CN103337659B - Compositions of additives, electrolyte - Google Patents
Compositions of additives, electrolyte Download PDFInfo
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- CN103337659B CN103337659B CN201310271793.6A CN201310271793A CN103337659B CN 103337659 B CN103337659 B CN 103337659B CN 201310271793 A CN201310271793 A CN 201310271793A CN 103337659 B CN103337659 B CN 103337659B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of compositions of additives, electrolyte, this compositions of additives comprises: 0.01 ~ 90wt% hydrogen fluorine ether; 0.01 ~ 90wt% fluoro carbonic ester; The fluorine-containing fire retardant of 0.01 ~ 90wt%; The fluorine-containing additives for overcharge protection agent of 0.01 ~ 10wt% and 0 ~ 2wt% fluorine-containing surfactant.Compared with prior art, first, in compositions of additives, comprise multiple additives, the interphase interaction of additive, the problem adding the electrolyte conductivity reduction that single additive brings can be solved; Secondly, comprise hydrogen fluorine ether and fluorine-containing additives for overcharge protection agent in compositions of additives, improve the withstand voltage properties of electrolyte, fluorine-containing fire retardant improves the resistance to elevated temperatures of electrolyte, and three's acting in conjunction improves the security performance of electrolyte of the present invention; Again, adopt the form of adding composition to add additive, can workload be reduced, reduce the cost of electrolyte.
Description
Technical field
The invention belongs to cell manufacturing techniques field, particularly relate to compositions of additives, electrolyte.
Background technology
Lithium ion battery has that energy density is large, average output voltage is high, self discharge is little, does not have memory effect, operating temperature range is wide, cycle performance is superior, can the advantage such as fast charging and discharging, charge efficiency is high, power output is large, long service life, it has been widely used in consumption electronic product power supply as the reliable energy, further, the application of lithium battery in electric bicycle and electric tool in recent years is also rapidly developed.But due under the application conditions of various complexity, there is the danger that burning and even blast occur in lithium ion battery, constrains the development of power and energy storage lithium ion battery.
All inherently can not be dealt with problems by modes such as external protector and positive and negative pole material modifications in the past, modification should be carried out from battery security source electrolyte.The current lithium-ion battery electrolytes problem relevant with battery security mainly comprises: organic solvent easy firing; Electrolyte lithium salt (mainly LiPF
6) unstable, to responsive to temperature; System resistance to pressure is lower.Novel dissolvent, additive, new lithium salts and ionic liquid etc. are are mainly researched and developed to the development trend that it carries out modification.
In recent years, the application of fluorine material in new energy technology obtains extensive concern, and it shows remarkable performance in lithium battery electrolytes, becomes the important source material of exploitation high-performance electrolyte solution.As fluorinated ethylene carbonate (FEC) be at present application more containing fluorous solvent and additive, the withstand voltage properties that FEC can improve electrolyte improves SEI membrane stability simultaneously, but it in use easily discharges hydrogen fluoride gas; Hydrogen fluorine ether (HFE) can improve the voltage endurance capability more than 20% of electrolyte, and can reduce the reaction between electrolyte and electrode material.
Adding fire retardant is equally also a kind of important means solving lithium rechargeable battery.Common fire retardant mainly contains phosphate compounds, phosphite ester compound, halophosphoric acid ester type compound, halogenated carboxylic acid ester type compound and halogen ether compounds.
Research shows, single additive is difficult to solve all problems of electrolyte, and also may bring some other problem, and the interpolation as phosphate ester flame retardants can draw its viscosity comparatively greatly, causes electrolyte conductance to reduce; Fluorine-containing flame-retardant additives can utilize its surface activity can reduce electrolyte viscosity, but not high with conventional carbonate solvent compatibility, the easy layering of electrolyte, thus causes the reduction of conductivity.
Application number be 200710028419.8 Chinese patent disclose a kind of lithium battery electrolytes, wherein with the addition of alkyl phosphate, the high temperature performance of battery is effectively improved, can use within the scope of-50 DEG C ~ 120 DEG C, but the electrochemistry compatibility of alkyl phosphate is poor, causes larger negative effect when using as additive to the chemical property of battery.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of compositions of additives, electrolyte, and this electrolyte conductivity is higher and security performance is better.
The invention provides a kind of compositions of additives, comprising:
Hydrogen fluorine ether 0.01 ~ 90wt%;
Fluoro carbonic ester 0.01 ~ 90wt%;
Fluorine-containing fire retardant 0.01 ~ 90wt%;
Fluorine-containing additives for overcharge protection agent 0.01 ~ 10wt%;
Fluorine-containing surfactant 0 ~ 2wt%.
