CN105006593B - Lithium ion secondary battery and electrolyte thereof - Google Patents
Lithium ion secondary battery and electrolyte thereof Download PDFInfo
- Publication number
- CN105006593B CN105006593B CN201410161690.9A CN201410161690A CN105006593B CN 105006593 B CN105006593 B CN 105006593B CN 201410161690 A CN201410161690 A CN 201410161690A CN 105006593 B CN105006593 B CN 105006593B
- Authority
- CN
- China
- Prior art keywords
- lithium
- rechargeable battery
- electrolyte
- lithium rechargeable
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides a lithium ion secondary battery and an electrolyte thereof. The electrolyte of the lithium ion secondary battery comprises: a non-aqueous organic solvent; a lithium salt dissolved in a non-aqueous organic solvent; and an additive dissolved in a non-aqueous organic solvent. The additive is Vinylene Carbonate (VC), lithium-containing compound LiN (C) of sulfoimidexF2x+1SO2)(CyF2y+1SO2) (wherein x and y are positive integers) and a junction of formula IStructural fluoro 1, 3-propane sultone;in the formula I, R1、R2、R3Each independently selected from fluorine atoms; the weight of the Vinylene Carbonate (VC) is 0.1-2% of that of the non-aqueous organic solvent; the lithium-containing compound LiN (C) of the sulfonyl imidexF2x+1SO2)(CyF2y+1SO2) The concentration of (A) is 0.02M-0.2M; the mass of the fluoro 1, 3-propane sultone with the structure of the formula I is 0.5-5% of that of the non-aqueous organic solvent. The lithium ion secondary battery comprises the electrolyte. The electrolyte of the lithium ion secondary battery can improve the low-temperature discharge performance and the high-temperature cycle performance of the lithium ion secondary battery.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of lithium rechargeable battery and its electrolyte.
Background technology
With the popularization of consumable electronic product such as notebook computer, mobile phone, handheld device, tablet personal computer etc., people
The requirement for the battery being used for is also increasingly stricter, has both required that battery was small and light, also require battery must have high power capacity,
Long-life and stable performance.In the secondary battery, lithium rechargeable battery is for the battery of other species, its compared with
High energy density makes it commercially occupy dominant position always.
At high temperature, the electrolyte in lithium rechargeable battery is further in the reactivity of positive electrode surface and negative terminal surface
Enhancing, the electrolyte and positive pole and negative pole for causing lithium rechargeable battery occur big quantitative response, produce accessory substance, increase both positive and negative polarity
Impedance on interface, normal removal lithium embedded is influenceed, cause the service life of lithium rechargeable battery to decline.
In order to solve the above problems, it is desirable to which the passivating film formed on positive pole and negative pole is sufficiently stable, so as to completely cut off
The further redox reaction of electrolyte and both positive and negative polarity.Such as 1,3- propane sultones（PS）Introducing so that the passivation of formation
Film has preferable stability at high temperature, it is not easy to is destroyed in charge and discharge process.But the resistance of the passivating film formed
It is anti-excessive, detrimental effect can be brought to the performance under lithium rechargeable battery low temperature, can such as make the low of lithium rechargeable battery
Warm discharge-rate reduces, and causes to analyse lithium, finally brings a series of potential safety hazard.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium rechargeable battery and its electricity
Liquid is solved, it can improve the low temperature performance of lithium rechargeable battery and high temperature cyclic performance.
To achieve these goals, in the first aspect of the present invention, the invention provides a kind of lithium rechargeable battery
Electrolyte, it includes：Non-aqueous organic solvent；Lithium salts, it is dissolved in non-aqueous organic solvent；And additive, being dissolved in non-aqueous has
In solvent.The additive is vinylene carbonate（VC）, sulfimide class lithium-containing compound LiN (CxF2x+1SO2)
(CyF2y+1SO2)（Wherein, x, y are positive integer）And the fluoro 1,3- propane sultones with Formulas I structure；
In Formulas I, R1、R2、R3It is each independently selected from fluorine atom；The vinylene carbonate（VC）Quality to be described non-
The 0.1%~2% of the quality of water organic solvent；Lithium-containing compound LiN (the C of the sulfimide classxF2x+1SO2)(CyF2y+1SO2)
Concentration be 0.02M~0.2M；The quality of the fluoro 1,3- propane sultones with Formulas I structure is described non-aqueous organic molten
The 0.5%~5% of the quality of agent.
