CN1925207A - High rate electrolyte for lithium ion battery - Google Patents

High rate electrolyte for lithium ion battery Download PDF

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Publication number
CN1925207A
CN1925207A CNA2006101222635A CN200610122263A CN1925207A CN 1925207 A CN1925207 A CN 1925207A CN A2006101222635 A CNA2006101222635 A CN A2006101222635A CN 200610122263 A CN200610122263 A CN 200610122263A CN 1925207 A CN1925207 A CN 1925207A
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Prior art keywords
lithium ion
electrolyte
carbonate
ion battery
multiplying power
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CN100463287C (en
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刘建生
左晓希
贺云鹏
周莉
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Guangzhou Tinci Materials Technology Co Ltd
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Guangzhou Tinci Materials Technology Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

This invention relates to lithium ion battery electrolyte with high times and discloses the main components as following: vinylene carbonate for 10 to 30 percentage; propylene carbonate for 4 to 20 percentage; dimethyl carbonate for 35 to 50 percentage; methyl carbonate for 10 t0 20 percentage; lithium salt for 12.5 to 16 percentage and B(OR)<3> with R representing carbon atoms less than 4 or crown ether of one or more function addictives for 0.1 to 5.0 percentage.

Description

Electrolyte for high multiplying power lithium ion battery
Technical field
The present invention relates to the electrolyte that a kind of battery is used, the electrolyte of the high-multiplying power discharge that specifically a kind of lithium battery is used.
Background technology
Lithium ion battery has operating voltage height, specific energy height, has extended cycle life, with characteristics such as environmental friendliness and memory-less effect, obtained development rapidly, be widely used on the portable electronics.The positive pole of lithium ion battery be can the removal lithium embedded ion transistion metal compound, but negative pole is the material with carbon element of removal lithium embedded ion.Lithium ion is deviate from the SEI film of interface through anodal and electrolyte, electrolyte, negative terminal surface from positive pole when battery charge, be diffused in the negative pole body again; Lithium ion is deviate from from negative pole during discharge, turns back to anodal body by former road.Can know from the operation principle of lithium ion battery, the power of lithium ion battery be decided by lithium ion in electrode body, electrode and the interface of electrolyte and the migration rate in the electrolyte.The interface of electrode and electrolyte (being the SEI of electrode surface) is that electrolyte is formed at the redox product of electrode surface, so the power of lithium ion battery is limited by the performance of electrolyte to a great extent.
Because operating voltage height, what lithium ion battery used electrolyte is the lithium salt solution of organic carbonate, with respect to the aqueous solution, the conductivity of organic solution is very low, the conductivity of existing electrolyte is 10mS/cm, and lithium ion is to the contribution of conductivity lower (60~70%), so the power ratio of lithium ion battery is lower.
Summary of the invention
The purpose of this invention is to provide a kind of electrolyte for high multiplying power lithium ion battery, its amount by selecting carbonate solvent to add, and functional additive, thereby improve the migration rate of lithium ion at electrolyte and electrode interface, thus the multiplying power discharging characteristic of lithium ion battery improved.
Technical solution of the present invention is that electrolyte is made up of following each material, and content of material is represented to account for the heavy w/w of total liquid:
A, carbonate solvent main component comprise ethylene carbonate 10~30%, propene carbonate 4~20%, dimethyl carbonate 35~50%, the mixed liquor of methyl ethyl carbonate 10~20%;
B, contain lithium salts 12.5~16.0%;
C, functional additive main component comprise the micromolecule amine, B (OR) 3, wherein R is that carbon number is less than 4 alkyl, or one or more of crown ether, account for total liquid heavy 0.1~5.0%.
More than carbonate solvent of the present invention comprise diethyl carbonate 0~10%, carbonic acid first propyl ester 0~10%, or carbonic acid first isopropyl ester 0~10%.
Lithium salts of the present invention is selected from LiPF 6, LiAsF 6, LiBOB, LiSO 3CF 3, LiBF 4, Li (CF 3SO 2) 2N, LiC (CF 3SO 2) 3One or more, addition is 13.0~15.0%.
