CN109860711A - A kind of low temperature electrolyte for lithium ion battery and application - Google Patents
A kind of low temperature electrolyte for lithium ion battery and application Download PDFInfo
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- CN109860711A CN109860711A CN201711240183.4A CN201711240183A CN109860711A CN 109860711 A CN109860711 A CN 109860711A CN 201711240183 A CN201711240183 A CN 201711240183A CN 109860711 A CN109860711 A CN 109860711A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of electrolyte for lithium ion battery and its applications, the solute of electrolyte is one of boracic lithium salts or two kinds or more, solvent is that perhaps two kinds or more electrolyte contain additive to one of acetic ester compounds is a kind of or two kinds or more film for additive；This low-temperature electrolyte conductivity with higher and lower Charge-transfer resistance and SEI membrane impedance at -40 DEG C, can reduce the polarization of lithium ion battery, improve its volumetric properties and high rate performance at low temperature.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to low temperature electrolytes for Li-ion batteries.
Background technique
The advantages that lithium ion battery is because of energy density with higher, power density, long, flexibly light service life cycle
It is widely used to many fields, such as electronic equipment and hybrid power electric car, becomes new energy field most application prospect
Energy storage technology.With the increasingly expansion of lithium ion battery applications range, especially in electric vehicle, aerospace and military project
The application in field has higher requirement, but lithium ion battery charge and discharge at low ambient temperatures to the low temperature charge-discharge performance of battery
Poor electrical performance, especially at subzero 30 degree hereinafter, common lithium ion battery is not available substantially, if lithium ion battery is low
Warm nature can be improved, and the application in more areas will obtain more significant progress.
The widely used positive electrode of lithium ion battery has LiFePO4, LiV2 (PO4) 3, LiMn2O4；Negative electrode material someone
Make graphite, natural graphite, carbonaceous mesophase spherules etc.；Traditional lithium-ion battery electrolytes use the organic solvent dissolved with lithium salts mixed
Object is closed, lithium salts is mainly that LiPF6, solvent are made of two or three of carbonate based organic solvent, such as: ethylene carbonate (EC),
Dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) etc.；Additive is generally VC and PS.
Medium of the electrolyte as conduction ion and electronics, is one of important component of battery, is formed for electricity
The room temperature performance in pond, especially cryogenic property have very big influence, by improve electrolyte component (including lithium salts, solvent and
Additive) improve lithium ion battery cryogenic property be a kind of more effective method, therefore develop lithium ion battery use
Low-temperature electrolyte is most important.Influence of the electrolyte to battery cryogenic property be mainly reflected in its to conductivity, SEI film character and
The influence of charge-transfer resistance.It is broken that now widely used lithium salts LiPF6 easily reacts generation HF with the minor amount of water in electrolyte
Bad electrode/electrolyte interface stability and LiF that can be thicker in electrode surface generation, increase the internal resistance of cell, so as to cause electricity
Polarization of the pond at -40 DEG C of low temperature is even more serious；Widely used solvent ethylene carbonate due to excellent film forming characteristics,
As component indispensable in electrolyte, but its fusing point is very high (36 DEG C), causes the electrolyte prepared by it at -40 DEG C of low temperature
Under viscosity it is big, to considerably reduce ionic conductivity.By optimizing electrolyte component, its conductance at low temperature is improved
Rate reduces charge transfer resistance, to achieve the purpose that improve lithium ion battery in -40 DEG C of cryogenic properties.At present about lithium from
The research of sub- battery low-temperature electrolyte is less, is worth further investigation.
Summary of the invention
The object of the present invention is to provide a kind of low temperature electrolyte for lithium ion battery, this electrolyte is at -40 DEG C of low temperature
There is down very high ionic conductivity, there is lesser charge transfer resistance, and LiF contains in the SEI film that electrode surface is formed
Amount is few, so that polarization of the battery at -40 DEG C of low temperature weakens, volumetric properties when improving the low temperature of battery and forthright again
Energy.
In order to achieve the above objectives, the concrete scheme that the present invention uses is as follows:
The low temperature electrolyte for lithium ion battery forms
1. the solute as electrolyte: one of boracic lithium salts or two kinds or more；The lithium salts is in electrolyte
Concentration is 0.05mol/L~5mol/L；
2. the solvent as electrolyte: one of acetic ester compounds or two kinds or more；
3. the additive as electrolyte: a kind of or two kinds or more film for additive；The film for additive is in electricity
Solving mass fraction in liquid is 0.01%~10%；
Boracic lithium salts is LiBF4, and boracic lithium salt is preferably 0.2mol/L~2mol/L.
Also added with LiPF6 as auxiliary solute in the solute, auxiliary solute concentration in electrolyte is preferably
0.1mol/L~1mol/L.
Ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid are also added in the electrolyte
One of dimethyl ester or two kinds or more, with acetic ester compounds collectively as the solvent of electrolyte, carbonates
Close volume ratio 1:10~10:1 of object and acetic ester compounds；
The additive is vinylene carbonate, propylene sulfite, dimethyl sulfite, diethyl sulfite
One or more of, additive concentration is preferably 0.1%~5%.
Acetic ester compounds are methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, in isoamyl acetate
It is a kind of or two kinds or more.
Application of the electrolyte in lithium ion battery.It is subzero 30 degrees Celsius to subzero 60 degrees Celsius using temperature.
Beneficial effects of the present invention:
Boracic lithium salts in the electrolyte degree of association in the solvent with acetate is smaller, dissociation is easy, so that electrolyte
The ionic conductivity with higher at -40 DEG C of low temperature, and the ionic conductivity for forming electrolyte reduces with temperature and changes slow
Slowly since the LiF content that the presence of the two generates in battery charge and discharge process electrode surface is substantially reduced, SEI film it is thin and
Densification, so that electrolyte has the charge transfer resistance and SEI membrane impedance of very little, so that the polarization of battery at low temperature is reduced,
Improve the volumetric properties and high rate performance when -40 DEG C of low temperature of battery.
Specific embodiment
Embodiment 1
Electrolyte lithium salt is LiPF6 and LiBF4, and the molar ratio of the two is 1:3, and the concentration of lithium salts in the electrolytic solution is
1.2mol/L；Solvent is that ethylene carbonate and methyl acetate solvent mix, and the two volume ratio is 1:2；Additive is VC, quality point
Number is 1%.；
The anode of lithium ion battery is prepared as follows: Li3V2(PO4)3, conductive black, binder three mass ratio
It is dissolved in appropriate N-Methyl pyrrolidone and being uniformly mixed for 8:1:1, be coated into the electrode with a thickness of 0.15mm with wet film maker
Film is cut into the electrode slice that diameter is 12mm with slicer after vacuum drying, weighs and calculate the quality of active material.Simultaneously with lithium
Piece is as cathode, using Celgard 2500 as diaphragm, adds 50 microlitres of electrolyte, dresses up knob in the glove box full of argon gas
Battery is detained, the battery of assembly is then subjected to electro-chemical test.Investigate the appearance of battery battery at 25 DEG C and -40 DEG C of low temperature of room temperature
Measure the ionic conductivity of performance and high rate performance and electrolyte；
Test result is as shown in table 1.
Embodiment 2
Electrolyte lithium salt is LiPF6 and LiBF4, and the molar ratio of the two is 1:3, and the concentration of lithium salts in the electrolytic solution is
1.2mol/L；Solvent is that ethylene carbonate and propyl acetate solvent mix, and the two volume ratio is 1:2；Additive is VC, quality point
Number is 1%；
Test result is as shown in table 2.
Embodiment 3
Electrolyte lithium salt is LiPF6 and LiODFB, and the molar ratio of the two is 1:3, and the concentration of lithium salts in the electrolytic solution is
1.2mol/L；Solvent is that ethylene carbonate and methyl acetate solvent mix, and the two volume ratio is 1:2；Additive is VC, quality point
Number is 1%；
Test result is as shown in table 1.
Embodiment 4
Electrolyte lithium salt is LiPF6 and LiODFB, and the molar ratio of the two is 1:3, and the concentration of lithium salts in the electrolytic solution is
1.2mol/L；Solvent is that ethylene carbonate and propyl acetate solvent mix, and the two volume ratio is 1:2；Additive is VC, quality point
Number is 1%；
Test result is as shown in table 1.
Embodiment 5
Electrolyte lithium salt is LiPF6, LiBF4 and LiODFB, the molar ratio of three is 2:3:3, and lithium salts is in the electrolytic solution
Concentration is 1.2mol/L；Solvent is ethylene carbonate, and methyl acetate, isopropyl acetate solvent mixing, three's volume ratio is 1:1:
1；Additive is VC, mass fraction 1%；
Test result is as shown in table 1.
Comparative example 1
Electrolyte lithium salt is LiPF6, and the concentration of lithium salts in the electrolytic solution is 1.2mol/L；Solvent is ethylene carbonate and carbon
The mixing of dimethyl phthalate solvent, the two volume ratio are 1:2；Additive is VC, mass fraction 1%；
Test result is as shown in table 2.
Comparative example 2
Electrolyte lithium salt is LiPF6, and the concentration of lithium salts in the electrolytic solution is 1.2mol/L；Solvent is ethylene carbonate and carbon
Sour first and second ester solvents mixing, the two volume ratio are 1:2；Additive is VC, mass fraction 1%；
Test result is as shown in table 2.