In the second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, and it includes：Positive plate；Negative pole
Piece；Barrier film, it is interval between positive plate and negative plate；And electrolyte.The electrolyte is according to first aspect present invention
Lithium rechargeable battery electrolyte.
Beneficial effects of the present invention are as follows：
The electrolysis liquid energy of the lithium rechargeable battery of the present invention improves the low temperature performance and height of lithium rechargeable battery
Warm cycle performance.
Embodiment
The following detailed description of the lithium rechargeable battery according to the present invention and its electrolyte and comparative example, embodiment and survey
Test result.
Illustrate the electrolyte of lithium rechargeable battery according to a first aspect of the present invention first.
The electrolyte of lithium rechargeable battery according to a first aspect of the present invention, including：Non-aqueous organic solvent；Lithium salts, it is molten
Solution is in non-aqueous organic solvent；And additive, it is dissolved in non-aqueous organic solvent.The additive is vinylene carbonate
（VC）, sulfimide class lithium-containing compound LiN (CxF2x+1SO2)(CyF2y+1SO2)（Wherein, x, y are positive integer）And have
The fluoro 1,3- propane sultones of Formulas I structure；
In Formulas I, R1、R2、R3It is each independently selected from fluorine atom；The vinylene carbonate（VC）Quality to be described non-
The 0.1%~2% of the quality of water organic solvent；Lithium-containing compound LiN (the C of the sulfimide classxF2x+1SO2)(CyF2y+1SO2)
Concentration be 0.02M~0.2M；The quality of the fluoro 1,3- propane sultones with Formulas I structure is described non-aqueous organic molten
The 0.5%~5% of the quality of agent.
Fluoro PS with Formulas I structure remains the structure of sultones, this sultones structure
Solid electrolyte interface may be formed in negative pole（SEI）Film, prevent electrolyte further reduction decomposition on negative pole, and SEI films
In have what the fluoro PS component of Formulas I structure can stablize be present in negative terminal surface, and then ensure lithium ion
Secondary cell has stable performance at high temperature.Meanwhile the fluoro PS with Formulas I structure is formed in negative pole
Some accessory substances during SEI films can be oxidized to diaphragm in positive pole, so as to isolate positive pole and electrolyte, protect electrolyte not by
Further oxidation Decomposition.Due to the introducing of fluorine atom, the fluoro PS with Formulas I structure is reduced in lithium ion
Reduction potential in secondary cell so that it is prior to vinylene carbonate（VC）It is reduced film forming.Fluorine atom may be reduced and
Stable SEI membrane component LiF are formed, improve the stability of SEI films, therefore alternative fluorinated ethylene carbonate.With Formulas I knot
The fluoro 1,3- propane sultones of structure can also be with vinylene carbonate in the reaction product of negative pole（VC）Synergy is produced, so as to
Reduce the interface impedance of SEI films.The introducing of fluorine atom can also increase the wellability of electrolyte, it is possible to improve lithium ion secondary electricity
The low temperature performance in pond.
