CN103715459A - Lithium ion secondary battery and electrolyte thereof - Google Patents
Lithium ion secondary battery and electrolyte thereof Download PDFInfo
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- CN103715459A CN103715459A CN201310722414.0A CN201310722414A CN103715459A CN 103715459 A CN103715459 A CN 103715459A CN 201310722414 A CN201310722414 A CN 201310722414A CN 103715459 A CN103715459 A CN 103715459A
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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
- H01M10/0566—Liquid materials
- 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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- 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
Abstract
The invention provides a lithium ion secondary battery and electrolyte thereof. The electrolyte of the lithium ion secondary battery comprises lithium salt, a non-aqueous organic solvent and an additive, wherein the additive contains at least one of compounds with the structure as shown in a general formula (1), R1 and R2 in the general formula (1) are respectively and independently expressed as a general formula (2), and R3 is hydrogen or alkyl groups of C1-C3; R4 and R5 in the general formula (2) are respectively and independently expressed as hydrogen or alkyl groups of C1-C3, and n is a natural number in the range from 0-2; the additive can also contain vinylene carbonate (VC). The lithium ion secondary battery comprises a positive plate, a negative plate, an isolating membrane for isolating the adjacent positive plate and negative plate, and the electrolyte. The lithium ion secondary battery provided by the invention has good first coulombic efficiency, cycle performance and good low-temperature charging property.
Description
Technical field
The present invention relates to field of batteries, relate in particular 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 to fields such as electric bicycle, electric automobiles, expands gradually.Along with deepening continuously of the lithium rechargeable battery marketization, people are more and more higher to the expectation of lithium rechargeable battery.Current commercial lithium rechargeable battery has been difficult to meet the needs of practical application.
Research shows that graphite material surface exists some irregular structures, and the irreversible decomposition of electrolyte is played to catalytic action, has caused the chemical property of graphite material to be 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.
In electrolyte of lithium-ion secondary battery, add a small amount of material, these materials are the SEI film of reduction decomposition formation function admirable on graphite cathode preferentially, it can effectively suppress solvent molecule (carbonates solvent) at the last decomposition of electrode surface, thereby improves the performance of lithium rechargeable battery.
Conventional additive is cyclic sulfite derivative at present, as ethylene sulfite (ES) etc., existence due to center sulphur atom, reproducibility at graphite cathode interface is stronger than corresponding carbonates solvent, apparently higher than the inlay current potential of solvation lithium ion, prior to carbonates solvent, at graphite cathode surface reduction, form stable SEI film, obviously suppress solvation lithium ion and embed altogether graphite layers, improved the cycle performance of lithium rechargeable battery.But also there is following deficiency in this compounds when being applied to electrolyte of lithium-ion secondary battery: poor at the SEI of graphite cathode interface formation membrane stability, increase along with cycle-index, electrode interface resistance raises gradually, the ohmic polarization phenomenon of lithium rechargeable battery is more and more serious, thereby causes the reversible capacity of electrode to reduce rapidly.
In electrolyte, add vinylene carbonate (VC), also can improve coulomb efficiency and the cycle performance first of lithium rechargeable battery.But, add VC to form fine and close SEI film in negative terminal surface, its impedance is larger, can worsen the charging performance of lithium rechargeable battery under cryogenic conditions.
Summary of the invention
In view of the problem 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 coulomb efficiency, cycle performance and low temperature charging performance first 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.At least one in the compound that described additive contains (1) structure that has general formula; R in general formula (1)
1, R
2be expressed as independently respectively general formula (2), R
3alkyl for hydrogen or C1～C3; R in general formula (2)
4, R
5be expressed as independently respectively 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 the electrolyte according to first aspect present invention.
With respect to prior art, beneficial effect of the present invention is:
Add the lithium rechargeable battery of the compound of (1) structure that there is general formula both to there is good coulomb efficiency, cycle performance first, there is again good low temperature charging performance.
Embodiment
Describe in detail according to lithium rechargeable battery of the present invention and electrolyte and its preparation method thereof below.
