CN106711504A - Lithium secondary battery and electrolyte thereof - Google Patents
Lithium secondary battery and electrolyte thereof Download PDFInfo
- Publication number
- CN106711504A CN106711504A CN201510433628.5A CN201510433628A CN106711504A CN 106711504 A CN106711504 A CN 106711504A CN 201510433628 A CN201510433628 A CN 201510433628A CN 106711504 A CN106711504 A CN 106711504A
- Authority
- CN
- China
- Prior art keywords
- lithium secondary
- lithium
- secondary battery
- electrolyte
- additive
- 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.)
- Granted
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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium secondary battery and electrolyte thereof. The electrolyte comprises a lithium salt, an organic solvent and an additive, wherein the lithium salt is dissolved in the organic solvent; the additive comprises a sulfonyl imide compound with a chemical structural formula shown in a formula I,
Description
Technical field
The invention belongs to lithium secondary battery field, it is more particularly related to a kind of lithium secondary battery and
Its electrolyte.
Background technology
With electronic product, power, the energy storage market demand continuous expansion, people at present it is widely used
The energy density of lithium ion battery proposes requirement higher.In due to the lithium ion battery with graphite as negative pole,
The performance of graphite capacity further improves graphite cathode lithium-ion electric already close to theoretical value (376mAh/g)
The capacity in pond is very difficult, therefore, develop the lithium secondary battery using lithium metal as negative pole and gradually cause section
Grind the concern of worker.However, the obstacle that limitation lithium secondary battery further develops mainly has two aspects：
One is that lithium secondary battery easily produces Li dendrite in cyclic process, causes battery short circuit occur and exists serious
Potential safety hazard；Two is the limitation of electrolyte, i.e., in lithium secondary battery charge and discharge process, its electrode with electricity
Solution liquid reaction is violent, causes that the cycle efficieny of battery is low, and cycle life is short.
On the other hand, people in the industry has found that to effective functional additive is added in electrolyte be to reduce electrolyte
Reactivity, the important channel of raising lithium secondary battery cycle performance between electrode material.According to existing document report
Road, propylene sulfite (being abbreviated as PS), ethylene sulfite (being abbreviated as ES), sulfuric acid vinyl ester (letter
Be written as DTD), many esters additives containing S=O groups such as methane-disulfonic acid methylene ester (MMDS),
Can during circulating battery, lithium secondary battery both positive and negative polarity surface formed by short chain organic sulfonic acid lithium,
The interfacial film of the material compositions such as inorganic lithium sulfite, interfacial film has good performance, advantageously reduces electrolysis
Lasting vigorous reaction between liquid solvent and electrode material, improves the reversible degree of lithium deposition and dissolution, improves electricity
The discharge and recharge coulombic efficiency in pond, improves the cycle performance of battery.
It can be seen that, further the compound of development and searching containing S=O groups, as electrolysis additive, is to improve
One of important channels of performance such as circulation, the safety of the lithium secondary battery with lithium metal as electrode, are also lithium two
One of technological development direction of primary cell electrolyte.
The content of the invention
It is an object of the invention to：A kind of lithium secondary cell electrolyte of use new additive agent is provided, and is carried
For the lithium secondary battery produced using the electrolyte, by the use of additive lithium secondary battery metal
Cathode of lithium surface forms excellent interfacial film, suppresses the continuing vigorous side reaction of electrode active material and electrolyte,
Slow down Li dendrite generation, improve head week coulombic efficiencies, stable circulation performance and the security performance of lithium secondary battery.
In order to realize foregoing invention purpose, the invention provides a kind of lithium secondary cell electrolyte, it includes lithium
Salt, organic solvent and additive, lithium salts dissolve in organic solvent；The additive includes having shown in Formulas I
The sulfonyl imide compounds of chemical structural formula,
In Formulas I, X, Y separately selected from fluorine, chlorine, cyano group, the alkyl that carbon number is 1~10,
Carbon number is 1~10 and contains the hydrocarbon selected from least one of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulphur element
Base.
The carbon number is 1~10 alkyl, be by carbon number 1~10 hydrocarbon molecules on
Lose what any hydrogen atom was formed, the hydrocarbon compound is saturated hydrocarbons or unsaturated hydrocarbons, including but not limited to
Alkane, cycloalkane, alkene, alkynes, aromatic hydrocarbon.
