CN103715459B - Lithium rechargeable battery and electrolyte thereof - Google Patents
Lithium rechargeable battery and electrolyte thereof Download PDFInfo
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- CN103715459B CN103715459B CN201310722414.0A CN201310722414A CN103715459B CN 103715459 B CN103715459 B CN 103715459B CN 201310722414 A CN201310722414 A CN 201310722414A CN 103715459 B CN103715459 B CN 103715459B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a kind of lithium rechargeable battery and electrolyte thereof.Described electrolyte of lithium-ion secondary battery comprises lithium salts; Non-aqueous organic solvent; And additive.Described additive contains at least one in the compound with general formula (1) structure; R in general formula (1)
1, R
2separately be expressed as general formula (2), R
3for the alkyl of hydrogen or C1 ~ C3; R in general formula (2)
4, R
5separately be expressed as the alkyl of hydrogen or C1 ~ C3, wherein n is the natural number in 0 to 2.Also vinylene carbonate (VC) can be contained in described additive.Described lithium rechargeable battery comprises positive plate; Negative plate; Barrier film, is interval between adjacent positive sheet and negative plate; And above-mentioned electrolyte.Lithium rechargeable battery of the present invention had both had good coulombic efficiency first, cycle performance, had again good low temperature charging performance.
Description
Technical field
The present invention relates to field of batteries, particularly relate to a kind of lithium rechargeable battery and electrolyte thereof.
Background technology
Lithium rechargeable battery has that operating voltage is high, the life-span is long and the advantage such as charging rate is fast, and expands to the field such as electric bicycle, electric automobile gradually.Along with deepening continuously of the lithium rechargeable battery marketization, the expectation of people to lithium rechargeable battery is more and more higher.Current commercial lithium rechargeable battery has been difficult to the needs meeting practical application.
Research shows that graphite material surface exists some irregular structures, plays catalytic action to the irreversible decomposition of electrolyte, and the chemical property that result in graphite material is degenerated, and has a strong impact on the performance of lithium rechargeable battery.The graphite of high-specific surface area has more chemical reactivity point, in charge and discharge process, graphite cathode and electrolyte interface can form one deck solid electrolytic liquid interface film (SEI film), because the reaction interface increase of graphite and electrolyte is more tending towards labile state.Therefore, the character of SEI film determines the chemical property of lithium rechargeable battery to a great extent.
A small amount of material is added in electrolyte of lithium-ion secondary battery, these materials can SEI film that preferentially reduction decomposition forming property is excellent on graphite cathode, it can effectively suppress solvent molecule (carbonate-based solvent) at the last decomposition of electrode surface, thus improves the performance of lithium rechargeable battery.
Additive conventional is at present cyclic sulfite derivative, as ethylene sulfite (ES) etc., due to the existence of central sulfur atoms, reproducibility at graphite cathode interface is stronger than corresponding carbonate-based solvent, apparently higher than the inlay current potential of solvation lithium ion, prior to carbonate-based solvent at graphite cathode surface reduction, form stable SEI film, obvious suppression solvation lithium ion embeds graphite layers altogether, improves the cycle performance of lithium rechargeable battery.But also there is following deficiency when being applied to electrolyte of lithium-ion secondary battery in this compounds: the SEI membrane stability formed at graphite cathode interface is poor, along with the increase of cycle-index, electrode-interface resistance raises gradually, the ohmic polarization phenomenon of lithium rechargeable battery is more and more serious, thus causes the reversible capacity of electrode to reduce rapidly.
Add vinylene carbonate (VC) in the electrolytic solution, also can improve coulombic efficiency first and the cycle performance of lithium rechargeable battery.But adding VC can form fine and close SEI film in negative terminal surface, and its impedance is comparatively large, can worsen lithium rechargeable battery charging performance under cryogenic.
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 has good coulombic efficiency first, cycle performance and low temperature charging performance simultaneously.
In order to realize foregoing invention object, in a first aspect of the present invention, the invention provides a kind of electrolyte of lithium-ion secondary battery, it comprises: lithium salts; Non-aqueous organic solvent; And additive.Described additive contains at least one in the compound with general formula (1) structure; R in general formula (1)
1, R
2separately be expressed as general formula (2), R
3for the alkyl of hydrogen or C1 ~ C3; R in general formula (2)
4, R
5separately be expressed as the alkyl of hydrogen or C1 ~ C3, wherein n is the natural number in 0 to 2,
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 adjacent positive sheet and negative plate; And electrolyte.Wherein, described electrolyte is electrolyte according to a first aspect of the present invention.
