CN105006593A - Lithium ion secondary battery and electrolyte thereof - Google Patents
Lithium ion secondary battery and electrolyte thereof Download PDFInfo
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- CN105006593A CN105006593A CN201410161690.9A CN201410161690A CN105006593A CN 105006593 A CN105006593 A CN 105006593A CN 201410161690 A CN201410161690 A CN 201410161690A CN 105006593 A CN105006593 A CN 105006593A
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Abstract
The present invention provides a lithium ion secondary battery and an electrolyte thereof. The lithium ion secondary battery electrolyte comprises a non-aqueous organic solvent, a lithium salt dissolved in the non-aqueous organic solvent, and an additive dissolved in the non-aqueous organic solvent, wherein the additive is vinylene carbonate (VC), a lithium-containing compound of sulfonimide LiN(CxF2x+1SO2)fluoro(CyF2y+1SO2) (wherein x and y are positive integers), and fluoro 1,3-propanesultone having a structure represented by a formula I, R1, R2 and R3 are respectively and independently selected from fluorine atom, the mass of the vinylene carbonate (VC) is 0.1-2% of the mass of the non-aqueous organic solvent, the concentration of the lithium-containing compound of sulfonimide LiN(CxF2x+1SO2)fluoro(CyF2y+1SO2) is 0.02-0.2 M, and the mass of the fluoro 1,3-propanesultone is 0.5-5% of the mass of the non-aqueous organic solvent. The lithium ion secondary battery comprises the electrolyte. With the Lithium ion secondary battery electrolyte of the present invention, the low temperature discharge performance and the high temperature cycle performance of the lithium ion secondary battery can be improved. The formula I is defined in the specification.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium rechargeable battery and electrolyte thereof.
Background technology
Along with consumable electronic product popularizing as notebook computer, mobile phone, handheld device, panel computer etc., the requirement of people to the battery that it uses is also more and more stricter, both required that battery was small and light, also required that battery must have high power capacity, long-life and stable performance.In the secondary battery, lithium rechargeable battery is relative to the battery of other kind, and its higher energy density makes it commercially occupy dominant position always.
At high temperature, electrolyte in lithium rechargeable battery strengthens further in the reactivity of positive electrode surface and negative terminal surface, cause the electrolyte of lithium rechargeable battery and positive pole and negative pole that large quantitative response occurs, produce accessory substance, increase impedance on both positive and negative polarity interface, affect normal removal lithium embedded, cause decline the useful life of lithium rechargeable battery.
In order to solve the problem, require that the passivating film formed on positive pole and negative pole is enough stable, thus the further redox reaction of electrolyte and both positive and negative polarity can be completely cut off.As the introducing of PS (PS), make the passivating film formed at high temperature have good stability, be not easy to be damaged in charge and discharge process.But the impedance of the passivating film formed is excessive, can bring adverse influence, as the low temperature discharge multiplying power of lithium rechargeable battery can be made to reduce, cause and analyse lithium, finally bring a series of potential safety hazard the performance under lithium rechargeable battery low temperature.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium rechargeable battery and electrolyte thereof, it can improve low temperature performance and the high temperature cyclic performance of lithium rechargeable battery.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of electrolyte of lithium rechargeable battery, it comprises: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; And additive, be dissolved in non-aqueous organic solvent.Described additive is the lithium-containing compound LiN (C of vinylene carbonate (VC), sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) (wherein, x, y are positive integer) and there is the fluoro PS of formula I structure;
In formula I, R
1, R
2, R
3independently be selected from fluorine atom separately; The quality of described vinylene carbonate (VC) is 0.1% ~ 2% of the quality of described non-aqueous organic solvent; Lithium-containing compound LiN (the C of described sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) concentration be 0.02M ~ 0.2M; The described quality with the fluoro PS of formula I structure is 0.5% ~ 5% of the quality of described non-aqueous organic solvent.