The carbon number is 1~10 and containing selected from least one of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulphur
The alkyl of element, it by carbon number is 1~10 and containing selected from fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulphur to be
Lose what any hydrogen atom was formed on the compound molecule of at least one element：As carbon number contains nitrogen for 1
The hydrogen cyanide of element, loses the itrile group that a hydrogen atom is formed；And for example carbon atom be 2 contain nitrogen and oxygen
The nitroethane of element, loses nitro-ethyl that a hydrogen atom is formed etc..
Preferably, described X, Y are separately 1~8 containing fluoroalkyl selected from F atom, carbon number
Chain, carbon number are one or more in 1~8 fluoroalkoxy chain.
Preferably, sulfonyl imide compounds weight/mass percentage composition in the electrolytic solution is 0.1%~8%.
It is further preferred that sulfonyl imide compounds weight/mass percentage composition in the electrolytic solution is
0.3%~1%.
Preferably, the organic solvent includes ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid
Diethylester, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propionic acid third
Ester, methyl butyrate, ethyl acetate, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N- methyl second
Acid amides, acetonitrile, sulfolane, dimethyl sulfoxide, ethene sulfite, propylene sulfite, methyl sulfide, two
Ethyl-sulfurous acid ester, dimethyl sulfite, tetrahydrofuran, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester
In at least one.
Preferably, organic solvent weight/mass percentage composition in the electrolytic solution is 60%~90%.
Preferably, the lithium salts is selected from least one in organic lithium salt or inorganic lithium salt.
Preferably, the lithium salts is selected from LiPF6、LiBF4、LiTFSI、LiClO4、LiAsF6、LiBOB、
LiDFOB、LiTFOB、LiN(SO2RF)2、LiN(SO2F)(SO2RF) at least one, wherein replacing
Base RF=CnF2n+1, it is saturation perfluoroalkyl, n is 1~10 integer.
Preferably, concentration of the lithium salts in the electrolyte of lithium secondary battery is 0.5mol/L~2mol/L.
It is further preferred that concentration of the lithium salts in the electrolyte of lithium secondary battery is
0.7mol/L~1.3mol/L.
Preferably, the lithium secondary cell electrolyte is made up of non-aqueous organic solvent, lithium salts and additive.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium secondary battery, it include positive plate,
Lithium anode piece, barrier film, the barrier film being interval between positive plate and lithium anode piece, Yi Ji electricity
Solution liquid；The electrolyte is electricity described in any of the above-described paragraph, containing sulfonyl imide compounds additive
Solution liquid.
Preferably, the positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body,
Positive pole diaphragm includes positive electrode active materials, binding agent and conductive agent.
Preferably, the positive electrode active materials are optionally from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2)、
LiFePO4 (LiFePO4), cobalt phosphate lithium (LiCoPO4), lithium manganese phosphate (LiMnPO4), LiNiPO
(LiNiPO4), LiMn2O4 (LiMnO2), binary material LiNixA(1-x)O2(wherein, A be selected from Co,
One kind in Mn, 0<x<1), ternary material LiNimBnC(1-m-n)O2(wherein, B, C independently selected from
At least one in Co, Al, Mn, and B and C differ, 0<m<1,0<n<1) one kind or several in
Kind；But not limited to this.
Preferably, the barrier film can be any diaphragm material used in existing lithium secondary battery, for example
Polyethylene, polypropylene, Kynoar and their multilayer complex films, but it is not limited only to these.
Compared with prior art, the present invention in the electrolyte of lithium secondary battery by adding sulfimide class
Compound, at least generation following beneficial effect：
(1) sulfonyl imide compounds are used in lithium secondary battery as electrolysis additive, can be in electrode table
Face forms the interfacial film of the materials such as fluoride, sulfonic acid lithium salts and polysulfonimides, so as to effectively suppress electrolysis
Continuing vigorous reaction between liquid solvent and lithium metal, positive electrode, slows down the generation of metal Li dendrite, improves
Lithium secondary battery discharge and recharge coulombic efficiency, significantly improves the cycle performance of lithium secondary battery, improves the peace of battery
Quan Xing；
(2) lithium secondary battery obtained by the present invention has excellent cycle performance and capability retention.
(3) lithium secondary battery obtained by the present invention has excellent security.
Specific embodiment
In order that goal of the invention of the invention, technical scheme and technique effect become apparent from, below in conjunction with implementation
Example, the present invention will be described in further detail.It should be appreciated that the embodiment described in this specification
Merely to explaining the present invention, it is not intended to limit the present invention.
