CN105449275A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN105449275A CN105449275A CN201510785312.2A CN201510785312A CN105449275A CN 105449275 A CN105449275 A CN 105449275A CN 201510785312 A CN201510785312 A CN 201510785312A CN 105449275 A CN105449275 A CN 105449275A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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Abstract
The invention discloses a lithium ion battery electrolyte and a lithium ion battery. The lithium ion batter electrolyte comprises non-aqueous organic solvent, lithium salt, a functional additive, a flame-retardant additive and a negative electrode film-forming agent. According to the scheme of the lithium ion batter electrolyte, perfluoroalkyl diphenyl sulfide is used as the functional additive on the basis of reasonably optimizing the non-aqueous organic solvent, the lithium salt and the negative electrode film-forming agent; the problem that the novel lithium salt corrodes an aluminium current collector can be effectively solved, wherein the novel lithium salt comprises lithium trifluoromethanesulfonate (LiCF3SO3), perfluoroalkyl sulfonyl lithium methide (LiC (CF3SO2)3, bi(trifluoromethyl sulfonyl) lithium imide (LTFSI), bi(sulfonyl fluoride) lithium imide (LiFSI) and the like; the cycling performance of the lithium ion battery is improved; the LiPF6 can be well replaced by the lithium ion battery electrolyte, and the lithium ion battery electrolyte can be widely applied to the secondary lithium ion battery electrolyte, and particularly suitable for lithium ion power batteries for improving the thermal stability of the lithium ion power batteries.
Description
Technical field
The present invention relates to field of lithium, particularly relate to a kind of lithium-ion battery electrolytes and lithium ion battery.
Background technology
Due to lithium ion battery have that energy density is high, operating voltage is high, have extended cycle life, memory-less effect, can the advantage such as fast charging and discharging, obtain a wide range of applications in the field such as electric automobile, Aero-Space.But, oneself is of common occurrence for the report that the fire caused about lithium ion battery in recent years even explodes, the concern that the safety problem of lithium ion battery causes people general is that limiting lithium ion cell realizes the major obstacle of industrial upgrading in power and extensive energy storage field.And electrolyte is as the important component part of lithium ion battery, it is one of major reason causing cell safety problem.
Lithium-ion battery electrolytes plays a crucial role as transmitting the performance of medium to battery of lithium ion, and be the capacity that an important factor affects battery, security performance and cycle life, govern development and the application of lithium ion battery always.The lithium-ion battery electrolytes generally adopted now is organic electrolyte, has the shortcomings such as higher vapour pressure and lower flash-point, thermal stability are low, serviceability temperature narrow range.In unconventional environment, be easy to the thermal runaway causing lithium ion battery, cause even blast on fire of smoldering to wait the adverse consequences of the harm person and property safety.Organic electrolyte; be made up of organic solvent and electric conducting lithium salt; conventional organic solvent is alkylcarbonic acid ester type compound; as ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) etc.; the flash-point of these organic solvents is all very low; the electrolyte solution of lithium ion battery (electrolyte) is very easily burnt; although battery is furnished with protective circuit, safety valve and semistor (PTC) etc., the fail safe of the situation electrolyte that leakage appears in these organic solvents, burning is even exploded can not be avoided completely.Except the problem that electrolyte is inflammable, another important aspect is exactly the thermal stability problems of electrolyte.Now conventional lithium salts is lithium hexafluoro phosphate (LiPF
6), there is higher conductivity and stable solid electrolyte interface (SEI) film can be formed.But LiPF
6thermal stability poor, can decompose generate PF
5and LiF, simultaneously LiPF
6can react with water and produce acidic materials HF, the dissolving of active material or broken ring SEI film can be accelerated, cause two-step film forming, have a strong impact on the cycle performance of battery, be difficult to the needs meeting high-temperature behavior lithium ion battery.Noninflammability and the thermal stability of improving electrolyte are important channels of improving battery security, therefore in the urgent need to developing a kind of novel electrolyte of high security.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of lithium-ion battery electrolytes and lithium ion battery of high temperature resistant, safety-type, this lithium-ion battery electrolytes is particularly useful for lithium-ion-power cell, is intended to solve the problem that the thermal stability of lithium ion battery in prior art and security performance have much room for improvement.