More than micromolecule amine of the present invention be selected from liquefied ammonia, methylamine, ethamine, acetamide, or formamide, addition is 0.5~2%.
Above-described B of the present invention (OR) 3, wherein R is that carbon number is less than 4 alkyl, addition is 0.5~2%.
Crown ether of the present invention is selected from 12 crown ethers, 4,15 crown ethers 5, or 18 crown ethers 6, and addition is 0.5~2%.
More than functional additive of the present invention comprise the unsaturated carbon acid esters, the halo carbonic ester, cyclic sulfates, sulphonic acid ester, unsaturated sulfone, or dioxide, addition is 0~5%.
More than functional additive of the present invention comprise chloroethylene carbonate ester, carbonic acid chloropropene ester, vinylene carbonate, vinylethylene carbonate, sulfonic acid propiolactone, sulfonic acid butyrolactone, sulfuric acid vinyl ester, sulfuric acid propylene ester, ethylene sulfite, propylene sulfite, diphenyl sulphone (DPS), vinyl sulfone, phenyl vinyl sulfone, carbon dioxide or sulfur dioxide, addition is 1~4%.
Electrolyte for high multiplying power lithium ion battery of the present invention adopts the optionally amount of carbonate solvent adding, lithium salts be in the present lithium-ion electrolyte the composition that generally uses, for making the raising of its organic solution lithium ion conductivity, thus electrolyte for lithium ion battery all in addition functional additive improve the power of lithium ion battery.All about 10mS/cm, lithium ion is to the contribution of conductivity lower (<70%) for the conductivity that existing market occurs, and the multiplying power property of battery is relatively poor.So the object of the invention pith is the selection in carbonate solvent and amount thereof, and adopt novel additive, improve contribution rate (>80%) and lithium ion in electrolyte and SEI film the migration rate of lithium ion to conductivity, the conductivity of electrolyte reaches 11~13mS/cm, increase substantially the power of lithium ion battery, obtained good effect.
Advantage of the present invention is to select appropriate solvent to form and functional additive; improve the degree of dissociation of lithium salts in solution and the mobility of lithium ion; make electrolyte form stability and the good passivation protection film of ionic conductivity, thereby improve the multiplying power discharging characteristic of lithium ion battery in negative terminal surface.
Description of drawings
Fig. 1 is the battery 10C discharge performance discharge contrast figure line of embodiments of the invention 1~4;
Fig. 2 is the battery 10C discharge performance discharge contrast figure line of embodiments of the invention 5~8;
Fig. 3 is the battery 10C discharge performance discharge contrast figure line of embodiments of the invention 9~13 and Comparative Examples.
Specific embodiment
Embodiment 1
At normal temperature and pressure moisture 1ppm, and under the environment of inert gas, with purity all at the solvent more than 99.95%, ethylene carbonate 22.6%, propene carbonate 5.7%, dimethyl carbonate 39.3%, methyl ethyl carbonate 16.6% mixes, the lithium salts LiPF of dissolving 13.3% in this mixed solvent 6, average mark adds for three times, each 1.5~2.0 hours time intervals that add, fully shake up after the adding, and add the vinylene carbonate and 1.0% acetamide of 1.5% functional additive at last.
Electrolyte is filled into and carries out the flash-over characteristic detection in the battery, and employed battery is:
Anodal: active material LiCoO 2Content 94%, carbon black 3.0%, binding agent PVDF3.0%, aluminium foil are collector.Pole piece width 5.0cm, thickness 147 μ m.
Negative pole: the content 90.0% of active material MCMB, the content 10.0% of binding agent PVDF, Copper Foil are collector, the wide 5.2cm of pole piece, thickness 178 μ m.
Barrier film is PE/PP/PE three strata compound films.
The model of preparation battery is square 063048, and the capacity of design battery is 850mAh.
Detection method:
With the moisture in the coulomb Ka Shi method mensuration electrolyte, the acidity in the acid base titration test electrolyte, measure the conductivity of electrolyte with DJS-307 type electric conductivity instrument.
Electrolyte prepares the multiplying power discharging characteristic detecting method of battery behind the battery:
1, with 1C electric current constant voltage charge to 4.2V, cut-off current is 20mA;
2, leave standstill 10 minutes, use secondary cell Performance Detection cabinet to detect battery capacity;
3, with the 5C current discharge to 3.0V;
4, leave standstill 10 minutes, use secondary cell Performance Detection cabinet to detect battery capacity;