Embodiment 1
Positive plate P1#Preparation：By positive electrode active materials cobalt acid lithium (molecular formula LiCoO2), conductive agent it is conductive
Carbon black (Super-P), binding agent polyvinylidene fluoride (being abbreviated as PVDF) are in solvent N-methyl pyrilidone
It is uniformly dispersed in (being abbreviated as NMP), is made anode sizing agent.Solids content is 77wt% in anode sizing agent,
Cobalt acid lithium, the conductive black of the PVDF and 0.84wt% of 0.9wt% comprising 98.26wt% in solid constituent.
Anode sizing agent is uniformly coated on the plus plate current-collecting body aluminium foil that thickness is 12 μm, one side coating amount is
0.0215g/cm2；The disk for a diameter of Φ 12mm is cut out after then being dried at 85 DEG C, it is true at 85 DEG C afterwards
4h is dried under empty condition, gained positive plate is designated as P1#。
Electrolyte L1#Preparation：In drying shed, by ethylene carbonate (being abbreviated as EC) and carbonic acid diethyl
Ester (being abbreviated as DEC) EC by volume:DEC=1:1 ratio is well mixed, and obtains organic solvent.To
Electric conducting lithium salt LiPF is added in organic solvent6With additive N- fluorosulfonyl sulfimides dimer (Formula II),
It is 0.1%, LiPF to obtain additive N- fluorosulfonyl sulfimide dimers weight/mass percentage composition6Concentration is
The solution of 1mol/L, as electrolyte, are designated as L1#；
Lithium secondary battery C1#Preparation：Polypropylene film (Φ 19mm) using 12 μm of thickness as barrier film,
By positive plate P1#, barrier film, lithium anode piece put well in order, barrier film is in the middle of positive/negative plate
Play a part of isolation.Injection electrolyte L1#, CR2030 button cells are assembled into, stand 24h, gained
Lithium secondary battery is designated as C1#.Battery sets as follows：With the constant current charge of 0.2C (1mA) to 4.5V,
Then 0.05C (0.25mA) is dropped to 4.5V constant-voltage charges to electric current, then with 0.2C's (1mA)
Constant current is discharged to 3.0V, repeats discharge and recharge.
Embodiment 2
Electrolyte L2#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 0.3%, gained electrolyte is designated as
L2#。
Lithium secondary battery C2#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L2#, gained lithium secondary battery is designated as C2#。
Embodiment 3
Electrolyte L3#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 0.5%, gained electrolyte is designated as
L3#。
Lithium secondary battery C3#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L3#, gained lithium secondary battery is designated as C3#。
Embodiment 4
Electrolyte L4#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 0.8%, gained electrolyte is designated as
L4#。
Lithium secondary battery C4#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L4#, gained lithium secondary battery is designated as C4#。
Embodiment 5
Electrolyte L5#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 1%, gained electrolyte is designated as L5#。
Lithium secondary battery C5#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L5#, gained lithium secondary battery is designated as C5#。
Embodiment 6
Electrolyte L6#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 3%, gained electrolyte is designated as L6#。
Lithium secondary battery C6#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L6#, gained lithium secondary battery is designated as C6#。
Embodiment 7
Electrolyte L7#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 5%, gained electrolyte is designated as L7#。
Lithium secondary battery C7#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L7#, gained lithium secondary battery is designated as C7#。
Embodiment 8
Electrolyte L8#Preparation：With electrolyte L1#Preparation method it is identical, difference is, additive
It is N- fluorosulfonyl sulfimides dimer (Formula II) of weight/mass percentage composition 8%, gained electrolyte is designated as L8#。
Lithium secondary battery C8#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference is,
Electrolyte changes into L8#, gained lithium secondary battery is designated as C8#。
Embodiment 9~16
Electrolyte L9~16#Preparation：With electrolyte L1~8#Preparation method it is identical, difference is,
Additive N- fluorosulfonyl sulfimides dimer (Formula II) is replaced with into additive N- trifluoromethyl sulphurs successively
Acyl group sulfimide dimer (formula III), gained electrolyte is designated as L9~16 respectively#；
Lithium secondary battery C9~16#Preparation：With lithium secondary battery C1~8#Preparation method it is identical, difference
Place is that electrolyte is changed into L9~16 successively#, gained lithium secondary battery is designated as C9~16 respectively#。
Embodiment 17~24
Electrolyte L17~24#Preparation：With electrolyte L1~8#Preparation method it is identical, difference is,
Additive N- fluorosulfonyl sulfimides dimer (Formula II) is replaced with into additive N- pentafluoroethyl group sulphurs successively
Acyl group sulfimide dimer (formula IV), gained electrolyte is designated as L17~24 respectively#；
Lithium secondary battery C17~24#Preparation：With lithium secondary battery C1~8#Preparation method it is identical, difference
Place is that electrolyte is changed into L17~24 successively#, gained lithium secondary battery is designated as C17~24 respectively#。
Embodiment 25
Positive plate P2#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi0.5Mn1.5O4。
Lithium secondary battery C25#Preparation：With lithium secondary battery C2#Preparation method it is identical, difference exists
In positive plate changes into P2#, gained lithium secondary battery is designated as C25#.Battery sets as follows：With 0.2C (1mA)
Constant current charge to 4.9V, 0.05C (0.25mA) is then dropped to 4.9V constant-voltage charges to electric current,
Then 3.5V is discharged to the constant current of 0.2C (1mA), repeats discharge and recharge.