Preferably, described hydrogen fluorine ether to be selected from following formula (I-1) to one or more in compound formula (I-3) Suo Shi:
H(CF
2CF
2)
n1CH
2O(CF
2)
n2H（I-1）；
F(CF
2CF
2)
n3CH
2CH
2O(CF
2)
n4H（I-2）；
CF
3CF
2CF
2O(CF(CF
3)CF
2O)
n5CF(CF
3)CH
2O(CF
2)
n6H（I-3）；
Wherein, 1≤n1≤15,1≤n3≤15,1≤n5≤15, n2, n4 and n6 are respectively the positive integer being more than or equal to 1.
Preferably, described fluoro carbonic ester is selected from and has with following formula (II-1) to one or more in formula (II-4) structural compounds:
Wherein, Rh-is H-or hydrocarbon chain group; Rf
1-, Rf
2-, Rf
3-with Rf
4-be H (CF independently of one another
2cF
2)
n7cH
2-, F (CF
2cF
2)
n8cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n9cF (CF
3) CH
2-; N7 and n8 is respectively positive integer, and n9 is nonnegative integer.
Preferably, described fluorine-containing fire retardant is selected from and has with one or more in following formula (III-1) and formula (III-2) structural compounds:
Wherein, Rf
5-, Rf
6-with Rf
7-be H (CF independently of one another
2cF
2)
n10cH
2-, F (CF
2cF
2)
n11cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n12cF (CF
3) CH
2-; N10 and n11 is respectively positive integer, and n12 is nonnegative integer; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be independently fluorocarbon group or hydrocarbon chain group separately, and at least one is fluorocarbon group; Described fluorocarbon group is H (CF
2cF
2)
n13cH
2-, F (CF
2cF
2)
n14cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n15cF (CF
3) CH
2-, wherein, 1≤n13≤15,1≤n14≤15,1≤n15≤15.
Preferably, described fluorine-containing additives for overcharge protection agent is selected from and has with one or more in following formula (IV-1) and formula (IV-2) structural compounds:
Li
2B
12F
xH
12-x（IV-2）；
Wherein, Rf
14-with Rf
15-be H (CF independently of one another
2cF
2)
n16cH
2-, F (CF
2cF
2)
n17cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n18cF (CF
3) CH
2-; N16 and n17 is respectively positive integer, and n18 is nonnegative integer; 1≤x≤12.
Preferably, described fluorine-containing surfactant has formula (V) structure:
Wherein, Rf-is H (CF
2cF
2)
n20cH
2-, F (CF
2cF
2)
n21cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n22cF (CF
3) CH
2-; N19, n20 and n21 are respectively positive integer, and n22 is nonnegative integer.
Present invention also offers a kind of electrolyte, comprising:
Compositions of additives described in lithium salts, solvent and claim 1 ~ 6.
Preferably, the concentration of described lithium salts is 0.7 ~ 1.4mol/L.
Preferably, described solvent is selected from one or more in ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate and ethylene carbonate.
Preferably, the quality of described solvent is 1% ~ 95% of electrolyte quality.
The invention provides a kind of compositions of additives, electrolyte, this compositions of additives comprises: the hydrogen fluorine ether of 0.01 ~ 90wt%; The fluoro carbonic ester of 0.01 ~ 90wt%; The fluorine-containing fire retardant of 0.01 ~ 90wt%; The fluorine-containing additives for overcharge protection agent of 0.01 ~ 10wt% and the fluorine-containing surfactant of 0 ~ 2wt%.Compared with lithium battery electrolytes of the prior art, the present invention adopts the mode of adding compositions of additives to carry out the configuration of electrolyte, first, multiple additives is comprised in compositions of additives, the interphase interaction of additive, can solve the problem adding the electrolyte conductivity reduction that single additive brings; Secondly, comprise hydrogen fluorine ether in compositions of additives, improve the withstand voltage properties of electrolyte, fluorine-containing fire retardant improves the resistance to elevated temperatures of electrolyte, and both actings in conjunction improve the security performance of electrolyte of the present invention; Again, adopt the form of adding composition to add additive, can workload be reduced, reduce the cost of electrolyte.
Accompanying drawing explanation
Fig. 1 is the cycle performance resolution chart of the simulated battery of the embodiment of the present invention 1, embodiment 2, comparative example 2 and comparative example 5 preparation.