5, with the 10C current discharge to 3.0V;
6, leave standstill 10 minutes, use secondary cell Performance Detection cabinet to detect battery capacity.
Battery circulation discharge detection method: recycle the 1st to the 6th step of battery multiplying power discharging characteristic detecting method.
Embodiment 2
With embodiment 1, be lithium salts LiPF 6Change LiAsF into 6, the functional additive acetamide changes 12 crown ethers 4 of crown ether into, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement.
Embodiment 3
With embodiment 1, be lithium salts LiPF 6Change 10.0%LiAsF into 6And 3.3%LiBOB, the functional additive vinylene carbonate changes carbon dioxide into, and the functional additive acetamide changes liquefied ammonia into, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement.
Embodiment 4
With embodiment 1, be lithium salts LiPF 6Change 10.0%LiPF into 6And 3.3%LiBOB, the functional additive vinylene carbonate changes sulfur dioxide into, and acetamide changes 0.1% first ammonia into, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement.
Embodiment 5
With embodiment 1, be lithium salts LiPF 6Change 10.0%LiC (CF into 3SO 2) 3And 3.3%LiSO 3CF 3, the functional additive vinylene carbonate changes sulfur dioxide into, and the functional additive acetamide changes 2.5%15 crown ethers 5 into, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement.
Embodiment 6
With embodiment 1, just the functional additive acetamide changes 2.0%18 crown ethers 6 and 3.0% formamide into, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement.
Embodiment 7
With embodiment 1, just the functional additive acetamide changes 1.0%B (OCF into 3) 3With 4.0%12 crown ethers 4, and do determination of moisture with regard to gained electrolyte, acid-base value is measured, and conductance measurement.
Embodiment 8
With embodiment 1, just the functional additive acetamide changes B (OC into 2H 5) 3, and do determination of moisture with regard to gained electrolyte, acid-base value is measured, and conductance measurement.
Embodiment 9
With embodiment 1, just the functional additive acetamide changes B (OC into 3H 7) 3, and do determination of moisture with regard to gained electrolyte, acid-base value is measured, and conductance measurement.
Embodiment 10-13
Each composition with embodiment 1 is a foundation, and manufacture method is adjusted embodiment 1 each composition addition with embodiment 1, as following table 1, and does determination of moisture with regard to gained electrolyte, and acid-base value is measured, and conductance measurement:
Embodiment 1 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13
Solvent Ethylene carbonate 22.6% 11.5% 19.5% 30.0% 10.0%
Dimethyl carbonate 39.3% 42.5% 35.5% 35.0% 50.0%
Methyl ethyl carbonate 16.6% 8.5% 20.0% 10.0% 15.0%
Propene carbonate 5.7% 20.0% 6.0% 12.0% 4.0%
Lithium salts LiPF 6 13.3% 14.0% 15.0% 12.5% 16.0%
Functional additive Vinylene carbonate 1.5% 3.0% 2.5% 0.40% 3.0%
Acetamide 1.0% 0.5% 1.5% 0.10% 2.0%
Table 2 is that the physics and chemistry of each embodiment and Comparative Examples 1 gained electrolyte detects contrast table:
Moisture (ppm) Acidity content (ppm) Conductivity (mS/cm)
Embodiment 1 8.9 12.3 11.2
Embodiment 2 7.8 13.5 13.0
Embodiment 3 9.3 11.5 11.7
Embodiment 4 8.6 15.6 11.8
Embodiment 5 10.2 13 11.4
Embodiment 6 9.1 14.5 12.8
Embodiment 7 8.7 15 11.7
Embodiment 8 7.9 12.5 11.6
Embodiment 9 8.2 14.1 11.9
Embodiment 10 8.1 15.5 11.3
Embodiment 11 9.1 12.1 11.8
Embodiment 12 9.8 13.1 11.1
Embodiment 13 8.8 14.3 12.5
Comparative Examples 1 7.7 14.3 10.5
Comparative Examples
Operating procedure is with the solvent of embodiment more than 1,99.95%, ethylene carbonate 28.83%, and dimethyl carbonate 28.83%, methyl ethyl carbonate 28.84% mixes, the LiPF of dissolving 12.5% in this mixed solvent 6, adding 1.0% vinylene carbonate at last, and do determination of moisture with regard to gained electrolyte, acid-base value is measured, and conductance measurement.
Table 3 prepares the multiplying power discharging characteristic contrast table of battery behind the battery for each embodiment and Comparative Examples 1 gained electrolyte:
Example 1C discharge capacity C 1C (mAh) 5C discharge capacity C 5C (mAh) C 5C/C 1C(%) 10C discharge capacity C 10C (mAh) C 10C/C 1C(%)
1 883 839.7 95.1 796.5 90.2
2 886 861.2 97.2 819.5 92.5
3 879 850 96.7 805.2 91.6
4 880 841.3 95.6 795.5 90.4
5 876 831.3 94.9 788.4 90
6 885 840.1 94.9 801.6 93.6
7 884 851 96.3 820.0 92.8
8 878 845.2 96.3 799.8 91.1
9 881 855.1 97.1 807.4 91.6
10 882 846.5 96.0 818.6 92.8
11 884 860 97.3 810.8 91.7
12 880 859.2 93.6 798.4 90.1
13 881 860.5 97.7 801.5 91.0
Contrast 1 884 688.1 85.5 384.5 43.5