Relative to prior art, beneficial effect of the present invention is:
The lithium rechargeable battery adding the compound with general formula (1) structure had both had good coulombic efficiency first, cycle performance, had again good low temperature charging performance.
Embodiment
The following detailed description of lithium rechargeable battery according to the present invention and electrolyte and its preparation method thereof.
First illustrate that electrolyte of lithium-ion secondary battery according to a first aspect of the present invention comprises: lithium salts; Non-aqueous organic solvent; And additive.Described additive contains at least one in the compound with general formula (1) structure; R in general formula (1)
1, R
2separately be expressed as general formula (2), R
3for the alkyl of hydrogen or C1 ~ C3; R in general formula (2)
4, R
5separately be expressed as the alkyl of hydrogen or C1 ~ C3, wherein n is the natural number in 0 to 2,
The compound with general formula (1) structure is joined in electrolyte of lithium-ion secondary battery, obviously can improve coulombic efficiency first and the cycle performance of lithium rechargeable battery, this is that compound owing to having general formula (1) structure also can form SEI film in negative terminal surface as ES or VC, prevent non-aqueous organic solvent to decompose in the redox of negative terminal surface, thus improve coulombic efficiency first and the cycle performance of lithium rechargeable battery.Compared with ES, the SEI film that the SEI film that the compound with general formula (1) structure is formed is formed than ES is more stable, makes lithium rechargeable battery have good cycle performance; Compared with VC, the SEI film that the compound with general formula (1) structure is formed has lower impedance, makes lithium rechargeable battery have good low temperature charging performance.
The compound in electrolyte of lithium-ion secondary battery with general formula (1) structure can have precedence over non-aqueous organic solvent and form SEI film on negative material surface, due to containing C=C functional group, the polymer film of certain molecular weight can be formed, add the stability of SEI film, and due to containing sulfurous acid functional group, formed SEI film is had and good leads ionic nature.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, preferably, described additive contains at least one in the compound with general formula (3) structure, R in general formula (3)
1, R
2separately be expressed as general formula (4), wherein n is the natural number in 0 to 2.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, more preferably, described additive contains at least one in the compound with general formula (5), general formula (6) or general formula (7) structure.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, described in there is general formula (1) structure the mass percentage of compound in electrolyte of lithium-ion secondary battery can be 0.1% ~ 10.0%, be preferably 0.3% ~ 3.0%.If the compounds content in electrolyte with general formula (1) structure is too much, then there is C=C in the compound of general formula (1) structure and form blocked up passivating film by polymerization, cause the impedance of lithium rechargeable battery to become large, affect the cycle performance of lithium rechargeable battery; If the compounds content in electrolyte with general formula (1) structure is very few, then there is C=C in the compound of general formula (1) structure and can not form effectively fine and close passivating film, effectively can not stop the reaction of electrolyte and pole piece, thus effectively can not improve the cycle performance of lithium rechargeable battery.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, described non-aqueous organic solvent can comprise the combination of cyclic carbonate and linear carbonate.Cyclic carbonate has higher dielectric constant, can very well and lithium ion form solvation lithium ion molecule; Linear carbonates has lower viscosity, is beneficial to the conduction of ion, can improve the cryogenic property of electrolyte.Described cyclic carbonate can comprise at least one in ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL) and butylene (BC); Described linear carbonate can comprise at least one in dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC) and ethyl propyl carbonic acid ester (EPC).
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, the mass percentage of described cyclic carbonate in electrolyte of lithium-ion secondary battery can be 10% ~ 70%; The mass percentage of described linear carbonate in electrolyte of lithium-ion secondary battery can be 15% ~ 80%.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, described lithium salts can comprise LiN(C
xf
2x+1sO
2) (C
yf
2y+1sO
2), LiPF
6, LiBF
4, LiBOB, LiAsF
6, Li(CF
3sO
2)
2n, LiCF
3sO
3and LiClO
4in at least one, wherein, x, y are natural number.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, described lithium salt can be 0.5M ~ 2M.
In electrolyte of lithium-ion secondary battery according to a first aspect of the present invention, described additive is also containing vinylene carbonate (VC).When the compound with general formula (1) structure uses together with VC, because the compound with general formula (1) structure has higher reduction potential, preferentially can form the lower SEI film of a layer impedance in negative terminal surface, then VC forms one deck SEI film again on the basis of the SEI film formed by the compound with general formula (1) structure, the composite S EI film that VC and the compound with general formula (1) structure are formed is more stable, to prevent in electrolyte non-aqueous organic solvent and additive in the further reduction reaction of negative terminal surface.Preferably, the described mass percentage of compound in electrolyte of lithium-ion secondary battery with general formula (1) structure can be 0.2% ~ 3.0%, and described vinylene carbonate (VC) mass percentage in electrolyte of lithium-ion secondary battery can be 0.2% ~ 2.0%.