First illustrate according to the electrolyte of lithium-ion secondary battery of first aspect present invention and comprise: lithium salts; Non-aqueous organic solvent; And additive.At least one in the compound that described additive contains (1) structure that has general formula; R in general formula (1)
1, R
2be expressed as independently respectively general formula (2), R
3alkyl for hydrogen or C1～C3; R in general formula (2)
4, R
5be expressed as independently respectively 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, can obviously improve coulomb efficiency and the cycle performance first of lithium rechargeable battery, this is also can as ES or VC, in negative terminal surface, form SEI film owing to having the compound of general formula (1) structure, stop non-aqueous organic solvent to decompose in the redox of negative terminal surface, thereby improved coulomb efficiency and the cycle performance first of lithium rechargeable battery.Compare with ES, there is the SEI film that SEI film that the compound of general formula (1) structure forms forms than ES more stable, make lithium rechargeable battery there is good cycle performance; Compare with VC, the SEI film with the compound formation of general formula (1) structure 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, owing to containing C=C functional group, can form the polymer film of certain molecular weight, increased the stability of SEI film, and owing to containing sulfurous acid functional group, make formed SEI film there is the good ionic nature of leading.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, preferably, at least one in the compound that described additive contains (3) structure that has general formula, R in general formula (3)
1, R
2be expressed as independently respectively general formula (4), wherein n is the natural number in 0 to 2.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, more preferably, at least one in the compound that described additive contains have general formula (5), general formula (6) or general formula (7) structure.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, described in there is general formula (1) structure the quality percentage composition of compound in electrolyte of lithium-ion secondary battery can be 0.1%～10.0%, be preferably 0.3%～3.0%.If it is too much to have the compounds content of general formula (1) structure in electrolyte, 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 it is very few to have the compounds content of general formula (1) structure in electrolyte, there is the passivating film that C=C in the compound of general formula (1) structure can not form effective densification, reacting of electrolyte and pole piece can not be effectively stoped, thereby the cycle performance of lithium rechargeable battery can not be effectively improved.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, described non-aqueous organic solvent can comprise the combination of cyclic carbonate and linear carbonate.Cyclic carbonate has higher dielectric constant, can finely form solvation lithium ion molecule with lithium ion; 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).
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, the quality percentage composition of described cyclic carbonate in electrolyte of lithium-ion secondary battery can be 10%～70%; The quality percentage composition of described linear carbonate in electrolyte of lithium-ion secondary battery can be 15%～80%.
According in the electrolyte of lithium-ion secondary battery of first aspect 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 is natural number.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, described lithium salt can be 0.5M～2M.
According in the electrolyte of lithium-ion secondary battery of first aspect present invention, described additive also contains vinylene carbonate (VC).When thering is the compound of general formula (1) structure and use together with VC, owing to thering is the compound of general formula (1) structure, there is higher reduction potential, can preferentially in negative terminal surface, form the lower SEI film of a layer impedance, on the basis of the SEI film that then VC forms at the compound by having general formula (1) structure, form again one deck SEI film, VC and to have the composite S EI film that the compound of general formula (1) structure forms more stable, has stoped in electrolyte non-aqueous organic solvent and additive in the further reduction reaction of negative terminal surface.Preferably, the quality percentage composition of the described compound with general formula (1) structure in electrolyte of lithium-ion secondary battery can be 0.2%～3.0%, and the quality percentage composition of described vinylene carbonate (VC) in electrolyte of lithium-ion secondary battery can be 0.2%～2.0%.
Secondly explanation is according to the lithium rechargeable battery of second aspect present invention.
According to the lithium rechargeable battery of second aspect present invention, comprise: positive plate; Negative plate; Barrier film, is interval between adjacent positive sheet and negative plate; And electrolyte.Wherein, described electrolyte is the electrolyte according to first aspect present invention.
Next illustrate 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 1-METHYLPYRROLIDONE (NMP) and mix and make anode sizing agent, anode sizing agent is coated on collector aluminium foil, and its coating weight is 0.0194g/cm
2, after drying at 85 ℃, cold pressing; Then carry out after trimming, cut-parts, itemize, then dry 4 hours under 85 ℃ 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 and mix and make cathode size, cathode size is coated on copper foil of affluxion body and at 85 ℃ and is dried, and coating weight is 0.0089g/cm
2; Then carry out after trimming, cut-parts, itemize, then dry 4 hours under 110 ℃ 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 be take concentration as 1M lithium hexafluoro phosphate (LiPF
6) be lithium salts, the mixture of ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) of take is non-aqueous organic solvent, the mass ratio of each carbonic ester is EC:PC:DEC=30:30:40.In addition, in electrolyte, also contain the additive that quality percentage composition is 1.0% the compound with general formula (5) structure.