Claims (5)

1, electrolyte for high multiplying power lithium ion battery is characterized in that electrolyte is made up of following each material, and content of material is represented to account for the heavy w/w of total liquid:
A, carbonate solvent main component comprise ethylene carbonate 10~30%, propene carbonate 4~20%, dimethyl carbonate 35~50%, the mixed liquor of methyl ethyl carbonate 10~20%;
B, contain lithium salts 12.5~16.0%;
C, functional additive main component comprise the micromolecule amine, B (OR) 3, wherein R is that carbon number is less than 4 alkyl, or one or more of crown ether, account for total liquid heavy 0.1~5.0%.
2,, it is characterized in that lithium salts is selected from LiPF according to the described electrolyte for high multiplying power lithium ion battery of claim 1 6, LiAsF 6, LiBOB, LiSO 3CF 3, LiBF 4, Li (CF 3SO 2) 2N, LiC (CF 3SO 2) 3One or more, addition is 13.0~15.0%.
3, according to the described electrolyte for high multiplying power lithium ion battery of claim 1, it is characterized in that the micromolecule amine is selected from liquefied ammonia, methylamine, ethamine, acetamide, or formamide, addition is 0.5~2%.
4,, it is characterized in that B (OR) according to the described electrolyte for high multiplying power lithium ion battery of claim 1 3, wherein R is that carbon number is less than 4 alkyl, addition is 0.5~2%.
5, according to the described electrolyte for high multiplying power lithium ion battery of claim 1, it is characterized in that crown ether is selected from 12 crown ethers, 4,15 crown ethers 5, or 18 crown ethers 6, addition is 0.5~2%.
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CN103107366A (en) * 2012-02-09 2013-05-15 多氟多化工股份有限公司 Power lithium ion battery and electrolyte thereof
CN104201417A (en) * 2014-09-23 2014-12-10 中国人民解放军国防科学技术大学 Li-S battery and Li-S reserve battery capable of performing impulsive discharge, and preparation methods thereof
CN104969401A (en) * 2012-12-17 2015-10-07 赛昂能源有限公司 Lithium-ion electrochemical cell, components thereof, and methods of making and using same
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WO2021261579A1 (en) * 2020-06-26 2021-12-30 三菱ケミカル株式会社 Nonaqueous electrolytic solution and nonaqueous electrolytic solution battery
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US11705555B2 (en) 2010-08-24 2023-07-18 Sion Power Corporation Electrolyte materials for use in electrochemical cells
CN102456916A (en) * 2010-10-29 2012-05-16 株式会社日立制作所 Lithium ion battery
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CN102969531A (en) * 2011-09-01 2013-03-13 索尼公司 Electrolytic solution for secondary battery, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device
US10854921B2 (en) 2011-09-07 2020-12-01 Sion Power Corporation Electrochemical cell including electrolyte having insoluble nitrogen-containing material and battery including the cell
CN103107366A (en) * 2012-02-09 2013-05-15 多氟多化工股份有限公司 Power lithium ion battery and electrolyte thereof
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