In addition, the fluoro PS with Formulas I structure is after fluorine atom is sloughed, it is possible to create efficient film forming
Compound propene sultone（PST）.But simple propene sultone（PST）It can make it that the reaction of film forming is more violent,
Cause to form finer and close and larger impedance SEI films, and the fluoro PS with Formulas I structure is capable of selectivity
Propene sultone is formed on the active site of negative pole（PST）To participate in film forming, thus will not produce it is larger into membrane impedance, and
And also ensure that the sultones structure of the fluoro PS with Formulas I structure forms diaphragm in positive pole, prevent
Reaction between positive pole and electrolyte, especially prevent vinylene carbonate under high temperature（VC）In the oxidation Decomposition accessory substance of positive pole
Accumulation caused by lithium rechargeable battery performance deterioration.Fluoro 1,3- propane sultones and carbonic acid with Formulas I structure
Vinylene（VC）With the lithium-containing compound LiN (C of sulfimide classxF2x+1SO2)(CyF2y+1SO2) collocation use, it can either increase
Add the electrical conductivity of lithium ion in the electrolytic solution, and can preferably prevents from being formed excessively fine and close SEI films on negative pole.
Fluoro PS with Formulas I structure is in the electrolytic solution with good solubility, when it has non-aqueous
When weight/mass percentage composition in solvent is less than 0.5%, because its content is very few, the both positive and negative polarity passivating film of formation is not enough to prevent
The further reaction of both positive and negative polarity and electrolyte, to the improvement unobvious of the high temperature cyclic performance of lithium rechargeable battery；When its
It when weight/mass percentage composition in non-aqueous organic solvent is higher than 5%, can to form the reaction of passivating film excessively violent, cause film forming
Impedance sharply increase, so as to deteriorate the high temperature cyclic performance of lithium rechargeable battery.This is due to the fluoro with Formulas I structure
The molecular weight of PS in itself is larger, and when its adding too much, the viscosity of electrolyte can increase, and cause what is formed
SEI is blocked up, and the electrical conductivity of electrolyte can be affected.The addition of the lithium-containing compound of sulfimide class not only increases electrolyte
Electrical conductivity but also participate in forming good SEI films in negative pole, so as to improve the high temperature performance of lithium rechargeable battery.When
When mole solubility of the lithium-containing compound of sulfimide class is less than 0.02M, the raising of its electrical conductivity to electrolyte and unobvious,
Improvement to the performance of lithium rechargeable battery also unobvious；When its mole of solubility is more than 0.2M, the viscosity of electrolyte becomes big,
The performance under lithium rechargeable battery low temperature is caused to start to deteriorate, and now the lithium-containing compound of sulfimide class is also possible to corrode
Current collector aluminum foil.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the sulfimide class contains
Lithium compound may be selected from LiN (SO2CF3)2Or LiN (SO2F)2。
It is described with Formulas I structure in the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention
Fluoro 1,3- propane sultones may be selected from the fluoro- 1,3- propane sultones of 1-（1-FPS）, the fluoro- 1,3- propane sultones of 2-（2-
FPS）, the fluoro- 1,3- propane sultones of 3-（3-FPS）In one kind.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the non-aqueous organic solvent can
Also include：Propene carbonate；And ethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate,
Methyl propyl carbonate, vinylene carbonate, fluorinated ethylene carbonate, methyl formate, ethyl acetate, methyl butyrate, methyl acrylate,
Ethene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, sulfuric acid vinyl ester, acid anhydrides, N- methyl
Pyrrolidones, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, N,N-dimethylformamide, sulfolane, dimethyl sulfoxide, first sulphur
In ether, gamma-butyrolacton, tetrahydrofuran, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester, the organic ester of ring-type containing unsaturated bond
It is one or more of.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the lithium salts may be selected from
LiPF6、LiBF4、LiBOB、LiClO4In one or more.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the concentration of the lithium salts can be
0.9M~1.15M.
Secondly the lithium rechargeable battery of explanation according to a second aspect of the present invention.
Lithium rechargeable battery according to a second aspect of the present invention, including：Positive plate；Negative plate；Barrier film, it is interval in just
Between pole piece and negative plate；And electrolyte.The electrolyte is the lithium rechargeable battery according to first aspect present invention
Electrolyte.
In lithium rechargeable battery described according to a second aspect of the present invention, the positive plate can include to deviate from, connect
By the material of lithium ion.
