CN105633457B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN105633457B CN105633457B CN201410583783.0A CN201410583783A CN105633457B CN 105633457 B CN105633457 B CN 105633457B CN 201410583783 A CN201410583783 A CN 201410583783A CN 105633457 B CN105633457 B CN 105633457B
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Abstract
The invention discloses a lithium ion battery electrolyte, which comprises an organic solvent, an electrolyte lithium salt and a combined additive containing gamma-butyrolactone, ethylene sulfate, adiponitrile and fluoroethylene carbonate, wherein the electrolyte contains 0.1-40 wt% of gamma-butyrolactone, 0.1-5 wt% of ethylene sulfate, 0.1-10 wt% of adiponitrile and 1-10 wt% of fluoroethylene carbonate. According to the invention, the combined additive is added into the lithium ion battery electrolyte, so that the safety performance, high-temperature storage and cycle performance of the lithium ion battery under a high-voltage system can be obviously improved. In addition, the invention also discloses a lithium ion battery.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of available for high voltage system
Lithium ion battery and its electrolyte.
Background technology
At present, the electrolyte of commercialized lithium ion battery is mainly based upon the carbonate group electrolysis of ethylene carbonate (EC)
Liquid, but when voltage is higher than 4.5V, carbonate group electrolyte solvent can decompose and cause entire performance of lithium ion battery
Decline.So far, there are no novel dissolvents can substitute carbonate-based solvent, therefore the test of high voltage material still base completely
In conventional electrolyte solvent system, such as EC/EMC/DMC, EC/DEC, EC/DMC and EC/EMC.
The use demand of high voltage material can be met using anode film for additive in conventional electrolysis liquid, selected excellent
Film for additive be used in combination, single additive advantage in some aspects can be embodied and improve it in some sides
The deficiency in face makes lithium ion battery show excellent comprehensive performance.
Gamma-butyrolacton (GBL) has liquid temperature scope wide (- 45 DEG C of fusing point, 204 DEG C of boiling point), suitable viscosity
(1.75mpa/s, 25 DEG C), higher dielectric constant (25 DEG C, εr=39.1) the advantages that and to the high-solvency of lithium salts, not
The high and low temperature performance of lithium ion battery can be improved on the basis of influence other performance.For example, in patent document CN1755974A
The gamma-butyrolacton of volume ratio 1%~50% is with the addition of, the high temperature and cryogenic property of electrolyte can be improved.Patent document
The gamma-butyrolacton of weight ratio 60%~90% is with the addition of in CN102306837A, the high temperature performance of electrolyte can be improved, is improved
The discharge performance of lithium ion battery in -40 DEG C~50 DEG C of environment so that it can work, and cell discharge performance is good, work temperature
It is bigger to spend window.Additive vinylene carbonate, gamma-butyrolacton and hexamethyl are disclosed in patent document CN103107358A
The lithium-ion battery electrolytes that disilazane is applied in combination have preferable low and high temperature cycle performance.
But viscosity increases after electrolyte adds in gamma-butyrolacton, is deteriorated to pole piece wellability, influences lithium ion battery
Cycle performance, the storage of lithium ion battery and cycle performance can further be deteriorated after 4.4V high voltages, therefore not be suitable for high electricity
Laminate system.
In view of this, can be used it is necessory to provide one kind in high voltage system with preferably safety, cycle, storage
The electrolyte of energy.
The content of the invention
Gamma-butyrolacton since its asymmetric five-membered ring structure is easier to by the transition metal-catalyzed scission of link such as iron, cobalt, nickel,
Anode protective film easily is formed in positive electrode surface catalysis oxidation in electrolyte, its effect under high voltages becomes apparent, and is very
Preferable high-voltage electrolyte additive or solvent.But gamma-butyrolacton makes it longer there are two more serious weakness
It is not used widely in time：First, gamma-butyrolacton and widely used lithium hexafluoro phosphate compatibility are bad, mutually promote
It decomposes, influences performance of lithium ion battery；Second is that gamma-butyrolacton is larger in the SEI membrane impedances that negative terminal surface is formed, to lithium-ion electric
The cycle performance and high rate performance in pond are unfavorable.
