CN105428719B - Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application - Google Patents
Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application Download PDFInfo
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- CN105428719B CN105428719B CN201511017147.2A CN201511017147A CN105428719B CN 105428719 B CN105428719 B CN 105428719B CN 201511017147 A CN201511017147 A CN 201511017147A CN 105428719 B CN105428719 B CN 105428719B
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- 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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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
A kind of wide temperature lithium-ion battery electrolytes of high voltage, belong to the technical field of lithium-ion battery electrolytes, including organic solvent, lithium salts and additive, the organic solvent is made of cyclic carbonate solvents, fluorinated solvents and carbonate solvent, the additive is 3- fluoro- 1,3 propene sultones, the content of additive is 0.5%-10% in the lithium-ion battery electrolytes.The invention also discloses the preparation method and application of the electrolyte.Electrolyte of the invention has good stability, and preparation method is simple, and the cycle life and high-temperature behavior of the wide temperature lithium ion battery of high voltage can be effectively improved by being applied in battery.
Description
Technical field
The invention belongs to the technical fields of lithium-ion battery electrolytes, and in particular to the wide temperature lithium ion battery electrolysis of high voltage
Liquid and preparation method and application.Electrolyte of the invention has good stability, and preparation method is simple, and being applied in battery can be effective
Improve the cycle life and high-temperature behavior of the wide temperature lithium ion battery of high voltage.
Background technique
Lithium ion battery because its specific energy is high, small in size, light weight, memory-less effect, have extended cycle life the advantages that form
For current with fastest developing speed also most valued novel high-energy battery.In recent years, portable electronic device is rapidly developed, but
The energy density proposition of lithium ion battery is got in soaring, the increase of screen size of hardware configuration, diversification of function etc.
Carry out higher requirement, traditional lithium-ion battery is no longer satisfied the demand of people.
Currently in order to improving the energy density of lithium ion battery, researcher generallys use exploitation high capacity, high working voltage
Positive electrode solve the problems, such as this, such as improve the operating voltage of lithium cobalt composite oxide, complex Li-Mn-oxide, develop senior engineer
Make the lithium nickel manganese composite oxide etc. of voltage.However, solvent recurring structure changes these positive electrodes under high voltages, transition gold
Category is easy to happen dissolution, and can deposit on cathode, in addition, common electrolyte, it will usually issue in the voltage higher than 4V
Solution estranged produces gas, to will lead to the reduction of battery performance.In order to solve problem above, researcher would generally be to positive electrode
Surface protection cladding or doping are carried out to improve the cycle performance under high voltage, but these methods are often along with battery
Can capacity loss, and manufacture craft is cumbersome, and manufacturing cost increases.Replaced by exploitation novel high voltage electrolyte normal at present
Electrolyte system is to realize one of commercialized improvement approach of high-voltage lithium ion batteries.At present due to commonly improving electricity
The electrolyte of pressure increases the dosage of FEC (fluorinated ethylene carbonate) often to improve withstanding voltage, however when voltage is increased to
When 4.5V or more, the dosage of FEC is continued growing, cycle performance of battery declines faster instead, thus develops the electricity of high voltage
Solution solution additive has been very urgent.
Summary of the invention
The present invention is in order to improve the energy density of lithium ion battery, and solves the electrolysis to improve voltage in the prior art
Liquid and the damage for causing cycle performance of battery, provide a kind of wide temperature lithium-ion battery electrolytes of high voltage and preparation method thereof and
Using.
The present invention be realize its purpose the technical solution adopted is that:
A kind of wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, lithium salts and additive, described is organic molten
Agent is made of cyclic carbonate solvents, fluorinated solvents and carbonate solvent, and the additive is 3- fluoro- 1, in 3 propene sulfonic acids
Ester, the content of additive is 0.5%-10% in the lithium-ion battery electrolytes.
The concentration of the lithium salts in organic solvent is 1-1.5mol/L, and mass percent is fluorinated solvents in the electrolytic solution
2-50%.
The cyclic carbonate solvents are one in ethylene carbonate, propene carbonate, gamma-butyrolacton, gamma-valerolactone
Kind is a variety of.
One of the fluorinated solvents addressing trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, butyl trifluoroacetate are more
Kind.
The carbonate solvent is selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propionate, propionic acid second
One of ester, propyl propionate are a variety of.