Embodiment
The invention provides a kind of compositions of additives, comprising:
Hydrogen fluorine ether 0.01 ~ 90wt%;
Fluoro carbonic ester 0.01 ~ 90wt%;
Fluorine-containing fire retardant 0.01 ~ 90wt%;
Fluorine-containing additives for overcharge protection agent 0.01 ~ 10wt%;
Fluorine-containing surfactant 0 ~ 2wt%.
Described hydrogen fluorine ether is Hydrofluoroether compounds well known to those skilled in the art, there is no special restriction, and the fluorine of hydrogen described in the present invention ether is preferably selected from following formula (I-1) to one or more in formula (I-3).
H(CF
2CF
2)
n1CH
2O(CF
2)
n2H（I-1）；
F(CF
2CF
2)
n3CH
2CH
2O(CF
2)
n4H（I-2）；
CF
3CF
2CF
2O(CF(CF
3)CF
2O)
n5CF(CF
3)CH
2O(CF
2)
n6H（I-3）；
Wherein, 1≤n1≤15, are preferably 1≤n1≤8, are more preferably 1≤n1≤4; 1≤n3≤15, are preferably 1≤n3≤8, are more preferably 1≤n3≤4; 1≤n5≤15, are preferably 1≤n5≤8, are more preferably 1≤n5≤4; N2, n4 and n6 be more than or equal to respectively 1 positive integer, be preferably respectively be more than or equal to 1 and be less than or equal to 15 positive integer, be more preferably respectively be more than or equal to 1 and be less than or equal to 8 positive integer.
Described hydrogen fluorine ether is more preferably selected from following formula (I-4) to one or more in formula (I-6) compound.
The content of described hydrogen fluorine ether is 0.01 ~ 90wt% of compositions of additives, is preferably 1 ~ 70wt%, is more preferably 5 ~ 50wt%, then is preferably 5 ~ 30wt%.
Hydrogen fluorine ether has good dissolving power, and viscosity is lower and have good thermal stability, safety, the voltage endurance capability of electrolyte can be improved, thus the capacity of battery is improved, hydrogen fluorine ether also can improve the stability of the SEI film of electrolyte simultaneously, reduces the reaction between electrolyte and electrode material.
According to the present invention, described fluoro carbonic ester is preferably selected to be had with following formula (II-1) to one or more in formula (II-4) structural compounds.
Wherein, Rh-is H-or hydrocarbon chain group, is preferably H-or the hydrocarbon chain group containing 1 ~ 20 carbon atom, is more preferably H-or the hydrocarbon chain group containing 1 ~ 10 carbon atom, then is preferably H-, CH
3-, CH
3cH
2-or CH
3cH
2cH
2-; Rf
1-, Rf
2-, Rf
3-with Rf
4-be H (CF independently of one another
2cF
2)
n7cH
2-, F (CF
2cF
2)
n8cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n9cF (CF
3) CH2-; N7 and n8 is respectively positive integer, and n9 is nonnegative integer; N8 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N8 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N9 is preferably the nonnegative integer of 0 ~ 100, is more preferably the nonnegative integer of 1 ~ 50, then is preferably the nonnegative integer of 1 ~ 20, most preferably is the nonnegative integer of 1 ~ 10.
Described formula (II-2) can be commercially available with the fluoro carbonic ester of described formula (II-3) structure, and also can be self-control, its preparation method is the Chinese patent of CN102417500A see publication number.
The content of described fluoro carbonic ester is 0.01 ~ 90wt% of compositions of additives, is preferably 1 ~ 70wt%, is more preferably 1 ~ 50wt%, then is preferably 1 ~ 30wt%.
Ring-type fluorine-containing carbonate products Oil repellent is higher, has good anti-flammability, can improve the high-temperature behavior of battery; Cohesive energy simultaneously between solvent molecule is low, and therefore under low temperature, viscosity is less, can improve the cryogenic property of battery; Moreover, fluorocarbon solvent has lower surface tension, can improve the wetability between electrolyte and electrode material, and then optimizes the chemical property of integral battery door.In addition, in the present invention, the fluorine-containing carbonic ester of ring-type has good compatibility, can form homogeneous phase solution with other electrolytic salt solvents, improves electrolyte conductance.
According to the present invention, described fluorine-containing fire retardant can be fluorine-containing fire retardant well known to those skilled in the art, there is no special restriction.Fluorine-containing fire retardant described in the present invention preferably has with one or more in following formula (III-1) and formula (III-2) structural compounds.
