CN109148960A - A kind of lithium ion battery nonaqueous electrolytic solution and the lithium ion battery using the electrolyte - Google Patents
A kind of lithium ion battery nonaqueous electrolytic solution and the lithium ion battery using the electrolyte Download PDFInfo
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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
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- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M10/05—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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
The invention discloses a kind of lithium ion battery nonaqueous electrolytic solution and use the lithium ion battery of the electrolyte.The lithium ion battery includes lithium salts, organic solvent and additive with nonaqueous electrolytic solution, and the lithium salts can be selected from LiPF6、LiBF4、LiClO4Deng one of or it is a variety of, the organic solvent is selected from one of linear carbonate class, cyclic carbonates, carboxylic acid esters or a variety of mixed organic solvents with as led to fluoro ether compound shown in formula (I), also may include common high voltage type additive.Lithium ion battery of the invention improves the oxygenolysis voltage of organic solvent with joined fluoro ether solvent, the addition of fluoro ethers in nonaqueous electrolytic solution, improves working performance of electrolyte under conditions of high voltage.
Description
Technical field
The present invention relates to field of batteries, it is specifically related to a kind of lithium ion battery nonaqueous electrolytic solution and uses the electrolyte
Lithium ion battery.
Background technique
In recent years, the development of lithium ion battery received significant attention, mobile phone digital field, electric car, it is electronic from
Driving, electric tool, energy storage etc. development are swift and violent.The raising of requirement due to people to cruising ability, high-energy density
Battery has become a hot topic of research.On the one hand, itself electrode material with high-energy density, such as high-nickel material, lithium-rich manganese-based, silicon
The electrode materials such as Carbon anode are concerned；On the other hand, high-voltage lithium ion batteries are the main trends studied at present, give battery
Material proposes new challenge.
In order to realize the high-energy of lithium ion secondary battery, generally by the operating voltage for improving lithium ion secondary battery
Or high-energy positive electrode is researched and developed to realize.It has been reported that high-voltage anode material have LiCoPO4、LiNiPO4And
LiNi0.5Mn1.5Deng charging voltage platform is close to or higher than 5V, but matching non-aqueous organic electrolyte seriously lags behind
The development of high-voltage anode material limits the application of lithium ion secondary battery.Currently used non-aqueous organic electrolyte, such as
1M LiPF6It is dissolved in the non-aqueous organic electrolyte formed in carbonate-based solvent, in high voltage (4.35V or more voltage) battery
In system, side reaction can occur with positive electrode in charging process and then be oxidized decomposition, generate CO2、H2The oxidation products such as O,
CO2Generation the security performance of battery is caused potentially to threaten；H2The generation of O is so that LiPF6/ carbonate electrolyte system
Self-catalyzed reaction occurs, the generation of in-between product HF will lead to LiMn1.5Ni0.5The dissolution of material metal ion Mn, Ni, are caused
The structure of material is distorted or collapses, and eventually leads to the decline of lithium ion secondary battery cycle performance, volume expansion and puts
Capacitance decline, therefore high-voltage lithium ion secondary battery system can not be applied to.
Summary of the invention
Fluorine has very strong electronegativity and low pole, and fluorinated solvents have low melting point, high-flash and high oxidation decomposition voltage
The advantages that, the inventors found that fluoro ether solvent overcomes fluorinated solvents to the disadvantage of lithium salts dissolubility difference, it is added
The organic solvent of fluoro ethers can improve the oxygenolysis voltage of electrolyte whole, and the spy of fluoro ether solvent low melting point
Property, it can also improve electrolyte ability to work at low temperature.In addition, wellability between fluoro ether solvent and electrode material compared with
It is good, reduce the impedance between interface, also improves cryogenic property.
In consideration of it, the present invention is in order to overcome the shortcomings of above-mentioned background technique, providing one kind can be stable under high voltages
The lithium ion battery nonaqueous electrolytic solution of work and lithium ion battery using the electrolyte, lithium ion battery of the invention is with non-
It joined fluoro ether solvent in water electrolysis liquid, the addition of fluoro ethers improves the oxygenolysis voltage of organic solvent, improves
Working performance of electrolyte under conditions of high voltage.