Embodiment 26
Positive plate P2#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi0.5Mn1.5O4。
Lithium secondary battery C26#Preparation：With lithium secondary battery C25#Preparation method it is identical, difference exists
In additive N- fluorosulfonyl sulfimides dimer (Formula II) replace with additive N- trifluoros in electrolyte
Methyl sulphonyl sulfimide dimer (formula III), gained lithium secondary battery is designated as C26#。
Embodiment 27
Positive plate P2#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi0.5Mn1.5O4。
Lithium secondary battery C27#Preparation：With lithium secondary battery C25#Preparation method it is identical, difference exists
In additive N- fluorosulfonyl sulfimides dimer (Formula II) replace with the fluorine of additive N- five in electrolyte
Ethylsulfonyl sulfimide dimer (formula IV), gained lithium secondary battery is designated as C27#。
Embodiment 28
Positive plate P3#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi1/3Co1/3Mn1/3O2。
Lithium secondary battery C28#Preparation：With lithium secondary battery C2#Preparation method it is identical, difference exists
In positive plate changes into P3#, gained lithium secondary battery is designated as C28#.Battery sets as follows：With 0.2C (1mA)
Constant current charge to 4.6V, 0.05C (0.25mA) is then dropped to 4.6V constant-voltage charges to electric current,
Then 3V is discharged to the constant current of 0.2C (1mA), repeats discharge and recharge.
Embodiment 29
Positive plate P3#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi1/3Co1/3Mn1/3O2。
Lithium secondary battery C29#Preparation：With lithium secondary battery C28#Preparation method it is identical, difference exists
In additive N- fluorosulfonyl sulfimides dimer (Formula II) replace with additive N- trifluoros in electrolyte
Methyl sulphonyl sulfimide dimer (formula III), gained lithium secondary battery is designated as C29#。
Embodiment 30
Positive plate P3#Preparation：With positive plate P1#Preparation method it is identical, difference is, positive pole is lived
Property material be LiNi1/3Co1/3Mn1/3O2。
Lithium secondary battery C30#Preparation：With lithium secondary battery C28#Preparation method it is identical, difference exists
In additive N- fluorosulfonyl sulfimides dimer (Formula II) replace with the fluorine of additive N- five in electrolyte
Ethylsulfonyl sulfimide dimer (formula IV), gained lithium secondary battery is designated as C30#。
Comparative example 1
Electrolyte DL1#Preparation：With electrolyte L1#Preparation method it is identical, difference is, is electrolysed
Additive-free in liquid, gained electrolyte is designated as DL1#。
Lithium secondary battery DC1#Preparation：With lithium secondary battery C1#Preparation method it is identical, difference exists
In electrolyte changes into DL1#, gained lithium secondary battery is designated as DC1#。
Comparative example 2
Electrolyte DL1#Preparation：With electrolyte L1#Preparation method it is identical, difference is, is electrolysed
Additive-free in liquid, gained electrolyte is designated as DL1#。
Lithium secondary battery DC2#Preparation：With lithium secondary battery C25#Preparation method it is identical, difference exists
In electrolyte changes into DL1#, gained lithium secondary battery is designated as DC2#。
Comparative example 3
Electrolyte DL1#Preparation：With electrolyte L1#Preparation method it is identical, difference is, is electrolysed
Additive-free in liquid, gained electrolyte is designated as DL1#。
Lithium secondary battery DC3#Preparation：With lithium secondary battery C28#Preparation method it is identical, difference exists
In electrolyte changes into DL1#, gained lithium secondary battery is designated as DC3#。