Present inventor is by discovery of concentrating on studies：In terms of anode, gamma-butyrolacton, ethyl sulfate combination make
With transesterification can occur due to the similitude of structure, in film forming procedure and form copolymer, the protective film of formation is more stable.In order to
Gamma-butyrolacton and lithium hexafluoro phosphate compatibility are improved, adds in adiponitrile in the electrolytic solution, itrile group can absorb hydrofluoric acid, may be used also
Slow down phosphorus pentafluoride decomposition to form hydrogen bond with phosphorus pentafluoride, improve the compatibility of gamma-butyrolacton and lithium hexafluoro phosphate.Adiponitrile
Good behaviour in the battery also from the good chemical stability and electrochemical stability of its own, is not easy to be aoxidized also
Original is so that it can the main reason for surmounting conventional acid absorbent.In terms of cathode, using the preferential γ-Ding Nei of fluorinated ethylene carbonate
Ester forms a film in negative terminal surface, is formed with the fluorinated polymer for haling electronic capability, can inhibit gamma-butyrolacton in cathode table
The film forming in face, so as to improve the cycle performance of lithium ion battery and high rate performance.It is advantageously implemented high voltage, long circulating, Gao Cun
Store up performance and security performance.
It is found based on above, it is an object of the invention to：Overcome lithium ion battery high temperature under high voltages in the prior art
The shortcomings that storage performance is poor, poor circulation provides one kind and can be used in high voltage system with desired Safety, cycling, storage
The lithium ion battery and its electrolyte of performance.
In order to realize foregoing invention purpose, the present invention provides a kind of lithium-ion battery electrolytes, it includes organic solvent,
Electrolyte lithium salt and combined additive, wherein, combined additive contains gamma-butyrolacton, ethyl sulfate, adiponitrile and fluoro carbon
Vinyl acetate, and the weight percentage of combined additive in the electrolytic solution is 1.3~65%.
As a kind of improvement of lithium ion battery of the present invention, by weight percentage, the electrolyte contains 0.1%~
40% gamma-butyrolacton (GBL), 0.1%~5% ethyl sulfate (DTD), 0.1%~10% adiponitrile (AND) and 1%~
10% fluorinated ethylene carbonate (FEC).
As a kind of improvement of lithium ion battery of the present invention, the weight percentages of the GBL in the electrolytic solution for 5%~
30%.When the weight percentages of GBL in the electrolytic solution are less than 0.1%, it is impossible to play the role of high voltage additive；When
When the weight percentages of GBL in the electrolytic solution are more than 40%, easily cause electrolysis fluid viscosity excessive, make electrolyte to pole piece
Infiltration is difficult.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the weight percentages of the DTD in the electrolytic solution
For 0.5%~3%.The weight percents of DTD in the electrolytic solution contain less than 0.5%, effect unobvious；The weights of DTD in the electrolytic solution
It measures percentage to contain higher than 3%, the deteriorated low temperature performance of lithium ion battery.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the weight percentages of the ADN in the electrolytic solution
For 1%~7%.The weight percentages of ADN in the electrolytic solution are less than 1% protective effect unobvious, the weights of ADN in the electrolytic solution
It measures percentage composition and is more than 7% high rate performance for influencing lithium ion battery.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the weight percentages of the FEC in the electrolytic solution
For 3%~7%.On the one hand the weight percentages of FEC in the electrolytic solution can not ensure the cycling under high voltage below 3%
On the other hand service life, the cycle life of especially siliceous cathode electric core architecture can not inhibit gamma-butyrolacton in cathode well
Surface filming, does not have protective effect, easily causes the problems such as storing flatulence.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the lithium salts is hexafluorophosphate, LiBF4,
Hexafluoro arsenate, lithium perchlorate, trifluoro sulphonyl lithium, two (trimethyl fluoride sulfonyl) imine lithiums, double (fluorine sulphonyl) imine lithiums and three (three
At least one of methyl fluoride sulphonyl) lithium methide.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the lithium salt is 0.7M~1.3M.Lithium salts is dense
Spend low, the electrical conductivity of electrolyte is low, can influence the multiplying power and cycle performance of entire battery system；Lithium salt is excessively high, electrolysis
Fluid viscosity is excessive, influences the multiplying power of entire battery system, and preferred lithium salt is 0.9~1.1M.