(4) preparation of lithium rechargeable battery
It is that 4.2mm, width are the lithium rechargeable battery that 34mm, length are 82mm that the positive plate of the lithium rechargeable battery of preparing according to step (1) and step (2), negative plate and barrier film polyethylene (PE) are made into thickness through winding process, at 75 ℃, vacuum bakeout is 10 hours, electrolyte prepared by implantation step (3), after standing 24 hours, with 0.1C(160mA) constant current charge to 4.2V, then with 4.2V constant voltage charge to electric current, drop to 0.05C(80mA); Then with 0.1C(160mA) be discharged to 3.0V, repeat to discharge and recharge for 2 times, finally again with 0.1C(160mA) battery is charged to 3.85V, complete the making of lithium rechargeable battery.
Embodiment 2
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 1.0% the compound with general formula (6) structure.
Embodiment 3
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 1.0% the compound with general formula (7) structure.
Embodiment 4
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 0.1% the compound with general formula (5) structure.
Embodiment 5
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 10.0% the compound with general formula (5) structure.
Embodiment 6
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 0.3% the compound with general formula (5) structure.
Embodiment 7
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 5.0% the compound with general formula (5) structure.
Embodiment 8
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 2.0% the compound with general formula (5) structure.
Embodiment 9
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 3.0% the compound with general formula (5) structure.
Embodiment 10
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.2% the compound with general formula (5) structure and quality percentage composition are 0.8%.
Embodiment 11
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.4% the compound with general formula (5) structure and quality percentage composition are 0.6%.
Embodiment 12
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.5% the compound with general formula (5) structure and quality percentage composition are 0.5%.
Embodiment 13
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.6% the compound with general formula (5) structure and quality percentage composition are 0.4%.
Embodiment 14
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.8% the compound with general formula (5) structure and quality percentage composition are 0.2%.
Embodiment 15
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 1.0% the compound with general formula (5) structure and quality percentage composition are 0.5%.
Embodiment 16
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 2.0% the compound with general formula (5) structure and quality percentage composition are 0.5%.
Embodiment 17
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 3.0% the compound with general formula (5) structure and quality percentage composition are 0.5%.
Embodiment 18
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 1.0% the compound with general formula (5) structure and quality percentage composition are 1.0%.
Embodiment 19
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 2.0% the compound with general formula (5) structure and quality percentage composition are 1.0%.
Embodiment 20
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 1.0% the compound with general formula (5) structure and quality percentage composition are 0.2%.
Embodiment 21
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 1.0% the compound with general formula (5) structure and quality percentage composition are 2.0%.
Embodiment 22
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.2% the compound with general formula (6) structure and quality percentage composition are 0.5%.
Embodiment 23
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.5% the compound with general formula (6) structure and quality percentage composition are 0.5%.
Embodiment 24
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 3.0% the compound with general formula (6) structure and quality percentage composition are 0.5%.
Embodiment 25
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.2% the compound with general formula (7) structure and quality percentage composition are 0.5%.
Embodiment 26
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 0.5% the compound with general formula (7) structure and quality percentage composition are 0.5%.
Embodiment 27
Method according to embodiment 1 is prepared lithium rechargeable battery, just in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is the VC that 3.0% the compound with general formula (7) structure and quality percentage composition are 0.5%.
Comparative example 1
Method according to embodiment 1 is prepared lithium rechargeable battery, just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, does not add any additive.
Comparative example 2
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 1.0% VC.
Comparative example 3
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 3.0% VC.
Comparative example 4
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 1.0% ES.
Comparative example 5
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 3.0% ES.
Comparative example 6
Method according to embodiment 1 is prepared lithium rechargeable battery, and just, in the preparation (being step (3)) of the electrolyte of lithium rechargeable battery, additive is that quality percentage composition is 0.5% VC.
Finally provide performance test process and the test result of the lithium rechargeable battery based on embodiment 1-27 and comparative example 1-6.
(1) coulomb efficiency test first
First with 0.1C(160mA) constant current lithium rechargeable battery is charged to 4.2V, further at 4.2V constant-potential charge to electric current, be less than 0.05C(80mA), obtain initial charge capacity; Then with 0.5C(800mA) constant current lithium rechargeable battery is discharged to 3.0V, obtain discharge capacity first.