Comparative example 3
Electrolyte lithium salt is LiPF6, and the concentration of lithium salts in the electrolytic solution is 1.2mol/L；Solvent is ethylene carbonate and second
Sour methyl esters solvent mixing, the two volume ratio are 1:2；Additive is VC, mass fraction 1%；
Test result is as shown in table 2.
Comparative example 4
Electrolyte lithium salt is LiPF6 and LiBF4, and the molar ratio of the two is 1:3, and the concentration of lithium salts in the electrolytic solution is
1.2mol/L；Solvent is that ethylene carbonate and methyl ethyl carbonate ester solvent mix, and the two volume ratio is 1:2；Additive is VC, quality
Score is 1%；
Test result is as shown in table 2.
Table 1: Examples 1 to 5 be battery at 25 DEG C of room temperature and -40 DEG C of low temperature the volumetric properties of battery, high rate performance and
The ionic conductivity of degree of polarization and electrolyte
Table 2: comparative example 1~3 be battery at 25 DEG C of room temperature and -40 DEG C of low temperature the volumetric properties of battery, high rate performance and
The ionic conductivity of degree of polarization and electrolyte
The result shows that the low temperature electrolytes for Li-ion batteries of this type ionic conductance with higher under -40 DEG C of low temperature,
And good volumetric properties are shown compared with having small polarization under high magnification for battery after battery.This electrolyte has very
Good application prospect.
Claims (8)
1. a kind of electrolyte for lithium ion battery, it is characterised in that: electrolyte, which forms, includes:
Solute as electrolyte: one of boracic lithium salts or two kinds or more；The boracic lithium salts is dense in electrolyte
Degree is 0.05mol/L~5mol/L；
Solvent as electrolyte: one of acetic ester compounds or two kinds or more；
A kind of additive as electrolyte: or two kinds or more film for additive；The film for additive is in electrolyte
Whole mass fraction is 0.01%~10%.
2. according to electrolyte for lithium ion battery described in claim 1, it is characterised in that:
Boracic lithium salts is LiBF4, and boracic lithium salt is preferably 0.2mol/L~2mol/L.
3. according to electrolyte for lithium ion battery described in claim 1, it is characterised in that:
Also added with LiPF6 as auxiliary solute in the solute, auxiliary solute concentration in electrolyte is preferably
0.1mol/L~1mol/L.
4. according to electrolyte for lithium ion battery described in claim 1, it is characterised in that:
The additive is vinylene carbonate, propylene sulfite, in dimethyl sulfite, diethyl sulfite
One or more, additive mass concentration are preferably 0.1%~5%.
5. according to electrolyte for lithium ion battery described in claim 1, it is characterised in that:
Acetic ester compounds are methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, one of isoamyl acetate
Or two kinds or more.
6. according to the electrolyte of claim 1 or 5, it is characterised in that: be also added with ethylene carbonate, carbonic acid third in electrolyte
Enester, diethyl carbonate, methyl ethyl carbonate, one of dimethyl carbonate or two kinds or more, with acetic ester compounds
Collectively as the solvent of electrolyte, volume ratio 1:10~10:1 of carbonats compound and acetic ester compounds.
7. a kind of application of any electrolyte of claim 1-6 in lithium ion battery.
8. application of the electrolyte as claimed in claim 7 in lithium ion battery is subzero 30 degrees Celsius extremely subzero using temperature
60 degrees Celsius.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112563569A (en) * | 2019-09-10 | 2021-03-26 | 中国科学院大连化学物理研究所 | Application of electrolyte additive in lithium battery |
| CN114628850A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Low-temperature lithium ion battery and charging and discharging method thereof |
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| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
| CN101740822A (en) * | 2008-11-21 | 2010-06-16 | 上海比亚迪有限公司 | Electrolyte and lithium ion battery containing same |
| CN103078136A (en) * | 2012-12-03 | 2013-05-01 | 湖州创亚动力电池材料有限公司 | Low-temperature rate lithium ion battery electrolyte |
| CN105047996A (en) * | 2015-05-28 | 2015-11-11 | 河南省法恩莱特新能源科技有限公司 | Lithium ion battery low temperature electrolyte and lithium ion battery |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1976111A (en) * | 2006-12-08 | 2007-06-06 | 中国科学院上海微系统与信息技术研究所 | Lithium ion battery electrolyte and constitutive lithium ion battery |
| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112563569A (en) * | 2019-09-10 | 2021-03-26 | 中国科学院大连化学物理研究所 | Application of electrolyte additive in lithium battery |
| CN114628850A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Low-temperature lithium ion battery and charging and discharging method thereof |
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