A kind of lithium-ion battery electrolytes, comprise non-aqueous organic solvent, lithium salts, functional additive, flame-retardant additive and cathode film formation agent, wherein, described functional additive is perfluoroalkyl diphenyl sulfide.
Described lithium-ion battery electrolytes, wherein, the molecular structural formula of described perfluoroalkyl diphenyl sulfide is shown below:
Wherein, R is carbon molecular number-CF
3,-C
2f
5,-C
3f
7,-C
4f
9within any one of perfluoroalkyl group.
Described lithium-ion battery electrolytes, wherein, described functional additive mass percentage is in the electrolytic solution 0.5-2.0%.
Described lithium-ion battery electrolytes, wherein, described flame-retardant additive is ionic liquid.
Described lithium-ion battery electrolytes, wherein, described ionic liquid be aliphatic quaternary ammonium salt, season phosphonium salt, pyrroles's salt, pyrrolidones salt, imidazole salts and piperidinium salt; General formula is C
+[A]
-, C in general formula
+cationic structural formula is as follows:
Wherein, R1, R2, R3 and R4 are any one in C1 ~ C3 alkyl, pi-allyl, ether; In general formula [A]
-anion is CF
3sO
3 -, TFSI
-, FSI
-, BOB
-or DFOB
-in any one.
Described lithium-ion battery electrolytes, wherein, described ionic liquid mass percentage is in the electrolytic solution 5% ~ 20%.
Described lithium-ion battery electrolytes, wherein, described lithium salts is selected from LiCF
3sO
3, LiC (CF
3sO
2)
3, the combination of one or more in LTFSI, LiFSI; The concentration of described lithium salts is 0.3mol/L ~ 1.0mol/L.
Described lithium-ion battery electrolytes, wherein, described non-aqueous organic solvent is cyclic carbonate or linear carbonate.
Described lithium-ion battery electrolytes, wherein, described cathode film formation agent is any one or a few the combination comprised in vinylene carbonate, vinylethylene carbonate or fluorinated ethylene carbonate, and addition is account for electrolyte gross mass 0.1 ~ 2%.
A kind of lithium ion battery, wherein, comprises lithium-ion battery electrolytes as above.
Beneficial effect: a kind of lithium-ion battery electrolytes with very high security provided by the present invention, on the basis of reasonably optimizing non-aqueous organic solvent, lithium salts, cathode film formation agent, adopts perfluoroalkyl diphenyl sulfide as a kind of functional additive; More preferably, using ionic liquid as flame-retardant additive, solve circulation and the security performance of ternary material lithium ion battery, the serviceability temperature of ternary material lithium ion battery can be made to be promoted to more than 80 DEG C.This lithium-ion battery electrolytes mainly comprises: non-aqueous organic solvent, lithium salts, functional additive, flame-retardant additive and cathode film formation agent.Novel lithium-ion battery electrolyte provided by the present invention effectively can not only solve trifluoromethanesulfonic acid lithium (LiCF
3sO
3), per-fluoroalkyl sulfonyl lithium methide (LiC (CF
3sO
2)
3), two (trimethyl fluoride sulfonyl) imine lithium (LTFSI), the above-mentioned new lithium salts such as two (fluorine sulphonyl) imine lithium (LiFSI) be to the etching problem of aluminium collector, improve the cycle performance of lithium ion battery, make them can replace LiPF well
6, and can also be widely used in secondary lithium ion cell electrolyte solution, be particularly useful for lithium-ion-power cell, improve the thermal stability of lithium-ion-power cell; Effectively solve the compatibility issue of ionic liquid flame-retardant additive and electrode material simultaneously, improve the security performance of lithium-ion-power cell, promote the development of lithium-ion-power cell.
Accompanying drawing explanation
Fig. 1 is LiMn prepared by the electrolyte of comparative example 1 and embodiment 1
1/3ni
1/3co
1/3o
2battery is at the cycle performance figure of 25 DEG C of normal temperature environment 1C multiplying power 2.7 ~ 4.3V discharge and recharge.
Fig. 2 a ~ Fig. 2 d is the electrode surface of battery after embodiment 1 and comparative example 1 circulate electrolyte and the SEM figure of Al paper tinsel.