By the discharge capacity first of lithium rechargeable battery and the ratio of initial charge capacity, evaluate its coulomb efficiency first, coulomb efficiency is calculated as follows first:
Coulomb efficiency (%)=(discharge capacity/initial charge capacity first) * 100% first
(2) cycle performance test
Under 25 ℃ and 45 ℃ of conditions first with 0.7C(1120mA) constant current lithium rechargeable battery is charged to 4.2V, further at 4.2V constant-potential charge to electric current, be less than 0.05C(80mA), then with 0.5C(800mA) constant current lithium rechargeable battery is discharged to 3.0V.Current discharge capacity is cyclic discharge capacity for the first time.Lithium rechargeable battery carries out cycle charge discharge electrical testing in a manner described, gets the discharge capacity of the 400th circulation.
Capability retention by lithium rechargeable battery carrys out its high temperature cyclic performance of par, and capability retention is calculated as follows:
Capability retention (%)=[discharge capacity of the circulation of discharge capacity/for the first time of the 400th circulation] * 100%
(3) low temperature charging performance test
Under 10 ℃ of conditions first with 0.35C(560mA) constant current lithium rechargeable battery is charged to 4.2V, further at 4.2V constant-potential charge to electric current, be less than 0.05C(80mA), then with 0.5C(800mA) constant current lithium rechargeable battery is discharged to 3.0V.After 10 circulations, with 0.35C(560mA) constant current lithium rechargeable battery is charged to 4.2V, further at 4.2V constant-potential charge to electric current, be less than 0.05C(80mA).Under dry anhydrous condition, lithium rechargeable battery is taken apart, is observed the negative plate of lithium rechargeable battery, with surface white or or grey number (lithium metal is separated out negative terminal surface) evaluate the low temperature charging performance of lithium rechargeable battery.Surface is golden yellow (without white or gray area) for best, and now to separate out be 0 to lithium metal; Surface be white in color completely or gray area for the poorest, now to separate out be 100% to lithium metal.
Next the performance test results of lithium rechargeable battery is analyzed.
Table 1 provides parameter and the performance test results based on embodiment 1-27 and comparative example 1-6.
(1) test result analysis of coulomb efficiency first
From embodiment 1-9 and comparative example 1(, do not add any additive, coulomb efficiency is 70.1% first) contrast in can find out, in electrolyte of lithium-ion secondary battery, added the lithium rechargeable battery with general formula (1) structural compounds and can effectively improve its coulomb efficiency first.
From the contrast of embodiment 1, embodiment 4-9 and comparative example 1, can find out, in electrolyte of lithium-ion secondary battery, add coulomb efficiency first that general formula (5) obviously improves lithium rechargeable battery; And along with the content of general formula (5) increases, coulomb efficiency first of lithium rechargeable battery first increases, when the content of general formula (5) reaches 3.0%, the coulomb first of lithium rechargeable battery is most effective; Content continuation increase along with general formula (5), coulomb efficiency first of lithium rechargeable battery starts to decline, when the content of general formula (5) is increased to 10.0%, worsened coulomb efficiency first of lithium rechargeable battery, but do not add any additive than comparative example 1(, coulomb efficiency is 70.1% first), still improved coulomb efficiency first of lithium rechargeable battery.This is because general formula (5) can preferentially form one deck SEI film in negative terminal surface, has stoped the further reduction reaction of non-aqueous organic solvent, so improved coulomb 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, reduced leading of SEI film ionic, while causing coulomb efficiency first of lithium rechargeable battery to be 3.0% than general formula (5) content, coulomb efficiency first of (embodiment 9) is low.
From the contrast of embodiment 1-3, comparative example 2 and comparative example 4, can find out, in electrolyte of lithium-ion secondary battery, add 1.0% compound with general formula (1) structure and in electrolyte of lithium-ion secondary battery, added 1.0% VC and compare and all there is higher coulomb efficiency first with the ES that has added 1.0% in electrolyte of lithium-ion secondary battery.From the contrast of embodiment 9, comparative example 3 and comparative example 5, also can find out, in electrolyte of lithium-ion secondary battery, add 3.0% general formula (5) than having added 3.0% VC and added 3.0% ES in electrolyte of lithium-ion secondary battery in electrolyte of lithium-ion secondary battery and there is obviously higher coulomb efficiency first.
From the contrast of embodiment 10-27, can find out: coulomb efficiency first of having added the lithium rechargeable battery of additive package in electrolyte of lithium-ion secondary battery is improved, its first coulomb efficiency all reached more than 89%.
From the contrast of embodiment 1 and embodiment 10-14, can find out, the additive package that has added general formula (5) and VC in electrolyte of lithium-ion secondary battery has added than independent coulomb efficiency first that lithium rechargeable battery has been improved in 1.0% general formula (5) (embodiment 1).From 2 contrasts of embodiment 10-14 and comparative example, can find out, in electrolyte of lithium-ion secondary battery, add the additive package of general formula (5) and VC than using separately 1.0%VC(comparative example 2) there is the higher efficiency of coulomb first.When this is because uses general formula (5) separately, general formula (5) can form SEI film in negative terminal surface, but the SEI film forming is fine and close not, cause non-aqueous organic solvent and additive can continue in negative terminal surface reduction, make coulomb efficiency first of lithium rechargeable battery excellent not; Diversion of the SEI film forming while using VC is separately poor, also can cause the efficiency first of lithium rechargeable battery excellent not; When general formula (5) and VC are used together, because general formula (5) has higher reduction potential, can preferentially in negative terminal surface, form the lower SEI film of a layer impedance, then VC forms one deck SEI film on the basis of the SEI film being formed by general formula (5) again, the composite S EI film that VC and general formula (5) form is more stable, stoped general formula (5) and VC in the further reduction reaction of negative terminal surface, so lithium rechargeable battery has higher coulomb efficiency first.
From the contrast of comparative example 2, comparative example 3 and comparative example 6, can find out, in electrolyte of lithium-ion secondary battery, add 1.0% VC and there is higher coulomb efficiency first than the VC that adds 0.5%, but when adding 3.0% VC, reduced on the contrary coulomb efficiency first of lithium rechargeable battery.This is because content along with VC increases, and causes more VC to form thicker SEI film in negative terminal surface reduction, and the SEI film forming has larger impedance, causes coulomb decrease in efficiency first of lithium rechargeable battery.
From the contrast of embodiment 12, embodiment 15-17 and comparative example 6, can find out, the additive package that adds the VC of 0.5%～3.0% general formula (5) and 0.5% in electrolyte of lithium-ion secondary battery has higher coulomb efficiency first than the VC that uses separately 0.5%; When the content of general formula (5) is less (embodiment 12), coulomb efficiency first of lithium rechargeable battery is higher; Along with the content increase of general formula (5), coulomb efficiency first of lithium rechargeable battery starts to reduce.Equally, from the contrast of embodiment 18, embodiment 19 and comparative example 2, also can see similar result.
From the contrast of embodiment 22-24 and comparative example 6, can find out, the additive package that adds the VC of 0.2%～3.0% general formula (6) and 0.5% in electrolyte of lithium-ion secondary battery has higher coulomb efficiency first than the VC that uses separately 0.5%; When the content of general formula (6) is less, coulomb efficiency first of lithium rechargeable battery is along with the content of general formula (6) increases and increases; But when the content of general formula (6) is more, coulomb efficiency first of lithium rechargeable battery starts to reduce.Equally, from the contrast of embodiment 25-27 and comparative example 6, also can see similar result.
From the contrast of embodiment 2-3, embodiment 23 and embodiment 26, can find out, the additive package that has added general formula (6) or general formula (7) and VC in electrolyte of lithium-ion secondary battery is compared coulomb efficiency first that independent 1.0% general formula (6) or general formula (7) have improved lithium rechargeable battery.
(2) test result analysis of cycle performance
From embodiment 1-9 and comparative example 1(, do not add any additive, 25 ℃ of capability retentions are 56%, 45 ℃ of capability retentions are 42%) contrast in can find out, in electrolyte of lithium-ion secondary battery, added the lithium rechargeable battery with general formula (1) structural compounds and can effectively improve its cycle performance.
From the contrast of embodiment 1, embodiment 4-9 and comparative example 1, can find out, in electrolyte of lithium-ion secondary battery, add the cycle performance that general formula (5) obviously improves lithium rechargeable battery; And along with the content of general formula (5) increases, the Capacitance reserve of lithium rechargeable battery takes the lead in increasing, and when the content of general formula (5) reaches 2.0% (when at 45 ℃, content reaches 3.0%), the capability retention of lithium rechargeable battery is the highest; Content continuation increase along with general formula (5), 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 improved the cycle performance of lithium rechargeable battery.This is because general formula (5) can preferentially form one deck SEI film in negative terminal surface, has stoped the reduction reaction of non-aqueous organic solvent and negative plate, so improved 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, has reduced leading of SEI film ionic, worsen the interface performance of negative plate and electrolyte, caused the cycle performance variation of lithium rechargeable battery.
