CN102709589A - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN102709589A CN102709589A CN201210036695XA CN201210036695A CN102709589A CN 102709589 A CN102709589 A CN 102709589A CN 201210036695X A CN201210036695X A CN 201210036695XA CN 201210036695 A CN201210036695 A CN 201210036695A CN 102709589 A CN102709589 A CN 102709589A
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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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- 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
- H01M4/00—Electrodes
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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 battery with a good high-temperature circulating performance. The lithium ion battery comprises a cathode, an anode, a separation plate and a non-water electrolyte, wherein an active substance of the cathode is LiFePO4; the separation plate is arranged between the cathode and the anode; the electrolyte contains an aromatic compound shown by a structural formula, wherein an X radical is selected from one of S, O, and NR; an R radical in the NR is independently selected from one of H, alkyl and an amino radical; and R1, R2, R3 and R4 are independent chain-shaped substituted radical or mutually connected to form a ring.
Description
Technical field
The present invention relates to a kind of lithium ion battery and lithium-ion battery electrolytes, relate in particular to a kind of ferric phosphate lithium cell and electrolyte thereof.
Background technology
Got into since 21 century, the recoverable amount of the automobile of countries in the world increases day by day, makes that the petroleum resources of the earth are deficient day by day, and the pollution of atmospheric environment is serious day by day.Under this background, 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 is high because of its energy density, and capacity is high, and advantages such as good cycle and environmental protection become the first-selected electrical source of power of current driving force automobile.And can power vehicle and hybrid vehicle be employed in daily life widely, and the performance of power lithium-ion rechargeable battery just becomes key.As electrokinetic cell, must have good high temperature performance, normal-temperature circulating performance, longer-term storage performance and security performance.
Anode material for lithium-ion batteries LiFePO
4Because of capacity is high, good cycle, Stability Analysis of Structures, environmental friendliness, advantage such as raw material are cheap becomes the research focus of present lithium-ion-power cell.During the actual use of electrokinetic cell, because itself can heating during battery discharge, its residing ambient temperature be generally than higher (40～80 ℃), with this understanding, the high-temperature behavior of lithium iron phosphate dynamic battery had higher requirement.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 addressing the above problem, the present invention provides a kind of high temperature cyclic performance good lithium ion battery, and it comprises:
Active material is LiFePO
4Negative electrode;
Anode;
Place the dividing plate between negative electrode and the anode; And
Nonaqueous electrolytic solution, and contain in this electrolyte just like structural formula 1 described aromatic compound:
Wherein the X group is selected from: S, and O, a kind of among the NR, the R group independently is selected from H among the said NR, alkyl, a kind of in the 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
1, with R
3, R
1With R
2,, or R
2, with R
4The independent Cheng Huan of difference, said ring is 4～6 yuan of rings, and said 4～6 yuan of rings are cyclic hydrocarbon or heterocycle, and said heterocycle is the heterocycle that contains O, S or N, and said cyclic hydrocarbon is cycloalkane, cycloolefin or benzene;
Said chain substituting group is selected from hydrogen atom, and halogen, carbon number are 1～10 alkyl; Carbon number is 1～10 alkoxyl, and carbon number is 1～10 acyl group, and carbon number is 2～10 alkenyl; Nitro; Sulfenyl, a kind of in sulfonyl and the phenyl, said chain substituting group is straight chain substituting group or branched chain substituting group;
The content of structural formula 1 described aromatic compound is counted 0.01～2 weight % by the total weight of electrolyte.When this heterocyclic aromatic compound content was very few in the electrolyte, it can't form conducting film on anodal surface, does not just have protective effect; When this heterocyclic aromatic compound content was too much in the electrolyte, therefore the internal resistance meeting of battery increased, and invertibity reduces, mis-behave.
More specifically, preferred one or more in following structural of the heterocyclic aromatic compound shown in the said structural formula 1:
As preferred version of the present invention, said lithium ion battery makes through following chemical synthesizing method: the charging cut-ff voltage when the high charge cut-ff voltage in initial 10 whens charging will be higher than operate as normal, and said high charge cut-ff voltage is lower than 4.8V.
As preferred version of the present invention, said nonaqueous electrolytic solution also comprises one or more of following additive: vinylene carbonate, vinyl ethylene carbonate, halogenated ethylene carbonate, ring-type sulphonic acid ester, cyclic sulfite, cyclic sulfates.
As preferred version of the present invention, the solvent in the said nonaqueous electrolytic solution contains one or more in the following composition: cyclic carbonate, linear carbonate and carboxylate;
Wherein cyclic carbonate is for being selected from: ethylene carbonate, propene carbonate, one or more in the butylene;
Linear carbonate or carboxylate are selected from: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, one or more in the carbonic acid first propyl ester;
Carboxylate is selected from: gamma-butyrolacton, ethyl acetate, ethyl propionate, methyl propionate, one or more in the methyl butyrate.
As preferred version of the present invention, the active material of said anode is a graphite.
The inventor finds that under hot conditions, the too fast reason of ferric phosphate lithium cell capacity attenuation mainly contains: the stripping of (1) anodal Fe ion.Under higher temperature (55 ℃), the as easy as rolling off a log decomposition of the LiPF6 in the electrolyte produces HF and PF
5Wherein HF can corrode positive pole, causes the stripping of Fe ion, thereby destroys the positive electrode structure, causes capacity to run off; (2) the Fe ion is in the reduction of negative pole.In the high temperature circulation process, the HF content in the electrolyte increases, and causes the Fe ion stripping quantity in the positive pole to increase.In the process of charge and discharge cycles, the Fe ion of stripping can be reduced into Fe simple substance on the SEI surface like this, makes the impedance of negative pole more and more come greatly along with becoming of discharging and recharging, and causes the battery irreversible capacity to increase, and finally makes the major cycle of battery.We can say that under hot conditions, the stripping of anodal Fe ion has destructive effect to both positive and negative polarity.If in electrolyte, add anodal film for additive, can reduce the stripping of Fe ion in the positive pole under the high temperature to a certain extent, thereby improve the high temperature cyclic performance of ferric phosphate lithium cell.
The inventor is through creationary research; Proposed to adopt thiophene, furans, pyrroles and the derivative thereof shown in the structural formula 1 as anodal film for additive; Be allowed to condition in the formation process and form an electric conductive polymer film on the anode active material of phosphate iron lithium surface; Suppressed ferric phosphate lithium cell Fe ion stripping at high temperature, the high temperature cyclic performance of ferric phosphate lithium cell is significantly improved.
After the present invention adopts technique scheme, at first, in the lithium iron phosphate dynamic battery electrolyte of routine, add the heterocyclic aromatic compound shown in the structural formula 1.This compounds can be used as anodal film for additive and uses in lithium-ion battery electrolytes.Because under certain charging voltage, this compounds can be oxidized, and electric polymerization reaction takes place, thereby form one deck conductive polymer membrane on the positive electrode surface of lithium battery.This polymer film covers anodal surface, can stop the reaction between electrolyte and the positive electrode.Under 60 ℃ high temperature, the free acid HF content in the electrolyte is higher; And the conducting film that covers anodal surface can reduce the corrosiveness of HF to positive pole, reduces anodal Fe ion stripping quantity at high temperature, thereby has protected positive pole, has reduced the loss of capacity; In addition, the Fe ionic weight stripping in the positive pole is suppressed, and to a certain degree also reduces the reduction of Fe ion in negative terminal surface, and therefore the destruction of negative pole in high temperature circulation obtain certain inhibition, thereby improves the invertibity of battery.So the heterocyclic aromatic compound shown in the structural formula 1 can effectively improve the high temperature cyclic performance of ferric phosphate lithium cell.
Moreover; After ferric phosphate lithium cell among the present invention adopts the electrolyte in the technique scheme; In battery initial charge process, adopt specific chemical synthesizing method: the charging cut-ff voltage when the high charge cut-ff voltage during initial 10 chargings will be higher than operate as normal, and this charging cut-ff voltage is lower than 4.8V.Purpose is that the heterocyclic aromatic compound shown in the structural formula 1 can be formed on anodal surface is better, and is more stable to conducting coating, further improves its high temperature cyclic performance.
In sum, LiFePO4 is after anodal lithium-ion-power cell adopts electrolyte of the present invention, can overcome the deficiency of present ferric phosphate lithium cell high-temperature behavior, improves its practicality in electrokinetic cell greatly.
Embodiment
By specifying technology contents of the present invention, structural feature, realized purpose and effect, give explanation below in conjunction with execution mode is detailed.
The present invention
By specifying technology contents of the present invention, structural feature, being realized purpose and effect, give explanation below in conjunction with execution mode is detailed, but the present invention is not limited to following embodiment.
Embodiment 1
1) said electrolyte prepares by following method: ethylene carbonate (EC) and methyl ethyl carbonate (EMC) are EC: EMC=1 by volume: 2 mix; Mix the back and add lithium hexafluoro phosphate (LiPF6); Concentration is 1.0mol/L; Further add thiophene, the content of thiophene counts 0.5% by the total weight of electrolyte.
2) negative pole is made: by 94: 1: 2.5: 2.5 mass ratio mixing negative active core-shell material modified natural graphite; Conductive carbon black Super-P; Binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC) are dispersed in them in the deionized water then, obtain cathode size.Slurry is coated on the two sides of Copper Foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and to obtain negative plate after the nickel making outlet, the thickness of pole plate is at 120-150 μ m.
3) the anodal making: the quality of pressing 90: 3: 7 are than blended anode active material LiFePO4 (LiFePO
4), conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF) are dispersed in them in the N-N-methyl-2-2-pyrrolidone N-(NMP) then, obtain anode sizing agent.Slurry is uniformly coated on the two sides of aluminium foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and to obtain positive plate behind the aluminum lead-out wire, the thickness of pole plate is at 120-150 μ m.
4) barrier film is made: adopt three layers of barrier film of polypropylene, polyethylene/polypropylene, thickness is 20 μ m.
5) electric core is prepared between positive plate and the negative plate that to place thickness be that the polyethene microporous membrane of 20 μ m is as barrier film; The sandwich structure of then positive plate, negative plate and barrier film being formed is reeled; Put into square aluminum metal-back after again coiling body being flattened; The lead-out wire of both positive and negative polarity is welded on respectively on the relevant position of cover plate, and cover plate and metal-back is welded as a whole, obtain treating the electric core of fluid injection with laser-beam welding machine.
6) fluid injection of electric core and changing at dew point in the glove box that is controlled at below-40 ℃ is injected electric core with the electrolyte of above-mentioned preparation through liquid injection hole, and the amount of electrolyte will guarantee to be full of the space in the electric core.The routine of carrying out initial charge then 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 shelves 1hr; Shaping is sealed; Then further with the electric current constant current charge of 0.2C to 3.65V, after normal temperature is shelved 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, get required lithium ion battery after changing into.
7) normal-temperature circulating performance test: under 25 ℃, the battery after changing into is charged to 3.65V with the 1C constant current constant voltage, uses the 1C constant-current discharge then to 2.0V.The conservation rate of the 200th circulation volume is calculated in 200 circulation backs of charge/discharge.
The 200th circulation volume conservation rate (%)=(the 200th cyclic discharge capacity/first time cyclic discharge capacity) * 100%
8) 60 ℃ of cycle performance tests: under 60 ℃, the battery after changing into is charged to 3.65V with the 1C constant current constant voltage, uses the 1C constant-current discharge then to 2.0V.The conservation rate of the 100th circulation volume is calculated in 100 circulation backs of charge/discharge.
The 100th circulation volume conservation rate (%)=(the 100th cyclic discharge capacity/first time cyclic discharge capacity) * 100%
9) high-temperature storage performance: the battery after will changing into is charged to 3.65V with the 1C constant current constant voltage at normal temperatures, measures the battery original depth, stores 7 days at 60 ℃ then, waits battery to be cooled to normal temperature at last and surveys the battery final thickness again, the counting cell thickness swelling.
Cell thickness expansion rate (%)=((final thickness-original depth)/original depth) * 100%
Embodiment 2
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 2-methylthiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 3
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, different is with in the electrolyte 0.5% thiophene replace to 0.5% 2-acetyl thiophene.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 4
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 3 methyl thiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 5
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 3-ethylthiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 6
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 2-n-pentyl thiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 7
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 3-octyl group thiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 8
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 3-certain herbaceous plants with big flowers base thiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 9
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, different is with 0.5% thiophene in the electrolyte replace to 0.5% 3, the 4-ethene dioxythiophene.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 10
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% benzothiophene with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 11
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% furans with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 12
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% 2-methylfuran with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Embodiment 13
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.5% N-methylpyrrole with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
Comparative example 1
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is not add any additive in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 1.
The data of 60 ℃ of circulations of table 1 embodiment 1～13 and comparative example 1, normal temperature circulation and high-temperature storage
Annotate: routine changes into: in the initial charge, and 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min.
Data by table 1 can be found out; Added the electrolyte of thiophene, thiophene derivant, furans, furan derivatives and N-methylpyrrole; Compare with the electrolyte that does not contain additive; The high temperature cyclic performance of prepared battery and high-temperature storage performance are significantly improved, and normal-temperature circulating performance slightly improves.
Embodiment 14
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.01% with the content of thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 2.
Embodiment 15
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 0.1% with the content of thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 2.
Embodiment 16
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 1% with the content of thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 2.
Embodiment 17
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 2% with the content of thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 2.
Embodiment 18
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 3% with the content of thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 2.
The data of 60 ℃ of circulations of table 2 embodiment 14～18, normal temperature circulation and high-temperature storage
Annotate: routine changes into: in the initial charge, and 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min.
Can find out by table 2 data, when the content of thiophene when 0.01% is increased to 2%, high temperature cyclic performance and high-temperature storage performance improve gradually, when content when 1% is increased to 2%, the increase rate of high temperature cyclic performance and high-temperature storage performance is less; But when content when 2% is increased to 5%, high temperature circulation and high-temperature storage performance descend very obvious.
Embodiment 19
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and also adds VEC in the electrolyte, and the content of VEC counts 1% by the total weight of electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Embodiment 20
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and also adds fluorinated ethylene carbonate (FEC) in the electrolyte, and the content of FEC counts 1% by the total weight of electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Embodiment 21
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and also adds VC in the electrolyte, and the content of VC counts 1% by the total weight of electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Embodiment 22
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 17; Different is that battery does not adopt conventional chemical synthesizing method when initial charge; And adopting following high voltage to change into method: first 0.05C charging 60min, 0.2C charges to 4.2V again, at last at 4.2V constant voltage 120min.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Comparative example 2
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 1% VEC with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Comparative example 3
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 1% FEC with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
Comparative example 4
Preparation method of electrolyte is identical with preparation method of lithium ion battery and embodiment's 1, and different is replaces to 1% VC with 0.5% thiophene in the electrolyte.The data of 60 ℃ of circulations that test obtains, normal temperature circulation and high-temperature storage are seen table 3.
The data of 60 ℃ of circulations of table 3 embodiment 19～22 and comparative example 2～4, normal temperature circulation and high-temperature storage
Annotate: routine changes into: in the initial charge, and 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min; High voltage changes into: in the initial charge, and 0.05C constant current charge 60min, 0.2C charges to 4.2V again, at last at 4.2V constant voltage 120min.
Data by table 3 can be found out, on the basis of using VC, FEC or VEC, further add thiophene and can make battery obtain better high temperature cyclic performance, high-temperature storage performance and normal-temperature circulating performance; In addition, behind the interpolation thiophene, the method that adopts high voltage to change into can further improve high temperature cyclic performance, high-temperature storage performance and normal-temperature circulating performance.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (6)
1. lithium ion battery, it comprises:
Active material is LiFePO
4Negative electrode;
Anode;
Place the dividing plate between negative electrode and the anode; And
Nonaqueous electrolytic solution, and contain in this electrolyte just like structural formula 1 described aromatic compound:
Wherein the X group is selected from: S, and O, a kind of among the NR, the R group independently is selected from H among the said NR, alkyl, a kind of in the 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
1, with R
3, R
1With R
2,, or R
2, with R
4The independent Cheng Huan of difference, said ring is 4～6 yuan of rings, and said 4～6 yuan of rings are cyclic hydrocarbon or heterocycle, and said heterocycle is the heterocycle that contains O, S or N, and said cyclic hydrocarbon is cycloalkane, cycloolefin or benzene;
Said chain substituting group is selected from hydrogen atom, and halogen, carbon number are 1～10 alkyl; Carbon number is 1～10 alkoxyl, and carbon number is 1～10 acyl group, and carbon number is 2～10 alkenyl; Nitro; Sulfenyl, a kind of in sulfonyl and the phenyl, said chain substituting group is straight chain substituting group or branched chain substituting group;
The content of structural formula 1 described aromatic compound is counted 0.01～2 weight % by the total weight of electrolyte.
2. lithium ion battery according to claim 1; It is characterized in that; Said lithium ion battery makes through following chemical synthesizing method: the charging cut-ff voltage when the high charge cut-ff voltage in initial 10 whens charging will be higher than operate as normal, and said high charge cut-ff voltage is lower than 4.8V.
3. lithium ion battery according to claim 1 and 2 is characterized in that said nonaqueous electrolytic solution also comprises one or more of following additive: vinylene carbonate; Vinyl ethylene carbonate, halogenated ethylene carbonate, ring-type sulphonic acid ester; Cyclic sulfite, cyclic sulfates.
4. lithium ion battery according to claim 1 and 2 is characterized in that, the solvent in the said nonaqueous electrolytic solution contains one or more in the following composition: cyclic carbonate, linear carbonate and carboxylate;
Wherein cyclic carbonate is for being selected from: ethylene carbonate, propene carbonate, one or more in the butylene;
Linear carbonate or carboxylate are selected from: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, one or more in the carbonic acid first propyl ester;
Carboxylate is selected from: gamma-butyrolacton, ethyl acetate, ethyl propionate, methyl propionate, one or more in the methyl butyrate.
5. lithium ion battery according to claim 1 and 2 is characterized in that, the active material of said anode is a graphite.
6. according to employed nonaqueous electrolytic solution in any lithium ion battery of claim 1 to 5.
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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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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013120376A1 (en) * | 2012-02-17 | 2013-08-22 | 深圳新宙邦科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN103384017A (en) * | 2013-07-04 | 2013-11-06 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte of high-voltage lithium ion batteries |
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| CN110931866A (en) * | 2019-11-26 | 2020-03-27 | 宁夏百川新材料有限公司 | Lithium ion battery electrolyte |
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| JP2020102348A (en) * | 2018-12-21 | 2020-07-02 | トヨタ自動車株式会社 | Manufacturing method of lithium ion battery, and lithium ion battery |
| US10991972B2 (en) | 2016-01-29 | 2021-04-27 | Byd Company Limited | Electrolyte solution, positive electrode, and lithium-ion battery comprising the electrolyte solution and/or the positive electrode |
| CN116936934A (en) * | 2023-09-13 | 2023-10-24 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery and electric equipment |
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| WO2013120376A1 (en) * | 2012-02-17 | 2013-08-22 | 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 |
| CN103384017A (en) * | 2013-07-04 | 2013-11-06 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte of high-voltage lithium ion batteries |
| WO2015082711A1 (en) * | 2013-12-05 | 2015-06-11 | Abengoa Research, S.L. | Alkali ion battery and method for producing the same |
| JP2016146315A (en) * | 2015-02-06 | 2016-08-12 | 寧徳新能源科技有限公司 | Electrolyte additive application and application thereof |
| US20160233545A1 (en) * | 2015-02-06 | 2016-08-11 | Ningde Amperex Technology Limited | Electrolyte additive and use thereof |
| CN105098243A (en) * | 2015-08-04 | 2015-11-25 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN105119016A (en) * | 2015-08-04 | 2015-12-02 | 宁德时代新能源科技有限公司 | Electrolyte and lithium ion battery with same |
| CN105119016B (en) * | 2015-08-04 | 2018-03-06 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| CN105119019A (en) * | 2015-09-11 | 2015-12-02 | 合肥国轩高科动力能源股份公司 | Electrolyte and lithium ion battery using same |
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| CN105406004A (en) * | 2015-12-05 | 2016-03-16 | 江苏天鹏电源有限公司 | Diaphragm for lithium-ion battery roll core |
| US10991972B2 (en) | 2016-01-29 | 2021-04-27 | Byd Company Limited | Electrolyte solution, positive electrode, and lithium-ion battery comprising the electrolyte solution and/or the positive electrode |
| CN107799820A (en) * | 2017-10-24 | 2018-03-13 | 广州天赐高新材料股份有限公司 | Lithium secondary cell electrolyte and its lithium secondary battery |
| CN110797572A (en) * | 2018-08-03 | 2020-02-14 | 惠州市豪鹏科技有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN109193028A (en) * | 2018-08-20 | 2019-01-11 | 杉杉新材料（衢州）有限公司 | A kind of lithium ion battery nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution |
| CN109244472A (en) * | 2018-09-26 | 2019-01-18 | 烟台大学 | A kind of lithium-sulfur cell comprising the protectant electrolyte of anode and comprising the electrolyte |
| CN111354977A (en) * | 2018-11-25 | 2020-06-30 | 合肥方耐特能源科技有限公司 | Lithium ion battery electrolyte, preparation method thereof and lithium battery comprising lithium ion battery electrolyte |
| JP2020102348A (en) * | 2018-12-21 | 2020-07-02 | トヨタ自動車株式会社 | Manufacturing method of lithium ion battery, and lithium ion battery |
| US11316196B2 (en) * | 2018-12-21 | 2022-04-26 | Toyota Jidosha Kabushiki Kaisha | Lithium-ion battery containing electrolyte including capacity restoration additives and method for restoring capacity of lithium-ion battery |
| CN109786830A (en) * | 2018-12-24 | 2019-05-21 | 杉杉新材料（衢州）有限公司 | A kind of electrolyte containing siloxane solvent and thiophene-based additive and the lithium ion battery using the electrolyte |
| CN110931866A (en) * | 2019-11-26 | 2020-03-27 | 宁夏百川新材料有限公司 | Lithium ion battery electrolyte |
| CN111106385A (en) * | 2019-12-25 | 2020-05-05 | 合肥国轩高科动力能源有限公司 | Electrolyte of lithium ion battery, preparation method of electrolyte and battery |
| CN116936934A (en) * | 2023-09-13 | 2023-10-24 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery and electric equipment |
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| WO2013120376A1 (en) | 2013-08-22 |
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