Wherein, Rf
5-, Rf
6-with Rf
7-be H (CF independently of one another
2cF
2)
n10cH
2-, F (CF
2cF
2)
n11cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n12cF (CF
3) CH
2-; N10 and n11 is respectively positive integer, and n12 is nonnegative integer; N10 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N11 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N12 is preferably the nonnegative integer of 0 ~ 100, is more preferably the nonnegative integer of 1 ~ 50, then is preferably the nonnegative integer of 1 ~ 20, most preferably is the nonnegative integer of 1 ~ 10; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be independently fluorocarbon group or hydrocarbon chain group separately, and at least one is fluorocarbon group; Described fluorocarbon group is H (CF
2cF
2)
n13cH
2-, F (CF
2cF
2)
n14cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n15cF (CF
3) CH
2-, wherein, 1≤n13≤15, are preferably 1≤n13≤8, are more preferably 1≤n13≤4; 1≤n14≤15, are preferably 1≤n14≤8, are more preferably 1≤n14≤4; 1≤n15≤15, are preferably 1≤n15≤8, are more preferably 1≤n15≤4; Hydrocarbon chain group includes but not limited to methyl, ethyl, propyl group, glycol monoethyl ether or diethylene glycol monomethyl ether.
Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be independently fluorocarbon group or hydrocarbon chain group separately.When fluorocarbon group and hydrocarbon chain group exist simultaneously in general formula is such as formula the fluorine-containing fire retardant shown in (III-2), anti-flammability and this conflicting problem of compatibility can be solved.In addition, at Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-in multiple substituting group when being fluorocarbon group, make the Oil repellent of phosphazene flame retardant higher, thus anti-flammability is better.Moreover, described general formula contains multiple substituting group, i.e. Rf such as formula in the fluorine-containing fire retardant shown in (IV-2)
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-, the plurality of substituted radical provides the flexibility of MOLECULE DESIGN, can optimizing product performance to greatest extent.
The fluorine-containing fire retardant of described formula (III-2) structure can be commercial, also can be self-control, and its preparation method is the Chinese patent of CN102516307A see publication number.
The content of described fluorine-containing fire retardant is 0.01 ~ 90wt% of compositions of additives, is preferably 0.1 ~ 70wt%, is more preferably 0.1 ~ 50wt%, then is preferably 0.1 ~ 30wt%.
Described in the present invention, fluorine-containing fire retardant is preferably phosphazene flame retardant, and this phosphazene flame retardant contains fluorocarbon group, and the having of fluorocarbon group is beneficial to the flash-point the viscosity reducing electrolyte that increase electrolyte, thus improves the conductivity of electrolyte.
According to the present invention, described compositions of additives comprises: the fluorine-containing additives for overcharge protection agent of 0.01 ~ 10wt%.
Described fluorine-containing additives for overcharge protection agent is preferably selected from following formula (IV-1) and the one in formula (IV-2) structure.
Li
2B
12F
xH
12-x（IV-2）；
Wherein, Rf
14-with Rf
15-be H (CF independently of one another
2cF
2)
n16cH
2-, F (CF
2cF
2)
n17cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n18cF (CF
3) CH2-; N16 and n17 is respectively positive integer, and n18 is nonnegative integer; N16 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N17 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N18 is preferably the nonnegative integer of 0 ~ 100, is more preferably the nonnegative integer of 1 ~ 50, then is preferably the nonnegative integer of 1 ~ 20, most preferably is the nonnegative integer of 1 ~ 10; 1≤x≤12, are preferably 1≤x≤10, are more preferably 1≤x≤8, then are preferably 1≤x≤6.
The withstand voltage properties that fluorine-containing additives for overcharge protection agent can improve electrolyte is added in the present invention.
According to the present invention, described compositions of additives preferably also comprises fluorine-containing surfactant 0 ~ 2wt%, is preferably 0.05 ~ 2wt%, is more preferably 0.01 ~ 1wt%.
Described fluorine-containing surfactant is fluorine-containing surfactant well known to those skilled in the art, there is no special restriction, and fluorine-containing surfactant described in the present invention is preferably the fluorine-containing surfactant of formula (V) structure.
Wherein, Rf-is H (CF
2cF
2)
n3cH
2-, F (CF
2cF
2)
n4cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n5cF (CF
3) CH
2-; H (CF
2cF
2)
n20cH
2-, F (CF
2cF
2)
n21cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n22cF (CF
3) CH
2-; N19, n20 and n21 are respectively positive integer, and n22 is nonnegative integer.; N20 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N21 is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10; N22 is preferably the nonnegative integer of 0 ~ 100, is more preferably the nonnegative integer of 1 ~ 50, then is preferably the nonnegative integer of 1 ~ 20, most preferably is the nonnegative integer of 1 ~ 10; N19 is positive integer, is preferably the positive integer of 1 ~ 100, is more preferably the positive integer of 1 ~ 50, then is preferably the positive integer of 1 ~ 20, most preferably is the positive integer of 1 ~ 10.