The lithium salts is selected from LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、LiC(CF3SO2)3In one
Kind is a variety of.
A method of prepare and state the wide temperature lithium-ion battery electrolytes of high voltage, by cyclic carbonate solvents, fluorinated solvents,
Carbonate solvent after mixing, removes impurity, and lithium salts is dissolved in above-mentioned mixed solvent by water removal at room temperature, stirs
Uniformly, 3- fluoro- 1 is then added, 3 propene sultones, filtering is electrolysed to get the wide temperature lithium ion battery of the high voltage after dissolved clarification
Liquid.
After mixing by cyclic carbonate solvents, fluorinated solvents, carbonate solvent, it usesMolecular sieve, lithium hydride removal of impurities
Matter, water removal.
The above-mentioned wide temperature lithium-ion battery electrolytes of high voltage are preparing the application in the wide temperature lithium ion battery of high voltage.
The chemical structural formula of fluoro- 1,3 propene sultone of additive 3- is as follows:
The beneficial effects of the present invention are:
It joined fluorinated solvents in electrolyte solvent, it is possible to reduce the decomposition of electrolyte under high voltages improves electricity
The antioxygenic property of liquid is solved, meanwhile, fluorinated solvents have good wellability, improve the wetting property of electrolyte, joined 3-
Fluoro- 1, anode can be effectively protected in 3 propene sultones, reduce dissolution of the transition metal on positive electrode, while can
SEI film is formed in cathode, inhibits deposition and reduction of the transition metal on cathode, so that cathode be effectively protected.Be conducive to mention
High battery stable circulation performance under high voltages and high temperature cyclic performance.And it is risen caused by effectively lithium battery being prevented to overcharge
The generation of the safety problems such as fire, explosion, increases the safety of battery；Charge and discharge is high-efficient, good cycle, is able to satisfy 500 times
Charge and discharge requirement greater than 85%, can especially improve the high temperature cyclic performance of lithium battery；The storge quality that battery can be increased, does not influence
Other performances of lithium battery.
The wide temperature lithium-ion battery electrolytes preparation method of high voltage of the present invention is simple, can improve anode and cathode simultaneously
With the interfacial property of electrolyte, electrolyte has good stability, can effectively improve high-voltage lithium ion batteries cycle life and
High-temperature behavior.
The wide temperature cycle life of lithium ion battery length of high voltage made from the wide temperature lithium-ion battery electrolytes of high voltage of the present invention,
Inflatable rate low and high temperature is functional, and battery operating voltage can be higher than 4.5V.
Wherein, fluoro- 1 3-, 3 propene sultones can also inhibit electrolyte in the oxidation or reduction of electrode material surface
It decomposes, reduces the destruction to electrode, improve the compatibility of electrolyte and electrode.
Detailed description of the invention
Fig. 1 is the cycle performance figure of the present invention with basic electrolyte comparison.
In figure, ▲ indicate basic electrolyte: EC:DMC=1:2,1MLiPF6, FEC1%；■ indicates electrolyte of the present invention.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
A kind of wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, LiPF6In 3- fluorine 1,3- propene sulfonic acid
Ester, wherein organic solvent is made of ethylene carbonate, methyl ethyl carbonate, the Trifluoroacetic Acid Ethyl Ester that weight ratio is 1:2:0.2, this electricity
The additive amount of the 3- fluorine 1 being added in solution liquid, 3- propene sultone is 2wt.%, and the concentration of lithium salts in organic solvent is
1mol/L, mass percent is 20% to Trifluoroacetic Acid Ethyl Ester in the electrolytic solution.
The preparation method of the above-mentioned wide temperature lithium-ion battery electrolytes of high voltage is:
1) it after mixing by organic solvent, usesMolecular sieve, lithium hydride remove impurity, water removal；
2) lithium salts is dissolved in above-mentioned mixed solvent at room temperature, is stirred evenly；
3) 3- fluoro- 1 is then added, 3 propene sultones, filtering is to get the wide temperature lithium-ion electric of the high voltage after dissolved clarification
Pond electrolyte.