Fig. 3 is aluminium foil at the cyclic voltammetry curve of the electrolyte of embodiment 1 and comparative example 1.
Fig. 4 is LiMn prepared by the electrolyte of embodiment 3 and comparative example 2
1/3ni
1/3co
1/3o
2battery is at the cycle performance figure of 85 DEG C of normal temperature environment 1C multiplying power 2.7 ~ 4.3V discharge and recharge.
Embodiment
The invention provides a kind of lithium-ion battery electrolytes and lithium ion battery, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In improved thermo stability, large quantifier elimination is devoted to the synthesis of new lithium salts at present, seeks to be expected to alternative existing commercialization lithium salts LiPF
6new material.Some novel lithium salts are progressively applied in recent years: trifluoromethanesulfonic acid lithium (LiCF
3sO
3), per-fluoroalkyl sulfonyl lithium methide (LiC (CF
3sO
2)
3), two (trimethyl fluoride sulfonyl) imine lithium (LTFSI), two (fluorine sulphonyl) imine lithium (LiFSI) etc., the interaction of they and water is slower, there is high oxidation resistance and thermal stability simultaneously, from this point, use them can improve cycle efficieny under battery high-temperature condition and thermal stability.But from current progress, these lithium salts performances can't replace LiPF completely
6, because they have strong corrosivity to aluminium collector, there is charge-discharge performance not good, the shortcomings such as coulombic efficiency is not high, cause its application in secondary lithium battery greatly to limit.
In improved safety, ameliorative way main at present adds flame-retardant additive in the electrolytic solution, when do not increase or substantially do not increase battery cost, do not change production technology, reduce battery heat release value and battery self-heating rate, make electrolyte nonflammable.Ionic liquid has Heat stability is good, conductivity is high, electrochemical window is wide, non-volatile, the characteristic of a series of excellence such as not fire, the security performance of battery can be improved preferably, but these additives can occur in the common embedding phenomenon of electrode layer along with lithium ion, there is fatal negative effect to the cycle performance of battery, limit its application in high-temperature lithium-ion battery electrolyte.
The present invention is then to provide a kind of lithium-ion battery electrolytes with very high security, and this electrolyte mainly comprises: non-aqueous organic solvent, lithium salts, functional additive, flame-retardant additive and cathode film formation agent.Novel lithium-ion battery electrolyte provided by the present invention effectively can not only solve trifluoromethanesulfonic acid lithium (LiCF
3sO
3), per-fluoroalkyl sulfonyl lithium methide (LiC (CF
3sO
2)
3), two (trimethyl fluoride sulfonyl) imine lithium (LTFSI), the above-mentioned new lithium salts such as two (fluorine sulphonyl) imine lithium (LiFSI) be to the etching problem of aluminium collector, improve the cycle performance of lithium ion battery, make them can replace LiPF well
6, and can also be widely used in secondary lithium ion cell electrolyte solution, improve the thermal stability of lithium-ion-power cell; Effectively solve the compatibility issue of ionic liquid flame-retardant additive and electrode material simultaneously, improve the security performance of lithium-ion-power cell, promote the development of lithium-ion-power cell.
Particularly, what described functional additive adopted is perfluoroalkyl diphenyl sulfide, its HOMO highest occupied molecular orbital (HOMO) can compare the much lower of conventional organic solvent EC, DMC, can take the lead in, on Al paper tinsel surface, oxidation reaction occurs and generate comparatively stable SEI film, improve the compatibility of new lithium salts and Al foil material; The stable SEI film of one deck can be formed at positive electrode surface on the other hand, stop ionic liquid flame-retardant additive to occur to embed phenomenon altogether at electrode surface, substantially increase circulation and the security performance of battery.To sum up, perfluoroalkyl diphenyl sulfide is the very potential electrolyte functional additive of one.
Described perfluoroalkyl diphenyl sulfide organic molecule structural formula is shown below:
Wherein, R is carbon molecular number-CF
3,-C
2f
5,-C
3f
7,-C
4f
9within any one of perfluoroalkyl group.
Preferably, described functional additive (perfluoroalkyl diphenyl sulfide) mass percentage is in the electrolytic solution 0.5-2.0%.