From the contrast of embodiment 1-3, comparative example 2 and comparative example 4, can find out, in electrolyte of lithium-ion secondary battery, having added 1.0% general formula (5), general formula (6) or general formula (7) and in electrolyte of lithium-ion secondary battery, having added 1.0% VC has suitable cycle performance (at 45 ℃ for slightly poor); But there is better cycle performance than the ES that has added 1.0% in electrolyte of lithium-ion secondary battery.Equally, comparative example 9, comparative example 3 and comparative example 5 can find out, in electrolyte of lithium-ion secondary battery, having added 3.0% general formula (5) and in electrolyte of lithium-ion secondary battery, having added 3.0% VC has suitable cycle performance (at 25 ℃ for better); But there is better cycle performance than the ES that has added 3.0% in electrolyte of lithium-ion secondary battery.
From the contrast of embodiment 10-27, can find out, the cycle performance of lithium rechargeable battery that has added additive package in electrolyte of lithium-ion secondary battery is better, capability retention at its 25 ℃ has reached more than 87%, and the capability retention at 45 ℃ has also reached more than 80%.
From the contrast of embodiment 1 and embodiment 10-14, can find out, the additive package that has added general formula (5) and VC in electrolyte of lithium-ion secondary battery has obviously improved the cycle performance of lithium rechargeable battery than independent 1.0% general formula (5) (embodiment 1).From the contrast of embodiment 10-14 and comparative example 2, can find out, the additive package that adds general formula (5) and VC in electrolyte of lithium-ion secondary battery is than using separately 1.0%VC(comparative example 2) there is on the whole better cycle performance.This is due to when general formula (5) and VC are used together, general formula (5) is owing to having higher reduction potential, can preferentially in negative terminal surface, form the lower SEI film of a layer impedance, then VC forms one deck SEI film on the basis of the SEI film being formed by general formula (5) again, the composite S EI film that VC and general formula (5) form is more stable, stop the further reduction reaction of non-aqueous organic solvent in negative terminal surface, improved the cycle performance of lithium rechargeable battery; And while using separately general formula (5), also can form SEI film in negative terminal surface, but the SEI film forming is fine and close not, causes non-aqueous organic solvent and additive can continue to reduce in negative terminal surface, and the cycle performance that makes lithium rechargeable battery is not enough excellences; And diversion of the SEI film forming while using VC is separately poor, also can cause the cycle performance of lithium rechargeable battery excellent not.
From the contrast of comparative example 2, comparative example 3 and comparative example 6, can find out, in electrolyte of lithium-ion secondary battery, add 1.0% VC and there is better cycle performance than the VC that adds 0.5%, still when adding 3.0% VC, worsened on the contrary the cycle performance (not occurring at 45 ℃ declining) of lithium rechargeable battery.
From the contrast of embodiment 12, embodiment 15-17 and comparative example 6, can find out, the additive package that adds the VC of 0.5%～3.0% general formula (5) and 0.5% in electrolyte of lithium-ion secondary battery has better cycle performance than the VC that uses separately 0.5%.Equally, from the contrast of embodiment 18, embodiment 19 and comparative example 2, also can see similar result.
From the contrast of embodiment 22-24 and comparative example 6, can find out, the additive package that adds the VC of 0.2%～3.0% general formula (6) and 0.5% in electrolyte of lithium-ion secondary battery has better cycle performance than the VC that uses separately 0.5%; When the content of general formula (6) is less, the capability retention of lithium rechargeable battery is along with the content of general formula (6) increases and increases; 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 can see similar result.
From the contrast of embodiment 2-3, embodiment 23 and embodiment 26, can find out, the additive package that has added general formula (6) or general formula (7) and VC in electrolyte of lithium-ion secondary battery is compared the cycle performance that independent 1.0% general formula (6) or general formula (7) have obviously improved lithium rechargeable battery.
(3) test result analysis of low temperature charging performance
From the contrast of embodiment 1, embodiment 4-9, can find out, 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) surpasses 5.0%, the low temperature charging performance of lithium rechargeable battery starts variation; When the content of general formula (5) reaches 10.0%, lithium metal is separated out completely, reaches 100%.