To achieve the object of the present invention, lithium ion battery of the invention with nonaqueous electrolytic solution include lithium salts, organic solvent and
Additive, wherein the organic solvent includes one of linear carbonate, cyclic carbonate, carboxylate or a variety of, Yi Jiru
Fluoro ether compound shown in logical formula (I):
In formula (I), Y1And Y2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or containing 1-6 carbon atom
Fluoro-alkyl or fluoroalkyl, and Y1Or Y2At least one is fluoro-alkyl or fluoroalkyl containing 1-6 carbon atom.
Further, an embodiment, compound shown in the logical formula (I) include but is not limited to followingization according to the present invention
Close object:
Preferably, compound shown in the logical formula (I) accounts for the 5-65% of electrolyte quality, such as 5-50%.
Further, the lithium salts can be selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN
(SO2CF3)2、LiN(SO2F)2One of or it is a variety of；Preferably, based on lithium ion, the concentration of the lithium salts in the electrolytic solution is
0.5-2M, further preferably 1-1.5M.
Further, the linear carbonate can be selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid first
One of ethyl ester (EMC), dipropyl carbonate (DPC) are a variety of.
Further, the cyclic carbonate can be selected from ethylene carbonate (EC), vinylene carbonate (VC), carbonic acid third
One of enester (PC) is a variety of.
Further, the carboxylate can be selected from ethyl acetate (EA), ethyl propionate (EP), methyl acetate (MA), second
One of propyl propionate (PE), methyl propionate (MP), methyl butyrate (MB), ethyl butyrate (EB) are a variety of.
Further, the additive can be selected from fluorinated ethylene carbonate (FEC), 1,3 propane sultones (PS), carbonic acid
Vinylethylene (VEC), vinylene carbonate (VC), propene carbonate (PC), difluorophosphate (LiPO2F2) one of or
It is a variety of.
The present invention also provides a kind of lithium ion battery, which has used lithium ion battery of the invention with non-
Water electrolysis liquid.
Preferably, the preparation method of the lithium ion battery includes infusing lithium ion battery of the invention with nonaqueous electrolytic solution
Enter to by sufficiently dry, the nickel of 4.35V: cobalt: manganese=5:2:3 nickel cobalt manganese (NCM)/graphite soft-package battery is put by 45 DEG C
It sets, high-temperature clamp is melted into and secondary sealing process.
Lithium ion battery nonaqueous electrolytic solution of the invention can effectively improve the oxidation voltage of electrolyte, enhancing electrolyte
The security performance of stability, raising battery under high voltage condition.Compared to the tradition for being not added with additive disclosed by the invention
Lithium ion secondary battery, due to containing fluoro ether compound in electrolyte of the present invention, fluorine has very strong electronegativity and weak pole
Property, fluoro ether organic solvent has many advantages, such as low melting point, high-flash and high oxidation decomposition voltage, electric in height to electrolyte is improved
The ability for depressing steady operation, there is good effect, and the high-flash performance of fluoro ether solvent, to the safety for improving electrolyte
Performance is helpful, the low melting point of fluoro ether solvent and the characteristic of low viscosity, to work energy of the raising electrolyte in low temperature
Power, it is also helpful.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.In present specification and claims, range restriction can be combined
And/or exchange, these ranges if not stated otherwise include all subranges contained therebetween.
Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
The nonaqueous electrolytic solution is prepared as follows: in glove box, by ethylene carbonate (EC), propene carbonate
(PC), methyl ethyl carbonate (EMC) and compound (1) are mixed according to the ratio of weight ratio 25:5:50:20, are then added six
Lithium fluophosphate is dissolved, and the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, mass fraction is added into electrolyte is
0.5% vinylene carbonate, 1% fluorinated ethylene carbonate (FEC), 1.5% 1,3 propane sulfonic acid lactones and the two of 1%
Lithium fluophosphate (LiPO2F2)。
By prepared lithium ion battery with nonaqueous electrolytic solution be injected by sufficiently dry 4.35V NCM (nickel: cobalt:
Manganese=5:2:3)/graphite soft-package battery, it shelves by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in embodiment 1.
Embodiment 2
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 2；The difference is that the ethylene carbonate in embodiment 2
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (1) are matched according to the ratio of weight ratio 25:5:60:10
It sets.
