CN102709589B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN102709589B CN102709589B CN201210036695.XA CN201210036695A CN102709589B CN 102709589 B CN102709589 B CN 102709589B CN 201210036695 A CN201210036695 A CN 201210036695A CN 102709589 B CN102709589 B CN 102709589B
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- H—ELECTRICITY
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- 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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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides the lithium ion battery that a kind of high temperature cyclic performance is good, it comprises: active material is LiFePO
4negative electrode; Anode; Be placed in the dividing plate between negative electrode and positive electrode; And nonaqueous electrolytic solution, and containing, for example the aromatic compound described in structural formula in this electrolyte, wherein X group is selected from: the one in S, O, NR, in described NR, R group is independently selected from H, alkyl, the one in amino; R
1, R
2, R
3, R
4be chain substituting group or be interconnected into ring independently.
Description
Technical field
The present invention relates to a kind of lithium ion battery and lithium-ion battery electrolytes, particularly relate to a kind of ferric phosphate lithium cell and electrolyte thereof.
Background technology
Since entering 21 century, the recoverable amount of the automobile of countries in the world increases day by day, makes the petroleum resources of the earth day by day deficient, and the pollution of atmospheric environment is day by day serious.In this context, each state all actively developing about green, the pure electric automobile of environmental protection and the research of hybrid vehicle, deals with increasingly serious petroleum resources and problem of environmental pollution with this.
Lithium rechargeable battery because of its energy density high, capacity is high, the advantage such as good cycle and environmental protection, becomes the electrical source of power of current driving force automobile first-selection.And can power vehicle and hybrid vehicle be employed in daily life widely, the performance of power lithium-ion rechargeable battery just becomes crucial.As electrokinetic cell, good high temperature performance must be had, normal-temperature circulating performance, longer-term storage performance and security performance.
Anode material for lithium-ion batteries LiFePO
4because capacity is high, good cycle, Stability Analysis of Structures, environmental friendliness, the advantages such as raw material are cheap become the study hotspot of current lithium-ion-power cell.During the actual use of electrokinetic cell, because during battery discharge, itself can generate heat, the ambient temperature residing for it general higher (40 ~ 80 DEG C), with this understanding, has had higher requirement to the high-temperature behavior of lithium iron phosphate dynamic battery.Ferric phosphate lithium cell in the market at high temperature circulates, and capacity attenuation is very fast, and high temperature cyclic performance does not still reach the requirement of electrokinetic cell.
Summary of the invention
For solving the problem, the invention provides the lithium ion battery that a kind of high temperature cyclic performance is good, it comprises:
Active material is LiFePO
4negative electrode;
Anode;
Be placed in the dividing plate between negative electrode and positive electrode; And
Nonaqueous electrolytic solution, and containing, for example the aromatic compound described in structural formula 1 in this electrolyte:
Wherein X group is selected from: the one in S, O, NR, and in described NR, R group is independently selected from H, alkyl, the one in amino;
R
1, R
2, R
3, R
4be chain substituting group or be interconnected into ring independently;
R
1, R
2, R
3, R
4when being interconnected into ring, R
1with R
3, R
1with R
2, or R
2with R
4independently Cheng Huan, described ring is 4 ~ 6 rings, and described 4 ~ 6 rings are cyclic hydrocarbon or heterocycle, and described heterocycle is the heterocycle containing O, S or N, and described cyclic hydrocarbon is cycloalkane, cycloolefin or benzene;
Described chain substituting group is selected from hydrogen atom, halogen, carbon number is the alkyl of 1 ~ 10, carbon number is the alkoxyl of 1 ~ 10, and carbon number is the acyl group of 1 ~ 10, and carbon number is the alkenyl of 2 ~ 10, nitro, sulfenyl, the one in sulfonyl and phenyl, described chain substituting group is straight chain substituent or branched chain substituting group;
The content of the aromatic compound described in structural formula 1 is 0.01 ~ 2 % by weight by the total weight of electrolyte.When in electrolyte, this heterocyclic aromatic compound content is very few, it cannot form conducting film at positive electrode surface, does not just have protective effect; When in electrolyte, this heterocyclic aromatic compound content is too much, therefore the internal resistance of battery can increase, and invertibity reduces, penalty.