To each comparative example of the invention and lithium secondary battery obtained in embodiment carries out following performance test, and will survey
Test result is listed in table 1：
1) efficiency test first：The first week specific discharge capacity (C of efficiency=battery firstd1)/first week charge specific capacity
(Cc1).Test process is：By the battery in embodiment 1~24 and comparative example 1, first week is with 0.2C (1mA)
Constant current charge to 4.5V, after 0.05C (0.25mA) is dropped to 4.5V constant-voltage charges to electric current, obtain
First week charge specific capacity (Cc1)；3.0V is discharged to the constant current of 0.2C (1mA) again, is obtained and is put in first week
Electric specific capacity (Cd1).By the battery in embodiment 25~27 and comparative example 2, first week is with 0.2C (1mA)
Constant current charge to 4.9V, after 0.05C (0.25mA) is dropped to 4.9V constant-voltage charges to electric current, obtain
First week charge specific capacity (Cc1)；3.5V is discharged to the constant current of 0.2C (1mA) again, is obtained and is put in first week
Electric specific capacity (Cd1).By the battery in embodiment 28~30 and comparative example 3, first week is with 0.2C (1mA)
Constant current charge to 4.6V, after 0.05C (0.25mA) is dropped to 4.6V constant-voltage charges to electric current, obtain
First week charge specific capacity (Cc1)；3V is discharged to the constant current of 0.2C (1mA) again, first Zhou Fang electricity is obtained
Specific capacity (Cd1)。
2) capability retention test：Specific discharge capacity (C after capability retention=circulation n weeksdn)/head is put in week
Electric specific capacity (Cd1).Test process is：By the battery in embodiment 1~24 and comparative example 1, first week is with 0.2C
The constant current charge of (1mA) to 4.5V, after 0.05C is dropped to 4.5V constant-voltage charges to electric current
(0.25mA), then 3.0V is discharged to the constant current of 0.2C (1mA), obtain first all specific discharge capacity (Cd1)；
To n-th week, battery discharge specific capacity was designated as C to such repeated chargedn.By embodiment 25~27 and comparative example
Battery in 2, first week with the constant current charge of 0.2C (1mA) to 4.9V, after with 4.9V constant-voltage charges
0.05C (0.25mA) is dropped to electric current, then 3.5V is discharged to the constant current of 0.2C (1mA), obtain first
All specific discharge capacity (Cd1)；To n-th week, battery discharge specific capacity was designated as C to such repeated chargedn.Will
Battery in embodiment 28~30 and comparative example 3, first week with the constant current charge of 0.2C (1mA) to 4.6V,
0.05C (0.25mA) is dropped to 4.6V constant-voltage charges to electric current afterwards, first all charge specific capacity (C are obtainedc1), then
3V is discharged to the constant current of 0.2C (1mA), first all specific discharge capacity (C are obtainedd1)；So fill repeatedly
It is discharged to n-th week, battery discharge specific capacity is designated as Cdn。
Additive and battery performance test result that table 1, each comparative example and embodiment are used
As can be seen from Table 1：
1) the lithium secondary battery C1 prepared using electrolyte of the present invention#~C30#, it is obvious that coulombic efficiency is circulated first
Higher than corresponding identical positive electrode (LiCoO2、LiNi0.5Mn1.5O4、LiNi1/3Co1/3Mn1/3O2) not
Use battery DC1~3 of additive#.The addition of sulfimine compound can in this explanation electrolyte of the present invention
The efficiency first of battery is effectively improved, is conducive to suppressing the loss of battery capacity.