In a second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it comprises: positive plate; Negative plate; Barrier film, is interval between positive plate and negative plate; And electrolyte.Described electrolyte is the electrolyte of lithium rechargeable battery according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
The electrolyte of lithium rechargeable battery of the present invention can improve low temperature performance and the high temperature cyclic performance of lithium rechargeable battery.
Embodiment
The following detailed description of lithium rechargeable battery according to the present invention and electrolyte thereof and comparative example, embodiment and test result.
First the electrolyte of lithium rechargeable battery is according to a first aspect of the present invention described.
The electrolyte of lithium rechargeable battery according to a first aspect of the present invention, comprising: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; And additive, be dissolved in non-aqueous organic solvent.Described additive is the lithium-containing compound LiN (C of vinylene carbonate (VC), sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) (wherein, x, y are positive integer) and there is the fluoro PS of formula I structure;
In formula I, R
1, R
2, R
3independently be selected from fluorine atom separately; The quality of described vinylene carbonate (VC) is 0.1% ~ 2% of the quality of described non-aqueous organic solvent; Lithium-containing compound LiN (the C of described sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) concentration be 0.02M ~ 0.2M; The described quality with the fluoro PS of formula I structure is 0.5% ~ 5% of the quality of described non-aqueous organic solvent.
There is the fluoro 1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone remains the structure of sultones, this sultones structure may form solid electrolyte interface (SEI) film at negative pole, prevent electrolyte further reduction decomposition on negative pole, and there is in SEI film the fluoro 1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone component can be stable be present in negative terminal surface, and then ensure lithium rechargeable battery at high temperature there is stable performance.Meanwhile, some accessory substances of fluoro PS when negative pole forms SEI film with formula I structure can be oxidized to diaphragm at positive pole, thus isolation positive pole and electrolyte, protection electrolyte is not further oxided decomposition.Due to the introducing of fluorine atom, reduce the reduction potential of fluoro PS in lithium rechargeable battery with formula I structure, make it be reduced film forming prior to vinylene carbonate (VC).Fluorine atom may be reduced and form stable SEI membrane component LiF, improves the stability of SEI film, therefore alternative fluorinated ethylene carbonate.The fluoro PS with formula I structure also can produce with vinylene carbonate (VC) in the product of negative pole and act synergistically, thus reduces the interface impedance of SEI film.The introducing of fluorine atom also can increase the wettability of electrolyte, likely improves the low temperature performance of lithium rechargeable battery.
In addition, the fluoro PS with formula I structure, after sloughing fluorine atom, may form efficient film forming compound propene sultone (PST).But simple propene sultone (PST) can make the reaction of film forming more violent, cause formation finer and close and the larger SEI film of impedance, and there is the fluoro 1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone optionally can form propene sultone (PST) to participate in film forming on the active site of negative pole, therefore larger one-tenth membrane impedance can not be produced, but also the fluoro 1 with formula I structure can be ensured, the sultones structure of 3-N-morpholinopropanesulfonic acid lactone forms diaphragm at positive pole, stop the reaction between positive pole and electrolyte, the deterioration of the performance of the lithium rechargeable battery especially stoping vinylene carbonate (VC) under high temperature to cause in the accumulation of the oxidation Decomposition accessory substance of positive pole.There is the fluoro PS of formula I structure and the lithium-containing compound LiN (C of vinylene carbonate (VC) and sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) collocation use, lithium ion conductivity in the electrolytic solution can either be increased, can prevent from again being formed too fine and close SEI film preferably on negative pole.