Be fluorochemical additive composition according to compositions of additives of the present invention, it comprises multiple additives, acting in conjunction can solve a series of safety problems that electrolyte causes, improve the resistance to pressure performance of electrolyte, fire resistance and additives for overcharge protection performance etc.
The invention provides a kind of electrolyte, comprising: lithium salts, solvent and compositions of additives; Wherein said compositions of additives is described identical with upper, does not repeat them here.
Described lithium salts is lithium salts well known to those skilled in the art, there is no special restriction.LiPF is preferably selected from the present invention
6, LiBF
4, LiBOB, LiODFB, LiClO
4, LiAlCl
4, LiAsF
6, LiSbF
6, LiCF
3sO
3, LiN (CF
3sO
2)
2, LiN (C
2f
5sO
2)
2, LiB (CF
3) F
3, LiCH
3sO
3, LiB (C
2o
4)
2, LiB (C
2f
5) F
3, LiCl, LiI and LiC (CF
3sO
2)
2in one or more, be more preferably selected from LiPF
6, LiBF
4, LiBOB, LiODFB, LiClO
4, LiAlCl
4, LiAsF
6, LiSbF
6and LiCF
3sO
3in one or more, then be preferably selected from LiPF
6, LiBF
4, LiBOB, LiODFB, LiClO
4, LiAlCl
4and LiAsF
6in one.
The concentration of described lithium salts is 0.7 ~ 1.4mol/L, is preferably 0.8 ~ 1.2mol/L.
Be organic solvent well known to those skilled in the art according to solvent of the present invention, there is no special restriction, solvent described in the present invention is fluorine-free solvent, be preferably selected from ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate and ethylene carbonate one or more, be more preferably the mixed system of linear carbonate and cyclic carbonate, then be preferably one or more in dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.Under normal temperature, the viscosity of mixed system is 1mPa.sec, even lower, therefore can improve the conductance of electrolyte.
The content of described solvent is proportioning content well known to those skilled in the art, determines, there is no special restriction according to the purposes of gained electrolyte, the content of solvent described in the present invention is 1% ~ 95% of electrolyte quality, be preferably 10% ~ 90%, be more preferably 10% ~ 70%, then be preferably 10% ~ 50%.
The present invention is in the form of compositions by various additive hydrogen fluorine ether, fluoro carbonic ester, fluorine-containing fire retardant and fluorine-containing additives for overcharge protection agent and lithium salts and solvent configure and form electrolyte, in composition, various additive interacts, influence each other, improve the security performances such as the withstand voltage properties of electrolyte, and the shortcomings such as conductance reduction can not be caused, as fluorine-containing fire retardant can utilize its surface activity to reduce electrolyte viscosity, avoid the shortcoming of fire retardant in the past, but the compatibility of fluorochemical additive and conventional carbonate solvent is not high, after standing and one-tenthization processes, the easy layering of electrolyte, conductivity is caused to reduce, and the present invention adds the problem that fluoro carbonic ester solves compatibility.Meanwhile, add additive in the form of compositions can reduce workload and reduce costs.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of compositions of additives provided by the invention, electrolyte are described in detail.
In following examples agents useful for same be our company development, agents useful for same structure and code name as shown in table 1.
Table 1 embodiment agents useful for same structure and code name
Embodiment 1
13g hydrogen fluorine ether HFE-C3,10g fluorinated ethylene carbonate FEC, 5g fluorine-containing fire retardant FPFR-1,1.8g fluorine-containing additives for overcharge protection agent RS-C3 mixes with 0.2g fluorine-containing surfactant FS-1 by 1.1, obtains compositions of additives.
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) mix as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1 by 1.2, solvent is mixed with the ratio of the additive agent mixture obtained in 1.1 according to mass ratio 7:3, and add lithium hexafluoro phosphate, lithium concentration is made to be 1mol/L, fully stir at 25 DEG C, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Embodiment 2
13g hydrogen fluorine ether HFE-C3,10g fluorinated ethylene carbonate FEC, 5g fluorine-containing fire retardant FPFR-1 and 2g fluorine-containing additives for overcharge protection agent RS-C3 mixes by 2.1, obtains compositions of additives.