Described lithium salts is selected from LiCF
3sO
3, LiC (CF
3sO
2)
3, the combination of one or more in LTFSI, LiFSI.New lithium salts can be suitable in electrolyte of the present invention, owing to the addition of perfluoroalkyl diphenyl sulfide, improve the compatibility of new lithium salts and Al foil material, them are made not deposit aggressive to aluminium collector, make new lithium salts can its application in secondary lithium battery, there is high oxidation resistance and thermal stability, use them can improve cycle efficieny under high-temperature lithium ion battery condition and thermal stability.Preferably, the concentration of described lithium salts is 0.3mol/L ~ 1.0mol/L.
Further, described flame-retardant additive adopts ionic liquid, described ionic liquid be preferably aliphatic quaternary ammonium salt, season phosphonium salt, pyrroles's salt, pyrrolidones salt, imidazole salts and piperidinium salt, general formula is C
+[A]
-, described C
+cationic structural formula is as follows:
Wherein R1, R2, R3 and R4 are any one in C1 ~ C3 alkyl, pi-allyl, ether, in general formula [A]
-anion is CF
3sO
3 -, TFSI
-, FSI
-, BOB
-or DFOB
-in any one.
Preferably, described ionic liquid mass percentage is in the electrolytic solution 5% ~ 20%.
Described non-aqueous organic solvent is cyclic carbonate or linear carbonate, is preferably selected from the one in ethylene carbonate (EC), propene carbonate (PC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP) and ethyl propionate (EP) or mixes arbitrarily.
Described cathode film formation agent can be comprise any one or a few the combination in vinylene carbonate (VC), vinylethylene carbonate (VEC) or fluorinated ethylene carbonate (FEC) etc., other cathode film formation agent with identity function are also suitable for, and the addition of cathode film formation agent is account for electrolyte gross mass 0.1 ~ 2%.
A kind of lithium ion battery is also provided, using above-mentioned lithium-ion battery electrolytes as electrolyte in described lithium ion battery in the present invention.Above-mentioned lithium-ion battery electrolytes can be widely used in secondary lithium ion cell electrolyte solution, is particularly useful for lithium-ion-power cell, improves the thermal stability of lithium-ion-power cell; Effectively solve the compatibility issue of ionic liquid flame-retardant additive and electrode material simultaneously, improve the security performance of lithium-ion-power cell, promote the development of lithium-ion-power cell.
The present invention will be further described by the following examples.
Comparative example 1: under room temperature, in the glove box being full of argon gas, ethylene carbonate (EC), dimethyl carbonate (DMC) are mixed according to mass ratio 1:1, add the vinylene carbonate (VC) that mass percentage is 2% wherein, adding two (trimethyl fluoride sulfonyl) imine lithium (LTFSI) again, to be dissolved to concentration be 1.0mol/L, is prepared into electrolyte.
Comparative example 2: under room temperature, in the glove box being full of argon gas, ethylene carbonate (EC), dimethyl carbonate (DMC), propene carbonate (PC), methyl ethyl carbonate (EMC) are mixed according to mass ratio 1:1:1:1, add the vinylene carbonate (VC) that mass percentage is 2% phenyl trifluoromethyl sulfide and 2% wherein, adding two (trimethyl fluoride sulfonyl) imine lithium (LTFSI) again, to be dissolved to concentration be 1.0mol/L, is prepared into electrolyte.
Embodiment 1: prepare electrolyte according to the method identical with comparative example 1, difference is to add the phenyl trifluoromethyl sulfide accounting for electrolyte quality 2%.
Embodiment 2: prepare electrolyte according to the method identical with comparative example 2, difference is to add the two fluorine oxalic acid borate (NMP-DFOB) of 10%1-methyl-2-oxygen-1-propyl pyrrole alkane ketone.
Embodiment 3: prepare electrolyte according to the method identical with comparative example 2, difference is to add the two fluorine oxalic acid borate (NMP-DFOB) of 15%1-methyl-2-oxygen-1-propyl pyrrole alkane ketone.
Embodiment 4: prepare electrolyte according to the method identical with comparative example 2, difference is to add the two fluorine oxalic acid borate (NMP-DFOB) of 20%1-methyl-2-oxygen-1-propyl pyrrole alkane ketone.