There is the fluoro 1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone has good solubility in the electrolytic solution, when its mass percentage in non-aqueous organic solvent lower than 0.5% time, because its content is very few, the both positive and negative polarity passivating film formed is not enough to the further reaction stoping both positive and negative polarity and electrolyte, not obvious to the improvement of the high temperature cyclic performance of lithium rechargeable battery; When its mass percentage in non-aqueous organic solvent higher than 5% time, the reaction forming passivating film can be made too violent, cause the impedance of film forming sharply to increase, thus worsen the high temperature cyclic performance of lithium rechargeable battery.This is that the molecular weight of fluoro PS owing to having formula I structure itself is comparatively large, and when its addition is too high, the viscosity of electrolyte can strengthen, and causes the SEI of formation blocked up, and the conductivity of electrolyte can be affected.The conductivity the adding of the lithium-containing compound of sulfimide class not only increasing electrolyte but also participate in forming good SEI film at negative pole, thus improve the high temperature performance of lithium rechargeable battery.When mole solubility of the lithium-containing compound of sulfimide class is lower than 0.02M, it is not obvious to the raising of the conductivity of electrolyte, also not obvious to the improvement of the performance of lithium rechargeable battery; When its mole of solubility is greater than 0.2M, the viscosity of electrolyte becomes large, cause the performance under lithium rechargeable battery low temperature to start to worsen, and now the lithium-containing compound of sulfimide class also may corrode current collector aluminum foil.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the lithium-containing compound of described sulfimide class can be selected from LiN (SO
2cF
3)
2or LiN (SO
2f)
2.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the described fluoro 1 with formula I structure, 3-N-morpholinopropanesulfonic acid lactone can be selected from 1-fluoro-1,3-N-morpholinopropanesulfonic acid lactone (1-FPS), 2-fluoro-1, one in 3-N-morpholinopropanesulfonic acid lactone (2-FPS), the fluoro-PS of 3-(3-FPS).
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, described non-aqueous organic solvent can also comprise: 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, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide, methyl sulfide, gamma-butyrolacton, oxolane, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester, containing one or more in unsaturated bond ring-type organic ester.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, described lithium salts can be selected from LiPF
6, LiBF
4, LiBOB, LiClO
4in one or more.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the concentration of described lithium salts can be 0.9M ~ 1.15M.
Secondly lithium rechargeable battery is according to a second aspect of the present invention described.
Lithium rechargeable battery according to a second aspect of the present invention, comprising: positive plate; Negative plate; Barrier film, is interval between positive plate and negative plate; And electrolyte.Described electrolyte is the electrolyte of lithium rechargeable battery according to a first aspect of the present invention.
In lithium rechargeable battery described according to a second aspect of the present invention, described positive plate can comprise the material deviating from, accept lithium ion.
In lithium rechargeable battery described according to a second aspect of the present invention, the material deviating from, accept lithium ion in described positive plate can be lithium-transition metal composite oxide.
One or more in lithium rechargeable battery described according to a second aspect of the present invention, in the compound that described lithium-transition metal composite oxide can be lithium transition-metal oxide, lithium transition-metal oxide adds other transition metal or nontransition metal obtains.
In lithium rechargeable battery described according to a second aspect of the present invention, described lithium-transition metal composite oxide can be selected from one or more in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
In lithium rechargeable battery described according to a second aspect of the present invention, described negative plate can comprise the material that can accept, deviate from lithium ion.
In lithium rechargeable battery described according to a second aspect of the present invention, the material that can accept, deviate from lithium ion in described negative plate can be selected from soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate, can with lithium formed in the metal of alloy one or more.
In lithium rechargeable battery described according to a second aspect of the present invention, the charge cutoff voltage of lithium rechargeable battery can be 3.8V ~ 4.4V.
Following explanation is according to the comparative example of lithium rechargeable battery of the present invention and electrolyte thereof and embodiment.
Comparative example 1
(1) preparation of the positive plate of lithium rechargeable battery
By active material LiNi
1/3co
1/3mn
1/3o
2, conductive agent acetylene black, binding agent Kynoar (PVDF) by weight after 96:2:2 is fully uniformly mixed in solvent N-methyl pyrilidone, be coated on collector Al paper tinsel and dry, cold pressing, obtain the positive plate of lithium rechargeable battery.
(2) preparation of the negative plate of lithium rechargeable battery
After active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener sodium carboxymethylcellulose (CMC) are fully uniformly mixed in solvent deionized water by weight 95:2:2:1, be coated on oven dry on collector Cu paper tinsel, cold pressing, obtain the negative plate of lithium rechargeable battery.
