CN103337659A - Additive composition and electrolyte - Google Patents
Additive composition and electrolyte Download PDFInfo
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- CN103337659A CN103337659A CN2013102717936A CN201310271793A CN103337659A CN 103337659 A CN103337659 A CN 103337659A CN 2013102717936 A CN2013102717936 A CN 2013102717936A CN 201310271793 A CN201310271793 A CN 201310271793A CN 103337659 A CN103337659 A CN 103337659A
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Abstract
The invention provides an additive composition and an electrolyte. The additive composition comprises 0.01-90 wt% of hydrofluoroether, 0.01-90 wt% of fluorinated carbonate, 0.01-90 wt% of fluorine-containing flame retardant, 0.01-10 wt% of fluorine-containing overcharge protection agent and 0-2 wt% of fluorine-containing surfactant. Compared with the prior art, the additive composition and the electrolyte have the advantages that the additive composition contains a variety of additives, and the additives interact with one another, so that the problem that the conductivity of the electrolyte is lowered caused by the addition of a single additive can be solved; the additive composition contains the hydrofluoroether and the fluorine-containing overcharge protection agent, so that the pressure resistance of the electrolyte is improved, the high temperature resistance of the electrolyte is improved due to the fluorine-containing flame retardant, and the safety performance of the electrolyte provided by the invention is improved due to the coaction of the hydrofluoroether, the fluorine-containing overcharge protection agent and the fluorine-containing flame retardant; and the additives are added in a composition manner, so that the workload can be reduced, and the cost of the electrolyte is reduced.
Description
Technical field
The invention belongs to battery manufacturing technology field, relate in particular to compositions of additives, electrolyte.
Background technology
Advantages such as lithium ion battery has, and energy density is big, average output voltage is high, self discharge is little, do not have memory effect, operating temperature range is wide, but the superior fast charging and discharging of cycle performance, charge efficiency height, power output are big, long service life, it has been widely used in the consumption electronic product power supply as the reliable energy, and the application of lithium battery in electric bicycle and electric tool in recent years also is rapidly developed.But owing under the application conditions of various complexity, there is the danger that burning and even blast take place in lithium ion battery, and has restricted the development that lithium ion battery is used in power and energy storage.
All can not should carry out modification from battery security source electrolyte from dealing with problems in essence by modes such as external protector and positive and negative pole material modifications in the past.The current lithium-ion battery electrolytes problem relevant with battery security mainly comprises: the organic solvent easy firing; Electrolyte lithium salt (mainly is LiPF
6) instability, to responsive to temperature; System's resistance to pressure is lower etc.Mainly be research and development novel dissolvent, additive, novel lithium salts and ionic liquid etc. to its development trend of carrying 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.Be to use at present more fluorous solvent and the additive of containing as fluorinated ethylene carbonate (FEC), the withstand voltage properties that FEC can improve electrolyte improves the SEI membrane stability simultaneously, but it in use easily discharges hydrogen fluoride gas; The voltage endurance capability that hydrogen fluorine ether (HFE) can improve electrolyte is more than 20%, and can reduce the reaction between electrolyte and the electrode material.
Adding fire retardant equally also is a kind of important means that solves 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.
Studies show that single additive be difficult to solve all problems of electrolyte, and also may bring some other problem, it is bigger to draw its viscosity as the interpolation of phosphoric acid ester fire retardant, causes the electrolyte conductance to reduce; Fluorine-containing flame-retardant additives can utilize its surface activity can reduce electrolyte viscosity, but not high with conventional carbon acid esters solvent compatibility, the easy layering of electrolyte, thus cause the reduction of conductivity.
Application number is that 200710028419.8 Chinese patent discloses a kind of lithium battery electrolytes, wherein added alkyl phosphate, the high temperature performance of battery has obtained effective improvement, can in-50 ℃～120 ℃ scopes, use, but the electrochemistry compatibility of alkyl phosphate is relatively poor, and the chemical property to battery when using as additive causes bigger negative effect.
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 is selected from following formula (I-1) one or more to the compound shown in the 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≤15,1≤n3≤15,1≤n5≤15, n2, n4 and n6 are respectively the positive integer more than or equal to 1.