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 comprises: positive plate; Negative plate; Barrier film, is interval between adjacent positive sheet and negative plate; And electrolyte.Wherein, described electrolyte is electrolyte according to a first aspect of the present invention.
Following explanation is according to the embodiment of lithium rechargeable battery of the present invention and electrolyte and its preparation method thereof and comparative example.
Embodiment 1
(1) preparation of the positive plate of lithium rechargeable battery
By active material cobalt acid lithium, conductive agent Super-P, bonding agent PVDF in mass ratio 96:2.0:2.0 join in solvent N-methyl pyrilidone (NMP) to mix and make anode sizing agent, be coated on by anode sizing agent in current collector aluminum foil, its coating weight is 0.0194g/cm
2, cold pressing after drying at 85 DEG C; Then after carrying out trimming, cut-parts, itemize, then dry 4 hours under 85 DEG C of vacuum conditions, soldering polar ear, makes the positive plate of lithium rechargeable battery.
(2) preparation of the negative plate of lithium rechargeable battery
By active material graphite, conductive agent Super-P, thickener CMC, bonding agent SBR in mass ratio 96.5:1.0:1.0:1.5 join in solvent deionized water to mix and make cathode size, being coated on by cathode size on copper foil of affluxion body and drying at 85 DEG C, coating weight is 0.0089g/cm
2; Then after carrying out trimming, cut-parts, itemize, then dry 4 hours under 110 DEG C of vacuum conditions, soldering polar ear, makes the negative plate of lithium rechargeable battery.
(3) preparation of the electrolyte of lithium rechargeable battery
Electrolyte of lithium-ion secondary battery take concentration as 1M lithium hexafluoro phosphate (LiPF
6) be lithium salts, with the mixture of ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) for non-aqueous organic solvent, the mass ratio of each carbonic ester is EC:PC:DEC=30:30:40.In addition, the additive with the compound of general formula (5) structure that mass percentage is 1.0% is also contained in electrolyte.
(4) preparation of lithium rechargeable battery
The positive plate of the lithium rechargeable battery prepared according to step (1) and step (2), negative plate and barrier film polyethylene (PE) are made into through winding process thickness is 4.2mm, width is 34mm, length is the lithium rechargeable battery of 82mm, vacuum bakeout 10 hours at 75 DEG C, implantation step (3) prepare electrolyte, leave standstill after 24 hours, with 0.1C(160mA) constant current charge to 4.2V, then drop to 0.05C(80mA with 4.2V constant voltage charge to electric current); Then with 0.1C(160mA) be discharged to 3.0V, repeat 2 discharge and recharges, finally again with 0.1C(160mA) and battery is charged to 3.85V, complete the making of lithium rechargeable battery.
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, additive to be mass percentage be 1.0% the compound with general formula (6) structure.
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, additive to be mass percentage be 1.0% the compound with general formula (7) structure.
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, additive to be mass percentage be 0.1% the compound with general formula (5) structure.
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, additive to be mass percentage be 10.0% the compound with general formula (5) structure.
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, additive to be mass percentage be 0.3% the compound with general formula (5) structure.
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, additive to be mass percentage be 5.0% the compound with general formula (5) structure.
Embodiment 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, additive to be mass percentage be 2.0% the compound with general formula (5) structure.
Embodiment 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, additive to be mass percentage be 3.0% the compound with general formula (5) structure.
Embodiment 10
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.2% the compound with general formula (5) structure and mass percentage be the VC of 0.8%.
Embodiment 11
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.4% the compound with general formula (5) structure and mass percentage be the VC of 0.6%.
Embodiment 12
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.5% the compound with general formula (5) structure and mass percentage be the VC of 0.5%.
Embodiment 13
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.6% the compound with general formula (5) structure and mass percentage be the VC of 0.4%.
Embodiment 14
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.8% the compound with general formula (5) structure and mass percentage be the VC of 0.2%.
Embodiment 15
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 1.0% the compound with general formula (5) structure and mass percentage be the VC of 0.5%.
Embodiment 16
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 2.0% the compound with general formula (5) structure and mass percentage be the VC of 0.5%.
Embodiment 17
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 3.0% the compound with general formula (5) structure and mass percentage be the VC of 0.5%.