2) lithium secondary battery prepared using electrolyte of the present invention, after certain all numbers are circulated, capacity keeps
Rate is also apparently higher than the battery of corresponding unused additive.With cobalt acid lithium (LiCoO2) as a example by battery, it is right
Battery (DC1 without additive in ratio 1#) decay comparatively fast, reason includes two aspects：One be due to
Continuous deposition/the dissolution of lithium, lithium metal surface produces dendrite, causes the long-term cycle performance reduction of battery, and two are
LiPF during circulating battery6Electrolyte and LiCoO2Positive electrode sustained response.By contrast, the present invention
Lithium secondary battery C1#~C24#After middle addition sulfimine compound is as additive, lithium can be effectively improved
Deposition and the reversible degree of dissolution, slow down the generation of Li dendrite；Simultaneously, additionally it is possible in LiCoO2Positive electrode surface shape
Into good interfacial film, the interfacial film includes the materials such as fluoride, sulfonic acid lithium salts, fluorine-containing polysulfonimides,
Electrolyte and LiCoO can effectively be suppressed2The continuing vigorous reaction of positive electrode, therefore, circulate at room temperature
After 100 weeks, LiCoO2Battery capacity conservation rate is still above 90%.Relative to comparative example (DC2~3#), electricity
After sulfonyl imide compounds being added in solution liquid, LiNi0.5Mn1.5O4And LiNi1/3Co1/3Mn1/3O2Battery system
Also good cycle performance (C25 is shown#~C30#).The lithium secondary battery surface after circulating 200 weeks is observed,
It was found that lithium surface conformance is poor during the battery of additive is not used, surface deposits the lithium of different-thickness, has substantially
Li dendrite exist；And after using sulfimide additive, lithium surface uniformity substantially increases, without obvious lithium
Dendrite is produced.The result also illustrates that sulfimide additive can be obviously improved the surface nature of lithium electrode, profit
In the deposition/dissolution of lithium, the cyclical stability of lithium secondary battery is improve.
3) consumption of sulfimide additive also has a certain impact to the performance of battery in the present invention：Fluorine-containing sulphur
When imide compound additive level is 0.5%, battery room temperature best performance (C3#, C11#, C19#)；
When fluorine-containing sulfimine compound additive concentration is too small (0.1%), electrode surface film forming is not obvious, for a long time
Battery capacity decay is obvious after circulation；And concentration it is too big when (8%), the interface that the material is formed in positive electrode surface
Film can thicken, and system electrolysis fluid viscosity is also larger, so as to influence lithium ion in electrolyte and electrode/electrolyte
Migration in interfacial film, causes cycle performance of battery to be deteriorated (capability retention is substantially reduced).Imines replaces base
(F → C after structure (X, Y) increase2F5), cause electrolysis fluid viscosity to increase, also cause deterioration of cell properties
(C9#~C24#)。
In sum, tradition LiPF is used with existing6The lithium secondary battery of carbonic ester electrolyte is compared, the present invention
Use to sulfimide additive can be obviously improved the room temperature cycles performance of lithium secondary battery, slow down Li dendrite
Generation, improve battery capability retention.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned
Implementation method carries out appropriate change and modification.Therefore, the invention is not limited in disclosed and described above
Some modifications and changes of the invention should also be as falling into the guarantor of claim of the invention by specific embodiment
In the range of shield.Although additionally, having used some specific terms in this specification, these terms are to be
Facilitate explanation, any limitation is not constituted to the present invention.
Claims (10)
1. a kind of lithium secondary cell electrolyte, including lithium salts, organic solvent and additive, lithium salts have been dissolved in
In machine solvent；It is characterized in that：The additive includes the sulfimide class with chemical structural formula shown in Formulas I
Compound,
In Formulas I, X, Y separately selected from fluorine, chlorine, cyano group, the alkyl that carbon number is 1~10,
Carbon number is 1~10 and contains the hydrocarbon selected from least one of fluorine, chlorine, bromine, iodine, nitrogen, oxygen, sulphur element
Base.
2. lithium secondary cell electrolyte according to claim 1, it is characterised in that：In the Formulas I, X,
It 1~8 is 1~8 containing fluoroalkyl chain, carbon number that Y is separately selected from F atom, carbon number
One or more in fluoroalkoxy chain.
3. lithium secondary cell electrolyte according to claim 1, it is characterised in that：The sulfimide
Class compound weight/mass percentage composition in the electrolytic solution is 0.1%~8%.
4. lithium secondary cell electrolyte according to claim 1, it is characterised in that：The sulfimide
Class compound weight/mass percentage composition in the electrolytic solution is 0.3%~1%.
5. lithium secondary cell electrolyte according to claim 1, it is characterised in that：The organic solvent
Including ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid
Methyl ethyl ester, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate,
Acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, sulfolane, diformazan
Sulfoxide, ethene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, sulfurous acid diformazan
At least one in ester, tetrahydrofuran, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester.
6. lithium secondary cell electrolyte according to claim 1, it is characterised in that：The organic solvent
Weight/mass percentage composition in the electrolytic solution is 60%~90%.
7. lithium secondary cell electrolyte according to claim 1, it is characterised in that：The lithium salts is selected from
At least one in organic lithium salt or inorganic lithium salt, its concentration in the electrolyte of lithium secondary battery is
0.5mol/L~2mol/L.