Embodiment 3
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 3；The difference is that the ethylene carbonate in embodiment 3
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (2) according to weight ratio 25:5:50:20 ratio into
Row mixing.
Embodiment 4
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 4；The difference is that the ethylene carbonate in embodiment 4
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (2) are matched according to the ratio of weight ratio 25:5:60:10
It sets.
Embodiment 5
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 5；The difference is that the ethylene carbonate in embodiment 4
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (3) according to weight ratio 25:5:50:20 ratio into
Row mixing.
Embodiment 6
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 6；The difference is that the ethylene carbonate in embodiment 6
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (3) are matched according to the ratio of weight ratio 25:5:60:10
It sets.
Embodiment 7
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 7；The difference is that the ethylene carbonate in embodiment 7
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (4) according to weight ratio 25:5:50:20 ratio into
Row mixing.
Embodiment 8
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 8；The difference is that the ethylene carbonate in embodiment 8
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (4) are matched according to the ratio of weight ratio 25:5:60:10
It sets.
Embodiment 9
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 9；The difference is that the ethylene carbonate in embodiment 9
Ester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (5) according to weight ratio 25:5:50:20 ratio into
Row mixing.
Embodiment 10
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 10；The difference is that the carbonic acid second in embodiment 10
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (5) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 11
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 11；The difference is that the carbonic acid second in embodiment 11
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (6) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 12
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 12；The difference is that the carbonic acid second in embodiment 12
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (6) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 13
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 13；The difference is that the carbonic acid second in embodiment 13
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (7) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 14
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 14；The difference is that the carbonic acid second in embodiment 14
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (7) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 15
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 15；The difference is that the carbonic acid second in embodiment 15
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (8) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 16
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 16；The difference is that the carbonic acid second in embodiment 16
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (8) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 17
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 17；The difference is that the carbonic acid second in embodiment 17
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (9) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 18
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 18；The difference is that the carbonic acid second in embodiment 18
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (9) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 19
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 19；The difference is that the carbonic acid second in embodiment 19
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (10) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 20
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 20；The difference is that the carbonic acid second in embodiment 20
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (10) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 21
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 21；The difference is that the carbonic acid second in embodiment 21
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (11) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 22
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 22；The difference is that the carbonic acid second in embodiment 22
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (11) according to weight ratio 25:5:60:10 ratio
It is mixed.
Embodiment 23
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 23；The difference is that the carbonic acid second in embodiment 23
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (12) according to weight ratio 25:5:50:20 ratio
It is mixed.
Embodiment 24
The preparation method is the same as that of Example 1 for the positive electrode and negative electrode of embodiment 24；The difference is that the carbonic acid second in embodiment 24
Enester (EC), propene carbonate (PC), methyl ethyl carbonate (EMC) and compound (12) according to weight ratio 25:5:60:10 ratio
It is mixed.
Comparative example 1
The nonaqueous electrolytic solution is prepared as follows: in glove box, by ethylene carbonate (EC), propene carbonate
(PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:50:20, then
Lithium hexafluoro phosphate is added to be dissolved, the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, quality is added into electrolyte
Score be 0.5% vinylene carbonate, 1% fluorinated ethylene carbonate (FEC), 1.5% 1,3 propane sulfonic acid lactones and
1% difluorophosphate.
By prepared lithium ion battery with nonaqueous electrolytic solution be injected by sufficiently dry 4.35V NCM (nickel: cobalt:
Manganese=5:2:3)/graphite soft-package battery, it shelves by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in comparative example 1.
Comparative example 2
The nonaqueous electrolytic solution is prepared as follows: in glove box, by ethylene carbonate (EC), propene carbonate
(PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the ratio of weight ratio 25:5:60:10, then
Lithium hexafluoro phosphate is added to be dissolved, the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, quality is added into electrolyte
Score be 0.5% vinylene carbonate, 1% fluorinated ethylene carbonate (FEC), 1.5% 1,3 propane sulfonic acid lactones and
1% difluorophosphate.
By prepared lithium ion battery with nonaqueous electrolytic solution be injected by sufficiently dry 4.35V NCM (nickel: cobalt:
Manganese=5:2:3)/graphite soft-package battery, it shelves by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in comparative example 2.
Comparative example 3
The nonaqueous electrolytic solution is prepared as follows: in glove box, by ethylene carbonate (EC), propene carbonate
(PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DMC) are mixed according to the ratio of weight ratio 25:5:50:20, then
Lithium hexafluoro phosphate is added to be dissolved, the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, quality is added into electrolyte
Score be 0.5% vinylene carbonate, 1% fluorinated ethylene carbonate (FEC), 1.5% 1,3 propane sulfonic acid lactones and
1% difluorophosphate.
By prepared lithium ion battery with nonaqueous electrolytic solution be injected by sufficiently dry 4.35V NCM (nickel: cobalt:
Manganese=5:2:3)/graphite soft-package battery, it shelves by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in comparative example 3.
Comparative example 4
The nonaqueous electrolytic solution is prepared as follows: in glove box, by ethylene carbonate (EC), propene carbonate
(PC), methyl ethyl carbonate (EMC) and diethyl carbonate (DMC) are mixed according to the ratio of weight ratio 25:5:60:10, then
Lithium hexafluoro phosphate is added to be dissolved, the electrolyte that hexafluorophosphoric acid lithium concentration is 1M is prepared.Later, quality is added into electrolyte
Score be 0.5% vinylene carbonate, 1% fluorinated ethylene carbonate (FEC), 1.5% 1,3 propane sulfonic acid lactones and
1% difluorophosphate.
By prepared lithium ion battery with nonaqueous electrolytic solution be injected by sufficiently dry 4.35V NCM (nickel: cobalt:
Manganese=5:2:3)/graphite soft-package battery, it shelves by 45 DEG C, after the processes such as high-temperature clamp chemical conversion and secondary sealing, carries out battery
Performance test obtains battery used in comparative example 4.
See Table 1 for details for each embodiment and comparative example electrolyte prescription.
Each embodiment and comparative example electrolyte prescription of table 1
Performance of lithium ion battery test
1. normal-temperature circulating performance
Under the conditions of room temperature (25 DEG C), above-mentioned lithium ion battery is charged to 4.35V in 1C constant current constant voltage, then in 1C constant current
Under the conditions of be discharged to 3.0V.After charge and discharge 500 circulations, the capacity retention ratio after recycling is calculated the 500th time:
2. high temperature cyclic performance
Under the conditions of high temperature (45 DEG C), above-mentioned lithium ion battery is charged to 4.35V in 1C constant current constant voltage, then in 1C constant current
Under the conditions of be discharged to 3.0V.After charge and discharge 500 circulations, the capacity retention ratio after recycling is calculated the 500th time:
3. high-temperature storage performance
Under the conditions of room temperature (25 DEG C), carrying out a 1C/1C charging and discharging to lithium ion battery, (discharge capacity is denoted as
DC0), then 4.2V is charged in 1C constant current constant voltage condition decline battery；Lithium ion battery is placed in 60 DEG C of high-temperature cabinets and saves 1
A month, after taking-up, carrying out 1C electric discharge under normal temperature conditions, (discharge capacity was denoted as DC1)；Then 1C/1C is carried out under normal temperature conditions
(discharge capacity is denoted as DC for charging and discharging2), the capacity retention ratio and capacity restoration of lithium ion battery are calculated using following formula
Rate:
4. low-temperature circulating performance
Under the conditions of low temperature (0 DEG C), above-mentioned lithium ion battery is charged to 4.35V in 1C constant current constant voltage, then in 1C constant current
Under the conditions of be discharged to 3.0V.After charge and discharge 150 circulations, the capacity retention ratio after recycling is calculated the 150th time:
The results are shown in Table 2 for the battery performance of above-mentioned each specific embodiment:
The performance of lithium ion battery test result of 2 comparative example of table and embodiment
The electrolyte that carbonate based organic solvent is used alone be can be seen that from upper table data for high potential 4.35V-
When 523/AG soft-package battery, normal temperature circulation, high temperature circulation, the effect of low-temperature circulating are all excessively poor, carbonates and carboxylic acid esters
The oxygenolysis voltage of organic solvent is all relatively low, and under conditions of 4.35V voltage, organic solvent is decomposed, and generates CO2、H2O etc.