More specifically, one or more preferably in following structural of the heterocyclic aromatic compound shown in described structural formula 1:
As preferred version of the present invention, described lithium ion battery is obtained by following chemical synthesizing method: the most high charge cut-ff voltage when initial 10 chargings is higher than charge cutoff voltage during normal work, and described most high charge cut-ff voltage is lower than 4.8V.
As preferred version of the present invention, described nonaqueous electrolytic solution also comprises one or more of following additive: vinylene carbonate, vinyl ethylene carbonate, halogenated ethylene carbonate, cyclic sulfonic acid ester, cyclic sulfite, cyclic sulfates.
As preferred version of the present invention, the solvent in described nonaqueous electrolytic solution contain in following composition one or more: cyclic carbonate, linear carbonate and carboxylate;
Wherein cyclic carbonate is for being selected from: ethylene carbonate, propene carbonate, one or more in butylene;
Linear carbonate or carboxylate are selected from: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, one or more in methyl propyl carbonate;
Carboxylate is selected from: gamma-butyrolacton, ethyl acetate, ethyl propionate, methyl propionate, one or more in methyl butyrate.
As preferred version of the present invention, the active material of described anode is graphite.
Inventor finds, under the high temperature conditions, the too fast reason of ferric phosphate lithium cell capacity attenuation mainly contains: the stripping of (1) positive pole Fe ion.Under higher temperature (55 DEG C), the as easy as rolling off a log decomposition of the LiPF6 in electrolyte, produces HF and PF
5.Wherein HF can corrode positive pole, causes the stripping of Fe ion, thus destroys cathode material structure, causes capacity to run off; (2) Fe ion is in the reduction of negative pole.In high temperature circulation process, the HF content in electrolyte increases, and causes the Fe Ion release amount in positive pole to increase.Like this in the process of charge and discharge cycles, the Fe ion of stripping can be reduced into Fe simple substance on SEI surface, makes the impedance of negative pole more and more come large along with the carrying out of discharge and recharge becomes, causes battery irreversible capacity to increase, finally make the major cycle of battery.Can say under the high temperature conditions, the stripping of positive pole Fe ion has destructive effect to both positive and negative polarity.If add positive pole film for additive in the electrolytic solution, the stripping of Fe ion in positive pole under high temperature can be reduced to a certain extent, thus improve the high temperature cyclic performance of ferric phosphate lithium cell.
Inventor is through creationary research, propose and adopt the thiophene shown in structural formula 1, furans, pyrroles and derivative thereof as positive pole film for additive, be allowed to condition in formation process and form an electric conductive polymer film on anode active material of phosphate iron lithium surface, inhibit ferric phosphate lithium cell Fe Ion release at high temperature, the high temperature cyclic performance of ferric phosphate lithium cell is significantly improved.
After the present invention adopts technique scheme, first, in the lithium iron phosphate dynamic battery electrolyte of routine, the heterocyclic aromatic compound shown in structural formula 1 is added.This compounds can be used as positive pole film for additive and uses in lithium-ion battery electrolytes.Because under certain charging voltage, this compounds can be oxidized, and electric polymerization reaction occurs, thus form one deck conductive polymer membrane on the positive electrode surface of lithium battery.This polymer film covers positive electrode surface, can stop the reaction between electrolyte and positive electrode.Under the high temperature of 60 DEG C, the free acid HF content in electrolyte is higher; And the conducting film covering positive electrode surface can reduce the corrosiveness of HF to positive pole, reduce positive pole Fe Ion release amount at high temperature, thus protect positive pole, decrease the loss of capacity; In addition, the Fe ionic weight stripping in positive pole is suppressed, and to a certain degree also reduce the reduction of Fe ion in negative terminal surface, therefore the destruction of negative pole in high temperature circulation obtain certain suppression, thus improve the invertibity of battery.So the heterocyclic aromatic compound shown in structural formula 1 effectively can improve the high temperature cyclic performance of ferric phosphate lithium cell.