From the contrast of embodiment 1-3, comparative example 2, can find out, in electrolyte of lithium-ion secondary battery, add 1.0% general formula (5), general formula (6) or general formula (7) than the lithium rechargeable battery that has added 1.0% VC in electrolyte of lithium-ion secondary battery and there is better low temperature charging performance.Equally, from the contrast of embodiment 9 and comparative example 3, can find out, in electrolyte of lithium-ion secondary battery, add 3.0% general formula (5) and compared with the VC that has added 3.0% in electrolyte of lithium-ion secondary battery, obviously improved the low temperature charging performance of lithium rechargeable battery.
From the contrast of embodiment 10-27, can find out, the low temperature charging performance of lithium rechargeable battery that has added additive package in electrolyte of lithium-ion secondary battery is whole better.
From the contrast of embodiment 10-14 and comparative example 2, can find out, in electrolyte of lithium-ion secondary battery, add the additive package of general formula (5) and VC and use separately 1.0%VC(comparative example 2) compare, obviously improved the low temperature charging performance of lithium rechargeable battery.This is due to when general formula (5) and VC are used together, general formula (5) is owing to having higher reduction potential, can preferentially in negative terminal surface, form the lower SEI film of a layer impedance, then VC forms one deck SEI film on the basis of the SEI film being formed by general formula (5) again, the composite S EI film that VC and general formula (5) form is more stable, stoped the further reduction reaction of non-aqueous organic solvent in negative terminal surface, make the interface impedance of negative plate and electrolyte lower, lithium rechargeable battery there is good low temperature charging performance; And while using separately general formula (5), also can form SEI film in negative terminal surface, but the SEI film forming 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 larger, the low temperature charging performance of lithium rechargeable battery is poor; And diversion of the SEI film forming while using VC is separately poor, also can cause the low temperature charging performance of lithium rechargeable battery poor.
From the contrast of embodiment 18, embodiment 19 and comparative example 2, can find out, on the VC basis of containing more amount at electrolyte of lithium-ion secondary battery, add again general formula (5), can improve lithium rechargeable battery low temperature charging performance.
From the contrast of comparative example 2, comparative example 3 and comparative example 6, can find out, in electrolyte of lithium-ion secondary battery, use separately VC, when use amount is less (0.5%VC, comparative example 6), the good cycle of the cycle performance of lithium rechargeable battery when example 2 is used 1.0%VC without comparison; But when using 1.0%VC (comparative example 2) or when 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 thering is the use amount of compound of general formula (1) structure when less (<0.1%) or when higher (>10.0%), all can not form very fine and close, the good composite S EI film of interface property, cannot obtain first that coulomb efficiency is high, good cycle and the good lithium rechargeable battery of low temperature charging performance simultaneously.And be 0.1%～10.0% when thering is the use amount of compound of general formula (1) structure, especially 0.3%～3.0% time, coulomb efficiency, cycle performance and the low temperature charging performance first of lithium rechargeable battery are all better.
The parameter of table 1 embodiment 1-27 and comparative example 1-6 and the performance test results
Claims (10)
1. an electrolyte of lithium-ion secondary battery, comprising:
Lithium salts;
Non-aqueous organic solvent; And
Additive;
It is characterized in that at least one in the compound that described additive contains (1) structure that has general formula; R in general formula (1)
1, R
2be expressed as independently respectively general formula (2), R
3alkyl for hydrogen or C1～C3; R in general formula (2)
4, R
5be expressed as independently respectively the alkyl of hydrogen or C1～C3, wherein n is the natural number in 0 to 2,
2. electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that, at least one in the compound that described additive contains (3) structure that has general formula, R in general formula (3)
1, R
2be expressed as independently respectively 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, at least one in the compound that described additive contains have 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 quality percentage composition 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 quality percentage composition 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 is natural number.
8. according to the electrolyte of lithium-ion secondary battery described in any one in claim 1-3,6-7, it is characterized in that, described additive also contains vinylene carbonate (VC).
9. electrolyte of lithium-ion secondary battery according to claim 8, it is characterized in that, the quality percentage composition of the described compound with general formula (1) structure in electrolyte of lithium-ion secondary battery is 0.2%～3.0%, and the quality percentage composition of described vinylene carbonate (VC) in electrolyte of lithium-ion secondary battery is 0.2%～2.0%.
10. 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 according to the electrolyte of lithium-ion secondary battery described in any one in claim 1-9.
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