8. lithium secondary cell electrolyte according to claim 7, it is characterised in that：The lithium salts is selected from
LiPF6、LiBF4、LiTFSI、LiClO4、LiAsF6、LiBOB、LiDFOB、LiTFOB、LiN(SO2RF)2、
LiN(SO2F)(SO2RF) at least one, wherein substituent RF=CnF2n+1, it is saturation perfluoroalkyl, n
It is 1~10 integer.
9. a kind of lithium secondary battery, it includes positive plate, lithium anode piece, barrier film, is interval in positive pole
Barrier film between piece and lithium anode piece, and electrolyte；It is characterized in that：The electrolyte is power
Profit requires the electrolyte containing sulfonyl imide compounds additive any one of 1 to 8.
10. lithium secondary battery according to claim 9, it is characterised in that：The positive plate with cobalt acid lithium,
Lithium nickelate, LiFePO4, cobalt phosphate lithium, lithium manganese phosphate, LiNiPO, LiMn2O4, binary material
LiNixA(1-x)O2, ternary material LiNimBnC(1-m-n)O2In one or more as positive electrode active materials；Two
First material LiNixA(1-x)O2In A be selected from Co, Mn in one kind, 0<x<1；Ternary material
LiNimBnC(1-m-n)O2In at least one in Co, Al, Mn of B, C, and B and C
Differ, 0<m<1,0<n<1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510433628.5A CN106711504B (en) | 2015-07-22 | 2015-07-22 | Lithium secondary battery and electrolyte thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510433628.5A CN106711504B (en) | 2015-07-22 | 2015-07-22 | Lithium secondary battery and electrolyte thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106711504A true CN106711504A (en) | 2017-05-24 |
| CN106711504B CN106711504B (en) | 2019-06-25 |
Family
ID=58895266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510433628.5A Active CN106711504B (en) | 2015-07-22 | 2015-07-22 | Lithium secondary battery and electrolyte thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106711504B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311170A (en) * | 2018-03-27 | 2019-10-08 | 丰田自动车株式会社 | Electrolyte and lithium ion battery |
| WO2020015234A1 (en) * | 2018-07-18 | 2020-01-23 | 青海泰丰先行锂能科技有限公司 | Electrolyte for metal lithium secondary battery and metal lithium secondary battery using same |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN111883828A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN111883835A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| WO2020248565A1 (en) * | 2019-06-12 | 2020-12-17 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte for reducing internal resistance of battery and lithium secondary battery |
| WO2021017759A1 (en) * | 2019-07-30 | 2021-02-04 | 宁德时代新能源科技股份有限公司 | Lithium-ion battery and related battery module, battery pack, and device |
| CN112467207A (en) * | 2019-09-09 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN115084648A (en) * | 2022-07-20 | 2022-09-20 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
| CN116960467A (en) * | 2023-09-15 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Battery cell, battery and electricity utilization device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290599A (en) * | 2010-06-18 | 2011-12-21 | 索尼公司 | Noaqueous electrolyte and nonaqueous electrolyte battery |
| CN103004006A (en) * | 2011-07-07 | 2013-03-27 | 住友精化株式会社 | Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device |
| CN103855428A (en) * | 2012-12-04 | 2014-06-11 | 三星Sdi株式会社 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
| EP2768064A1 (en) * | 2013-02-15 | 2014-08-20 | Basf Se | Use of substituted alkynyl sulfonates, carbonates and oxalates as additives in electrolytes of secondary lithium-ion batteries |
| JP2014194866A (en) * | 2013-03-28 | 2014-10-09 | Daikin Ind Ltd | Electrolytic solution, electrochemical device, lithium ion secondary battery, module, and cyclic n-acyl sulfonamide compound |
| CN104393343A (en) * | 2014-12-04 | 2015-03-04 | 张家港市国泰华荣化工新材料有限公司 | Organic silicon electrolyte and lithium ion battery |
-
2015
- 2015-07-22 CN CN201510433628.5A patent/CN106711504B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290599A (en) * | 2010-06-18 | 2011-12-21 | 索尼公司 | Noaqueous electrolyte and nonaqueous electrolyte battery |
| CN103004006A (en) * | 2011-07-07 | 2013-03-27 | 住友精化株式会社 | Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device |
| CN103855428A (en) * | 2012-12-04 | 2014-06-11 | 三星Sdi株式会社 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
| EP2768064A1 (en) * | 2013-02-15 | 2014-08-20 | Basf Se | Use of substituted alkynyl sulfonates, carbonates and oxalates as additives in electrolytes of secondary lithium-ion batteries |