Moreover, after ferric phosphate lithium cell in the present invention adopts the electrolyte in technique scheme, specific chemical synthesizing method is adopted: most high charge cut-ff voltage during initial 10 chargings is higher than charge cutoff voltage during normal work, and this charge cutoff voltage is lower than 4.8V in battery initial charge process.Object makes the heterocyclic aromatic compound shown in structural formula 1 can be formed better at positive electrode surface, and more stable arrives conducting coating, improves its high temperature cyclic performance further.
In sum, LiFePO4 is after the lithium-ion-power cell of positive pole adopts electrolyte of the present invention, can overcome the deficiency of current ferric phosphate lithium cell high-temperature behavior, greatly improves its practicality in electrokinetic cell.
Embodiment
By describing technology contents of the present invention, structural feature in detail, being realized object and effect, be explained in detail below in conjunction with execution mode.
The present invention
By describing technology contents of the present invention, structural feature in detail, being realized object and effect, be explained in detail below in conjunction with execution mode, but the present invention is not limited to following embodiment.
Embodiment 1
1) described electrolyte is prepared by the following method: by ethylene carbonate (EC) and methyl ethyl carbonate (EMC) by volume for mix at EC: EMC=1: 2, lithium hexafluoro phosphate (LiPF6) is added after mixing, concentration is 1.0mol/L, add thiophene further, the content of thiophene is 0.5% by the total weight of electrolyte.
2) negative pole makes: by the mass ratio mixing negative active core-shell material modified natural graphite of 94: 1: 2.5: 2.5, conductive carbon black Super-P, binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC), then by their dispersions in deionized water, cathode size is obtained.Be coated on by slurry on the two sides of Copper Foil, through drying, calendering and vacuumize, and burn-on after nickel making outlet with supersonic welder and obtain negative plate, the thickness of pole plate is at 120-150 μm.
3) positive pole makes: the quality by 90: 3: 7 is than blended anode active material LiFePO4 (LiFePO
4), then they are dispersed in METHYLPYRROLIDONE (NMP), obtain anode sizing agent by conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF).Be uniformly coated on by slurry on the two sides of aluminium foil, through drying, calendering and vacuumize, and burn-on after aluminum lead-out wire with supersonic welder and obtain positive plate, the thickness of pole plate is at 120-150 μm.
4) barrier film makes: adopt polypropylene, polyethylene/polypropylene three layers of barrier film, thickness is 20 μm.
5) battery core be prepared in that to place thickness between positive plate and negative plate be that the polyethene microporous membrane of 20 μm is as barrier film, then the sandwich structure that positive plate, negative plate and barrier film form is reeled, square aluminum metal-back is put into after being flattened by coiling body again, the lead-out wire of both positive and negative polarity is welded on the relevant position of cover plate respectively, and with laser-beam welding machine, cover plate and metal-back are welded as a whole, obtain the battery core treating fluid injection.
6), in the glove box that the fluid injection and changing into of battery core controls below-40 DEG C at dew point, the electrolyte of above-mentioned preparation is injected battery core by liquid injection hole, and the amount of electrolyte will ensure the space be full of in battery core.The routine of then carrying out initial charge according to the following steps changes into: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min, shelve 1hr, shaping is sealed, then further with the electric current constant current charge of 0.2C to 3.65V, after normal temperature shelf 24hr, with the electric current constant-current discharge of 0.2C to 2.0V.In this patent, if no special instructions, all ferric phosphate lithium cells all change into by this conventional chemical synthesizing method, obtain required lithium ion battery after changing into.
7) normal-temperature circulating performance test: at 25 DEG C, the battery 1C constant current constant voltage after changing into is charged to 3.65V, then uses 1C constant-current discharge to 2.0V.The conservation rate of the 200th circulation volume is calculated after charge/discharge 200 circulations.