Embodiment 18
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 1.0% the compound with general formula (5) structure and mass percentage be the VC of 1.0%.
Embodiment 19
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 2.0% the compound with general formula (5) structure and mass percentage be the VC of 1.0%.
Embodiment 20
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 1.0% the compound with general formula (5) structure and mass percentage be the VC of 0.2%.
Embodiment 21
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 1.0% the compound with general formula (5) structure and mass percentage be the VC of 2.0%.
Embodiment 22
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.2% the compound with general formula (6) structure and mass percentage be the VC of 0.5%.
Embodiment 23
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.5% the compound with general formula (6) structure and mass percentage be the VC of 0.5%.
Embodiment 24
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 3.0% the compound with general formula (6) structure and mass percentage be the VC of 0.5%.
Embodiment 25
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.2% the compound with general formula (7) structure and mass percentage be the VC of 0.5%.
Embodiment 26
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 0.5% the compound with general formula (7) structure and mass percentage be the VC of 0.5%.
Embodiment 27
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive to be mass percentage be 3.0% the compound with general formula (7) structure and mass percentage be the VC of 0.5%.
Comparative example 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, does not add any additive.
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, additive to be mass percentage be 1.0% VC.
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, additive to be mass percentage be 3.0% VC.
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, additive to be mass percentage be 1.0% ES.
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, additive to be mass percentage be 3.0% ES.
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, additive to be mass percentage be 0.5% VC.
Finally provide the performance test process based on the lithium rechargeable battery of embodiment 1-27 and comparative example 1-6 and test result.
(1) coulombic efficiency test first
First with 0.1C(160mA) constant current 4.2V is charged to lithium rechargeable battery, be less than 0.05C(80mA at 4.2V constant-potential charge to electric current further), obtain initial charge capacity; Then with 0.5C(800mA) constant current 3.0V is discharged to lithium rechargeable battery, obtain discharge capacity first.
Evaluate its coulombic efficiency first by the discharge capacity first of lithium rechargeable battery and the ratio of initial charge capacity, coulombic efficiency is calculated as follows first:
Coulombic efficiency (%) first=(discharge capacity first/initial charge capacity) × 100%
(2) cycle performance test
First with 0.7C(1120mA under 25 DEG C and 45 DEG C of conditions) constant current 4.2V is charged to lithium rechargeable battery, be less than 0.05C(80mA at 4.2V constant-potential charge to electric current further), then with 0.5C(800mA) constant current 3.0V is discharged to lithium rechargeable battery.Current discharge capacity is first time cyclic discharge capacity.Lithium rechargeable battery carries out cycle charge discharge electrical testing in a manner described, gets the discharge capacity of the 400th circulation.
Carry out its high temperature cyclic performance of par by the capability retention of lithium rechargeable battery, capability retention is calculated as follows:
Capability retention (%)=[discharge capacity of the discharge capacity/first time circulation of the 400th circulation] × 100%
(3) low temperature charging performance test
First with 0.35C(560mA under 10 DEG C of conditions) constant current 4.2V is charged to lithium rechargeable battery, be less than 0.05C(80mA at 4.2V constant-potential charge to electric current further), then with 0.5C(800mA) constant current 3.0V is discharged to lithium rechargeable battery.Through 10 circulation after, with 0.35C(560mA) constant current 4.2V is charged to lithium rechargeable battery, be less than 0.05C(80mA at 4.2V constant-potential charge to electric current further).Under the anhydrous condition of drying, lithium rechargeable battery is taken apart, observes the negative plate of lithium rechargeable battery, with superficial white or or grey number (lithium metal is in the precipitation of negative terminal surface) evaluate the low temperature charging performance of lithium rechargeable battery.Surface is in golden yellow (without white or gray area) for best, and now lithium metal is separated out is 0; Surface is white or gray area is completely the poorest, and now lithium metal is separated out is 100%.
Next the performance test results of lithium rechargeable battery is analyzed.
Table 1 provides parameter based on embodiment 1-27 and comparative example 1-6 and the performance test results.
(1) test result analysis of coulombic efficiency first
Any additive is not added from embodiment 1-9 and comparative example 1(, coulombic efficiency is 70.1% first) contrast in can find out, in electrolyte of lithium-ion secondary battery, with the addition of the lithium rechargeable battery with general formula (1) structural compounds effectively can improve its coulombic efficiency first.