In lithium rechargeable battery described according to a second aspect of the present invention, it can deviate from the positive plate, receive lithium
The material of ion can be lithium-transition metal composite oxide.
In lithium rechargeable battery described according to a second aspect of the present invention, the lithium-transition metal composite oxide can
Added for lithium transition-metal oxide, lithium transition-metal oxide in the compound that other transition metal or nontransition metal obtain
One or more.
In lithium rechargeable battery described according to a second aspect of the present invention, the lithium-transition metal composite oxide can
Selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt alumina
One or more in thing.
In lithium rechargeable battery described according to a second aspect of the present invention, the negative plate, which can include, can receive, be de-
Go out the material of lithium ion.
In lithium rechargeable battery described according to a second aspect of the present invention, it can receive in the negative plate, deviate from lithium
The material of ion may be selected from soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate,
The one or more that can be formed with lithium in the metal of alloy.
In lithium rechargeable battery described according to a second aspect of the present invention, the charge cutoff electricity of lithium rechargeable battery
Pressure can be 3.8V~4.4V.
Next explanation is according to the lithium rechargeable battery of the present invention and its comparative example and embodiment of electrolyte.
Comparative example 1
（1）The preparation of the positive plate of lithium rechargeable battery
By active material LiNi1/3Co1/3Mn1/3O2, conductive agent acetylene black, binding agent Kynoar（PVDF）By weight
Than 96:2:2 be thoroughly mixed in solvent N-methyl pyrilidone uniformly after, coated on collector Al paper tinsels dry, be cold-pressed,
Obtain the positive plate of lithium rechargeable battery.
（2）The preparation of the negative plate of lithium rechargeable battery
By active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber（SBR）, thickener sodium carboxymethylcellulose
（CMC）By weight 95:2:2:After 1 is thoroughly mixed uniformly in solvent deionized water, coated on being dried on collector Cu paper tinsels
Dry, cold pressing, obtains the negative plate of lithium rechargeable battery.
（3）The preparation of the electrolyte of lithium rechargeable battery
By ethylene carbonate（EC）, propene carbonate（PC）, diethyl carbonate（DEC）By weight 30:30:40 mixing
（As non-aqueous organic solvent）, and dissolve 1M LiPF6Lithium salts is in non-aqueous organic solvent, the electrolysis as lithium rechargeable battery
Liquid.
（4）The preparation of lithium rechargeable battery
By positive plate, barrier film（PE porous polymer films）, negative plate fold in order, make barrier film be in positive plate and
Play a part of isolation among negative plate, winding obtains naked battery core afterwards, naked battery core is placed in battery outer packing, injection prepares
Electrolyte and encapsulation, soldering polar ear, complete the preparation of lithium rechargeable battery.
Comparative example 2
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, weight/mass percentage composition is also added in electrolyte（In terms of non-aqueous organic solvent）It is sub- for 0.5% carbonic acid
Vinyl acetate（VC）.
Comparative example 3
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, weight/mass percentage composition is also added in electrolyte（In terms of non-aqueous organic solvent）For 1% carbonic acid Asia second
Alkene ester（VC）.
Comparative example 4
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, weight/mass percentage composition is also added in electrolyte（In terms of non-aqueous organic solvent）For 2% carbonic acid Asia second
Alkene ester（VC）.
Comparative example 5
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, weight/mass percentage composition is also added in electrolyte（In terms of non-aqueous organic solvent）For 0.01% 3- fluorine
Generation -1,3- propane sultones（3-FPS）.
Comparative example 6
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, weight/mass percentage composition is also added in electrolyte（In terms of non-aqueous organic solvent）For 6% 3- fluoro -1,
3-N-morpholinopropanesulfonic acid lactone（3-FPS）.
Comparative example 7
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2。
Comparative example 8
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 4% propene sultone
（PST）.
Comparative example 9
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 4% 1,3- propane sultones
（PS）.
