CN103107364B - A kind of electrolyte of low temp lithium ion battery and lithium ion battery - Google Patents
A kind of electrolyte of low temp lithium ion battery and lithium ion battery Download PDFInfo
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- CN103107364B CN103107364B CN201210029082.3A CN201210029082A CN103107364B CN 103107364 B CN103107364 B CN 103107364B CN 201210029082 A CN201210029082 A CN 201210029082A CN 103107364 B CN103107364 B CN 103107364B
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of electrolyte of low temp lithium ion battery, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.8 ~ 1.5mol/l, described mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 20% ~ 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 30% ~ 50%, the vinylene carbonate VC of 0.5% ~ 5% of 5% ~ 30%.The present invention by adding organic solvent methyl ethyl carbonate alkene ester EMC and the methyl acetate MA and film for additive vinylene carbonate VC of low melting point in basic solvent ethylene carbonate EC, the cryogenic property of lithium ion battery is improved, improve lithium ion battery chemical property under cryogenic, greatly widen the range of application of lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium batteries, the lithium ion battery being specifically related to a kind of electrolyte of low temp lithium ion battery and adopting 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 the high (3.6V of operating voltage, be cadmium-nickel, three times of nickel-hydrogen battery), volume little (less than nickel-hydrogen battery 30%), quality light (lighter than nickel-hydrogen battery 50%), 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, plays a part to transmit lithium ion in lithium ion battery.Lithium-ion battery electrolytes usually by carbonate based 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 obtains and develops rapidly, but with current technology, lithium ion battery still comes with some shortcomings, and therefore its scope of application is also restricted, and the ambient temperature wherein used is exactly an important limiting factor.When the ambient temperature used is too low, the performance of lithium ion battery will decline.The main cause of lithium ion battery poor performance is under cryogenic: because lithium battery electrolytes can solidify at low temperatures, therefore the viscosity of electrolyte becomes large, lithium ion mobility becomes difficulty, positive pole and barrier film and the impedance between negative pole and barrier film also can increase, under cryogenic conditions, electrolyte all can be poor to the penetrability of barrier film to the soakage of barrier film and lithium ion, therefore causes lithium ion battery hydraulic performance decline under cryogenic.Therefore, improve lithium ion battery electrical property under cryogenic, become a focus in Study on Li-ion batteries field with the range of application 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 object, the technical solution adopted in the present invention is: a kind of electrolyte of low temp lithium ion battery, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.8 ~ 1.5mol/l, described mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 20% ~ 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 30% ~ 50%, the vinylene carbonate VC of 0.5% ~ 5% of 5% ~ 30%.
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, comprise electrode group and lithium-ion battery electrolytes, 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
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.8 ~ 1.5mol/l, described mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 20% ~ 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 30% ~ 50%, the vinylene carbonate VC of 0.5% ~ 5% of 5% ~ 30%.
For improving lithium battery chemical property under cryogenic, solve the application problem of current lithium battery in low temperature environment, electrolyte of low temp lithium ion battery provided by the invention adds the consumption of the lower organic solvent of fusing point, to widen the temperature limit of electrolyte, reduce the solidifying point of electrolyte; Add film for additive simultaneously, ensure the steadiness of battery SEI film, make circulating effect better.Electrolyte of low temp lithium ion battery provided by the invention is using the high organic solvent ethylene carbonate EC of conductivity as basic solvent, select fusing point lower and there is methyl ethyl carbonate alkene ester EMC, the methyl acetate MA part as dicyandiamide solution of high conductance, 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, there is higher conductivity.Add film for additive vinylene carbonate VC, the filming performance of electrolyte can be improved.Because ring-type EC has higher dielectric constant and viscosity, add low viscous chain EMC (fusing point-55 DEG C) and there is lower fusing point, the ionic conductivity of mixed solvent can be improved, widen the serviceability temperature scope of mixed solvent, increase the fail safe of battery; MA (fusing point-98 DEG C, viscosity 0.37mPa.s, dielectric constant 6.7c/v.m) has lower fusing point and higher dielectric constant, significantly can improve the cryogenic property of electrolyte under cryogenic.In addition, vinylene carbonate (VC) is a kind of ring-type organic solvent containing unsaturated double-bond, can the stable SEI film-alkoxyl carbonic ester lithium of forming property in lithium ion battery first charge-discharge, the one-tenth film potential of VC is all lower than the one-tenth film potential of above several solvent simultaneously, thus reduce the loss of lithium ion, increase battery capacity, be conducive to the cycle life improving lithium ion battery.The present invention, by adding organic solvent methyl ethyl carbonate alkene ester EMC and the methyl acetate MA and film for additive vinylene carbonate VC of low melting point in basic solvent ethylene carbonate EC, makes the cryogenic property of lithium ion battery be improved.