As can be seen from the contrast of embodiment 1, embodiment 4-9 and comparative example 1, in electrolyte of lithium-ion secondary battery, with the addition of the coulombic efficiency first that general formula (5) significantly improves lithium rechargeable battery; And increase along with the content of general formula (5), the coulombic efficiency first of lithium rechargeable battery first increases, and when the content of general formula (5) reaches 3.0%, the coulombic efficiency first of lithium rechargeable battery is the highest; Content along with general formula (5) continues to increase, the coulombic efficiency first of lithium rechargeable battery starts to decline, when the content of general formula (5) is increased to 10.0%, worsen the coulombic efficiency first of lithium rechargeable battery, but do not add any additive compared to comparative example 1(, coulombic efficiency is 70.1% first), still improve the coulombic efficiency first of lithium rechargeable battery.This is because general formula (5) preferentially can form one deck SEI film in negative terminal surface, prevents the further reduction reaction of non-aqueous organic solvent, so improve the coulombic efficiency first of lithium rechargeable battery; But when the content of general formula (5) is increased to a certain degree (10.0%, embodiment 5), general formula (5) can form thicker SEI film in negative terminal surface, reduce leading of SEI film ionic, when causing the coulombic efficiency first of lithium rechargeable battery to be 3.0% than general formula (5) content, the coulombic efficiency first of (embodiment 9) is low.
As can be seen from the contrast of embodiment 1-3, comparative example 2 and comparative example 4, in electrolyte of lithium-ion secondary battery, with the addition of 1.0% compound with general formula (1) structure and the VC that with the addition of 1.0% in electrolyte of lithium-ion secondary battery compare with the ES that with the addition of 1.0% in electrolyte of lithium-ion secondary battery all there is higher coulombic efficiency first.As can be seen from the contrast of embodiment 9, comparative example 3 and comparative example 5 also, the general formula (5) that with the addition of 3.0% in electrolyte of lithium-ion secondary battery has obviously higher coulombic efficiency first than the VC that with the addition of 3.0% in electrolyte of lithium-ion secondary battery and the ES that with the addition of 3.0% in electrolyte of lithium-ion secondary battery.
As can be seen from the contrast of embodiment 10-27: the coulombic efficiency first that with the addition of the lithium rechargeable battery of additive package in electrolyte of lithium-ion secondary battery is improved, its first coulombic efficiency all reach more than 89%.
As can be seen from the contrast of embodiment 1 and embodiment 10-14, the additive package that with the addition of general formula (5) and VC in electrolyte of lithium-ion secondary battery improves the coulombic efficiency first of lithium rechargeable battery compared to the general formula (5) (embodiment 1) that with the addition of separately 1.0%.In contrasting as can be seen from embodiment 10-14 and comparative example 2, the additive package ratio adding general formula (5) and VC in electrolyte of lithium-ion secondary battery is used alone 1.0%VC(comparative example 2) there is higher coulombic efficiency first.This is because when being used alone general formula (5), general formula (5) can form SEI film in negative terminal surface, but the SEI film formed is fine and close not, cause non-aqueous organic solvent and additive can continue, in negative terminal surface reduction, to make the coulombic efficiency first of lithium rechargeable battery excellent not; Diversion of the SEI film formed when being used alone VC is poor, and the efficiency first of lithium rechargeable battery also can be caused excellent not; When by general formula (5) and VC uses together time, because general formula (5) has higher reduction potential, preferentially can form the lower SEI film of a layer impedance in negative terminal surface, then VC forms one deck SEI film again on the basis of the SEI film formed by general formula (5), the composite S EI film that VC and general formula (5) are formed is more stable, prevent general formula (5) and VC in the further reduction reaction of negative terminal surface, so lithium rechargeable battery has higher coulombic efficiency first.
As can be seen from the contrast of comparative example 2, comparative example 3 and comparative example 6, the VC adding 1.0% in electrolyte of lithium-ion secondary battery has higher coulombic efficiency first than the VC of interpolation 0.5%, but reduces the coulombic efficiency first of lithium rechargeable battery on the contrary as the VC of interpolation 3.0%.This is because the content along with VC increases, and cause more VC to form thicker SEI film in negative terminal surface reduction, and the SEI film formed has larger impedance, causes the coulombic efficiency first of lithium rechargeable battery to decline.
As can be seen from the contrast of embodiment 12, embodiment 15-17 and comparative example 6, the additive package adding the general formula (5) of 0.5% ~ 3.0% and the VC of 0.5% in electrolyte of lithium-ion secondary battery has higher coulombic efficiency first than the VC being used alone 0.5%; When the content of general formula (5) is less (embodiment 12), the coulombic efficiency first of lithium rechargeable battery is higher; Along with the content of general formula (5) increases, the coulombic efficiency first of lithium rechargeable battery starts to reduce.Equally, from the contrast of embodiment 18, embodiment 19 and comparative example 2, also similar result can be seen.
As can be seen from the contrast of embodiment 22-24 and comparative example 6, the additive package adding the general formula (6) of 0.2% ~ 3.0% and the VC of 0.5% in electrolyte of lithium-ion secondary battery has higher coulombic efficiency first than the VC being used alone 0.5%; When the content of general formula (6) is less, the coulombic efficiency first of lithium rechargeable battery increases along with the content increase of general formula (6); But when the content of general formula (6) is more, the coulombic efficiency first of lithium rechargeable battery starts to reduce.Equally, from the contrast of embodiment 25-27 and comparative example 6, also similar result can be seen.
As can be seen from the contrast of embodiment 2-3, embodiment 23 and embodiment 26, with the addition of in electrolyte of lithium-ion secondary battery general formula (6) or general formula (7) compare with the additive package of VC independent 1.0% general formula (6) or general formula (7) improve the coulombic efficiency first of lithium rechargeable battery.
(2) test result analysis of cycle performance
Any additive is not added from embodiment 1-9 and comparative example 1(, 25 DEG C of capability retentions are 56%, 45 DEG C of capability retentions are 42%) contrast in can find out, in electrolyte of lithium-ion secondary battery, with the addition of the lithium rechargeable battery with general formula (1) structural compounds can effectively improve its cycle performance.
As can be seen from the contrast of embodiment 1, embodiment 4-9 and comparative example 1, in electrolyte of lithium-ion secondary battery, with the addition of the cycle performance that general formula (5) obviously improves lithium rechargeable battery; And increase along with the content of general formula (5), the capability retention of lithium rechargeable battery first increases, and when the content of general formula (5) reaches 2.0% (when at 45 DEG C, content reaches 3.0%), the capability retention of lithium rechargeable battery is the highest; Content along with general formula (5) continues to increase, the capability retention of lithium rechargeable battery starts to decline, and when the content of general formula (5) is increased to 10.0%, has worsened the cycle performance of lithium rechargeable battery, but compare comparative example 1, still improve the cycle performance of lithium rechargeable battery.This is because general formula (5) preferentially can form one deck SEI film in negative terminal surface, prevents the reduction reaction of non-aqueous organic solvent and negative plate, so improve the cycle performance of lithium rechargeable battery; But when the content of general formula (5) is increased to a certain degree (10%, embodiment 5), general formula (5) can form thicker SEI film in negative terminal surface, reduces leading of SEI film ionic, be degrading the interface performance of negative plate and electrolyte, cause the cycle performance of lithium rechargeable battery to be deteriorated.
As can be seen from the contrast of embodiment 1-3, comparative example 2 and comparative example 4, the VC that with the addition of 1.0% general formula (5), general formula (6) or general formula (7) and with the addition of 1.0% in electrolyte of lithium-ion secondary battery in electrolyte of lithium-ion secondary battery has suitable cycle performance (for slightly poor at 45 DEG C); But than the ES that with the addition of 1.0% in electrolyte of lithium-ion secondary battery, there is better cycle performance.Equally, comparative example 9, comparative example 3 and comparative example 5 can be found out, the VC that with the addition of 3.0% general formula (5) and with the addition of 3.0% in electrolyte of lithium-ion secondary battery in electrolyte of lithium-ion secondary battery has suitable cycle performance (being better at 25 DEG C); But than the ES that with the addition of 3.0% in electrolyte of lithium-ion secondary battery, there is better cycle performance.
As can be seen from the contrast of embodiment 10-27, the cycle performance that with the addition of the lithium rechargeable battery of additive package in electrolyte of lithium-ion secondary battery is better, capability retention at its 25 DEG C reaches more than 87%, and the capability retention at 45 DEG C also reaches more than 80%.
As can be seen from the contrast of embodiment 1 and embodiment 10-14, the additive package that with the addition of general formula (5) and VC in electrolyte of lithium-ion secondary battery significantly improves the cycle performance of lithium rechargeable battery compared to independent 1.0% general formula (5) (embodiment 1).As can be seen from the contrast of embodiment 10-14 and comparative example 2, the additive package ratio adding general formula (5) and VC in electrolyte of lithium-ion secondary battery is used alone 1.0%VC(comparative example 2) there is better cycle performance on the whole.This be due to when by general formula (5) and VC uses together time, general formula (5) is owing to having higher reduction potential, preferentially can form the lower SEI film of a layer impedance in negative terminal surface, then VC forms one deck SEI film again on the basis of the SEI film formed by general formula (5), the composite S EI film that VC and general formula (5) are formed is more stable, prevent non-aqueous organic solvent in the further reduction reaction of negative terminal surface, improve the cycle performance of lithium rechargeable battery; And when being used alone general formula (5), also can form SEI film in negative terminal surface, but the SEI film formed is fine and close not, causes non-aqueous organic solvent and additive can continue in negative terminal surface reduction, makes the cycle performance of lithium rechargeable battery not be enough excellent; And diversion of the SEI film formed when being used alone VC is poor, the cycle performance of lithium rechargeable battery also can be caused excellent not.