Embodiment 1
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 0.5% 3- fluoro -1,3-
Propane sultone（3-FPS）.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 1% 3- fluoro -1,3- third
Sultones（3-FPS）.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 2% 3- fluoro -1,3- third
Sultones（3-FPS）.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 4% 3- fluoro -1,3- third
Sultones（3-FPS）.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 5% 3- fluoro -1,3- third
Sultones（3-FPS）.
Embodiment 6
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 4% 1- fluoro -1,3- third
Sultones（1-FPS）.
Embodiment 7
Method according to embodiment 1 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte system
It is standby（That is step（3））In, 0.1M LiN (SO are also added in electrolyte2CF3)2, weight/mass percentage composition（With non-aqueous organic solvent
Meter）For 1% vinylene carbonate（VC）And weight/mass percentage composition（In terms of non-aqueous organic solvent）For 4% 2- fluoro -1,3- third
Sultones（2-FPS）.
Finally illustrate the test process and test result of the lithium rechargeable battery and its electrolyte according to the present invention.
（1）High temperature cyclic performance is tested
Lithium rechargeable battery in comparative example 1-9 and embodiment 1-7 is respectively taken 5, puts the high-low temperature chamber as 45 DEG C
In, after temperature stabilization, in normal temperature（25℃）Under 4.35V is higher than with 0.5C multiplying powers constant current charge to voltage, further exist
Electric current is charged under 4.35V constant voltages and is less than 0.05C, 4.35V fully charged states are at, afterwards by lithium rechargeable battery
Voltage is discharged to as 3V using 1C multiplying power constant currents（Blanking voltage）, 1 circulation is recorded as with this, discharge capacity record now
For discharge capacity D first0.The circulating repetition is carried out 200 times, and the discharge capacity for recording last time is D1。
Capability retention=D after the high temperature circulation of lithium rechargeable battery1/D0×100%。
The average value of the capability retention after the high temperature circulation of every group of 5 lithium rechargeable batteries is taken as the lithium ion
Capability retention after the high temperature circulation of secondary cell.
（2）Low temperature performance is tested
Lithium rechargeable battery in comparative example 1-9 and embodiment 1-7 is respectively taken 5, in normal temperature（25℃）Under with 0.5C
Multiplying power constant current charge to voltage is higher than 4.35V, and electric current is further charged under 4.35V constant voltages and is less than 0.05C, is made
It is in 4.35V fully charged states, after standing 60min at 25 DEG C and -20 DEG C respectively afterwards, is discharged with 0.2C multiplying powers constant current
It is 3.0V to voltage, records discharge capacity of the lithium rechargeable battery at 25 DEG C and -20 DEG C respectively.
The low-temperature phase of lithium rechargeable battery to the discharge capacity at discharge capacity/25 DEG C at discharge-rate=- 20 DEG C ×
100%。
Take the low-temperature phase of every group of 5 lithium rechargeable batteries electric as the lithium ion secondary to the average value of discharge-rate
The low-temperature phase in pond is to discharge-rate.
Table 1 provides comparative example 1-9 and embodiment 1-7 parameter and the performance test results.
Next comparative example 1-9 and embodiment 1-7 the performance test results are analyzed.
As can be seen that the high temperature of the lithium rechargeable battery of the present invention follows from embodiment 1-7 and comparative example 1-9 contrast
Ring performance and low temperature performance are good compared with comparative example 1-7.