(3) preparation of the electrolyte of lithium rechargeable battery
Ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) by weight 30:30:40 mixing (as non-aqueous organic solvent), and are dissolved 1M LiPF
6lithium salts in non-aqueous organic solvent, as the electrolyte of lithium rechargeable battery.
(4) preparation of lithium rechargeable battery
Positive plate, barrier film (PE porous polymer film), negative plate are folded in order, barrier film is made to be in the effect playing isolation in the middle of positive plate and negative plate, winding obtains naked battery core afterwards, naked battery core is placed in battery external packing, inject the electrolyte for preparing and encapsulate, soldering polar ear, complete the preparation of lithium rechargeable battery.
Comparative example 2
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, in electrolyte, also added the vinylene carbonate (VC) that mass percentage (in non-aqueous organic solvent) is 0.5%.
Comparative example 3
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, in electrolyte, also added the vinylene carbonate (VC) that mass percentage (in non-aqueous organic solvent) is 1%.
Comparative example 4
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, in electrolyte, also added the vinylene carbonate (VC) that mass percentage (in non-aqueous organic solvent) is 2%.
Comparative example 5
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, 3-fluoro-PS (3-FPS) that mass percentage (in non-aqueous organic solvent) is 0.01% is also added in electrolyte.
Comparative example 6
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, 3-fluoro-PS (3-FPS) that mass percentage (in non-aqueous organic solvent) is 6% is also added in electrolyte.
Comparative example 7
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2.
Comparative example 8
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 4% propene sultone (PST).
Comparative example 9
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 4% PS (PS).
Embodiment 1
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 0.5% 3-fluoro-PS (3-FPS).
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 1% 3-fluoro-PS (3-FPS).
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 2% 3-fluoro-PS (3-FPS).
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 4% 3-fluoro-PS (3-FPS).
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 5% 3-fluoro-PS (3-FPS).
Embodiment 6
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 4% 1-fluoro-PS (1-FPS).
Embodiment 7
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, also added the LiN (SO of 0.1M in electrolyte
2cF
3)
2, mass percentage (in non-aqueous organic solvent) be 1% vinylene carbonate (VC) and mass percentage (in non-aqueous organic solvent) be 4% 2-fluoro-PS (2-FPS).
Test process according to lithium rechargeable battery of the present invention and electrolyte thereof and test result are finally described.
(1) high temperature cyclic performance test
Lithium rechargeable battery in comparative example 1-9 and embodiment 1-7 is respectively got 5, put in the high-low temperature chamber as 45 DEG C, after temperature stabilization, under normal temperature (25 DEG C) with 0.5C multiplying power constant current charge to voltage higher than 4.35V, electric current is charged to lower than 0.05C further under 4.35V constant voltage, it is made to be in 4.35V fully charged state, afterwards lithium rechargeable battery is discharged to voltage for 3V(cut-ff voltage with 1C multiplying power constant current), be recorded as 1 circulation with this, discharge capacity is now recorded as discharge capacity D first
0.This is cycled to repeat and carries out 200 times, and recording last discharge capacity is D
1.
Capability retention=D after the high temperature circulation of lithium rechargeable battery
1/ D
0× 100%.
Get the mean value of the capability retention after the high temperature circulation of 5 lithium rechargeable batteries often organized as the capability retention after the high temperature circulation of this lithium rechargeable battery.
(2) low temperature performance test
Lithium rechargeable battery in comparative example 1-9 and embodiment 1-7 is respectively got 5, under normal temperature (25 DEG C) with 0.5C multiplying power constant current charge to voltage higher than 4.35V, electric current is charged to lower than 0.05C further under 4.35V constant voltage, it is made to be in 4.35V fully charged state, after leaving standstill 60min respectively at 25 DEG C and-20 DEG C afterwards, be discharged to voltage for 3.0V with 0.2C multiplying power constant current, record the discharge capacity of lithium rechargeable battery at 25 DEG C and-20 DEG C respectively.