As can be seen from the contrast of comparative example 2, comparative example 3 and comparative example 6, the VC adding 1.0% in electrolyte of lithium-ion secondary battery has better cycle performance than the VC of interpolation 0.5%, but is degrading the cycle performance (not occurring at 45 DEG C declining) of lithium rechargeable battery on the contrary as the VC of interpolation 3.0%.
As can be seen from the contrast of embodiment 12, embodiment 15-17 and comparative example 6, the additive package adding the general formula (5) of 0.5% ~ 3.0% and the VC of 0.5% in electrolyte of lithium-ion secondary battery has better cycle performance than the VC being used alone 0.5%.Equally, from the contrast of embodiment 18, embodiment 19 and comparative example 2, also similar result can be seen.
As can be seen from the contrast of embodiment 22-24 and comparative example 6, the additive package adding the general formula (6) of 0.2% ~ 3.0% and the VC of 0.5% in electrolyte of lithium-ion secondary battery has better cycle performance than the VC being used alone 0.5%; When the content of general formula (6) is less, the capability retention of lithium rechargeable battery increases along with the content increase of general formula (6); But when the content of general formula (6) is more, the capability retention of lithium rechargeable battery starts to decline.Equally, from the contrast of embodiment 25-27 and comparative example 6, also similar result can be seen.
As can be seen from the contrast of embodiment 2-3, embodiment 23 and embodiment 26, with the addition of in electrolyte of lithium-ion secondary battery general formula (6) or general formula (7) compare with the additive package of VC independent 1.0% general formula (6) or general formula (7) significantly improve the cycle performance of lithium rechargeable battery.
(3) test result analysis of low temperature charging performance
As can be seen from the contrast of embodiment 1, embodiment 4-9, when the content of general formula (5) is less, the low temperature charging performance of lithium rechargeable battery is better; When the content of general formula (5) is more than 5.0%, the low temperature charging performance of lithium rechargeable battery starts to be deteriorated; When the content of general formula (5) reaches 10.0%, lithium metal is separated out completely, reaches 100%.
As can be seen from the contrast of embodiment 1-3, comparative example 2, in electrolyte of lithium-ion secondary battery, with the addition of 1.0% general formula (5), general formula (6) or general formula (7), than the lithium rechargeable battery of the VC that with the addition of 1.0% in electrolyte of lithium-ion secondary battery, there is better low temperature charging performance.Equally, as can be seen from the contrast of embodiment 9 and comparative example 3, in electrolyte of lithium-ion secondary battery, with the addition of 3.0% general formula (5) compare with the VC that with the addition of 3.0% in electrolyte of lithium-ion secondary battery, significantly improve the low temperature charging performance of lithium rechargeable battery.
As can be seen from the contrast of embodiment 10-27, the low temperature charging performance that with the addition of the lithium rechargeable battery of additive package in electrolyte of lithium-ion secondary battery is better overall.
As can be seen from the contrast of embodiment 10-14 and comparative example 2, the additive package adding general formula (5) and VC in electrolyte of lithium-ion secondary battery be used alone 1.0%VC(comparative example 2) compare, significantly improve the low temperature charging performance of lithium rechargeable battery.This be due to when by general formula (5) and VC uses together time, general formula (5) is owing to having higher reduction potential, preferentially can form the lower SEI film of a layer impedance in negative terminal surface, then VC forms one deck SEI film again on the basis of the SEI film formed by general formula (5), the composite S EI film that VC and general formula (5) are formed is more stable, prevent non-aqueous organic solvent in the further reduction reaction of negative terminal surface, make the interface impedance of negative plate and electrolyte lower, lithium rechargeable battery there is good low temperature charging performance; And when being used alone general formula (5), also SEI film can be formed in negative terminal surface, but the SEI film formed is fine and close not, cause non-aqueous organic solvent and additive can continue to reduce in negative terminal surface, make the interface impedance of negative plate and electrolyte comparatively large, the low temperature charging performance of lithium rechargeable battery is poor; And diversion of the SEI film formed when being used alone VC is poor, the low temperature charging performance of lithium rechargeable battery also can be caused poor.