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) mix as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1 by 2.2, solvent is mixed with the ratio of the additive agent mixture obtained in 2.1 according to mass ratio 7:3, and add lithium hexafluoro phosphate, lithium concentration is made to be 1mol/L, fully stir at 25 DEG C, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Comparative example 1
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1,90g solvent is mixed with 10g fluorinated ethylene carbonate FEC, and add lithium hexafluoro phosphate, lithium concentration is made to be 1mol/L, fully stir at 25 DEG C, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Comparative example 2
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1,87g solvent is mixed with 13g hydrogen fluorine ether HFE-C3, and add lithium hexafluoro phosphate, lithium concentration is made to be 1mol/L, fully stir at 25 DEG C, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Comparative example 3
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1,95g solvent is mixed with the fluorine-containing fire retardant FPFR-1 of 5g, and add lithium hexafluoro phosphate, lithium concentration is made to be 1mol/L, fully stir at 25 DEG C, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Comparative example 4
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1; 98g solvent is mixed according to the ratio of mass ratio 98:2 with 2g fluorine-containing additives for overcharge protection agent RS-C3 mixture; and add lithium hexafluoro phosphate; lithium concentration is made to be 1mol/L; fully stir at 25 DEG C; obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
Comparative example 5
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent with dimethyl carbonate (DMC) according to the ratio of volume ratio 1:1:1, add lithium hexafluoro phosphate, make lithium concentration be 1mol/L, obtain electrolyte, component and each constituent content of electrolyte are as shown in table 2.
The component of table 2 electrolyte and each constituent content
Electrolyte is evaluated:
Electrolytic conductivity detects: adopt Cond7400 to test desk-top conductivity measurement under 25 DEG C of conditions, carry out conductivity test, obtain the results are shown in Table 3 to the electrolyte prepared by embodiment 1 ~ 2 and comparative example 1 ~ 5.
Electrolyte viscosity is tested: utilize Brookfield rotational viscometer ,-20 DEG C, under 60rpm condition to embodiment 1 ~ 2 and comparative example 1 ~ 5 in the electrolyte of preparation carry out viscosity measurement, obtain the results are shown in Table 3.The measuring range of the rotor adopted is 1-150mPa.sec.
Anti-flammability: fire resistance test is carried out to the electrolyte of preparation in embodiment 1 ~ 2 and comparative example 1 ~ 5, obtains the results are shown in Table 3.Anti-flammability adopts self-extinguishing time (SET) to quantize flame retardant effect, and SET refers to that homogeneous immersion is the 1ml electrolyte in the fire-resistant cotton balls of 0.5cm at diameter, and from the time that self-gravitation of igniting consumes, unit is s/ml.The self-extinguishing time of the electrolyte do not used containing fluorous solvent and fluorochemical additive is set as SET0, the self-extinguishing time adding the electrolyte containing fluorous solvent and/or fluorochemical additive is set as SET(JElectrochemSoc. as described in document, 2003,150 (2): A161-A169), so as 1. SET/SET0<0.1, definition electrolyte is fire-retardant; 2., during 0.1<SET/SET0<0.33, be defined as closely fire-retardant; 3., during SET/SET0>0.33, be defined as flammable.
Simulated battery makes and test:
Battery makes: aluminium housing battery, m(LiFePO4 in positive plate): m(acetylene black): m(Kynoar)=85:7:8, Delanium is negative pole, Celgard2500 polypropylene micropore diaphragm, electrolyte is respectively the electrolyte obtained in embodiment 1 ~ 2, comparative example 1 ~ 5, obtains simulated battery.
Loop test: cycle performance of battery test is carried out to simulated battery obtained above.Cycle performance of battery test condition is: in the environment of 25 DEG C, constant current is carried out and constant voltage charge to electric current is 0.1C under the current value of 0.5C and the voltage of 4.2V, the final voltage of constant-current discharge to 2.5V is carried out under 0.5C multiplying power, carry out the charging and discharging of 100 circulations, simulated battery rated capacity is 15mAh.By carrying out cycle performance of battery test to simulated battery, obtain result as shown in Figure 1, in Fig. 1,1 is the simulated battery prepared by the electrolyte obtained in comparative example 5,2 is the simulated battery prepared by the electrolyte obtained in comparative example 2,3 is the simulated battery prepared by the electrolyte obtained in embodiment 2, and 4 is the simulated battery prepared by the electrolyte obtained in embodiment 1.As shown in Figure 1, comparative example 5 is relative to embodiment 1, embodiment 2 and comparative example 2, show less discharge capacity and cyclical stability, mainly because fluorochemical additive is in battery charge and discharge process, stable SEI film can be formed at negative pole, prevent the further decomposition of electrolyte and the structure collapses etc. of negative material, improve its cycle life; The discharge capacity of embodiment 1 is the highest, and this mainly can improve electrode material wettability in the electrolytic solution due to fluorine-containing surfactant, and therefore when electrode slice compresses, active material utilization is higher, improves its cycle life.