From embodiment 1-5 and comparative example 5-6 contrast as can be seen that with the fluoro- PSs of 3-（3-FPS）
Weight/mass percentage composition in non-aqueous organic solvent increases, capability retention and low temperature after lithium rechargeable battery high temperature circulation
Relative discharge multiplying power first increases to be reduced afterwards.When the fluoro- 1,3- propane sultones of 3-（3-FPS）Quality in non-aqueous organic solvent
When percentage composition is less than 0.5%（Comparative example 5）, because its content is very few, the both positive and negative polarity passivating film of formation is not enough to prevent electrolyte
Further reaction, the improvement unobvious of high temperature cyclic performance and low temperature performance to lithium rechargeable battery；When it is non-
When weight/mass percentage composition in water organic solvent is higher than 5%（Comparative example 6）, can make it that reaction is excessively violent, cause the impedance of film forming
Sharply increase, so as to deteriorate the high temperature cyclic performance of lithium rechargeable battery and low temperature performance.This is due to the fluoro- 1,3- of 3-
Propane sultone（3-FPS）The molecular weight of itself is larger, and when its adding too much, the viscosity of electrolyte can increase, and cause shape
Into SEI it is blocked up, the electrical conductivity of electrolyte can be affected, so as to influence the high temperature cyclic performance of lithium rechargeable battery and low
Warm discharge performance.
As can be seen that working as single vinylene carbonate from comparative example 1-4 contrast（VC）During as additive, with
Vinylene carbonate（VC）The increase of weight/mass percentage composition in non-aqueous organic solvent, the low temperature of lithium rechargeable battery are put
Electrical property runs down.This may be with vinylene carbonate（VC）Double bond structure it is relevant, its matter in non-aqueous organic solvent
Amount percentage composition is excessive to be easily caused it excessively fine and close SEI films is formed on negative pole, increases interface impedance, especially in low temperature
When, deintercalation speed that can be to lithium ion causes very big negative effect, so as to deteriorate the low temperature discharge property of lithium rechargeable battery
Energy；But vinylene carbonate（VC）Be advantageous to the high temperature cyclic performance of lithium rechargeable battery, this is due to vinylene carbonate
Ester（VC）Stable polymer film can be formed with higher reduction efficiency and in negative terminal surface, but excessive vinylene carbonate
Ester（VC）It is likely to result in and blocked up SEI films is produced in negative terminal surface, increases interface impedance, while vinylene carbonate（VC）
Oxidation Decomposition easily occurs in positive pole under high voltage so that excessive accessory substance is accumulated in positive pole, and then deteriorates lithium ion secondary
The high temperature cyclic performance of battery.
It is from comparative example 7-9, embodiment 4 and embodiment 6-7 contrast as can be seen that a certain amount of with Formulas I structure
Fluoro -1,3- propane sultones are relative to propene sultone（PST）With 1,3- propane sultones（PS）It can show preferably
High temperature cyclic performance and low temperature performance.Possible cause is：Propene sultone（PST）Reactivity it is too high, can produce
Life is larger into membrane impedance, and the deterioration in the case where its content is higher to lithium rechargeable battery is clearly.The sulphurs of 1,3- third
Acid lactone（PS）Although being advantageous to the high temperature cyclic performance of lithium rechargeable battery, due to its to positive pole into membrane impedance also
It is larger, therefore causes the low temperature performance of lithium rechargeable battery to deteriorate.And the sulphurs of fluoro -1,3- third with Formulas I structure
Fluorine atom is introduced in acid lactone, is advantageous to increase the wellability of electrolyte, so as to be advantageous to the low temperature of lithium rechargeable battery
Discharge performance；And fluoro-PS optionally film forming on the active site of both positive and negative polarity with Formulas I structure,
Avoid propene sultone（PST）Violent film formation reaction, and can be formed with fluoro-PS of Formulas I structure
Stable LiF film-forming components, so as to increase the stability of both positive and negative polarity film forming, avoid follow-up vinylene carbonate（VC）And sulphonyl
The excessive decomposition of the lithium-containing compound of imines.
To sum up, vinylene carbonate is worked as（VC）, sulfimide class lithium-containing compound and with Formulas I structure fluoro-
The collective effect of 1,3- propane sultones can obviously improve the high temperature cyclic performance and low temperature performance of lithium rechargeable battery.