Embodiment 5: prepare electrolyte according to the method identical with comparative example 2, difference is to add the two fluorine oxalic acid borate (NMP-DFOB) of 25%1-methyl-2-oxygen-1-propyl pyrrole alkane ketone.
To the electrolyte of embodiment 1 and comparative example 1 respectively with tertiary cathode (LiMn
1/3ni
1/3co
1/3o
2), negative pole lithium sheet is assembled into CR2023 button cell, carry out the constant current charge-discharge loop test that 25 DEG C of 1C circulate 100 weeks, voltage range 2.7-4.3V, test result is as shown in Figure 1.Result shows, and battery capacity after the electrolyte 1C not adding phenyl trifluoromethyl sulfide is circulated to 30 circles is decayed rapidly, and after adding circulate electrolyte 100 circle of 2% phenyl trifluoromethyl sulfide, capability retention is 90.2%, and cycle performance is good.
Button cell after the circulate electrolyte of above-described embodiment 1 and comparative example 1 is disassembled, with dimethyl carbonate (DMC), ternary electrode is cleaned and ultrasonic clean Al paper tinsel, after room temperature vacuumizing and drying, observed the configuration of surface of electrode and Al paper tinsel by SEM, test result is as shown in Fig. 2 a ~ Fig. 2 d.Result shows, and do not add the electrolyte of phenyl trifluoromethyl sulfide, aluminium foil there occurs obvious corrosion, as shown in Figure 2 a; And the electrolyte that with the addition of 2% phenyl trifluoromethyl sulfide has good compatibility, do not corrode, and surface defines one deck SEI film, as shown in Figure 2 b.In addition; ternary electrode is after the circulate electrolyte of not adding phenyl trifluoromethyl sulfide; electrode shows as loose; as shown in Figure 2 c; and with the addition of the electrolyte of 2% phenyl trifluoromethyl sulfide, define the stable SEI film of one deck on ternary electrode surface, play the effect of guard electrode; improve the long circulating performance of battery, as shown in Figure 2 d.
By electrochemical workstation respectively to the electrolyte of embodiment 1 and comparative example 1, composition Li sheet metal/electrolyte/Al paper tinsel button cell, arranges voltage range (1.7-4.6V), sweep speed: 0.1mV/s, carry out cyclic voltammetry, result as shown in Figure 3.Result shows, obvious response current is there is in aluminium foil in the electrolyte not adding phenyl trifluoromethyl sulfide, reflect the phenomenon of LiTFSI lithium salts corrosive aluminum foil, and after with the addition of 2% phenyl trifluoromethyl sulfide, this side reaction is effectively suppressed, and substantially improves the compatibility of new lithium salts and aluminium foil.
Combustion experiment is carried out to the electrolyte of embodiment 2-5 and comparative example 2, evaluates its fire resistance.The step of burning test is: the tested electrolyte being added dropwise to 2 milliliters in glass fibre (width 20mm, length 60mm), be positioned in an atmosphere experiment flame in after 10 seconds, away from experiment flame, caught fire by visualization the form of flame, record leaves flame until flame-out time; The situation of burnout time less than 10 seconds is set to anti-flammability, and the situation of more than 10 seconds is set to flammability, and measurement result is as shown in table 1.
The electrolyte related experiment result of table 1, embodiment 2-5 and comparative example 2
| Flame-retardant additive NMP-DFOB (%) | Self-extinguishing time (s) | |
| Comparative example 2 | 0 | 56.8 |
| Embodiment 2 | 5 | 28.6 |
| Embodiment 3 | 10 | 12.7 |
| Embodiment 4 | 15 | 3.5 |
| Embodiment 5 | 20 | 0 |
As can be seen from Table 1: comparing embodiment 2-5 and comparative example 2, to electrolyte add mass fraction be 5%, 10% two fluorine oxalic acid borate (NMP-DFOB) ionic liquid of 1-methyl-2-oxygen-1-propyl pyrrole alkane ketone obviously reduce the combustibility of electrolyte, illustrate that it has good fire resistance, and when addition reaches 15%, electrolyte does not all fire, and greatly can improve the security performance of electrolyte.
To electrolyte and the tertiary cathode (LiMn of embodiment 3 and comparative example 2
1/3ni
1/3co
1/3o
2), negative pole lithium sheet is assembled into CR2023 button cell, carry out the constant current charge-discharge loop test that 80 DEG C of 1C circulate 50 weeks, voltage range 2.7-4.3V, test result is as shown in Figure 4.Result shows, and battery is not adding flame-retardant electrolyte 1C circulation 50 circle of the two fluorine oxalic acid borate (NMP-DFOB) of 1-methyl-2-oxygen-1-propyl pyrrole alkane ketone, and capacity attenuation is serious; And after adding flame-retardant electrolyte circulation 50 circle of 15%NMP-DFOB, capability retention is 88.86%, and cycle performance is good.Illustrate that ionic liquid is mixed with functional additive phenyl trifluoromethyl sulfide, the high temperature cyclic performance of lithium ion battery can be considerably improved.
In sum, when containing 0.5%-2.0% perfluoroalkyl diphenyl sulfide functional additive in non-aqueous electrolyte for lithium ion cell, in charge and discharge process, can at Al paper tinsel surface and the stable SEI film of tertiary cathode material Surface Creation one deck, suppression trifluoromethanesulfonic acid lithium (LiCF
3sO
3), per-fluoroalkyl sulfonyl lithium methide (LiC (CF
3sO
2)
3), two (trimethyl fluoride sulfonyl) imine lithium (LTFSI), the new lithium salts such as two (fluorine sulphonyl) imine lithium (LiFSI) to the corrosion of aluminium foil, solving above-mentioned lithium salts can not replace LiPF completely
6the problem of extensive use, and positive pole ternary material is played a protective role, thus improve the cycle performance of battery.Meanwhile because this compound has more fluorine element, therefore there is good flame retardant effect, the effect of cooperative flame retardant is played with flame-retardant additive, greatly reduce the consumption of flame-retardant additive, when interpolation accounts for the ionic liquid of the quality 5%-20% of electrolyte as flame-retardant additive, lithium-ion battery electrolytes just can be made not only to have fire-retardant noninflammability even completely, thus the oxidation resistance of electrolyte and battery, thermal stability and security performance can be promoted all sidedly.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection range that all should belong to claims of the present invention.
Claims (10)
1. a lithium-ion battery electrolytes, comprises non-aqueous organic solvent, lithium salts, functional additive, flame-retardant additive and cathode film formation agent, it is characterized in that, described functional additive is perfluoroalkyl diphenyl sulfide.
2. lithium-ion battery electrolytes according to claim 1, is characterized in that, the molecular structural formula of described perfluoroalkyl diphenyl sulfide is shown below:
Wherein, R is carbon molecular number-CF
3,-C
2f
5,-C
3f
7,-C
4f
9within any one of perfluoroalkyl group.
3. lithium-ion battery electrolytes according to claim 2, is characterized in that, described functional additive mass percentage is in the electrolytic solution 0.5-2.0%.
4. lithium-ion battery electrolytes according to claim 3, is characterized in that, described flame-retardant additive is ionic liquid.
5. lithium-ion battery electrolytes according to claim 4, is characterized in that, described ionic liquid be aliphatic quaternary ammonium salt, season phosphonium salt, pyrroles's salt, pyrrolidones salt, imidazole salts and piperidinium salt; General formula is C
+[A]
-, C in general formula
+cationic structural formula is as follows:
Wherein, R1, R2, R3 and R4 are any one in C1 ~ C3 alkyl, pi-allyl, ether; In general formula [A]
-anion is CF
3sO
3 -, TFSI
-, FSI
-, BOB
-or DFOB
-in any one.
6. lithium-ion battery electrolytes according to claim 5, is characterized in that, described ionic liquid mass percentage is in the electrolytic solution 5% ~ 20%.
7., according to the arbitrary described lithium-ion battery electrolytes of claim 1 ~ 6, it is characterized in that, described lithium salts is selected from LiCF
3sO
3, LiC (CF
3sO
2)
3, the combination of one or more in LTFSI, LiFSI; The concentration of described lithium salts is 0.3mol/L ~ 1.0mol/L.
8. lithium-ion battery electrolytes according to claim 7, is characterized in that, described non-aqueous organic solvent is cyclic carbonate or linear carbonate.
9. lithium-ion battery electrolytes according to claim 7, it is characterized in that, described cathode film formation agent is any one or a few the combination comprised in vinylene carbonate, vinylethylene carbonate or fluorinated ethylene carbonate, and addition is account for electrolyte gross mass 0.1 ~ 2%.
10. a lithium ion battery, is characterized in that, comprise as arbitrary in claim 1 ~ 9 as described in lithium-ion battery electrolytes.
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| CN105762412A (en) * | 2016-05-17 | 2016-07-13 | 华南师范大学 | High-voltage electrolyte and lithium ion battery containing electrolyte |
| CN106785033A (en) * | 2016-11-22 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of method for suppressing fluorine sulfimide lithium electrolyte corrosion |
| CN106876787A (en) * | 2016-12-08 | 2017-06-20 | 盐城利庞新型材料科技有限公司 | A kind of il electrolyte and the serondary lithium battery containing the electrolyte |
| CN110299561A (en) * | 2018-03-21 | 2019-10-01 | 比亚迪股份有限公司 | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution |
| CN111048833A (en) * | 2019-10-30 | 2020-04-21 | 深圳市卓能新能源股份有限公司 | High-voltage electrolyte and high-voltage lithium ion power battery |
| CN112216864A (en) * | 2019-07-09 | 2021-01-12 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
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| CN113675473A (en) * | 2021-08-12 | 2021-11-19 | 湖州昆仑亿恩科电池材料有限公司 | Electrolyte and battery containing same |
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| US11495824B2 (en) | 2017-10-17 | 2022-11-08 | Lg Energy Solution, Ltd. | Electrolyte for lithium metal battery and lithium metal battery comprising same |
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| CN105762412A (en) * | 2016-05-17 | 2016-07-13 | 华南师范大学 | High-voltage electrolyte and lithium ion battery containing electrolyte |
| CN106785033A (en) * | 2016-11-22 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of method for suppressing fluorine sulfimide lithium electrolyte corrosion |
| CN106785033B (en) * | 2016-11-22 | 2018-11-20 | 江苏英能新能源科技有限公司 | A method of inhibiting fluorine sulfimide lithium electrolyte corrosion |
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| US11495824B2 (en) | 2017-10-17 | 2022-11-08 | Lg Energy Solution, Ltd. | Electrolyte for lithium metal battery and lithium metal battery comprising same |
| CN110299561A (en) * | 2018-03-21 | 2019-10-01 | 比亚迪股份有限公司 | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution |
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| CN111048833A (en) * | 2019-10-30 | 2020-04-21 | 深圳市卓能新能源股份有限公司 | High-voltage electrolyte and high-voltage lithium ion power battery |
| CN113054246B (en) * | 2019-12-27 | 2022-11-29 | 张家港市国泰华荣化工新材料有限公司 | Safety electrolyte, preparation method thereof and solid-state battery |
| CN113054246A (en) * | 2019-12-27 | 2021-06-29 | 张家港市国泰华荣化工新材料有限公司 | Safety electrolyte, preparation method thereof and solid-state battery |
| CN113675473A (en) * | 2021-08-12 | 2021-11-19 | 湖州昆仑亿恩科电池材料有限公司 | Electrolyte and battery containing same |
| CN114221023B (en) * | 2021-12-14 | 2023-10-20 | 苏州大学 | Ionic liquid for adsorbing water in lithium battery electrolyte and eliminating hydrofluoric acid, lithium battery electrolyte and lithium battery |
| CN114221023A (en) * | 2021-12-14 | 2022-03-22 | 苏州大学 | Ionic liquid for adsorbing water in lithium battery electrolyte and eliminating hydrofluoric acid, lithium battery electrolyte and lithium battery |
| CN116154177A (en) * | 2023-04-18 | 2023-05-23 | 蔚来电池科技(安徽)有限公司 | Secondary battery and device |
| CN116706238A (en) * | 2023-08-08 | 2023-09-05 | 河北省科学院能源研究所 | High-low temperature electrolyte and preparation method and application thereof |
| CN116706238B (en) * | 2023-08-08 | 2023-10-27 | 河北省科学院能源研究所 | High-low temperature electrolyte and preparation method and application thereof |
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