Overcharge test: overcharge test is carried out to simulated battery, first by simulated battery on ArbinBT2000 tester (U.S.'s product) with 0.2C(412 ~ 310V) change into 2 times, treat stable performance, then with 3C constant current overcharge to 10V, obtain the results are shown in Table 4.
Testing impedance: adopt AC impedence method to carry out testing impedance to simulated battery, inspecting electrode is in 4.2V/4.5V high pressure bottom electrode polarization resistance in the electrolytic solution respectively, the change of comparison electrode resistance before and after 30 circulations, obtains withstand voltage properties and the results are shown in Table 5; Respectively electrolysis is inserted in the electrolyte of-10 DEG C, 25 DEG C, 85 DEG C, under high temperature and low temperature, understand electrode temperature sensitivity in the electrolytic solution by impedance, obtain the results are shown in Table 6.
Test result:
Table 3 electrolyte property test result
As shown in Table 3, the use of fluorochemical additive is little on the dicyandiamide solution impact containing fluoro carbonic ester, this mainly excellent with fluoro carbonic ester compatibilization is relevant, fluoro carbonic ester had both remained the dissolubility of carbonate solution, simultaneously again can the compatibility of other fluorochemical additives and ester system in Promotion system, in conductivity, therefore show comparison in difference little; From low temperature viscosity data, still current system can be kept under the electrolyte low temperature of fluorine-containing ether and fluoro carbonic ester, and show less viscosity, this is main relevant with the low-temperature stability of fluoro carbonic ester and fluorine ether, hydrogen fluorine ether has excellent low-temperature stability, and fluorine-containing fire retardant and fluorine-containing additives for overcharge protection agent are when being used alone, because the compatibility with carbonic ester system is slightly poor, show higher viscosity, but the solidification phenomenon all shown at low temperatures than conventional carbonate system is slightly good; From fire resistance, the system being added with fluorochemical additive all has certain fire resistance.
Table 4 simulated battery overcharge test result
All can overcharge not explode to 10V containing the battery of additives for overcharge protection agent and the battery of fluorine-containing ether additive as shown in Table 4, this is because: fluorine material (fluorine ether and additives for overcharge protection agent) all has good thermal stability in higher temperature range, and its share in the electrolytic solution reduces solvolysis amount originally; Additives for overcharge protection agent preferential and electrolyte solvent composition under overcharge current potential reacts and there occurs effect, prevents other solvent compositions to decompose the battery caused further in a large number out of control.
Table 5 withstand voltage properties test result
Shown by table 5 impedance data: when electrode both end voltage is from after 4.2V rises to 4.5V, in embodiment 2 and comparative example 2 hydrogeneous fluorine ether electrolyte, electrode polarization resistance is consistent with 4.2V at the intensity of variation of 1 ~ 30 circulation; And comparative example 5 general electrolytic liquid is after voltage raises, situation at 4.2v when electrode polarization internal resistance is identical much larger than cycle-index after 30 circulations, this is because the SEI film of electrode surface is destroyed under 4.5V in general electrolytic liquid, hinder the electronic conductivity of electrode interior.
The internal resistance of table 6 electrode is to temperature sensitivity test result
As shown in Table 6, the interpolation (comparative example 1) of fluoro carbonic ester FEC is conducive to reducing the internal resistance of low temperature bottom electrode, namely improves the cold weather sensitivity of electrolyte, but does not have effect to the internal resistance of high temperature bottom electrode; The interpolation (comparative example 2) of hydrogen fluorine ether (HFE-C3) is effective to suppressing the rising of electrolyte at high temperature resistance; Can find out from embodiment 1 and embodiment 2, additives for overcharge protection agent RS-C3 and the coupling of hydrogen fluorine ether all have good stability under high temperature and low temperature, suppress the increase of electrode resistance, and under high temperature and low temperature, are all better than the effect being used alone fluoro carbonic ester FEC.
Shown by above-mentioned electrochemical property test result: fluorochemical additive composition of the present invention not only remains the function of former fluorine-containing one-component, weaken the performance deficiency of part one-component composition, in lithium ion battery uses, serve the effect of Synergistic simultaneously, as fluoro carbonic ester plays the effect with other component increase-volumes, hydrogen fluorine ether and fluorine-containing additives for overcharge protection agent component serve improves electrolyte high/low temperature, the effect of the security features such as anti-over-charging, therefore fluorochemical additive composition of the present invention serves good effect to the safety and stability improving lithium-ion battery electrolytes.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1., for a compositions of additives for lithium-ion battery electrolytes, it is characterized in that, composed of the following components:
Described electrolyte also comprises lithium salts and solvent.