。
Claims (9)
1. a kind of electrolyte of lithium rechargeable battery, including：
Non-aqueous organic solvent；
Lithium salts, it is dissolved in non-aqueous organic solvent；And
Additive, it is dissolved in non-aqueous organic solvent；
Characterized in that,
The additive is vinylene carbonate, the lithium-containing compound LiN (C of sulfimide classxF2x+1SO2)(CyF2y+1SO2) with
And the fluoro PS with Formulas I structure, wherein, x, y are 0 or positive integer；
In Formulas I, R1、R2、R3It is each independently selected from fluorine atom, or the fluoro PS choosing with Formulas I structure
One kind from the fluoro- PSs of 1-, the fluoro- PSs of 2-, the fluoro- PSs of 3-, its structure
Formula difference is as follows：
The quality of the vinylene carbonate is the 0.1%~2% of the quality of the non-aqueous organic solvent；
Lithium-containing compound LiN (the C of the sulfimide classxF2x+1SO2)(CyF2y+1SO2) concentration be 0.02M~0.2M；
The quality of the fluoro 1,3- propane sultones with Formulas I structure is the 0.5% of the quality of the non-aqueous organic solvent
~5%.
2. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that the sulfimide class contains
Lithium compound is selected from LiN (SO2CF3)2Or LiN (SO2F)2。
3. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that the non-aqueous organic solvent is also
Including：
Propene carbonate；And
Ethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbonic acid are sub-
Vinyl acetate, fluorinated ethylene carbonate, methyl formate, ethyl acetate, methyl butyrate, methyl acrylate, ethene sulfite, propylene
Sulfite, dimethyl sulfite, diethyl sulfite, sulfuric acid vinyl ester, acid anhydrides, 1-METHYLPYRROLIDONE, N- methyl first
Acid amides, N- methylacetamides, acetonitrile, N,N-dimethylformamide, sulfolane, dimethyl sulfoxide, methyl sulfide, gamma-butyrolacton, tetrahydrochysene
One or more in furans.
4. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that the lithium salts is selected from LiPF6、
LiBF4、LiBOB、LiClO4In one or more.
5. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that the concentration of the lithium salts is
0.9M~1.15M.
6. a kind of lithium rechargeable battery, including：
Positive plate；
Negative plate；
Barrier film, it is interval between positive plate and negative plate；And
Electrolyte；
Characterized in that,
The electrolyte is the electrolyte of the lithium rechargeable battery according to any one of claim 1-5.
7. lithium rechargeable battery according to claim 6, it is characterised in that the positive plate includes to deviate from, receive
The material of lithium ion, it is described can abjection, the material that receives lithium ion be lithium-transition metal composite oxide, the lithium transition-metal
Composite oxides are that lithium transition-metal oxide, the other transition metal of lithium transition-metal oxide addition or nontransition metal obtain
Compound in one or more, the lithium-transition metal composite oxide be selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese
One or more in oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
8. lithium rechargeable battery according to claim 6, it is characterised in that the negative plate, which includes, can receive, deviate from
The material of lithium ion, the material that can receive, deviate from lithium ion are selected from soft carbon, hard carbon, Delanium, native graphite, silicon, silicon
Oxygen compound, silicon-carbon compound, lithium titanate, can with lithium formed alloy metal in one or more.