The low-temperature phase of lithium rechargeable battery is to discharge capacity × 100% at discharge capacity/25 at discharge-rate=-20 DEG C DEG C.
The low-temperature phase getting 5 lithium rechargeable batteries often organized to the mean value of discharge-rate as the low-temperature phase of this lithium rechargeable battery to discharge-rate.
Table 1 provides parameter and the performance test results of comparative example 1-9 and embodiment 1-7.
Next the performance test results of comparative example 1-9 and embodiment 1-7 is analyzed.
As can be seen from the contrast of embodiment 1-7 and comparative example 1-9, the high temperature cyclic performance of lithium rechargeable battery of the present invention and low temperature performance all comparatively comparative example 1-7 are good.
As can be seen from the contrast of embodiment 1-5 and comparative example 5-6, along with 3-fluoro-1, the mass percentage of 3-N-morpholinopropanesulfonic acid lactone (3-FPS) in non-aqueous organic solvent increases, and the capability retention after lithium rechargeable battery high temperature circulation and low-temperature phase all first increase discharge-rate and reduce afterwards.As 3-fluoro-1, the mass percentage of 3-N-morpholinopropanesulfonic acid lactone (3-FPS) in non-aqueous organic solvent lower than 0.5% time (comparative example 5), because its content is very few, formed both positive and negative polarity passivating film be not enough to stop electrolyte react further, to the high temperature cyclic performance of lithium rechargeable battery and the improvement of low temperature performance not obvious; When its mass percentage in non-aqueous organic solvent higher than 5% time (comparative example 6), reaction can be made too violent, cause the impedance of film forming sharply to increase, thus worsen high temperature cyclic performance and the low temperature performance of lithium rechargeable battery.This is due to 3-fluoro-1, the molecular weight of 3-N-morpholinopropanesulfonic acid lactone (3-FPS) itself is larger, when its addition is too high, the viscosity of electrolyte can strengthen, cause the SEI of formation blocked up, the conductivity of electrolyte can be affected, thus affects high temperature cyclic performance and the low temperature performance of lithium rechargeable battery.
As can be seen from the contrast of comparative example 1-4, when independent vinylene carbonate (VC) is as additive, along with the increase of vinylene carbonate (VC) mass percentage in non-aqueous organic solvent, the low temperature performance of lithium rechargeable battery runs down.This may be relevant with the double bond structure of vinylene carbonate (VC), its mass percentage in non-aqueous organic solvent is excessive easily causes it on negative pole, form too fine and close SEI film, increase interface impedance, especially when low temperature, very large negative effect can be caused to the deintercalation speed of lithium ion, thus worsen the low temperature performance of lithium rechargeable battery; But vinylene carbonate (VC) is conducive to the high temperature cyclic performance of lithium rechargeable battery, this has higher reduction efficiency due to vinylene carbonate (VC) and can form stable polymer film in negative terminal surface, but too much vinylene carbonate (VC) may cause and produce blocked up SEI film in negative terminal surface, increase interface impedance, vinylene carbonate (VC) is easy in positive pole generation oxidation Decomposition under high voltages simultaneously, too much accessory substance is piled up at positive pole, and then worsens the high temperature cyclic performance of lithium rechargeable battery.
As can be seen from the contrast of comparative example 7-9, embodiment 4 and embodiment 6-7, a certain amount of fluoro-1 with formula I structure, 3-N-morpholinopropanesulfonic acid lactone can show good high temperature cyclic performance and low temperature performance relative to propene sultone (PST) and PS (PS).Possible cause is: the reactivity of propene sultone (PST) is too high, can produce larger one-tenth membrane impedance, when its content is higher to the deterioration of lithium rechargeable battery clearly.PS (PS), although be conducive to the high temperature cyclic performance of lithium rechargeable battery, because it is still comparatively large to the one-tenth membrane impedance of positive pole, therefore causes the low temperature performance of lithium rechargeable battery to worsen.And have in the fluoro-PS of formula I structure and introduce fluorine atom, be conducive to the wettability increasing electrolyte, thus be conducive to the low temperature performance of lithium rechargeable battery; And there is the fluoro-1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone is film forming on the active site of both positive and negative polarity optionally, avoid the violent film formation reaction of propene sultone (PST), and there is the fluoro-1 of formula I structure, 3-N-morpholinopropanesulfonic acid lactone can form stable LiF film-forming components, thus increase the stability of both positive and negative polarity film forming, avoid the excessive decomposition of the lithium-containing compound of follow-up vinylene carbonate (VC) and sulfimide class.