Electrolyte of low temp lithium ion battery tool provided by the invention has the following advantages: this electrolyte is in the environment of low temperature-40 DEG C, leave standstill 16 ~ 24h, then discharge with 0.2C, discharge capacity is 55% of normal temperature (25 DEG C) 0.2C discharge capacity ,-20 DEG C, 1C discharge capacity is 90% of normal temperature (25 DEG C) 0.2C discharge capacity.
Generally speaking, when current lithium ion battery is applied in low temperature environment, chemical property can be affected.Electrolyte of low temp lithium ion battery provided by the invention reduces the fusing point of electrolyte, adds the consumption of low melting point solvent, improves lithium ion battery chemical property under cryogenic, has greatly widened the range of application of lithium ion battery.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
The electrolyte of low temp lithium ion battery that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.8mol/l, mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 20%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 45%, the vinylene carbonate VC of 5% of 30%.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained lithium ion battery.
Embodiment 2
The electrolyte of low temp lithium ion battery that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.0mol/l, mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 50%, the vinylene carbonate VC of 0.5% of 9.5%.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained lithium ion battery.
Embodiment 3
The electrolyte of low temp lithium ion battery that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.5mol/l, mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 30%, the vinylene carbonate VC of 3% of 27%.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained lithium ion battery.
Embodiment 4
The electrolyte of low temp lithium ion battery that the present embodiment provides, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 1.2mol/l, mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 50%, the vinylene carbonate VC of 5% of 5%.
Randomly draw 1665132 batteries of 20 non-fluid injections, these 20 pieces of batteries are injected respectively the electrolyte of low temp lithium ion battery that the present embodiment provides in constant temperature and humidity room, according to a conventional method the battery of fluid injection is carried out aging, change into, degasification, sealing, partial volume, obtained lithium ion battery.
The raw material lithium hexafluoro phosphate LiPF used 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 adopted 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 referring to this batch of battery all, and uniquely different unlike the electrolyte injected in fluid injection operation.In the battery of this model, negative pole is composite graphite, just very LiMn2O4.
The cryogenic property of the lithium ion battery that difference testing example 1-embodiment 4 makes and cycle performance, test result is shown in Table 1.In table the data obtained survey by 20 lithium ion batteries obtained in each embodiment the mean value of data.
The performance test results of the lithium ion battery that table 1 embodiment 1-4 obtains
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| -40 DEG C of 0.2C discharge capacitances | 54.1％ | 55.1％ | 55.5％ | 54.8％ |
| -20 DEG C of 1C discharge capacitances | 88.2％ | 89.3％ | 90.5％ | 90.1％ |
| The efficiency of 25 DEG C of 1C circulation in 300 weeks | 90.6％ | 91.1％ | 91.8％ | 90.6％ |
Can be found out by the test result of table 1, cryogenic property and the cycle performance of the lithium ion battery adopting electrolyte of low temp lithium ion battery provided by the invention to obtain are excellent.
Claims (2)
1. an electrolyte of low temp lithium ion battery, is characterized in that, by lithium hexafluoro phosphate LiPF
6with mixed solvent composition, lithium hexafluoro phosphate LiPF
6concentration be 0.8 ~ 1.5mol/L, described mixed solvent is made up of the component of following weight percentage: the ethylene carbonate EC of 20 ~ 40%, methyl ethyl carbonate alkene ester EMC, the methyl acetate MA of 30% ~ 50%, the vinylene carbonate VC of 0.5% ~ 5% of 5% ~ 30%;
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 content≤5ppm.
2. a lithium ion battery, comprise electrode group and lithium-ion battery electrolytes, 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, it is characterized in that, described lithium-ion battery electrolytes is electrolyte according to claim 1.
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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 true CN103107364B (en) | 2016-04-20 |
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| 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 |
| CN106531984B (en) * | 2016-09-30 | 2019-04-02 | 罗仕雄 | A kind of 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN101252207B (en) * | 2008-04-02 | 2011-01-05 | 中南大学 | Low temperature electrolyte for lithium ion battery |
| US8920981B2 (en) * | 2008-04-08 | 2014-12-30 | California Institute Of Technology | Lithium ion electrolytes and lithium ion cells with good low temperature performance |
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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 |
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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. |