Preferably, described fluoro carbonic ester is selected from and has with following formula (II-1) one or more to 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 are respectively positive integer, and n9 is nonnegative integer.
Preferably, described fluorine-containing fire retardant is selected from and has with in following formula (III-1) and formula (III-2) structural compounds one or more:
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 are respectively positive integer, and n12 is nonnegative integer; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be fluorocarbon group or hydrocarbon chain group independently 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 in following formula (IV-1) and formula (IV-2) structural compounds one or more:
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 are 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.
The present invention also provides a kind of electrolyte, comprising:
The described compositions of additives of 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, carbonic acid first propyl ester, dimethyl carbonate, diethyl carbonate and the 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%; 0.01 the fluoro carbonic ester of～90wt%; 0.01 the fluorine-containing fire retardant of～90wt%; 0.01 the fluorine-containing additives for overcharge protection agent of～10wt% and the fluorine-containing surfactant of 0～2wt%.Compare 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, at first, comprise multiple additives in the compositions of additives, interact between the additive, can solve and add the problem that electrolyte conductivity that single additive brings reduces; Secondly, comprise hydrogen fluorine ether in the compositions of additives, improved the withstand voltage properties of electrolyte, fluorine-containing fire retardant has improved the resistance to elevated temperatures of electrolyte, and both actings in conjunction have improved the security performance of electrolyte of the present invention; Again, adopt the form of adding composition to add additive, can reduce workload, reduce the cost of electrolyte.
Description of drawings
Fig. 1 is the cycle performance resolution chart of the simulated battery of the embodiment of the invention 1, embodiment 2, comparative example 2 and comparative example 5 preparations.
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) one or more to the 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, more preferably 1≤n1≤4; 1≤n3≤15 are preferably 1≤n3≤8, more preferably 1≤n3≤4; 1≤n5≤15 are preferably 1≤n5≤8, more preferably 1≤n5≤4; N2, n4 and n6 are respectively more than or equal to 1 positive integer, preferably are respectively more than or equal to 1 and are less than or equal to 15 positive integer, more preferably are respectively more than or equal to 1 and are less than or equal to 8 positive integer.
Described hydrogen fluorine ether more preferably is selected from following formula (I-4) one or more to formula (I-6) compound.
The content of described hydrogen fluorine ether is 0.01～90wt% of compositions of additives, is preferably 1～70wt%, and more preferably 5～50wt% is preferably 5～30wt% again.
Hydrogen fluorine ether has good dissolving power, and viscosity is lower and have thermal stability preferably, safety, can improve the voltage endurance capability of electrolyte, thereby the capacity of battery is improved, and hydrogen fluorine ether also can improve the stability of the SEI film of electrolyte simultaneously, reduces the reaction between electrolyte and the electrode material.
According to the present invention, described fluoro carbonic ester is preferably selected to have with following formula (II-1) one or more to formula (II-4) structural compounds.
Wherein, Rh-is H-or hydrocarbon chain group, is preferably H-or contains the hydrocarbon chain group of 1～20 carbon atom, and more preferably H-or contain the hydrocarbon chain group of 1～10 carbon atom is preferably H-, CH again
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 are respectively positive integer, and n9 is nonnegative integer; N8 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N8 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N9 is preferably 0～100 nonnegative integer, and more preferably 1～50 nonnegative integer is preferably 1～20 nonnegative integer again, most preferably is 1～10 nonnegative integer.
The fluoro carbonic ester of described formula (II-2) and described formula (II-3) structure can be commercially available, also can be self-control, and its preparation method is the Chinese patent of CN102417500A referring to publication number.
The content of described fluoro carbonic ester is 0.01～90wt% of compositions of additives, is preferably 1～70wt%, and more preferably 1～50wt% is preferably 1～30wt% again.
The fluorine-containing carbonate products fluorine of ring-type content is higher, has excellent flame-retardant performance, can improve the high-temperature behavior of battery; Cohesive energy between the solvent molecule is low simultaneously, so viscosity is littler under the low temperature, can improve the cryogenic property of battery; Moreover, fluorocarbon solvent has lower surface tension, can improve the wetability between electrolyte and the electrode material, and then has optimized the chemical property of integral battery door.In addition, the fluorine-containing carbonic ester of ring-type has compatibility preferably among the present invention, can form homogeneous phase solution with other electrolytic salt solvents, improves the 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 is preferably to have with in following formula (III-1) and formula (III-2) structural compounds one or more.
