comparative example 1, this comparative example provide a kind of conventional nonaqueous electrolytic solution, and each component and its content are as follows: lithium salts is
LiPF610 parts, solvent is conventional 80 parts of vinyl acetate of cyclic carbonate, and no film for additive, functional additive is fluorosulfonyl difluoro
10 parts of methyl acetate.
LSV test: carrying out LSV test verifying to the conventional electrolysis liquid in above-mentioned 5 kinds of electrolyte and comparative example 1 respectively,
Test is using platinized platinum as working electrode, and lithium piece is to electrode and reference electrode, and sweeping speed is 0.1mVs-1.Test result is as follows Fig. 1 institute
Show.
High temperature storage experiment: battery is prepared with the electrolyte in above-described embodiment 5 and comparative example 1, it is real to carry out high temperature storage
It tests and is tested with high temperature circulation.By battery it is fully charged first test its internal resistance, thickness is then placed in 85 DEG C of insulating boxs, every 3 days test
Its thickness calculates the internal resistance growth rate and its thickness swelling of its storage front and back after the completion of to be tested.As a result such as table 1.
Table 1
High temperature circulation experiment: battery being placed in 55 DEG C of high temperature ovens, is recycled using 1C multiplying power, test result is as follows Fig. 2
It is shown.
Test result shows: being replaced using at least one of two nitrile solvents, sulfone class solvent, ionic liquid as solvent
Currently used carbonate solvent can effectively improve the oxidation stability of electrolyte really；And above-mentioned solvent has flammable low
The advantages that, it is expected to fundamentally improve the security performance of lithium ion battery；The film for additive can be prior to solvent molecule
Oxidation/reduction decomposition reaction occurs, and forms one layer in electrode surface and film is effectively protected, be formed by film or even can inhibit just
The dissolution of pole material metal ion and deposition in cathode, to significantly improve electrode/electrolyte interface stability and battery
Cycle performance.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
It imitates embodiment and is applied to other fields, but without departing from the technical solutions of the present invention, according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling to the above embodiments, still fall within the protection scope of technical solution of the present invention.
Claims (7)
1. a kind of high voltage nonaqueous electrolytic solution of resistance to combustion, which is characterized in that according to weight fraction include following substance:
。
2. the high voltage nonaqueous electrolytic solution of resistance to combustion according to claim 1, which is characterized in that the electrolyte lithium salt is double fluorine
Sulfimide lithium (LiFSI), bis trifluoromethyl sulfimide lithium (LiTFSI), (LiBOB), oxalic acid difluoro in dioxalic acid lithium borate
Lithium borate (LiDFOB), difluorophosphate (LiPF2O2), 4,5- dicyano -2- trifluoromethyl imidazoles lithium (LiDTI) at least one
Kind.
3. the high voltage nonaqueous electrolytic solution of resistance to combustion according to claim 1, which is characterized in that the high pressure solvent is two nitriles
At least one of solvent, sulfone class solvent and ionic liquid.
4. the high voltage nonaqueous electrolytic solution of resistance to combustion according to claim 3, which is characterized in that two nitrile solvents are penta 2
At least one of nitrile, adiponitrile, pimelic dinitrile, hexamethylene dicyanide, sebacic dinitrile and dinitrile；The sulfone class solvent is sulfolane
(TMS), at least one of first and second sulfones (EMSF)；The ionic liquid is (the trifluoromethyl sulphur of Methyl-N-propyl piperidines two
Acyl) imines (PP13TFSI), N- methyl-N- butyl piperidine sulfonyloxy methyl imines (PP14TFSI), N- methyl-N- butyl pyrroles is double
Trifluoromethanesulp-onyl -onyl imide (C4Mpyr-TFSI), bis- (trimethyl fluoride sulfonyl) the imines ion liquid of 1- methyl-1-ethyl piperidine
At least one of (EMP-TFSI).
5. the high voltage nonaqueous electrolytic solution of resistance to combustion according to claim 1, which is characterized in that the film for additive is front three
Base phosphate (TMP), (1,1,1,3,3,3- hexafluoro isopropyl) phosphate (HFiP), three (trimethyl silicane) phosphates (TMSP),
At least one of 1- propyl phosphoric acid cyclic anhydride (PACA), 1,3- propane sultone (PS).
6. the high voltage nonaqueous electrolytic solution of resistance to combustion according to claim 1, which is characterized in that the functional additive is carbonic acid
Vinylene, methane-disulfonic acid methylene ester, 1,3-(1- propylene) in sultone, cyclohexyl benzene and fluorosulfonyl methyl difluoroacetate
It is at least one.
7. a kind of high temperature high safety nonaqueous electrolytic solution described in -6 any one according to claim 1, which is characterized in that the height
Warm nonaqueous electrolytic solution is applied in lithium secondary battery.
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| CN113540564A (en) * | 2020-04-21 | 2021-10-22 | 安徽盟维新能源科技有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN114006044A (en) * | 2021-10-25 | 2022-02-01 | 惠州亿纬锂能股份有限公司 | High-voltage electrolyte and application thereof |
| CN114300749A (en) * | 2021-12-30 | 2022-04-08 | 江苏卫蓝新能源电池有限公司 | Wide-temperature flame-retardant lithium ion battery electrolyte |
| CN114447428A (en) * | 2020-10-30 | 2022-05-06 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and lithium battery |
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Application publication date: 20190604 |