2. compositions of additives according to claim 1, is characterized in that, described hydrogen fluorine ether to be selected from following formula (I-1) to one or more in compound formula (I-3) Suo Shi:
H(CF
2CF
2)
n1CH
2O(CF
2)
n2H(I-1)；
F(CF
2CF
2)
n3CH
2CH
2O(CF
2)
n4H(I-2)；
CF
3CF
2CF
2O(CF(CF
3)CF
2O)
n5CF(CF
3)CH
2O(CF
2)
n6H(I-3)；
Wherein, 1≤n1≤15,1≤n3≤15,1≤n5≤15, n2, n4 and n6 are respectively the positive integer being more than or equal to 1.
3. compositions of additives according to claim 1, is characterized in that, described fluoro carbonic ester is selected to be had with following formula (II-1) to one or more in formula (II-4) structural compounds:
Wherein, Rh-is H-or hydrocarbon chain group; Rf
1-, Rf
2-, Rf
3-with Rf
4-be H (CF independently of one another
2cF
2)
n7cH
2-, F (CF
2cF
2)
n8cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n9cF (CF
3) CH
2-; N7 and n8 is respectively positive integer, and n9 is nonnegative integer.
4. compositions of additives according to claim 1, is characterized in that, described fluorine-containing fire retardant is selected to be had with one or more in following formula (III-1) and formula (III-2) structural compounds:
Wherein, Rf
5-, Rf
6-with Rf
7-be H (CF independently of one another
2cF
2)
n10cH
2-, F (CF
2cF
2)
n11cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n12cF (CF
3) CH
2-; N10 and n11 is respectively positive integer, and n12 is nonnegative integer; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be independently fluorocarbon group or hydrocarbon chain group separately, and at least one is fluorocarbon group; Described fluorocarbon group is H (CF
2cF
2)
n13cH
2-, F (CF
2cF
2)
n14cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n15cF (CF
3) CH
2-, wherein, 1≤n13≤15,1≤n14≤15,1≤n15≤15.
5. compositions of additives according to claim 1, is characterized in that, described fluorine-containing additives for overcharge protection agent is selected to be had with one or more in following formula (IV-1) and formula (IV-2) structural compounds:
Li
2B
12F
xH
12-x(IV-2)；
Wherein, Rf
14-with Rf
15-be H (CF independently of one another
2cF
2)
n16cH
2-, F (CF
2cF
2)
n17cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n18cF (CF
3) CH
2-; N16 and n17 is respectively positive integer, and n18 is nonnegative integer; 1≤x≤12.
6. compositions of additives according to claim 1, is characterized in that, described fluorine-containing surfactant has formula (V) structure:
Wherein, Rf-is H (CF
2cF
2)
n20cH
2-, F (CF
2cF
2)
n21cH
2cH
2-or CF
3cF
2cF
2o (CF (CF
3) CF
2o)
n22cF (CF
3) CH
2-; N19, n20 and n21 are respectively positive integer, and n22 is nonnegative integer.
7. an electrolyte, is characterized in that, comprising:
Compositions of additives described in lithium salts, solvent and claim 1 ~ 6.
8. electrolyte according to claim 7, is characterized in that, the concentration of described lithium salts is 0.7 ~ 1.4mol/L.
9. electrolyte according to claim 7, is characterized in that, described solvent be selected from ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate and ethylene carbonate one or more.
10. electrolyte according to claim 7, is characterized in that, the quality of described solvent is 1% ~ 95% of electrolyte quality.
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| CN103633371A (en) * | 2013-12-13 | 2014-03-12 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
| CN104900914A (en) * | 2014-03-06 | 2015-09-09 | 汕头市金光高科有限公司 | High-permeability lithium ion battery electrolyte solution |
| US10249449B2 (en) | 2016-03-01 | 2019-04-02 | Maxwell Technologies, Inc. | Electrolyte formulations for energy storage devices |
| CN109713367B (en) * | 2018-12-28 | 2022-02-22 | 安普瑞斯（南京）有限公司 | Silicon-containing high-energy-density lithium ion battery |
| CN109935783B (en) * | 2019-02-21 | 2021-02-19 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN112820941B (en) * | 2019-11-15 | 2022-10-28 | 浙江中蓝新能源材料有限公司 | Composition for electrolyte |
| CN114291881B (en) * | 2021-12-24 | 2023-03-03 | 湖南有色郴州氟化学有限公司 | Ammonia nitrogen wastewater treatment agent and use method and application thereof |
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