200th circulation volume conservation rate (%)=(the 200th cyclic discharge capacity/first time cyclic discharge capacity) × 100%
8) 60 DEG C of cycle performance tests: at 60 DEG C, the battery 1C constant current constant voltage after changing into is charged to 3.65V, then uses 1C constant-current discharge to 2.0V.The conservation rate of the 100th circulation volume is calculated after charge/discharge 100 circulations.
100th circulation volume conservation rate (%)=(the 100th cyclic discharge capacity/first time cyclic discharge capacity) × 100%
9) high-temperature storage performance: the battery after changing into is charged to 3.65V with 1C constant current constant voltage at normal temperatures, measures initial battery thickness, then stores 7 days at 60 DEG C, finally waits battery to be cooled to normal temperature and surveys battery final thickness again, calculate cell thickness expansion rate.
Cell thickness expansion rate (%)=((final thickness-original depth)/original depth) × 100%
Embodiment 2
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 2-methylthiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 3
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 2-acetyl thiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 4
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 3 methyl thiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 5
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 3-ethylthiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 6
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 2-n-pentyl thiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 7
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 3-octyl thiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 8
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 3-certain herbaceous plants with big flowers base thiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 9
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 3,4-rthylene dioxythiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 10
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% benzothiophene.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 11
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% furans.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 12
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% 2-methylfuran.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Embodiment 13
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 0.5% N-methylpyrrole.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
Comparative example 1
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, does not add any additive unlike in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 1.
The data of 60 DEG C of circulations of table 1 embodiment 1 ~ 13 and comparative example 1, normal temperature circulation and high-temperature storage
Note: routine changes into: in initial charge, 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min.
As can be seen from the data of table 1, with the addition of the electrolyte of thiophene, thiophene derivant, furans, furan derivatives and N-methylpyrrole, compared with not containing the electrolyte of additive, high temperature cyclic performance and the high-temperature storage performance of obtained battery are significantly improved, and normal-temperature circulating performance slightly improves.
Embodiment 14
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, replaces to 0.01% unlike by the content of thiophene in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 2.
Embodiment 15
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, replaces to 0.1% unlike by the content of thiophene in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 2.
Embodiment 16
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, replaces to 1% unlike by the content of thiophene in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 2.
Embodiment 17
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, replaces to 2% unlike by the content of thiophene in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 2.
Embodiment 18
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, replaces to 3% unlike by the content of thiophene in electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 2.
The data of 60 DEG C of circulations of table 2 embodiment 14 ~ 18, normal temperature circulation and high-temperature storage
Note: routine changes into: in initial charge, 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min.
As can be seen from table 2 data, when the content of thiophene is increased to 2% from 0.01%, high temperature cyclic performance and high-temperature storage performance improve gradually, and when content is increased to 2% from 1%, the increase rate of high temperature cyclic performance and high-temperature storage performance is less; But when content is increased to 5% from 2%, high temperature circulation and high-temperature storage performance decline clearly.
Embodiment 19
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, and also add VEC in electrolyte, the content of VEC is 1% by the total weight of electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Embodiment 20
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, and in electrolyte, also add fluorinated ethylene carbonate (FEC), the content of FEC is 1% by the total weight of electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Embodiment 21
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, and also add VC in electrolyte, the content of VC is 1% by the total weight of electrolyte.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Embodiment 22
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 17 identical, conventional chemical synthesizing method is not adopted when initial charge unlike battery, and adopt following high voltage chemical synthesizing method: first 0.05C charging 60min, then 0.2C charges to 4.2V, finally at 4.2V constant voltage 120min.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Comparative example 2
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 1% VEC.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Comparative example 3
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 1% FEC.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
Comparative example 4
Preparation method of electrolyte and preparation method of lithium ion battery and embodiment 1 identical, unlike by electrolyte 0.5% thiophene replace to 1% VC.Test the 60 DEG C of circulations, the normal temperature that obtain circulate and the data of high-temperature storage in table 3.
The data of 60 DEG C of circulations of table 3 embodiment 19 ~ 22 and comparative example 2 ~ 4, normal temperature circulation and high-temperature storage
Note: routine changes into: in initial charge, 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min; High voltage changes into: in initial charge, 0.05C constant current charge 60min, then 0.2C charges to 4.2V, finally at 4.2V constant voltage 120min.
As can be seen from the data of table 3, on the basis using VC, FEC or VEC, add thiophene further and battery can be made to obtain better high temperature cyclic performance, high-temperature storage performance and normal-temperature circulating performance; In addition, after adding thiophene, the method adopting high voltage to change into, can improve high temperature cyclic performance, high-temperature storage performance and normal-temperature circulating performance further.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (4)
1. a lithium ion battery, it comprises:
Active material is LiFePO
4negative electrode;
Anode;
Be placed in the dividing plate between negative electrode and positive electrode; And
Nonaqueous electrolytic solution, described electrolyte comprises solvent and film for additive, and described film for additive is made up of the aromatic compound as described in structural formula 1:
Wherein X group is selected from: the one in S, O, NR, and in described NR, R group is independently selected from H, alkyl, the one in amino;
R
1, R
2, R
3, R
4be chain substituting group or be interconnected into ring independently;
R
1, R
2, R
3, R
4when being interconnected into ring, R
1with R
3, R
1with R
2, or R
2with R
4independently Cheng Huan, described ring is 4 ~ 6 rings, and described 4 ~ 6 rings are cyclic hydrocarbon or heterocycle, and described heterocycle is the heterocycle containing O, S or N, and described cyclic hydrocarbon is cycloalkane, cycloolefin or benzene;
Described chain substituting group is selected from halogen, carbon number is the alkyl of 1 ~ 10, carbon number is the alkoxyl of 1 ~ 10, carbon number is the acyl group of 1 ~ 10, carbon number is the alkenyl of 2 ~ 10, nitro, sulfenyl, one in sulfonyl and phenyl, described chain substituting group is straight chain substituent or branched chain substituting group;
The content of the aromatic compound described in structural formula 1 is 0.5 ~ 2 % by weight by the total weight of electrolyte;
Solvent in described nonaqueous electrolytic solution is made up of one or more in following composition: cyclic carbonate, linear carbonate and carboxylate;
Wherein cyclic carbonate is selected from: ethylene carbonate, propene carbonate, one or more in butylene;
Linear carbonate is selected from: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, one or more in methyl propyl carbonate;
Carboxylate is selected from: gamma-butyrolacton, ethyl acetate, ethyl propionate, methyl propionate, one or more in methyl butyrate;
Described lithium ion battery is obtained by following chemical synthesizing method: the most high charge cut-ff voltage when initial 10 chargings is higher than charge cutoff voltage during normal work, and described most high charge cut-ff voltage is lower than 4.8V.
2. lithium ion battery according to claim 1, is characterized in that, described nonaqueous electrolytic solution also comprises one or more of following additive: vinylene carbonate, vinyl ethylene carbonate, halogenated ethylene carbonate, cyclic sulfonic acid ester, cyclic sulfite, cyclic sulfates.
3. lithium ion battery according to claim 1, is characterized in that, the active material of described anode is graphite.
4. according to the nonaqueous electrolytic solution used in claims 1 to 3 any one lithium ion battery.
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| PCT/CN2012/086253 WO2013120376A1 (en) | 2012-02-17 | 2012-12-10 | Lithium ion battery and electrolyte thereof |
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| JP7135833B2 (en) | 2018-12-21 | 2022-09-13 | トヨタ自動車株式会社 | Manufacturing method of lithium ion battery and lithium ion battery |
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| CN102709589B (en) * | 2012-02-17 | 2016-04-13 | 深圳新宙邦科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN103384017B (en) * | 2013-07-04 | 2016-04-13 | 珠海市赛纬电子材料有限公司 | A kind of nonaqueous electrolytic solution of high-voltage lithium ion batteries |
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| WO2013120376A1 (en) | 2013-08-22 |
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