To sum up, when the lithium-containing compound of vinylene carbonate (VC), sulfimide class and the acting in conjunction of fluoro-PS with formula I structure obviously can improve high temperature cyclic performance and the low temperature performance of lithium rechargeable battery.
。
Claims (10)
1. an electrolyte for lithium rechargeable battery, comprising:
Non-aqueous organic solvent;
Lithium salts, is dissolved in non-aqueous organic solvent; And
Additive, is dissolved in non-aqueous organic solvent;
It is characterized in that,
Described additive is the lithium-containing compound LiN (C of vinylene carbonate (VC), sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) (wherein, x, y are positive integer) and there is the fluoro PS of formula I structure;
In formula I, R
1, R
2, R
3independently be selected from fluorine atom separately;
The quality of described vinylene carbonate (VC) is 0.1% ~ 2% of the quality of described non-aqueous organic solvent;
Lithium-containing compound LiN (the C of described sulfimide class
xf
2x+1sO
2) (C
yf
2y+1sO
2) concentration be 0.02M ~ 0.2M;
The described quality with the fluoro PS of formula I structure is 0.5% ~ 5% of the quality of described non-aqueous organic solvent.
2. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, the lithium-containing compound of described sulfimide class is selected from LiN (SO
2cF
3)
2or LiN (SO
2f)
2.
3. the electrolyte of lithium rechargeable battery according to claim 1, it is characterized in that, the described fluoro 1 with formula I structure, 3-N-morpholinopropanesulfonic acid lactone is selected from 1-fluoro-1,3-N-morpholinopropanesulfonic acid lactone (1-FPS), 2-fluoro-1, one in 3-N-morpholinopropanesulfonic acid lactone (2-FPS), the fluoro-PS of 3-(3-FPS).
。
4. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described non-aqueous organic solvent also comprises:
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, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide, methyl sulfide, gamma-butyrolacton, oxolane, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester, containing one or more in unsaturated bond ring-type organic ester.
5. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described lithium salts is selected from LiPF
6, LiBF
4, LiBOB, LiClO
4in one or more.
6. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, the concentration of described lithium salts is 0.9M ~ 1.15M.
7. a lithium rechargeable battery, comprising:
Positive plate;
Negative plate;
Barrier film, is interval between positive plate and negative plate; And
Electrolyte;
It is characterized in that,
Described electrolyte is the electrolyte of the lithium rechargeable battery according to any one of claim 1-6.
8. lithium rechargeable battery according to claim 7, it is characterized in that, described positive plate comprises can be deviate from, accept the material of lithium ion, describedly to deviate from, the material accepting lithium ion is lithium-transition metal composite oxide, described lithium-transition metal composite oxide is lithium transition-metal oxide, lithium transition-metal oxide adds one or more in the compound that other transition metal or nontransition metal obtain, described lithium-transition metal composite oxide is selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, one or more in lithium nickel cobalt aluminum oxide.
9. lithium rechargeable battery according to claim 7, it is characterized in that, described negative plate comprises the material that can accept, deviate from lithium ion, the material describedly to accept, deviate from lithium ion be selected from soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate, can with lithium formed in the metal of alloy one or more.
10. lithium rechargeable battery according to claim 7, is characterized in that, the charge cutoff voltage of lithium rechargeable battery is 3.8V ~ 4.4V.
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