9. lithium rechargeable battery according to claim 6, it is characterised in that the charge cutoff electricity of lithium rechargeable battery
Press as 3.8V~4.4V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410161690.9A CN105006593B (en) | 2014-04-21 | 2014-04-21 | Lithium ion secondary battery and electrolyte thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410161690.9A CN105006593B (en) | 2014-04-21 | 2014-04-21 | Lithium ion secondary battery and electrolyte thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105006593A CN105006593A (en) | 2015-10-28 |
| CN105006593B true CN105006593B (en) | 2017-12-12 |
Family
ID=54379179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410161690.9A Active CN105006593B (en) | 2014-04-21 | 2014-04-21 | Lithium ion secondary battery and electrolyte thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105006593B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105261791A (en) * | 2015-11-11 | 2016-01-20 | 东莞市凯欣电池材料有限公司 | Ultra-temperature high-voltage lithium-ion battery electrolyte and lithium-ion battery using electrolyte |
| CN105428719B (en) * | 2015-12-31 | 2018-12-18 | 石家庄圣泰化工有限公司 | Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application |
| CN106684446A (en) * | 2017-02-06 | 2017-05-17 | 深圳市斯诺实业发展股份有限公司 | Lithium battery electrolyte and preparation method thereof |
| JP6974434B2 (en) * | 2017-03-17 | 2021-12-01 | 旭化成株式会社 | Non-aqueous electrolyte |
| CN106920988B (en) * | 2017-04-01 | 2019-07-26 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, preparation method and application |
| CN109888390A (en) * | 2019-03-08 | 2019-06-14 | 东莞市坤乾新能源科技有限公司 | A kind of electrolyte and lithium battery that the dedicated high magnification high temperature resistant of electronic cigarette is taken into account |
| CN111883842A (en) * | 2020-08-07 | 2020-11-03 | 香河昆仑化学制品有限公司 | Functional non-aqueous organic additive for non-aqueous electrolyte |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578725A (en) * | 2007-11-02 | 2009-11-11 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN102340006A (en) * | 2011-09-30 | 2012-02-01 | 湖南大学 | Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments |
| CN103268956A (en) * | 2013-05-18 | 2013-08-28 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for high-voltage lithium ion batteries |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130337342A1 (en) * | 2012-06-06 | 2013-12-19 | Peter B. Hallac | Electrolyte Formulation for High Voltage and Wide Temperature Lithium-Ion Cells |
-
2014
- 2014-04-21 CN CN201410161690.9A patent/CN105006593B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578725A (en) * | 2007-11-02 | 2009-11-11 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN102340006A (en) * | 2011-09-30 | 2012-02-01 | 湖南大学 | Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments |
| CN103268956A (en) * | 2013-05-18 | 2013-08-28 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for high-voltage lithium ion batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105006593A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105006593B (en) | Lithium ion secondary battery and electrolyte thereof | |
| KR100751205B1 (en) | Electrolyte for improving performance of battery and lithium secondary battery comprising the same | |
| CN104051786B (en) | A kind of electrolyte and preparation method thereof and a kind of high-voltage lithium ion batteries | |
| CN104269576B (en) | A kind of electrolyte and the lithium ion battery using the electrolyte | |
| CN103730688B (en) | Lithium ion battery and electrolyte thereof | |
| CN104466250A (en) | High-voltage lithium-ion battery electrolyte | |
| CN105428719A (en) | High-voltage wide-temperature lithium ion battery electrolyte, preparation method therefor and applications | |
| CN104022310B (en) | Lithium rechargeable battery and the lithium ion battery containing this electrolyte | |
| CN103078139B (en) | Lithium-ion battery electrolytes | |
| CN103972588A (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN107017433B (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN104979586B (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN105336984B (en) | Lithium ion battery and its electrolyte | |
| CN105390742A (en) | High-voltage lithium-ion battery electrolyte as well as preparation method and application thereof | |
| CN105470571B (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN105895958A (en) | Electrolyte and lithium ion battery | |
| CN105633460B (en) | Lithium ion secondary battery electrolyte and lithium ion secondary battery | |
| CN105789684A (en) | Lithium ion secondary battery and electrolyte thereof | |
| US20060068297A1 (en) | Electrolytes for lithium ion batteries | |
| CN103779604A (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN104868096B (en) | Lithium ion battery | |
| TW201542519A (en) | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device | |
| CN103825048B (en) | Lithium rechargeable battery and electrolyte thereof | |
| CN108352572B (en) | Additive for nonaqueous electrolyte solution, and electricity storage device | |
| CN103078133B (en) | Lithium rechargeable battery and its electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 Applicant after: Contemporary Amperex Technology Co.,Ltd. Address before: 352100 Jiaocheng District of Ningde City, Fujian Province Zhang Wan Zhen Xingang Road No. 1 West Building 1F- research Applicant before: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |