CN103107364A - Low-temperature type lithium ion battery electrolyte and lithium ion battery - Google Patents
Low-temperature type lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN103107364A CN103107364A CN2012100290823A CN201210029082A CN103107364A CN 103107364 A CN103107364 A CN 103107364A CN 2012100290823 A CN2012100290823 A CN 2012100290823A CN 201210029082 A CN201210029082 A CN 201210029082A CN 103107364 A CN103107364 A CN 103107364A
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- ion battery
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a low-temperature type lithium ion battery electrolyte. The electrolyte comprises lithium hexafluorophosphate LiPF6 and a mixed solvent, wherein the concentration of the lithium hexafluorophosphate LiPF6 is 0.8-1.5mol/l, and the mixed solvent comprises the following components in percent by weight: 20-40 percent of ethylene carbonate (EC), 5-30 percent of ethyl methyl carbonate (EMC), 30-50 percent of methyl acetate (MA) and 0.5-5 percent of vinylene carbonate (VC). According to the electrolyte, the low-melting-point organic solvents, namely, the EMC and the MA, and a film-forming agent, namely, the VC, are added to the basic solvent, namely, the EC to ensure that the low temperature performance of the lithium ion battery is improved, the electrochemical property of the lithium ion battery under the low temperature condition is improved, and the application range of the lithium ion battery is greatly enlarged.
Description
Technical field
The present invention relates to technical field of lithium batteries, the lithium ion battery that is specifically related to a kind of electrolyte of low temp lithium ion battery and adopts this electrolyte to make.
Background technology
Lithium ion battery is the novel high-energy battery of 20th century exploitation.Lithium ion battery is owing to having operating voltage high (3.6V is cadmium-nickel, nickel-hydrogen battery three times), volume little (less by 30% than nickel-hydrogen battery), quality light (lighter by 50% than nickel-hydrogen battery), the high (140WHKg of specific energy
-1, be 2～3 times of nickel-cadmium cell, 1～2 times of nickel-hydrogen battery), memory-less effect, the advantage such as pollution-free, self discharge is little, have extended cycle life, become the desirable energy of 21 century development.Lithium-ion battery electrolytes is the important component part of lithium ion battery, is the blood of lithium ion battery, works to transmit lithium ion in lithium ion battery.Lithium-ion battery electrolytes usually by carbonates organic solvent (as ethylene carbonate, dimethyl carbonate, propene carbonate), electrolyte lithium salt (as LiPF
6, LiBF
4) etc. composition.
In recent years, lithium ion battery has obtained developing rapidly, but with present technology, lithium ion battery still comes with some shortcomings, so its scope of application also is restricted, and use therein ambient temperature is exactly an important limiting factor.When the ambient temperature of using was too low, the performance of lithium ion battery will descend.The main cause of lithium ion battery poor performance under cryogenic conditions is: because lithium battery electrolytes can solidify at low temperatures, therefore the viscosity of electrolyte becomes large, the lithium ion migration becomes difficult, impedance between positive pole and barrier film and negative pole and barrier film also can increase, under cryogenic conditions, electrolyte all can be relatively poor to the penetrability of barrier film to soakage and the lithium ion of barrier film, therefore causes lithium ion battery hydraulic performance decline under cryogenic conditions.Therefore, improve the electrical property of lithium ion battery under cryogenic conditions, become a focus in Study on Li-ion batteries using field with the range of application of widening lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind of electrolyte of low temp lithium ion battery.
The present invention also aims to provide a kind of lithium ion battery.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of electrolyte of low temp lithium ion battery, and by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 0.8～1.5mol/l, described mixed solvent is comprised of the component of following weight percentage: 20%～40% ethylene carbonate EC, 5%～30% methyl ethyl carbonate alkene ester EMC, 30%～50% methyl acetate MA, 0.5%～5% vinylene carbonate VC.
Described lithium hexafluoro phosphate LiPF
6, ethylene carbonate EC, methyl ethyl carbonate alkene ester EMC, methyl acetate MA, vinylene carbonate VC be LITHIUM BATTERY reagent, main content is all greater than 99.95%, moisture≤5PPm.
A kind of lithium ion battery comprises electrode group and lithium-ion battery electrolytes, and described electrode group and lithium-ion battery electrolytes are sealed in battery container, and described electrode group comprises positive pole, negative pole and barrier film, and described lithium-ion battery electrolytes is by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 0.8～1.5mol/l, described mixed solvent is comprised of the component of following weight percentage: 20%～40% ethylene carbonate EC, 5%～30% methyl ethyl carbonate alkene ester EMC, 30%～50% methyl acetate MA, 0.5%～5% vinylene carbonate VC.
For improving the chemical property of lithium battery under cryogenic conditions, solve the application problem of present lithium battery in low temperature environment, electrolyte of low temp lithium ion battery provided by the invention has increased the consumption of the lower organic solvent of fusing point, to widen the temperature limit of electrolyte, reduce the solidifying point of electrolyte; Added simultaneously film for additive, guaranteed the steadiness of battery SEI film, made circulating effect better.Electrolyte of low temp lithium ion battery provided by the invention with the high organic solvent ethylene carbonate EC of conductivity as basic solvent, the selection fusing point is lower and have methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of high conductance as the part of dicyandiamide solution, methyl ethyl carbonate alkene ester EMC and methyl acetate MA can improve the low-temperature conductive performance of electrolyte, make whole electrolyte keep modest viscosity, have higher conductivity.Add film for additive vinylene carbonate VC, can improve the filming performance of electrolyte.Because ring-type EC has higher dielectric constant and viscosity, add low viscous chain EMC (fusing point-55 ℃) to have lower fusing point, can improve the ionic conductivity of mixed solvent, widen the serviceability temperature scope of mixed solvent, increase the fail safe of battery; MA (fusing point-98 ℃, viscosity 0.37mPa.s, dielectric constant 6.7c/v.m) has lower fusing point and higher dielectric constant, can significantly improve the cryogenic property of electrolyte under cryogenic conditions.In addition, vinylene carbonate (VC) is a kind of ring-type organic solvent that contains unsaturated double-bond, can form the SEI film of stable performance-alkoxyl carbonic ester lithium in the lithium ion battery first charge-discharge, simultaneously the one-tenth film potential of VC is all lower than the one-tenth film potential of above several solvents, thereby reduce the loss of lithium ion, increase battery capacity, be conducive to improve the cycle life of lithium ion battery.The present invention is improved the cryogenic property of lithium ion battery by add organic solvent methyl ethyl carbonate alkene ester EMC and methyl acetate MA and the film for additive vinylene carbonate VC of low melting point in basic solvent ethylene carbonate EC.
Electrolyte of low temp lithium ion battery provided by the invention has following advantage: this electrolyte is in the environment of low temperature-40 ℃, standing 16～24h, then discharge with 0.2C, discharge capacity is that 55% ,-20 ℃ of normal temperature (25 ℃) 0.2C discharge capacity, 1C discharge capacity are 90% of normal temperature (25 ℃) 0.2C discharge capacities.
Generally speaking, when present lithium ion battery was used in low temperature environment, chemical property can be affected.Electrolyte of low temp lithium ion battery provided by the invention has reduced the fusing point of electrolyte, has increased the consumption of low melting point solvent, has improved the chemical property of lithium ion battery under cryogenic conditions, has greatly widened the range of application of lithium ion battery.
Embodiment
Below by specific embodiment, technical scheme of the present invention is elaborated.
Embodiment 1
The electrolyte of low temp lithium ion battery that the present embodiment provides is by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 0.8mol/l, mixed solvent is comprised of the component of following weight percentage: 20% ethylene carbonate EC, 30% methyl ethyl carbonate alkene ester EMC, 45% methyl acetate MA, 5% vinylene carbonate VC.
Randomly draw 20 not 1665132 batteries of fluid injection, in the constant temperature and humidity room, these 20 batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides, according to a conventional method will be the battery of fluid injection carry out aging, change into, degasification, sealing, partial volume, make lithium ion battery.
Embodiment 2
The electrolyte of low temp lithium ion battery that the present embodiment provides is by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 1.0mol/l, mixed solvent is comprised of the component of following weight percentage: 40% ethylene carbonate EC, 9.5% methyl ethyl carbonate alkene ester EMC, 50% methyl acetate MA, 0.5% vinylene carbonate VC.
Randomly draw 20 not 1665132 batteries of fluid injection, in the constant temperature and humidity room, these 20 batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides, according to a conventional method will be the battery of fluid injection carry out aging, change into, degasification, sealing, partial volume, make lithium ion battery.
Embodiment 3
The electrolyte of low temp lithium ion battery that the present embodiment provides is by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 1.5mol/l, mixed solvent is comprised of the component of following weight percentage: 40% ethylene carbonate EC, 27% methyl ethyl carbonate alkene ester EMC, 30% methyl acetate MA, 3% vinylene carbonate VC.
Randomly draw 20 not 1665132 batteries of fluid injection, in the constant temperature and humidity room, these 20 batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides, according to a conventional method will be the battery of fluid injection carry out aging, change into, degasification, sealing, partial volume, make lithium ion battery.
Embodiment 4
The electrolyte of low temp lithium ion battery that the present embodiment provides is by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 1.2mol/l, mixed solvent is comprised of the component of following weight percentage: 40% ethylene carbonate EC, 5% methyl ethyl carbonate alkene ester EMC, 50% methyl acetate MA, 5% vinylene carbonate VC.
Randomly draw 20 not 1665132 batteries of fluid injection, in the constant temperature and humidity room, these 20 batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides, according to a conventional method will be the battery of fluid injection carry out aging, change into, degasification, sealing, partial volume, make lithium ion battery.
The raw material lithium hexafluoro phosphate LiPF that uses in embodiment 1-embodiment 4
6, ethylene carbonate EC, methyl ethyl carbonate alkene ester EMC, methyl acetate MA, vinylene carbonate VC be LITHIUM BATTERY reagent, main content is all greater than 99.95%, moisture≤5PPm.
For ease of comparing, the intercell that adopts in above-described embodiment 1-4 all refers to the battery with a collection of same model (1665132S), said with a collection of preorder production technology that refers to this batch battery all, and unique different be that the electrolyte that injects in the fluid injection operation is different.In the battery of this model, negative pole is composite graphite, just very LiMn2O4.
Cryogenic property and the cycle performance of the lithium ion battery that difference test implementation example 1-embodiment 4 makes, test result is shown in Table 1.In table, the data obtained is the mean value of 20 data that lithium ion battery is surveyed making in each embodiment.
The performance test results of the lithium ion battery that table 1 embodiment 1-4 makes
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| -40 ℃ of 0.2C discharge capacitances | 54.1％ | 55.1％ | 55.5％ | 54.8％ |
| -20 ℃ of 1C discharge capacitances | 88.2％ | 89.3％ | 90.5％ | 90.1％ |
| The efficient of 25 ℃ of 1C 300 week circulations | 90.6％ | 91.1％ | 91.8％ | 90.6％ |
Test result by table 1 can find out, adopts cryogenic property and the cycle performance of the lithium ion battery that electrolyte of low temp lithium ion battery provided by the invention makes good.
Claims (3)
1. an electrolyte of low temp lithium ion battery, is characterized in that, by lithium hexafluoro phosphate LiPF
6Form lithium hexafluoro phosphate LiPF with mixed solvent
6Concentration be 0.8～1.5mol/l, described mixed solvent is comprised of the component of following weight percentage: 20%～40% ethylene carbonate EC, 5%～30% methyl ethyl carbonate alkene ester EMC, 30%～50% methyl acetate MA, 0.5%～5% vinylene carbonate VC.
2. electrolyte of low temp lithium ion battery according to claim 1, is characterized in that, described lithium hexafluoro phosphate LiPF
6, ethylene carbonate EC, methyl ethyl carbonate alkene ester EMC, methyl acetate MA, vinylene carbonate VC be LITHIUM BATTERY reagent, main content is all greater than 99.95%, moisture≤5PPm.
3. lithium ion battery, comprise electrode group and lithium-ion battery electrolytes, described electrode group and lithium-ion battery electrolytes are sealed in battery container, described electrode group comprises positive pole, negative pole and barrier film, it is characterized in that, described lithium-ion battery electrolytes is the described electrolyte of claim 1 or 2.
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| CN201210029082.3A CN103107364B (en) | 2012-02-09 | 2012-02-09 | A kind of electrolyte of low temp lithium ion battery and lithium ion battery |
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| CN201210029082.3A CN103107364B (en) | 2012-02-09 | 2012-02-09 | A kind of electrolyte of low temp lithium ion battery and lithium ion battery |
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| CN103107364B CN103107364B (en) | 2016-04-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN106058318A (en) * | 2016-08-22 | 2016-10-26 | 河南省法恩莱特新能源科技有限公司 | Dynamic ternary battery electrolyte |
| CN106531984A (en) * | 2016-09-30 | 2017-03-22 | 罗仕雄 | Low-temperature lithium-ion battery |
| CN112421111A (en) * | 2020-10-29 | 2021-02-26 | 电子科技大学 | Low-temperature electrolyte applied to NCM111 lithium battery |
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| CN101252207A (en) * | 2008-04-02 | 2008-08-27 | 中南大学 | Low temperature electrolyte for lithium ion battery |
| US20090253046A1 (en) * | 2008-04-08 | 2009-10-08 | California Institute Of Technology | Lithium ion electrolytes and lithium ion cells with good low temperature performance |
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2012
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| CN2760776Y (en) * | 2004-07-28 | 2006-02-22 | 哈尔滨光宇电源股份有限公司 | Lithium ion secondary battery |
| CN101252207A (en) * | 2008-04-02 | 2008-08-27 | 中南大学 | Low temperature electrolyte for lithium ion battery |
| US20090253046A1 (en) * | 2008-04-08 | 2009-10-08 | California Institute Of Technology | Lithium ion electrolytes and lithium ion cells with good low temperature performance |
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| H.-C.ALEXSHIAO,ET AL.: ""Low temperature electrolytes for Li-ion PVDF cells"", 《JOURNAL OF POWER SOURCES》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN103500850B (en) * | 2013-10-23 | 2016-01-20 | 山东大学 | A kind of low-temperature electrolyte of ferric phosphate lithium cell |
| CN106058318A (en) * | 2016-08-22 | 2016-10-26 | 河南省法恩莱特新能源科技有限公司 | Dynamic ternary battery electrolyte |
| CN106531984A (en) * | 2016-09-30 | 2017-03-22 | 罗仕雄 | Low-temperature lithium-ion battery |
| CN112421111A (en) * | 2020-10-29 | 2021-02-26 | 电子科技大学 | Low-temperature electrolyte applied to NCM111 lithium battery |
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| CN103107364B (en) | 2016-04-20 |
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Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd Patentee after: Duofudo New Material Co.,Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Patentee before: DO-FLUORIDE CHEMICALS Co.,Ltd. |