Oxidation product, CO2Generation, cause battery volume expansion, H2The generation of O is so that LiPF6/ carbonate electrolyte system occurs certainly
Catalysis reaction, the generation of in-between product HF will lead to LiMn1.5Ni0.5The dissolution of material metal ion Mn, Ni, cause material
Structure is distorted or collapses, and eventually leads to the decline of lithium ion secondary battery cycle performance, volume expansion and discharge capacity
Decline, becomes apparent under the high temperature conditions；Under cryogenic, it is followed using the battery for the electrolyte for containing only carbonate based organic solvent
Ring performance is also excessively poor, on the one hand, is that high voltage causes organic solvent to decompose, is because of carbonate-based solvent on the other hand
Fusing point is high, for example, the fusing point of DMC is at 0 DEG C or more, low temperature also reduces the mobility of electrolyte, and cycle performance is made to be deteriorated.
It is added after this component of fluoro ether compound in the organic solvent of electrolyte, since fluorine has very strong electricity
Negativity and low pole, fluorinated solvents have many advantages, such as low melting point, high-flash and high oxidation decomposition voltage, improve entire electrolyte
The oxygenolysis voltage of organic solvent allows battery to be also able to maintain the stabilization of overall performance under high voltages；The eutectic of fluorinated solvents
Dot characteristics allow electrolyte to be also able to maintain good mobility under cryogenic, these characteristics are to improving battery at low temperature
Ability to work has good help.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of lithium ion battery nonaqueous electrolytic solution, which is characterized in that the lithium ion battery with nonaqueous electrolytic solution include lithium salts,
Organic solvent and additive, wherein the organic solvent include one of linear carbonate, cyclic carbonate, carboxylate or
It is a variety of, and the fluoro ether compound as shown in logical formula (I):
In formula (I), Y1And Y2Respectively indicate alkyl or alkoxy containing 1-6 carbon atom, or the fluoro containing 1-6 carbon atom
Alkyl or fluoroalkyl, and Y1Or Y2At least one is fluoro-alkyl or fluoroalkyl containing 1-6 carbon atom.
2. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that logical formula (I) shownization
It closes object and is selected from following compound:
3. lithium ion battery nonaqueous electrolytic solution according to claim 1 or 2, which is characterized in that shown in the logical formula (I)
Compound accounts for the 5-65% of electrolyte quality, such as 5-50%.
4. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that the lithium salts is selected from LiPF6、
LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2One of or it is a variety of；Preferably, it presses
Lithium ion meter, the concentration of the lithium salts in the electrolytic solution are 0.5-2M, further preferably 1-1.5M.
5. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that the linear carbonate is selected from
One of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC) are more
Kind.
6. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that the cyclic carbonate is selected from
One of ethylene carbonate (EC), vinylene carbonate (VC), propene carbonate (PC) are a variety of.
7. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that the carboxylate is selected from acetic acid
Ethyl ester (EA), ethyl propionate (EP), methyl acetate (MA), propyl acetate (PE), methyl propionate (MP), methyl butyrate (MB), fourth
One of acetoacetic ester (EB) is a variety of.
8. lithium ion battery nonaqueous electrolytic solution according to claim 1, which is characterized in that the additive is selected from fluoro
Ethylene carbonate (FEC), 1,3 propane sultones (PS), vinylethylene carbonate (VEC), vinylene carbonate (VC), carbonic acid third
Enester (PC), difluorophosphate (LiPO2F2) one of or it is a variety of.
9. a kind of lithium ion battery, which is characterized in that the lithium ion battery used the described in any item lithiums of claim 1-8 from
Sub- nonaqueous electrolyte for battery.
10. a kind of lithium ion battery according to claim 9, which is characterized in that the preparation method of the lithium ion battery
Including being injected into lithium ion battery of the invention with nonaqueous electrolytic solution by sufficiently dry, the nickel of 4.35V: cobalt: manganese=5:2:3
Nickel cobalt manganese (NCM)/graphite soft-package battery, shelved by 45 DEG C, high-temperature clamp chemical conversion and secondary sealing process.
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| CN112242563A (en) * | 2019-07-18 | 2021-01-19 | 杉杉新材料（衢州）有限公司 | High-compaction high-voltage lithium cobalt oxide lithium ion battery electrolyte and lithium ion battery |
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