As a kind of improvement of lithium-ion battery electrolytes of the present invention, the organic solvent is ethylene carbonate (EC), carbon
Acid propylene ester (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl formate (MF), first
At least two in acetoacetic ester (MA), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB) and tetrahydrofuran (THF).
In addition, the present invention also provides a kind of lithium ion battery, including anode, cathode, be arranged at anode and cathode it
Between isolation film and electrolyte, anode includes plus plate current-collecting body and the positive electrode active material layer that is arranged on plus plate current-collecting body,
Positive electrode active material layer includes positive active material, bonding agent and conductive agent, and cathode includes negative current collector and is arranged at cathode
Negative electrode active material layer on collector, negative electrode active material layer include negative electrode active material, bonding agent and conductive agent, electrolyte
For foregoing lithium-ion battery electrolytes.
As a kind of improvement of lithium ion battery of the present invention, the positive active material is LiCoO2、LiMn2O4And Li
(CoxNiyMn1-x-y)O2At least one of, wherein, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9 is described negative
Pole active material is graphite and/or silicon.
As a kind of improvement of lithium ion battery of the present invention, PVDF, SBR or CMC, the conduction can be selected in the bonding agent
Superconduction carbon, carbon nanotubes, graphene and carbon nano-fiber can be selected in agent.
As a kind of improvement of lithium ion battery of the present invention, the charging upper limit of the lithium ion battery is by voltage
4.5V, for example, charging upper limit is 4.2-4.5V by voltage.
Compared with the prior art, the present invention has the following advantages：
1. combined additive can reduce the thickness and impedance in anode surface SEI films, the cycling of lithium ion battery is improved
Performance, while form a film in cathode surface, it reduces solvent and is aoxidized, improve the storage performance under high-temperature lithium ion battery and voltage.
For the charging upper limit of lithium ion battery by voltage up to 4.5V, charge and discharge have higher capacity retention ratio；
2. the thickness swelling of lithium ion battery and internal resistance increase small, residual capacity and capacity height can be recovered；
3. intermittent cyclic capacity retention ratio is high under high temperature.
Embodiment
In order to make the present invention goal of the invention, technical solution and its technique effect become apparent from, with reference to embodiments and
The present invention is described in more detail for comparative example.It should be appreciated that the embodiment described in this specification is intended merely to explain
The present invention, is not intended to limit the present invention, the formula of embodiment, ratio can adaptation to local conditions make a choice and essence had no to result
Property influence.
Lithium ion battery of the present invention includes anode, cathode and electrolyte, positive active material LiCoO2、LiMn2O4And Li
(CoxNiyMn1-x-y)O2At least one of, wherein, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9；Cathode is
The mixture of the silicon of graphite or silicon weight percentage less than 20% and graphite；Electrolyte includes organic solvent, electrolyte lithium
Salt and combined additive, wherein, organic solvent is dimethyl carbonate (DMC), ethylene carbonate (EC) and propene carbonate (PC)
Mixture, weight ratio 1：1：1；Lithium salts is LiPF6, concentration 1M；Combined additive contains fluorinated ethylene carbonate
(FEC), gamma-butyrolacton (GBL), ethyl sulfate (DTD) and adiponitrile (ADN).Respectively by the organic solvent of different content, electricity
Solution matter lithium salts contains gamma-butyrolacton (GBL), ethyl sulfate (DTD), adiponitrile (ADN) and fluorinated ethylene carbonate (FEC)
Combined additive prepare electrolyte by the amount shown in table 1, wherein, the amount of each additive is the gross weight based on electrolyte solution
Amount.
The dry battery core that electrolyte injection prepared above has been dried again, when then standing 24 is small, after chemical conversion, is compared
1~18 lithium ion battery of example 1~5 and embodiment, wherein, comparative example is weight percentage with the percentage in embodiment,
The ratio of non-aqueous organic solvent is weight ratio.
1 comparative example 1~5 of table and 1~18 lithium ion battery of embodiment
Wherein, LCO LiCoO2；C is graphite；NCM is NCM333；Si is silicon
Below in conjunction with the lithium ion battery for testing to illustrate lithium-ion battery electrolytes of the present invention and use this electrolyte
Performance.
Test one：High-temperature storage performance of lithium ion battery is tested
The lithium ion battery that comparative example 1~5 and embodiment 1~18 provide store at 60 DEG C to the performance of 35 days to survey
Examination.High temperature storage test concrete operations be：The lithium ion battery that comparative example 1~5 and embodiment 1~18 are provided is with 0.5C's
Then multiplying power constant-current charge is placed 35 days at 60 DEG C to 4.5V, measures the thickness swelling of lithium ion battery, internal resistance increases
Rate, residual capacity and recovery capacity, the results are shown in Table 2.
The calculating of capacity retention ratio：The capacity retention ratio=(discharge capacity of corresponding cycle/of corresponding cycle cycles for the first time
Discharge capacity) × 100%.
The data comparison of high-temperature storage performance shows that each embodiment lithium ion battery has compared with comparative example lithium ion battery
There is a better storage performance, with the variation of each additive capacity in each embodiment lithium ion battery, storage performance is also with change
Change.
FEC additives are only used in comparative example 1, storage performance, cycle performance and security performance all show poor；Comparison
The combination of FEC and ADN is used in example 2, storage performance slightly improves, but its cycle performance and security performance are still poor；It is right
FEC, ADN and DTD are applied in combination in ratio 3, and cycle performance slightly improves, but its storage performance deteriorates；Comparative example 4 uses
FEC, ADN and GBL are combined, and storage and cycling increase, but still cannot meet the requirements；Comparative example 5 uses FEC, ADN and DTD
Combination is all improved a lot in terms of storage, and security performance also increases, but cycle performance is still poor.Only when four kinds
When additive is applied in combination, preferable cycle performance, storage performance and security performance can be just shown.
Influence of the various additives to storage performance is as follows：
The weight ratios that uses of the GBL in combined additive be：0.1%th, 5%, 30% and 40% (Examples 1 to 4), lithium
The thickness increment rate and internal resistance increase rate of ion battery reduce with the increase of GBL dosages, the conservation rate of residual capacity and extensive
Multiple capacity ratio but first increases to be reduced afterwards.GBL can form passivating film in cathode surface, and GBL is more, and protective film is thicker, protective value
Better；The conservation rate of capacity and recover Capacity Ratio and take the lead in increasing to be the formation due to passivating film, rear reduce is because protective film mistake
Thickness can consume more active materials.
The weight ratios that uses of the DTD in combined additive be：0.1%th, 0.5%, 3% and 5% (embodiment 5~8), lithium
Thickness increment rate, internal resistance increase rate, the conservation rate of residual capacity and the recovery capacity ratio of ion battery are with the increasing of DTD dosages
Add first to reduce increases afterwards, and DTD can form passivating film on anode and cathode surface, and DTD is more, and protective film is thicker, and protective value is better；But
Excessive DTD exists when not forming protective film, for a long time in battery core has the anti-raw side reaction influence storage performance of decomposed.
When dosage is less than 0.5%, storage performance is slightly poor, and storage performance has variation during more than 3%.
The weight ratios that uses of the FEC in combined additive be：1%th, 3%, 5%, 7% and 10% (embodiment 9~13),
Storage performance is deteriorated with the increase of FEC, and storage performance is worse particularly when FEC is more than 5%, and has aerogenesis phenomenon, this
It is primarily due to FEC and decomposed easily occurs at high temperature in the SEI films that anode surface is formed, the FEC not formed a film especially
It is easier to decompose at high temperature, it is unfavorable to high temperature storage, since the advantage in terms of cycling still will optimize use.
The weight ratios that uses of the ADN in combined additive be：0.1%th, 3%, 5%, 7% and 9% (embodiment 14~
18), when dosage be less than 3% when store it is poor, more than 3% storage it is basicly stable, can be in cathode surface this is mainly due to AND
The oxidation that passivating film reduces electrolyte is formed, more ADN constantly improve cannot be stored.
60 DEG C of memory capacity of 2 comparative example 1~5 of table and 1~18 lithium ion battery 4.5V of embodiment, thickness and internal resistance
Test two：Battery efficiency and 45 DEG C of cycle performance tests for the first time
At 45 DEG C, lithium ion battery that comparative example 1~5 and embodiment 1~18 are provided, with the multiplying power constant-current charge of 0.5C
To 4.5V, then constant-voltage charge to electric current is 0.05C, then with 0.5C constant current discharges to 3.0V, such charge/discharge, point
Capacity retention ratio that Ji Suan be after circulating battery 50 times, 100 times, 200 times and 300 times, test result are as shown in table 3.
Efficiency and 45 DEG C of repeated charge capacity are kept for the first time for 3 comparative example 1~5 of table and 1~18 lithium ion battery of embodiment
Rate test result
The weight ratios that uses of the GBL in combined additive be：0.1%th, 5%, 30% and 40% (Examples 1 to 4), electricity
The efficiency for the first time in pond reduces with the increase of GBL dosages, the increase of capacity retention ratio GBL dosages after cycling and increase.GBL exists
Cathode surface can form passivating film, and GBL is more, and protective film is thicker, and cycle performance is better；Efficiency is with the increasing of GBL dosages for the first time
Add and reduce, be that can consume more active materials because protective film is blocked up, cycle performance can be carried more than 0.1%
It is high.
The weight ratios that uses of the DTD in combined additive be：0.1%th, 0.5%, 3% and 5% (embodiment 5~8), electricity
The efficiency for the first time in pond is stablized afterwards as DTD increases first increase, after capacity retention ratio first increases with the increase of DTD dosages after cycling
Reduce.The protective film that DTD is formed is more thin and dense, and the active material of consumption is less, therefore efficiency improves for the first time.Work as protective film
It is thin to it is suitable when, more DTD cannot continue to improve efficiency for the first time.DTD can form passivating film on anode and cathode surface, and DTD is got over
More protective films are thicker, and protective value is better；But excessive DTD exists in battery core when not forming protective film and has portion for a long time
It decomposes and side reaction influence cycle performance occurs.
The weight ratios that uses of the FEC in combined additive be：1%th, 3%, 5%, 7% and 10% (embodiment 9~13),
The efficiency for the first time of battery first increases and stablizes afterwards with FEC increase, the increase of capacity retention ratio FEC dosages after cycling and increase.DTD
The protective film formed is more thin and dense, and the active material of consumption is less, therefore efficiency improves for the first time, when protective film is thin to suitable
When, more FEC cannot continue to improve efficiency for the first time, and the ability that FEC improves efficiency for the first time is slightly weaker than DTD；What FEC was formed
SEI films are highly stable, in the circulating cycle impedance smaller, and invertibity is more preferable.
The weight ratios that uses of the ADN in combined additive be：0.1%th, 3%, 5%, 7% and 9% (embodiment 14~
18), the efficiency for the first time of battery reduces as ADN increases, steady after capacity retention ratio first increases with the increase of ADN dosages after cycling
It is fixed.The addition of ADN increases electrolysis fluid viscosity, polarization increase, therefore efficiency decreases for the first time；ADN can be in cathode surface
Good protective film is formed, is increased as content increases cycle performance, but later will not be constantly improve higher than 5%.
Test three：Intermittent charge is tested
At 50 DEG C, each 4 constant-voltage charge to electric currents of lithium ion battery that comparative example 1~5 and embodiment 1~18 are provided are
0.05C stands 20hrs, then 0.5C constant current discharges to 3.0V, such charge/discharge, calculate circulating battery respectively 10 times,
Capacity retention ratio after 30 times, 50 times and 100 times, test result are as shown in table 4.4 test result of table shows：It is added using combination
The intermittent charge capacity retention ratio of agent is greatly improved, and the performance of battery core is had been further upgraded.
Capacity retention ratio after 4 comparative example 1~5 of table and 1~18 lithium ion battery intermittent charge of embodiment Xun Huan
The weight that uses of the GBL in combined additive is：0.1%th, 5%, 30% and 40% (Examples 1 to 4), battery
Intermittent charge cycle after capacity retention ratio increase with the increase of GBL dosages, GBL can form passivation in cathode surface
Film, GBL is more, and protective film is thicker, and protective value is better, and the capacity retention ratio after intermittent charge Xun Huan is higher.
The weight that uses of the DTD in combined additive is：0.1%th, 0.5%, 3% and 5% (embodiment 5~8), battery
Intermittent charge cycle after capacity retention ratio first increase with the increase of DTD dosages and reduce afterwards.DTD can be with shape on anode and cathode surface
Into passivating film, DTD can form passivating film on anode and cathode surface, and DTD is more, and protective film is thicker, and protective value is better；It is but excessive
DTD when not forming protective film, for a long time in battery core exist have decomposed occur side reaction influence intermittent charge cycle
Performance.
The weight that uses of the FEC in combined additive is：1%th, 3%, 5%, 7% and 10% (embodiment 9~13), electricity
Capacity retention ratio after the intermittent charge Xun Huan in pond first increases with the increase of FEC dosages to be reduced afterwards.This is primarily due to：FEC exists
The SEI films that anode surface is formed are favourable to cycling, but decomposed easily occurs at high temperature, and the FEC not formed a film especially exists
It is easier to decompose under high temperature, the excessively multipair intermittent charge Xun Huan of dosage is unfavorable.
The weight that uses of the ADN in combined additive is：0.1%th, 3%, 5%, 7% and 9% (embodiment 14~18),
Capacity retention ratio after the intermittent charge Xun Huan of battery increases with the increase of ADN dosages, and ADN can form good in cathode surface
Good protective film increases as content increases cycle performance.
Test four：Over-charging of battery performance test
At 25 DEG C, each 5 constant currents with 1C of lithium ion battery that comparative example 1~5 and embodiment 1~18 are provided and
The constant voltage of 10V is started to charge up until overcharging, measuring the peak temperature of battery and reaching the time used in peak temperature
(timing since 4.5V), and the state for overcharging rear battery is observed, over-charging test result is as shown in table 5.
1~18 lithium ion battery over-charging test result of 5 comparative example 1~5 of table and embodiment
| Peak temperature (DEG C) | Reach used in peak temperature the time (min) | Battery status after test | |
| Comparative example 1 | 529.2 | 20.3 | 5/5fire |
| Comparative example 2 | 523.6 | 25.2 | 4/5OK,1/5leakage |
| Comparative example 3 | 498.4 | 32.1 | 4/5fire,1/5leakage |
| Comparative example 4 | 89.3 | 29.8 | 5/5OK |
| Comparative example 5 | 511.9 | 25.3 | 4/5fire,1/5leakage |
| Embodiment 1 | 503.9 | 48.7 | 3/5fire,2/5leakage |
| Embodiment 2 | 498.2 | 49.6 | 4/5fire,1/5leakage |
| Embodiment 3 | 77.7 | 51.1 | 5/5OK |
| Embodiment 4 | 76.7 | 51.6 | 5/5OK |
| Embodiment 5 | 76.8 | 50.6 | 5/5OK |
| Embodiment 6 | 77.2 | 50.2 | 5/5OK |
| Embodiment 7 | 77.7 | 49.3 | 5/5OK |
| Embodiment 8 | 79.7 | 49.2 | 5/5OK |
| Embodiment 9 | 76.9 | 50 | 5/5OK |
| Embodiment 10 | 77.3 | 50 | 5/5OK |
| Embodiment 11 | 76.9 | 51.3 | 5/5OK |
| Embodiment 12 | 77.8 | 49.9 | 5/5OK |
| Embodiment 13 | 77.7 | 50.6 | 5/5OK |
| Embodiment 14 | 77.9 | 46.3 | 5/5OK |
| Embodiment 15 | 79.4 | 48.8 | 5/5OK |
| Embodiment 16 | 79.1 | 50.4 | 5/5OK |
| Embodiment 17 | 78.1 | 51.1 | 5/5OK |
| Embodiment 18 | 78.4 | 52.6 | 5/5OK |
The weight ratios that uses of the GBL in combined additive be：0.1%th, 5%, 30% and 40% (Examples 1 to 4), with
GBL content increase, battery core 1C10V overcharge percent of pass have larger promotion, lithium ion battery overcharge after peak temperature not
It is disconnected to reduce, reach the time increase used in peak temperature.Generally, the anti-over-charging ability of battery core has a distinct increment, this is because
One side GBL has higher flash-point, raises the flash-point of whole electrolyte；On the other hand passivating film is formed in cathode surface again,
Side reaction inside smaller battery core when overcharging occurs, and the security performance of battery core is improved.
The weight ratios that uses of the DTD in combined additive be：0.1%th, 0.5%, 3% and 5% (embodiment 5~8), with
The content of DTD increases, and overcharges percent of pass without significant change, the peak temperature after over-charging of battery constantly raises, and reaches peak value temperature
The degree time used constantly reduces.This is because DTD is easier to decompose in the case where overcharging high temperature, heating rate and the heat increasing generated
It is more.
The weight ratios that uses of the FEC in combined additive be：1%th, 3%, 5%, 7% and 10% (embodiment 9~13),
Increase with the content of FEC, overcharge the peak temperature after percent of pass, over-charging of battery and reach time used in peak temperature without bright
Aobvious variation, FEC have not significant impact to overcharging.
The weight ratios that uses of the ADN in combined additive be：0.1%th, 3%, 5%, 7% and 9% (embodiment 14~
18), increase with the content of ADN, overcharge the peak temperature after percent of pass and over-charging of battery without significant change, reach peak temperature
Time used is continuously increased.This is because ADN can inhibit to overcharge to a certain extent in the protective film formed in cathode surface
The side reaction for being, exothermic reaction when having delayed to overcharge.
In summary test result is understood, compared with comparative example lithium ion battery, lithium ion battery of the embodiment of the present invention
Cycle performance, storage performance are all significantly improved, and the operating voltage of lithium ion battery can be improved to 4.5V, can not only
Improve the energy density of lithium ion battery, moreover it is possible to significantly improve the overcharge resistance performance energy of electrolyte, improve the safety of lithium ion battery
Property.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in specific embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (10)
1. a kind of lithium-ion battery electrolytes, it includes organic solvent, electrolyte lithium salt and combined additives, which is characterized in that
The combined additive contains gamma-butyrolacton, ethyl sulfate, adiponitrile and fluorinated ethylene carbonate, and combined additive is in electricity
It is 1.3~65% to solve the weight percentage in liquid；The weight percentage of the fluorinated ethylene carbonate in the electrolytic solution is
1%~10%.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that by weight percentage, the electrolysis
Liquid contains 0.1%~40% gamma-butyrolacton, 0.1%~5% ethyl sulfate and 0.1%~10% adiponitrile.
3. lithium-ion battery electrolytes according to claim 1, which is characterized in that the gamma-butyrolacton is in the electrolytic solution
Weight percentage be 5%~30%.
4. lithium-ion battery electrolytes according to claim 1, which is characterized in that the ethyl sulfate is in the electrolytic solution
Weight percentage be 0.5%~3%.
5. lithium-ion battery electrolytes according to claim 1, which is characterized in that the weight of the adiponitrile in the electrolytic solution
It is 1%~7% to measure percentage composition.
6. lithium-ion battery electrolytes according to claim 1, which is characterized in that the fluorinated ethylene carbonate is being electrolysed
Weight percentage in liquid is 3%~7%.
7. lithium-ion battery electrolytes according to claim 1, which is characterized in that the organic solvent contains ethylene carbonate
Ester, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, third
At least two in propyl propionate, methyl butyrate and tetrahydrofuran.
8. a kind of lithium ion battery, including anode, cathode, the isolation film and electrolyte being arranged between anode and cathode,
In, anode includes plus plate current-collecting body and the positive electrode active material layer being arranged on plus plate current-collecting body, and positive electrode active material layer includes
Positive active material, bonding agent and conductive agent, cathode include negative current collector and the negative electrode active being arranged on negative current collector
Material layer, negative electrode active material layer include negative electrode active material, bonding agent and conductive agent, which is characterized in that the electrolyte is
Lithium-ion battery electrolytes any one of claim 1-7.
9. lithium ion battery according to claim 8, which is characterized in that the positive active material is LiCoO2、
LiMn2O4With Li (CoxNiyMn1-x-y)O2At least one of, wherein, 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤
0.9, the negative electrode active material is graphite and/or silicon.
10. lithium ion battery according to claim 8 or claim 9, which is characterized in that the charging upper limit of the lithium ion battery is cut
It is 4.5V to voltage.
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| CN103000944A (en) * | 2012-12-03 | 2013-03-27 | 湖州创亚动力电池材料有限公司 | Lithium ion battery electrolyte with high-temperature and low-temperature properties |
| CN104269576A (en) * | 2014-10-09 | 2015-01-07 | 东莞新能源科技有限公司 | Electrolyte and lithium ion battery adopting same |
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| CN103000944A (en) * | 2012-12-03 | 2013-03-27 | 湖州创亚动力电池材料有限公司 | Lithium ion battery electrolyte with high-temperature and low-temperature properties |
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