| JP2014194866A (en) * | 2013-03-28 | 2014-10-09 | Daikin Ind Ltd | Electrolytic solution, electrochemical device, lithium ion secondary battery, module, and cyclic n-acyl sulfonamide compound |
| CN104393343A (en) * | 2014-12-04 | 2015-03-04 | 张家港市国泰华荣化工新材料有限公司 | Organic silicon electrolyte and lithium ion battery |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311170B (en) * | 2018-03-27 | 2022-10-25 | 丰田自动车株式会社 | Electrolyte and lithium ion battery |
| CN110311170A (en) * | 2018-03-27 | 2019-10-08 | 丰田自动车株式会社 | Electrolyte and lithium ion battery |
| WO2020015234A1 (en) * | 2018-07-18 | 2020-01-23 | 青海泰丰先行锂能科技有限公司 | Electrolyte for metal lithium secondary battery and metal lithium secondary battery using same |
| WO2020248565A1 (en) * | 2019-06-12 | 2020-12-17 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte for reducing internal resistance of battery and lithium secondary battery |
| WO2021017759A1 (en) * | 2019-07-30 | 2021-02-04 | 宁德时代新能源科技股份有限公司 | Lithium-ion battery and related battery module, battery pack, and device |
| US11888115B2 (en) | 2019-09-09 | 2024-01-30 | Contemporary Amperex Technology Co., Limited | Electrolytic solution and lithium metal battery containing the same, battery module, battery pack, and device |
| CN112467207A (en) * | 2019-09-09 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN113690489A (en) * | 2019-09-09 | 2021-11-23 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN113690489B (en) * | 2019-09-09 | 2022-11-08 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN111883835A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN111883828B (en) * | 2020-07-24 | 2022-12-30 | 香河昆仑新能源材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN111883828A (en) * | 2020-07-24 | 2020-11-03 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN115084648A (en) * | 2022-07-20 | 2022-09-20 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
| CN115084648B (en) * | 2022-07-20 | 2023-12-15 | 中南大学 | Solid electrolyte membrane and lithium metal solid battery |
| CN116960467A (en) * | 2023-09-15 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Battery cell, battery and electricity utilization device |
| CN116960467B (en) * | 2023-09-15 | 2024-02-20 | 宁德时代新能源科技股份有限公司 | Battery cell, battery and electricity utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106711504B (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106711504B (en) | Lithium secondary battery and electrolyte thereof | |
| CN106505249B (en) | Lithium ion battery electrolyte and lithium ion battery containing same | |
| JP6163189B2 (en) | Electrolyte additive and its application | |
| CN106356561B (en) | Overcharge-preventing electrolyte and lithium ion battery | |
| CN102983361B (en) | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same | |
| CN106558732B (en) | A kind of lithium-ion battery electrolytes and lithium ion battery | |
| CN104766995A (en) | Electrolyte additive and application thereof in lithium ion battery | |
| US20190214680A1 (en) | Lithium ion battery and electrolytic soluton thereof | |
| CN109904521A (en) | Electrolyte and battery comprising same | |
| CN107591557B (en) | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte | |
| CN105580193A (en) | Nonaqueous liquid electrolyte for use in secondary battery, and lithium-ion secondary battery | |
| CN107666007B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN104852087A (en) | Electrolyte additive and lithium ion battery using the same | |
| CN103682443A (en) | Lithium ion battery electrolyte containing LiFSI | |
| CN109994776B (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN104466247A (en) | Nonaqueous electrolyte and lithium ion battery utilizing same | |
| CN109326823A (en) | Non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| WO2023124604A1 (en) | Secondary battery | |
| CN106299472A (en) | A kind of high security lithium ion battery electrolyte and application thereof | |
| CN112216870A (en) | High-temperature-resistant high-voltage electrolyte of high-nickel lithium ion battery | |
| WO2013097596A1 (en) | Lithium ion secondary battery and electrolyte therefor and use of amide compound therein | |
| CN103794819A (en) | Nonaqueous electrolyte containing sulfonyl fluoride imidogen lithium salt as well as application of electrolyte | |
| CN105580188A (en) | Monaqueous liquid electrolyte for use in secondary battery, and lithium-ion secondary battery | |
| CN108390098A (en) | A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries | |
| CN105336983A (en) | Non-aqueous electrolyte and lithium ion battery adopting same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |