CN102780040A - Flame retardant long-life electrolyte and lithium ion battery using same - Google Patents
Flame retardant long-life electrolyte and lithium ion battery using same Download PDFInfo
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- CN102780040A CN102780040A CN2012102638836A CN201210263883A CN102780040A CN 102780040 A CN102780040 A CN 102780040A CN 2012102638836 A CN2012102638836 A CN 2012102638836A CN 201210263883 A CN201210263883 A CN 201210263883A CN 102780040 A CN102780040 A CN 102780040A
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Abstract
The invention discloses a multi-component electrolyte for lithium ion batteries. The multi-component electrolyte is good in ionic conductivity and is characterized by containing the following multiple components: (1) carbonic ester solvents, (2) flame retardant additives, (3) single or composite film-forming additives and (4) composite lithium salt. One of the film-forming additives (3) is selected from haloketones, the general formula of the haloketones is normally: XH2mCm-(C=O)-CnH2n+1, wherein both m and n are natural numbers, m is identical to or different from n, and X can be one of F, Cl, Br and I. The electrolyte can improve safety, magnification performance and cycle life of the lithium ion batteries.
Description
Technical field
The present invention relates to secondary battery technology, particularly relate to a kind of anti-flammability that improves lithium ion battery, the nonaqueous electrolyte of high rate performance and cycle life.
Background technology
Lithium ion battery has had the history in more than 20 year from 1990 nearly since by the exploitation commercialization of Japanese Sony company.Because it has higher volumetric specific energy, gravimetric specific energy and favorable environment protection; Just progressively replace traditional lead-acid battery, NI-G and Ni-MH battery; And be widely used in the portable 3C electronic equipments such as mobile phone, notebook computer, captured very big market and fast development rapidly.In addition; Lithium ion battery is used for electric tool and electric bicycle and mixes moving; The exploitation of electric automobile is a very large industry of various countries' dynamics of investment in recent years, this field succeed in developing the petroleum resources that can alleviate growing tension, therefore very high international economy strategy meaning is arranged.Except requiring lower price, pursuing higher energy density and cycle life and fail safe becomes the strong actuating force of improving these chemical power source products,
Lithium ion battery is mainly by positive/negative plate, barrier film, and electrolyte and battery case are formed.Wherein, electrolyte is as " blood " of lithium ion battery, wields influence very big to the performance of battery.The electrolyte of forming suitable (salt, the selection of solvent and additive and consumption) can effectively be assisted the chemical property of performance of battery plus-negative plate active material performance and lifting entire lithium ion battery, comprising the positive and negative pole material first charge-discharge efficiency; The platform time of discharge; Cycle life, capacity keeps, high temperature performance; Security performance, and the multiplying power discharging characteristic or the like.
Usually in the process of lithium ion battery first charge-discharge, the surface that some component in the electrolyte (solvent or additive) generation reduction decomposition and product are deposited on negative material graphite forms solid electrolyte interface film (SEI).Good and fine and close interface diaphragm can effectively be alleviated the decomposition of electrolyte, thereby reduces the irreversible capacity of battery and improve its cycle performance.Make people urgently pay attention to the usage safety performance of battery because the increasing of power lithium-ion battery in transportation system used at present, fail safe is the key issue that the Application and Development high performance lithium ion battery at first will be considered.People attempt the security performance that the whole bag of tricks improves battery for this reason.Present normally used method can be divided two types: one is to use the solvent with low combustion property or flame retardancy, like halogen solvent or ionic liquid; Another method is to use the flame-retardant additives of using usually in the plastic processing, as contains Phosphorus compound.Problems such as the former is big owing to use amount, and factor that price is high or solvent viscosity are big are difficult to realize industrialization usually.Latter's method is because addition is little, and functioning efficiency is high and obtain widespread usage.Representational contain phosphorus type flame retardant have trimethyl phosphate (TMP), triethyl phosphate (TEP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2,3-two chloropropyls) (TDCPP), triphenyl phosphate (TPP) or the like.It is to be cost with the chemical property of sacrificing battery that but these additives have improved the thermal stability of electrolyte.For example TMP has good oxidation stability; But it reduces poor stability; It decomposes in 1.3V (vsLi/Li+) reduction; The TMP that decomposes not only destroys by the SEI film that on negative pole graphite, generates such as film for additive such as VC, and it resolves into branch and inserts graphite layers and cause caving in of graphite-structure and battery cycle life is reduced.When reduction potential is reduced to 1.1V (vs Li/Li+); Have a large amount of gases (methane, ethene) simultaneously and produce [Non-flammable electrolytes based on trimethyl phosphate solvent for lithium ion batteries, Trans.Nonferrous Met.Soc.China; 2005; Vol.15, No.6,1380-1387].In addition, VC can not regenerate change into generation SEI film through battery after, therefore causes the permanent damage of TMP to the SEI film.These problems finally cause battery performance to reduce the battery premature failure.In addition; We find; LiBF4 not only can generate than organics additives such as VC stable SEI film more in negative terminal surface generation reduction reaction, and can repair the organic membrane that destroys because of flame-retardant additive and make it more stable, but LiBF4 can make the ionic conductivity of whole electrolyte reduce; Therefore need to cooperate use together, and its addition to be controlled at certain scope with other salt.In sum; The present invention cooperates the polynary method of electrolyte of complex salt to overcome the negative effect that common flame-retardant additive and film for additive brings through using the composite membrane-forming additive, when improving battery security, prolongs battery cycle life and improves high rate performance.
Summary of the invention
Main purpose of the present invention provides a kind of anti-flammability electrolyte single or composite membrane-forming additive and cooperation adding complex salt that contains; Wherein halo ketone film for additive separately or with film for additive such as VC common use more effective than the independent use film forming of VC; The merging of complex salt is used can stablize the SEI film more; Not only improve battery security, and can prolong battery cycle life and improve high rate performance.Another object of the present invention is to provide the lithium ion battery of making by the electrolyte of foregoing invention.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind ofly be used to improve battery security, high rate performance and the anti-flammability electrolyte that contains single film for additive and complex salt that prolongs cycle life is characterized in that said electrolyte comprises following composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) single halo ketone film for additive;
(4) compound lithium salts.
Preferably, the carbonates solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC) two or more in the wherein said electrolyte.
Preferably; Wherein said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2,2, the 2-trifluoroethyl) methyl phosphorodithioate (TFMP), tricresyl phosphate (2; 2,2-trifluoroethyl) a kind of in the ester.
Preferably, general formula is as the wherein said halo ketone film for additive one of which: XH2mCm-(C=O)-CnH2n+1; M, n is identical or different; X can be F, Cl, Br, a kind of among the I.
Preferably, wherein said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
Preferably, wherein said flame-retardant additive content is between 0.01%-25%.
Preferably, wherein said halo ketone film for additive content is between 0.01%-10%.
Preferably, the concentration of wherein said compound lithium salts is between 0.5M-2M.
Another object of the present invention is to provide a kind of battery security that is used to improve, high rate performance and the anti-flammability electrolyte that contains single film for additive and complex salt that prolongs cycle life is characterized in that said electrolyte comprises following composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) single film for additive;
(4) compound lithium salts.
Preferably, the carbonates solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC) two or more in the wherein said electrolyte.
Preferably; Wherein said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2,2, the 2-trifluoroethyl) methyl phosphorodithioate (TFMP), tricresyl phosphate (2; 2,2-trifluoroethyl) a kind of in the ester.
Preferably; Film for additive is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), coke dimethyl phthalate (DMPC), pyrocarbonic acid diethyl ester (DEPC), coke dibutyl phthalate (DBPC), single fluorinated ethylene carbonate (FEC), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), tetrafluoro oxalic acid lithium phosphate (LiPF4 (C2O4)), ethylene sulfite (ES), propylene sulfite (PS), sulfurous acid butene esters (BS), vinylacetate (VA), maleic anhydride (MA), 2-vinylpyridine in the wherein said electrolyte; The vinyl silanes class, a kind of in the 2-cyanide furan.
Preferably, wherein said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
Preferably, wherein said flame-retardant additive content is between 0.01%-25%.
Preferably, wherein said film for additive content is between 0.01%-10%.
Preferably, the concentration of wherein said compound lithium salts is between 0.5M-2M.
Another object of the present invention is to provide a kind of battery security that is used to improve, high rate performance and the anti-flammability electrolyte that contains composite membrane-forming additive and complex salt that prolongs cycle life is characterized in that said electrolyte comprises following composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) composite membrane-forming additive;
(4) compound lithium salts.
Preferably, the carbonates solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC) two or more in the wherein said electrolyte.
Preferably; Wherein said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2,2, the 2-trifluoroethyl) methyl phosphorodithioate (TFMP), tricresyl phosphate (2; 2,2-trifluoroethyl) a kind of in the ester.
Preferably, the composite membrane-forming additive has a kind of halogenated ketone compounds that is selected from least in the wherein said electrolyte, and general formula is as the one of which: XH
2mC
m-(C=O)-C
nH
2n+1; M, n are natural number, m, and n is identical or different; X can be a kind of among F, Cl, Br, the I.
Preferably; Wherein said composite membrane-forming additive is a kind of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), coke dimethyl phthalate (DMPC), pyrocarbonic acid diethyl ester (DEPC), coke dibutyl phthalate (DBPC), single fluorinated ethylene carbonate (FEC), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), tetrafluoro oxalic acid lithium phosphate (LiPF4 (C2O4)), ethylene sulfite (ES), propylene sulfite (PS), sulfurous acid butene esters (BS), vinylacetate (VA), maleic anhydride (MA), 2-vinylpyridine of being selected from addition; The vinyl silanes class, at least a in the 2-cyanide furan.
Preferably, wherein said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
Preferably, wherein said flame-retardant additive content is between 0.01%-25%.
Preferably, wherein said composite membrane-forming additive level is between 0.01%-10%.
Preferably, the concentration of wherein said compound lithium salts is between 0.5M-2M.
Another purpose of the present invention is to provide a kind of lithium ion battery, comprising:
(1) anode;
(2) electrolyte; Wherein electrolyte is a kind of by above-mentioned any described polynary composite electrolyte; This electrolyte can improve battery security and cycle performance;
(3) negative electrode;
(4) barrier film.
In sum; Visible by above technical scheme provided by the present invention; Compared with prior art, the present invention overcomes negative effect that common flame-retardant additive and film for additive bring (as destroying the SEI film, low ionic conductivity through the polynary electrolyte method of using single or compound additive and being used complex salt; Cycle performance reduces), when improving battery security, prolong battery cycle life and improve high rate performance.
Embodiment
Below in conjunction with specific embodiment such scheme is further specified.Should be understood that these embodiment are used to the present invention is described and are not limited to limit scope of the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Introduce and general introduction
The present invention by way of example but not the mode that provides restriction describe.It should be noted, may not be meant with a kind of embodiment " " described in the disclosure file or " a kind of " execution mode, and be meant have at least a kind of.
Hereinafter will be described various aspects of the present invention.Yet it is obvious that for those of skill in the art, can come embodiment of the present invention in only some or all of aspects according to the present invention.For purposes of illustration, this paper provides concrete numbering, material and configuration, so that people can thoroughly understand the present invention.Yet for those of skill in the art will it is obvious that, the present invention need not concrete details and can implement.In other examples, the present invention is obscure to omit or has simplified well-known characteristic in order not make.
Various operations as the step of a plurality of separations and describe successively, and are explained to help most understanding mode of the present invention; Yet, should in-order description be interpreted as that these operations of hint must depend on order.
To various execution modes be described according to the reactant of type species.For those of skill in the art will it is obvious that, the present invention can use different types of reactant of any amount to implement, and is not those reactants that provide for the purpose of illustration and here.In addition, also will it is obvious that, the present invention is not limited to any specific mixing example.
1 one kinds of anti-flammability electrolyte that contain single halogenated ketone film for additive and complex salt of embodiment
Electrolyte consists of: 1.0M/0.2M LiPF
6/ LiBF
4, EC/EMC=3/7 (v/v), fluoro acetone (FA) 2%, TMP 3%, and recording electrolyte room temperature ionic conductivity is 7.2*10-3S/cm.
2 one kinds of anti-flammability electrolyte that contain single film for additive and complex salt of embodiment
Electrolyte consists of: 1.1M/0.2M LiPF
6/ LiBF
4, EC/EMC=3/7 (v/v), ethylene carbonate (VC) 2%, TMP 3%, and recording electrolyte room temperature ionic conductivity is 6.8*10-3S/cm.
3 one kinds of anti-flammability electrolyte that contain composite membrane-forming additive and complex salt of embodiment,
Electrolyte consists of: 1.1M/0.2M LiPF
6/ LiBF
4, EC/EMC=3/7 (v/v), fluoro acetone (FA) 1%, ethylene carbonate (VC) 1%, TMP 3%, and recording electrolyte room temperature ionic conductivity is 6.7*10-3S/cm.
Comparative example 1 electrolyte 1
Electrolyte consists of: 1.0M/0.2M LiPF
6/ LiBF
4, EC/EMC=3/7 (v/v), fluoro acetone (FA) 2%, recording electrolyte room temperature ionic conductivity is 8.3*10-3S/cm.
Comparative example 2 electrolyte 2
Electrolyte consists of: 1.2M LiPF
6, EC/EMC=3/7 (v/v), ethylene carbonate (VC) 2%, recording electrolyte room temperature ionic conductivity is 8.6*10-3S/cm.Result such as table 1.Table 1 is the acupuncture experimental result of various electrolyte in 18650 type 2Ah NCM/AG electricity core in embodiment and the comparative example.
The acupuncture experimental result of the various electrolyte of table 1 in 18650 type 2Ah NCM/AG electricity core
The extrusion experiment result of the various electrolyte of table 2 in 18650 type 2Ah NCM/AG electricity core
Through table 1 and the electric core safety test contrast of table 2, prove that polynary electrolyte of the present invention can improve the fail safe of nickel-cobalt-manganese ternary lithium ion battery.
In sum; Compared with prior art, a kind of method that is used to prepare lithium ion battery security long life electrolysis liquid provided by the invention, this method is through using single or compound additive and cooperating the polynary electrolyte method of complex salt to overcome negative effect that common flame-retardant additive and film for additive bring (like destruction SEI film; Low ionic conductivity; Cycle performance reduces), when improving battery security, prolong battery cycle life and improve high rate performance, it is simply effective to have implementation method; Be convenient to the advantage of extensive industrialization, help improving the market application foreground of lithium ion battery.
Above-mentioned specific embodiment only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (17)
1. polynary electrolyte that is used for lithium ion battery comprises following composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) single halo ketone film for additive;
(4) compound lithium salts.
2. electrolyte according to claim 1 is characterized in that said carbonates solvent is selected from least two kinds in ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC).
3. electrolyte according to claim 1; It is characterized in that said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2,2, the 2-trifluoroethyl) methyl phosphorodithioate (TFMP), tricresyl phosphate (2; 2,2-trifluoroethyl) at least a in the ester.
4. electrolyte according to claim 1 is characterized in that said halo ketone film for additive general formula is: XH
2mC
m-(C=O)-C
nH
2n+1; M, n is natural number, m, n is identical or different; X is selected from a kind of among F, Cl, Br, the I.
5. electrolyte according to claim 1 is characterized in that said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
6. polynary electrolyte that is used for lithium ion battery comprises the mixture of following composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) single film for additive;
(4) compound lithium salts.
7. electrolyte according to claim 6 is characterized in that said carbonates solvent is selected from two or more in ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC).
8. electrolyte according to claim 6; It is characterized in that said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2,2, the 2-trifluoroethyl) methyl phosphorodithioate (TFMP), tricresyl phosphate (2; 2,2-trifluoroethyl) at least a in the ester.
9. electrolyte according to claim 6 is characterized in that said film for additive is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), coke dimethyl phthalate (DMPC), pyrocarbonic acid diethyl ester (DEPC), coke dibutyl phthalate (DBPC), single fluorinated ethylene carbonate (FEC), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)), ethylene sulfite (ES), propylene sulfite (PS), sulfurous acid butene esters (BS), vinylacetate (VA), maleic anhydride (MA), 2-vinylpyridine, vinyl silanes class, a kind of in the 2-cyanide furan.
10. electrolyte according to claim 6 is characterized in that said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
11. a polynary electrolyte that is used for lithium ion battery comprises following mixture composition:
(1) carbonates solvent;
(2) flame-retardant additive;
(3) composite membrane-forming additive;
(4) compound lithium salts.
12. electrolyte according to claim 11 is characterized in that said carbonates solvent is selected from two or more in ethylene carbonate (EC), propene carbonate (PC), butylene (BC), single fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), the carbonic acid first propyl ester (MPC).
13. electrolyte according to claim 11; It is characterized in that said flame-retardant additive is selected from trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tricresyl phosphate (2-chloropropyl) ester (TCPP), tricresyl phosphate (2-chloroethyl) ester (TCEP), tricresyl phosphate (2; 3-two chloropropyls) ester (TDCPP), triphenyl phosphate (TPP), two (2; 2; The 2-trifluoroethyl) at least a in methyl phosphorodithioate (TFMP), tricresyl phosphate (2,2, the 2-trifluoroethyl) ester.
14. electrolyte according to claim 11 is characterized in that said composite membrane-forming additive has a kind of halogenated ketone compounds that is selected from least, general formula is as the one of which: XH
2mC
m-(C=O)-C
nH
2n+1; M, n is identical or different; X can be F, Cl, Br, a kind of among the I.
15. electrolyte according to claim 11; It is characterized in that said composite membrane-forming additive a kind of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), coke dimethyl phthalate (DMPC), pyrocarbonic acid diethyl ester (DEPC), coke dibutyl phthalate (DBPC), single fluorinated ethylene carbonate (FEC), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), tetrafluoro oxalic acid lithium phosphate (LiPF4 (C2O4)), ethylene sulfite (ES), propylene sulfite (PS), sulfurous acid butene esters (BS), vinylacetate (VA), maleic anhydride (MA), 2-vinylpyridine of being selected from addition; The vinyl silanes class, at least a in the 2-cyanide furan.
16. electrolyte according to claim 11 is characterized in that said lithium salts is by lithium hexafluoro phosphate (LiPF
6) and be selected from LiBF4 (LiBF
4), Li (C
2F
5)
3PF
3(LiFAP), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), hexafluoroarsenate lithium (LiAsF
6), lithium perchlorate (LiClO
4), TFMS lithium (LiCF
3SO
3), two (trifluoromethane sulfonic acid) imines lithium (LiN (SO
2CF
3)
2), tetrafluoro oxalic acid lithium phosphate (LiPF
4(C
2O
4)) at least a compound composition.
17. a lithium ion battery comprises:
(1) anode;
(2) electrolyte; Wherein electrolyte is any described polynary composite electrolyte of claim 1 ~ 16;
(3) negative electrode;
(4) barrier film.
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Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326064A (en) * | 2013-05-24 | 2013-09-25 | 中国科学技术大学 | A safe lithium ion battery electrolyte |
| CN104022309A (en) * | 2014-05-28 | 2014-09-03 | 武汉大学 | Fire retardant for electrolytes, electrolyte containing fire retardant and secondary lithium ion battery |
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| CN104733780A (en) * | 2015-03-27 | 2015-06-24 | 山东海容电源材料有限公司 | Electrolyte solution capable of improving safety performance of lithium battery |
| CN105047991A (en) * | 2015-06-08 | 2015-11-11 | 山东鸿正电池材料科技有限公司 | Electrolyte capable of improving high-voltage performance of lithium ion battery |
| CN105514494A (en) * | 2016-01-25 | 2016-04-20 | 山东玉皇新能源科技有限公司 | Preparation method of lithium-ion battery flame-retardant electrolyte |
| CN105680097A (en) * | 2016-01-25 | 2016-06-15 | 山东玉皇新能源科技有限公司 | High-safety lithium-ion battery electrolyte solution |
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| CN106025338A (en) * | 2016-06-08 | 2016-10-12 | 湖州创亚动力电池材料有限公司 | Electrolyte for rechargeable micro lithium battery |
| CN106058320A (en) * | 2016-08-22 | 2016-10-26 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery fire retardation electrolyte and preparation method thereof |
| CN106133989A (en) * | 2014-03-28 | 2016-11-16 | 大金工业株式会社 | Electrolyte, electrochemical device, secondary cell and module |
| CN107069087A (en) * | 2016-11-29 | 2017-08-18 | 北京万源工业有限公司 | It is a kind of to be applicable high/low temperature electrolyte of lithium iron phosphate dynamic battery and preparation method thereof |
| CN107293788A (en) * | 2017-06-28 | 2017-10-24 | 常州市万昌化工有限公司 | A kind of lithium ion battery flame-retardant electrolyte and preparation method thereof |
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| CN109950625A (en) * | 2019-04-19 | 2019-06-28 | 湖北诺邦科技股份有限公司 | A kind of anti-overcharge type lithium ion battery flame-retardant electrolyte |
| CN111082145A (en) * | 2020-01-16 | 2020-04-28 | 珠海市赛纬电子材料股份有限公司 | Lithium ion battery electrolyte matched with silicon-carbon graphite cathode and lithium ion battery |
| CN113161615A (en) * | 2021-06-04 | 2021-07-23 | 湖州昆仑亿恩科电池材料有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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| CN115360417A (en) * | 2022-07-21 | 2022-11-18 | 华中科技大学 | Lithium-sulfur battery electrolyte containing fluoroketone additive and lithium-sulfur battery |
| WO2024072964A1 (en) * | 2022-09-29 | 2024-04-04 | Tesla, Inc. | Carbon dioxide saturated electrolytes for energy storage device, and methods thereof |
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| CN103326064B (en) * | 2013-05-24 | 2016-12-28 | 中国科学技术大学 | A kind of electrolyte of safe lithium ion battery |
| CN103326064A (en) * | 2013-05-24 | 2013-09-25 | 中国科学技术大学 | A safe lithium ion battery electrolyte |
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| CN109193029A (en) * | 2018-08-21 | 2019-01-11 | 东莞市杉杉电池材料有限公司 | A kind of nickelic ternary non-aqueous electrolyte for lithium ion cell and the nickelic ternary lithium ion battery containing the electrolyte |
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