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 are respectively positive integer, and n12 is nonnegative integer; N10 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N11 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N12 is preferably 0～100 nonnegative integer, and more preferably 1～50 nonnegative integer is preferably 1～20 nonnegative integer again, most preferably is 1～10 nonnegative integer; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be fluorocarbon group or hydrocarbon chain group independently 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, more preferably 1≤n13≤4; 1≤n14≤15 are preferably 1≤n14≤8, more preferably 1≤n14≤4; 1≤n15≤15 are preferably 1≤n15≤8, more preferably 1≤n15≤4; The 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 fluorocarbon group or hydrocarbon chain group independently separately.General formula suc as formula the fluorine-containing fire retardant shown in (III-2) in fluorocarbon group and hydrocarbon chain group when existing simultaneously, can solve this conflicting problem of anti-flammability and compatibility.In addition, at Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-in a plurality of substituting groups when being fluorocarbon group, make the fluorine content of phosphazene flame retardant higher, thereby anti-flammability is better.Moreover, described general formula is suc as formula containing a plurality of substituting groups in the fluorine-containing fire retardant shown in (IV-2), i.e. Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-, these a plurality of substituted radicals provide the flexibility of MOLECULE DESIGN, can optimize properties of product 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 referring to publication number.
The content of described fluorine-containing fire retardant is 0.01～90wt% of compositions of additives, is preferably 0.1～70wt%, and more preferably 0.1～50wt% is preferably 0.1～30wt% again.
Fluorine-containing fire retardant is preferably phosphazene flame retardant described in the present invention, and this phosphazene flame retardant contains fluorocarbon group, and having of fluorocarbon group is beneficial to the flash-point that increases electrolyte and the viscosity that reduces electrolyte, thereby has improved 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 a kind of with in following formula (IV-1) and 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 are respectively positive integer, and n18 is nonnegative integer; N16 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N17 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N18 is preferably 0～100 nonnegative integer, and more preferably 1～50 nonnegative integer is preferably 1～20 nonnegative integer again, most preferably is 1～10 nonnegative integer; 1≤x≤12 are preferably 1≤x≤10, and more preferably 1≤x≤8 are preferably 1≤x≤6 again.
Add the withstand voltage properties that fluorine-containing additives for overcharge protection agent can improve electrolyte among 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%, 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 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N21 is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer; N22 is preferably 0～100 nonnegative integer, and more preferably 1～50 nonnegative integer is preferably 1～20 nonnegative integer again, most preferably is 1～10 nonnegative integer; N19 is positive integer, is preferably 1～100 positive integer, and more preferably 1～50 positive integer is preferably 1～20 positive integer again, most preferably is 1～10 positive integer.
Be the fluorochemical additive composition according to compositions of additives of the present invention, it comprises multiple additives, but acting in conjunction solves a series of safety problems that electrolyte causes, improves resistance to pressure performance, fire resistance and the additives for overcharge protection performance etc. of electrolyte.
The invention provides a kind of electrolyte, comprising: lithium salts, solvent and compositions of additives; Wherein said compositions of additives is identical with the above, does not repeat them here.
Described lithium salts is lithium salts well known to those skilled in the art, there is no special restriction.Be preferably selected from LiPF among 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, more preferably be selected from LiPF
6, LiBF
4, LiBOB, LiODFB, LiClO
4, LiAlCl
4, LiAsF
6, LiSbF
6And LiCF
3SO
3In one or more, be preferably selected from LiPF again
6, LiBF
4, LiBOB, LiODFB, LiClO
4, LiAlCl
4And LiAsF
6In a kind of.
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 the fluorine-free solvent, be preferably selected from ethylene carbonate, propene carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dimethyl carbonate, diethyl carbonate and the ethylene carbonate one or more, the mixed system of linear carbonate and cyclic carbonate more preferably is preferably in dimethyl carbonate, diethyl carbonate and the methyl ethyl carbonate one or more again.The viscosity of mixed system is 1mPa.sec under the normal temperature, 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, decides according to the purposes of gained electrolyte, there is no special restriction, the content of solvent described in the present invention is 1%～95% of electrolyte quality, be preferably 10%～90%, more preferably 10%～70%, be preferably 10%～50% again.
The present invention with the form of composition with various additive hydrogen fluorine ethers; the fluoro carbonic ester; fluorine-containing fire retardant and fluorine-containing additives for overcharge protection agent and lithium salts and solvent configuration form electrolyte; various additives interact in the composition; influence each other; the security performances such as withstand voltage properties of electrolyte have been improved; and can not cause shortcomings such as conductance reduction; can utilize its surface activity to reduce electrolyte viscosity as fluorine-containing fire retardant; avoid the shortcoming of fire retardant in the past; but the compatibility of fluorochemical additive and traditional carbonate solvent is not high; leave standstill and one-tenth processing after; the easy layering of electrolyte cause conductivity to reduce, and the present invention adds the problem that the fluoro carbonic ester has solved compatibility.Simultaneously, adding additive with the form of composition can reduce workload and reduce cost.
In order to further specify the present invention, below in conjunction with embodiment a kind of compositions of additives provided by the invention, electrolyte are described in detail.
Agents useful for same is our company's development in following examples, and agents useful for same structure and code name are as shown in table 1.
Table 1 embodiment agents useful for same structure and code name
1.1 13g hydrogen fluorine ether HFE-C3, the fluorine-containing fire retardant FPFR-1 of 10g fluorinated ethylene carbonate FEC, 5g, the fluorine-containing additives for overcharge protection agent of 1.8g RS-C3 are mixed with 0.2g fluorine-containing surfactant FS-1, obtain compositions of additives.
1.2 dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), the additive agent mixture that obtains in the solvent and 1.1 is mixed according to the ratio of mass ratio 7:3, and adding lithium hexafluoro phosphate, making lithium concentration is 1mol/L, fully stir at 25 ℃, obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
2.1 13g hydrogen fluorine ether HFE-C3, the fluorine-containing fire retardant FPFR-1 of 10g fluorinated ethylene carbonate FEC, 5g are mixed with the fluorine-containing additives for overcharge protection agent of 2g RS-C3, obtain compositions of additives.
2.2 dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), the additive agent mixture that obtains in the solvent and 2.1 is mixed according to the ratio of mass ratio 7:3, and adding lithium hexafluoro phosphate, making lithium concentration is 1mol/L, fully stir at 25 ℃, obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
Comparative example 1
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), the 90g solvent is mixed with 10g fluorinated ethylene carbonate FEC, and adding lithium hexafluoro phosphate, making lithium concentration is 1mol/L, fully stir at 25 ℃, obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
Comparative example 2
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), the 87g solvent is mixed with 13g hydrogen fluorine ether HFE-C3, and adding lithium hexafluoro phosphate, making lithium concentration is 1mol/L, fully stir at 25 ℃, obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
Comparative example 3
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), the 95g solvent is mixed with the fluorine-containing fire retardant FPFR-1 of 5g, and adding lithium hexafluoro phosphate, making lithium concentration is 1mol/L, fully stir at 25 ℃, obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
Comparative example 4
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC); the 98g solvent is mixed according to the ratio of mass ratio 98:2 with the fluorine-containing additives for overcharge protection agent of 2g RS-C3 mixture; and adding lithium hexafluoro phosphate; making lithium concentration is 1mol/L; fully stir at 25 ℃; obtain electrolyte, the component of electrolyte and each constituent content are as shown in table 2.
Comparative example 5
Dimethyl carbonate ethene (EC), diethyl carbonate (DEC) are mixed as solvent according to the ratio of volume ratio 1:1:1 with dimethyl carbonate (DMC), add lithium hexafluoro phosphate, making lithium concentration is 1mol/L, obtains electrolyte, and the component of electrolyte and each constituent content are as shown in table 2.
The component of table 2 electrolyte and each constituent content
Electrolyte is estimated:
Electrolytic conductivity detects: adopt Cond7400 to test desk-top conductivity measurement under 25 ℃ of conditions, embodiment 1～2 and comparative example 1～5 prepared electrolyte are carried out the conductivity test, obtain the results are shown in Table 3.
Electrolyte viscosity test: utilize the Brookfield rotational viscometer, under-20 ℃, 60rpm condition to embodiment 1～2 and comparative example 1～5 in the electrolyte of preparation carry out viscosity and measure, obtain the results are shown in Table 3.The measuring range of the rotor that adopts is 1-150mPa.sec.
Anti-flammability: the electrolyte to preparation in embodiment 1～2 and the comparative example 1～5 carries out the fire resistance test, obtains the results are shown in Table 3.Anti-flammability adopts self-extinguishing time (SET) to quantize flame retardant effect, and SET refers to the 1ml electrolyte of homogeneous immersion in diameter is the fire-resistant cotton balls of 0.5cm, and from the time that the self-gravitation of igniting consumes, unit is s/ml.To not use the self-extinguishing time of the electrolyte that contains fluorous solvent and fluorochemical additive to be set at SET0, the self-extinguishing time that adds the electrolyte contain fluorous solvent and/or fluorochemical additive is set at SET(as J Electrochem Soc. as described in the document, 2003,150 (2): A161-A169), when 1. SET/SET0＜0.1, definition electrolyte is fire-retardant so; 2. 0.1＜SET/SET0＜0.33 o'clock is defined as closely fire-retardant; 3. SET/SET0〉0.33 o'clock, be defined as flammable.
Simulated battery is made and test:
Battery is made: the aluminium housing battery, m(LiFePO4 in the positive plate): m(acetylene black): the m(Kynoar)=85:7:8, Delanium is negative pole, Celgard2500 polypropylene micro-pore septum, electrolyte is respectively the electrolyte that obtains in embodiment 1～2, the comparative example 1～5, obtains simulated battery.
Loop test: the above-mentioned simulated battery that obtains is carried out the cycle performance of battery test.The cycle performance of battery test condition is: in 25 ℃ environment, under the voltage of the current value of 0.5C and 4.2V, carry out constant current and constant voltage charge to electric current is 0.1C, under the 0.5C multiplying power, carry out constant-current discharge to the final voltage of 2.5V, carry out charging and the discharge of 100 circulations, the simulated battery rated capacity is 15mAh.By simulated battery being carried out the cycle performance of battery test, obtain the result as shown in Figure 1,1 is the simulated battery by the electrolyte preparation that obtains in the comparative example 5 among Fig. 1,2 are the simulated battery by the electrolyte preparation that obtains in the comparative example 2,3 are the simulated battery by the electrolyte preparation that obtains among the embodiment 2, and 4 are the simulated battery by the electrolyte preparation that obtains among the embodiment 1.As shown in Figure 1, Comparative Examples 5 is with respect to embodiment 1, embodiment 2 and Comparative Examples 2, show less discharge capacity and cyclical stability, mainly be because fluorochemical additive in battery charge and discharge process, can form stable SEI film at negative pole, prevent that the further decomposition of electrolyte and the structure of negative material from caving in etc., improved its cycle life; The discharge capacity of embodiment 1 is the highest, and this mainly is because fluorine-containing surfactant can improve the wettability of electrode material in electrolyte, and therefore active material utilization is higher under the situation that electrode slice compresses, and has improved its cycle life.
Overcharge test: to the simulated battery test of overcharging, earlier with simulated battery on ArbinBT2000 tester (U.S.'s products) with 0.2C(412～310V) change into 2 times, treat stable performance, overcharge to 10V with the 3C constant current again, obtain the results are shown in Table 4.
Testing impedance: adopt AC impedence method that simulated battery is carried out testing impedance, inspecting electrode is in the polarization resistance of 4.2V/4.5V high pressure bottom electrode in electrolyte respectively, and the variation of comparison electrode resistance before and after 30 circulations obtains withstand voltage properties and the results are shown in Table 5; In the electrolyte with-10 ℃, 25 ℃, 85 ℃ of electrolysis insertions, under high temperature and low temperature, understand the temperature sensitivity of electrode in electrolyte by impedance respectively, 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 to the dicyandiamide solution influence that contains the fluoro carbonic ester, this mainly is relevant with the good compatibilization of fluoro carbonic ester, the fluoro carbonic ester had both kept the dissolubility of carbonate solution, can promote simultaneously the compatibility of interior other fluorochemical additives of system and ester system again, therefore less in conductivity performance diversity ratio; From low temperature viscosity data as can be known, still can keep current system 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 good low-temperature stability, and fluorine-containing fire retardant and fluorine-containing additives for overcharge protection agent are when using separately, because of poor slightly with the compatibility of carbonic ester system, show higher viscosity, but the curing phenomenon that all shows at low temperatures than conventional carbon acid esters system is good slightly; From fire resistance as can be known, the system that is added with fluorochemical additive all has certain fire resistance.
The table 4 simulated battery test result of overcharging
The battery that contains the battery of additives for overcharge protection agent and fluorine-containing ether additive as shown in Table 4 all can overcharge and not explode to 10V, this be because: fluorine material (fluorine ether and additives for overcharge protection agent) all has good thermal stability, its share in electrolyte to reduce solvolysis amount originally in higher temperature range; The additives for overcharge protection agent is preferential under the current potential that overcharges with the reaction of electrolyte solvent composition effect has taken place, and further the battery that causes of a large amount of decomposition is out of control to have stoped other solvent compositions.
Table 5 withstand voltage properties test result
Shown by table 5 impedance data: when the electrode both end voltage after 4.2V rises to 4.5V, electrode polarization resistance is consistent with 4.2V at the intensity of variation of 1～30 circulation in embodiment 2 and the Comparative Examples 2 hydrogeneous fluorine ether electrolyte; And comparative example 5 common electrolyte are after voltage raises, situation when the electrode polarization internal resistance is identical much larger than cycle-index after 30 circulations under 4.2V, this is because the SEI film of electrode surface is destroyed under 4.5V in the common electrolyte, has hindered the electronic conductivity of electrode interior.
The internal resistance of table 6 electrode is to the temperature sensitivity test result
As shown in Table 6, the interpolation of fluoro carbonic ester FEC (comparative example 1) is conducive to reduce the internal resistance of low temperature bottom electrode, namely improves the low-temperature sensitive of electrolyte, but internal resistance does not have effect to the high temperature bottom electrode; The interpolation of hydrogen fluorine ether (HFE-C3) (comparative example 2) produces effect to suppressing the electrolyte rising of resistance at high temperature; Can find out that from embodiment 1 and embodiment 2 additives for overcharge protection agent RS-C3 and the coupling of hydrogen fluorine ether all have stability preferably under high temperature and low temperature, suppress the increase of electrode resistance, and under high temperature and low temperature, all be better than using separately the effect of fluoro carbonic ester FEC.
Shown by above-mentioned electrochemical property test result: fluorochemical additive composition of the present invention has not only kept the function of former fluorine-containing one-component; weakened the performance deficiency of part one-component composition; in using, played lithium ion battery the effect of Synergistic simultaneously; play effect with other component increase-volumes as the fluoro carbonic ester; hydrogen fluorine ether and fluorine-containing additives for overcharge protection agent component have played improves the high low temperature of electrolyte; the effect of security features such as anti-over-charging, so fluorochemical additive composition of the present invention has played good effect to fail safe and the stability of improving lithium-ion battery electrolytes.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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. a compositions of additives is characterized in that, 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%.
2. compositions of additives according to claim 1 is characterized in that, described hydrogen fluorine ether is selected from following formula (I-1) one or more to the compound shown in the 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≤15,1≤n3≤15,1≤n5≤15, n2, n4 and n6 are respectively the positive integer 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 have with following formula (II-1) one or more to 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 are 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 have with in following formula (III-1) and formula (III-2) structural compounds one or more:
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 are respectively positive integer, and n12 is nonnegative integer; Rf
8-, Rf
9-, Rf
10-, Rf
11-, Rf
12-and Rf
13-be fluorocarbon group or hydrocarbon chain group independently 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 have with in following formula (IV-1) and formula (IV-2) structural compounds one or more:
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 are 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:
The described compositions of additives of 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 is selected from one or more in ethylene carbonate, propene carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dimethyl carbonate, diethyl carbonate and the ethylene carbonate.
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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