As can be seen from the contrast of embodiment 18, embodiment 19 and comparative example 2, general formula (5) is added on the VC basis containing more amount again, lithium rechargeable battery low temperature charging performance can be improved at electrolyte of lithium-ion secondary battery.
As can be seen from the contrast of comparative example 2, comparative example 3 and comparative example 6, VC is used alone in electrolyte of lithium-ion secondary battery, when use amount is less (0.5%VC, comparative example 6), the good cycle when cycle performance of lithium rechargeable battery does not have comparative example 2 to use 1.0%VC; But when using 1.0%VC time (comparative example 2) or more (comparative example 3), the low temperature charging performance of lithium rechargeable battery is poor.
In sum: in electrolyte of lithium-ion secondary battery when the use amount of the compound with general formula (1) structure is less (<0.1%) or higher time (>10.0%), all can not form very fine and close, interface characteristics good composite S EI film, cannot obtain that coulombic efficiency is first high simultaneously, good cycle and the good lithium rechargeable battery of low temperature charging performance.And when the use amount of the compound with general formula (1) structure is 0.1% ~ 10.0%, especially 0.3% ~ 3.0% time, the coulombic efficiency first of lithium rechargeable battery, cycle performance and low temperature charging performance are all better.
The parameter of table 1 embodiment 1-27 and comparative example 1-6 and the performance test results
Claims (9)
1. an electrolyte of lithium-ion secondary battery, comprising:
Lithium salts;
Non-aqueous organic solvent; And
Additive;
It is characterized in that, described additive contains at least one in the compound with general formula (1) structure; R in general formula (1)
1, R
2separately be expressed as general formula (2), R
3for the alkyl of hydrogen or C1 ~ C3; R in general formula (2)
4, R
5separately be expressed as the alkyl of hydrogen or C1 ~ C3, wherein n is the natural number in 0 to 2,
Described additive is also containing vinylene carbonate (VC).
2. electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that, described additive contains at least one in the compound with general formula (3) structure, R in general formula (3)
1, R
2separately be expressed as general formula (4), wherein n is the natural number in 0 to 2.
3. electrolyte of lithium-ion secondary battery according to claim 2, is characterized in that, described additive contains at least one in the compound with general formula (5), general formula (6) or general formula (7) structure.
4. electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that, described in there is general formula (1) structure the mass percentage of compound in electrolyte of lithium-ion secondary battery be 0.1% ~ 10%.
5. electrolyte of lithium-ion secondary battery according to claim 4, is characterized in that, described in there is general formula (1) structure the mass percentage of compound in electrolyte of lithium-ion secondary battery be 0.3% ~ 3%.
6. electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that, described non-aqueous organic solvent comprises the combination of cyclic carbonate and linear carbonate.
7. electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that, described lithium salts comprises LiN (C
xf
2x+1sO
2) (C
yf
2y+1sO
2), LiPF
6, LiBF
4, LiBOB, LiAsF
6, Li (CF
3sO
2)
2n, LiCF
3sO
3and LiClO
4in at least one, wherein, x, y are natural number.
8. electrolyte of lithium-ion secondary battery according to claim 1, it is characterized in that, the described mass percentage of compound in electrolyte of lithium-ion secondary battery with general formula (1) structure is 0.2% ~ 3.0%, and the mass percentage of described vinylene carbonate (VC) in electrolyte of lithium-ion secondary battery is 0.2% ~ 2.0%.
9. a lithium rechargeable battery, comprising:
Positive plate;
Negative plate;
Barrier film, is interval between adjacent positive sheet and negative plate; And
Electrolyte;
It is characterized in that, described electrolyte is the electrolyte of lithium-ion secondary battery according to any one of claim 1-8.
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| CN1330044C (en) * | 2002-09-30 | 2007-08-01 | 三洋电机株式会社 | Nonaqueous electrolytic storage battery |
| CN103178295A (en) * | 2011-12-26 | 2013-06-26 | 张家港市国泰华荣化工新材料有限公司 | Electrolytic solution capable of improving performance of lithium ion battery |
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| CN1330044C (en) * | 2002-09-30 | 2007-08-01 | 三洋电机株式会社 | Nonaqueous electrolytic storage battery |
| CN103178295A (en) * | 2011-12-26 | 2013-06-26 | 张家港市国泰华荣化工新材料有限公司 | Electrolytic solution capable of improving performance of lithium ion battery |
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