Above-mentioned additive 3- fluorine 1, the preparation method of 3- propene sultone is: with 1,3- propene sultone for raw material,
1, the 3- propene sultone of 1mol 600mL methylene chloride is dissolved, the NBS of 1.05mol is added portionwise at 50 DEG C, is reacted
10h obtains bromo- 1, the 3- propene sultone of intermediate 3-, and then gained intermediate and sodium fluoride are placed in methylene chloride,
Reaction is swapped in the presence of cyclodextrin, obtains fluoro- 1, the 3- propene sultone of product 3-.The fluoro- 1,3 propene sultone phase of 3-
Cell voltage more can be improved due to the presence of F element compared with 1,3- propene sultone, can be widely applied to lithium from
Sub- battery high voltage field, meanwhile, the high temperature that fluoro- 1, the 3- propene sultone of 3- can also improve current ternary battery material follows
Ring property can improve the cycle life of battery.
The wide temperature lithium-ion battery electrolytes of the high voltage of the present embodiment are used for cobalt acid lithium/graphite soft-package battery, test cobalt
Sour lithium/graphite flexible-packed battery 3.0~4.95V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks,
Capacity retention ratio is 94% or more, and circulation is after 300 weeks, and capacity retention ratio is 91% or more, and circulation is after 400 weeks, capacity retention ratio
90% or so, for circulation after 500 weeks, capacity retention ratio still can achieve 85% or more.
Embodiment 2
A kind of wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, LiN (CF3SO2)2With 3- fluorine 1,3- propylene
Sultones, wherein organic solvent is made of propene carbonate, methyl propionate, the trifluoro-acetate that weight ratio is 1:2:0.2,
The additive amount of the 3- fluorine 1 being added in this electrolyte, 3- propene sultone is 4wt.%, and the concentration of lithium salts in organic solvent is
1.5mol/L, mass percent is 30% to Trifluoroacetic Acid Ethyl Ester in the electrolytic solution.
The preparation method of the above-mentioned wide temperature lithium-ion battery electrolytes of high voltage is:
1) it after mixing by organic solvent, usesMolecular sieve, lithium hydride remove impurity, water removal；
2) lithium salts is dissolved in above-mentioned mixed solvent at room temperature, is stirred evenly；
3) 3- fluoro- 1 is then added, 3 propene sultones, filtering is to get the wide temperature lithium-ion electric of the high voltage after dissolved clarification
Pond electrolyte.
The wide temperature lithium-ion battery electrolytes of the high voltage of the present embodiment are used for cobalt acid lithium/graphite soft-package battery, test cobalt
Sour lithium/graphite flexible-packed battery 3.0~4.95V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks,
Capacity retention ratio is 93%, and circulation is after 300 weeks, and capacity retention ratio is 90%, and after 400 weeks, capacity retention ratio follows circulation 89%
After ring 500 weeks, capacity retention ratio still can achieve 85% or more.
Embodiment 3
A kind of wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, LiClO4With 3- fluorine 1,3- propene sulfonic acid
Lactone, wherein organic solvent is made of the gamma-butyrolacton, ethyl propionate, butyl trifluoroacetate that weight ratio is 1:2:0.2, this electricity
The additive amount of the 3- fluorine 1 being added in solution liquid, 3- propene sultone is 6wt.%, and the concentration of lithium salts in organic solvent is
1.2mol/L, mass percent is 40% to Trifluoroacetic Acid Ethyl Ester in the electrolytic solution.
The preparation method of the above-mentioned wide temperature lithium-ion battery electrolytes of high voltage is:
1) it after mixing by organic solvent, usesMolecular sieve, lithium hydride remove impurity, water removal；
2) lithium salts is dissolved in above-mentioned mixed solvent at room temperature, is stirred evenly；
3) 3- fluoro- 1 is then added, 3 propene sultones, filtering is to get the wide temperature lithium-ion electric of the high voltage after dissolved clarification
Pond electrolyte.
The wide temperature lithium-ion battery electrolytes of the high voltage of the present embodiment are used for cobalt acid lithium/graphite soft-package battery, test cobalt
Sour lithium/graphite flexible-packed battery 3.0~4.95V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks,
Capacity retention ratio is 94%, and circulation is after 300 weeks, and capacity retention ratio is 91%, and after 400 weeks, capacity retention ratio follows circulation 90%
After ring 500 weeks, capacity retention ratio still can achieve 85% or more.
Embodiment 4
A kind of wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, LiSO3CF3With 3- fluorine 1,3- propene sulfonic acid
Lactone, wherein organic solvent is made of gamma-valerolactone, propyl propionate, the trifluoro-acetate that weight ratio is 1:2:0.2, this electricity
The additive amount of the 3- fluorine 1 being added in solution liquid, 3- propene sultone is 2.5wt.%, and the concentration of lithium salts in organic solvent is
1.2mol/L, mass percent is 35% to Trifluoroacetic Acid Ethyl Ester in the electrolytic solution.
The preparation method of the above-mentioned wide temperature lithium-ion battery electrolytes of high voltage is:
1) it after mixing by organic solvent, usesMolecular sieve, lithium hydride remove impurity, water removal；
2) lithium salts is dissolved in above-mentioned mixed solvent at room temperature, is stirred evenly；
3) 3- fluoro- 1 is then added, 3 propene sultones, filtering is to get the wide temperature lithium-ion electric of the high voltage after dissolved clarification
Pond electrolyte.
The wide temperature lithium-ion battery electrolytes of the high voltage of the present embodiment are used for cobalt acid lithium/graphite soft-package battery, test cobalt
Sour lithium/graphite flexible-packed battery 3.0~4.95V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks,
Capacity retention ratio is 94%, and circulation is after 300 weeks, and capacity retention ratio is 91%, and after 400 weeks, capacity retention ratio follows circulation 90%
After ring 500 weeks, capacity retention ratio still can achieve 85% or more.
Comparative example 1
A kind of high-voltage lithium-ion battery electrolyte, mainly include the following raw material: organic solvent, electric conducting lithium salt and function add
Add agent；The organic solvent is by ethylene carbonate (EC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC) and fluoro-ether
(CF2HCF2CH2-O-CF2CF2H it) forms, the weight ratio of EC and EMC are EC:EMC=1:2, and FEC dosage is 10wt.%, fluoro-ether
CF2HCF2CH2-O-CF2CF2H dosage is 5wt.%.The electric conducting lithium salt is LiPF6, in organic solvent dense
Degree is 1.2mol/L；The functional additive is the acrylic -1,3- sultones (PES) of dosage 2wt.%.
The preparation method of above-mentioned high-voltage lithium-ion battery electrolyte is:
(1) it is used after mixing organic solvent in proportionMolecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at room temperature, electric conducting lithium salt is dissolved in above-mentioned organic solvent, and stirred evenly；
(3) functional additive PES is added to get the high-voltage lithium-ion battery electrolyte.
The high-voltage lithium-ion battery electrolyte of the present embodiment is used for nickel ion doped (LiNi0.5Mn1.5O4) battery.Test
LiNi0.5Mn1.5O4Battery 3.5~4.95V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks, hold
Conservation rate is measured 92%, circulation is after 300 weeks, and capacity retention ratio is 90%, and after 400 weeks, capacity retention ratio recycles circulation 88%
After 500 weeks, capacity retention ratio is up to 80%.
Comparative example 2
A kind of high-voltage lithium-ion battery electrolyte, it is described organic mainly comprising organic solvent, electric conducting lithium salt and additive
Solvent is by cyclic carbonate solvents (ethylene carbonate EC) and linear carbonate solvent (methyl ethyl carbonate EMC and diethyl carbonate
DEC it) forms, the weight ratio of EC and linear carbonate is EC:EMC:DEC=1:1:1.The electric conducting lithium salt LiPF6Organic molten
Concentration in agent is 1.0mol/L, and the typical additives are the vinylene carbonate of 1.0wt.% dosage and dosage is
The propane sultone of 1.0wt.%, the additive are that tetrafluoro terephthalonitrile's dosage 1.0wt.%, 3- fluorobenzonitrile dosage are
2.0wt.%.
The preparation method of above-mentioned electrolyte is:
(1) it is used after mixing organic solvent in proportionMolecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at room temperature, electric conducting lithium salt is dissolved in above-mentioned organic solvent, and stirred evenly；
(3) typical additives vinylene carbonate and propane sultone is added, and stirs evenly.
(4) additive tetrafluoro terephthalonitrile and 3- fluorobenzonitrile is added to get high-voltage lithium ion described in the present embodiment
Battery electrolyte.
High-voltage lithium-ion battery electrolyte of the invention is used for cobalt acid lithium/graphite flexible-packed battery, test cobalt acid lithium/
Graphite flexible-packed battery 3.0-4.5V under normal temperature environment, the cycle performance of 1C rate charge-discharge.After recycling 200 weeks, capacity is protected
Holdup is 90%, and circulation is after 300 weeks, and capacity retention ratio is 85%, and for circulation after 400 weeks, capacity retention ratio recycles 500 80%
Zhou Hou, capacity retention ratio is up to 70%.
Claims (8)
1. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage, it is characterised in that:
The wide temperature lithium-ion battery electrolytes of high voltage, including organic solvent, lithium salts and additive, the organic solvent by
Cyclic carbonate solvents, fluorinated solvents and carbonate solvent composition, it is characterised in that: the additive is 3- fluoro- 1,3 propylene
Sultones, the content of additive is 0.5%-10% in the lithium-ion battery electrolytes；
The 3- fluorine 1,3- propene sultone are prepared by the following method: with 1,3- propene sultone for raw material, by 1mol
1,3-propene sultones dissolved with 600mL methylene chloride, be added portionwise the NBS of 1.05mol at 50 DEG C, react 10h,
Bromo- 1, the 3- propene sultone of intermediate 3- is obtained, then gained intermediate and sodium fluoride are placed in methylene chloride, is pasted in ring
Reaction is swapped in the presence of essence, obtains fluoro- 1, the 3- propene sultone of product 3-；
After mixing by cyclic carbonate solvents, fluorinated solvents, carbonate solvent, impurity, water removal, at room temperature by lithium salts are removed
It is dissolved in above-mentioned mixed solvent, stirs evenly, the 3- fluoro- 1 of above-mentioned preparation, 3 propene sultones, dissolved clarification is then added
After filter to get the wide temperature lithium-ion battery electrolytes of the high voltage.
2. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, it is characterised in that:
The concentration of the lithium salts in organic solvent is 1-1.5mol/L, and mass percent is 2-50% to fluorinated solvents in the electrolytic solution.
3. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, it is characterised in that:
The cyclic carbonate solvents are a kind of or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, gamma-valerolactone
Kind.
4. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, it is characterised in that:
The fluorinated solvents are selected from one of trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, butyl trifluoroacetate or a variety of.
5. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, it is characterised in that:
The carbonate solvent is selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propionate, ethyl propionate, propionic acid third
One of ester is a variety of.
6. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, it is characterised in that:
The lithium salts is selected from LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、 LiC(CF3SO2)3One of or it is more
Kind.
7. a kind of method for preparing the wide temperature lithium-ion battery electrolytes of high voltage according to claim 1, which is characterized in that
After mixing by cyclic carbonate solvents, fluorinated solvents, carbonate solvent, impurity is removed with 4 molecular sieves, lithium hydride, removed water.
8. the wide temperature lithium-ion battery electrolytes of high voltage described in -6 any one are preparing the wide temperature lithium of high voltage according to claim 1
Application in ion battery.
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| CN201511017147.2A CN105428719B (en) | 2015-12-31 | 2015-12-31 | Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application |
| JP2017509778A JP6712588B2 (en) | 2015-12-31 | 2016-08-22 | Electrolyte solution for high voltage and wide temperature range lithium ion battery, its preparation method and its application |
| PCT/CN2016/096166 WO2017113820A1 (en) | 2015-12-31 | 2016-08-22 | High-voltage wide-temperature lithium ion battery electrolyte, preparation method therefor and application thereof |
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| CN201511017147.2A CN105428719B (en) | 2015-12-31 | 2015-12-31 | Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application |
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| CN105428719B (en) * | 2015-12-31 | 2018-12-18 | 石家庄圣泰化工有限公司 | Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application |
| MX2019001629A (en) * | 2016-08-12 | 2019-09-16 | Pellion Tech Inc | Additive containing electrolytes for high energy rechargeable metal anode batteries. |
| CN106450462B (en) * | 2016-12-27 | 2019-01-08 | 石家庄圣泰化工有限公司 | The wide temperature lithium-ion battery electrolytes of high voltage |
| CN108270035B (en) * | 2016-12-30 | 2020-07-07 | 浙江省化工研究院有限公司 | Battery electrolyte containing high-concentration lithium salt |
| JP6944644B2 (en) * | 2017-10-19 | 2021-10-06 | トヨタ自動車株式会社 | Electrolyte for lithium secondary battery |
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| CN103956517A (en) * | 2014-05-14 | 2014-07-30 | 华南师范大学 | High-voltage lithium ion battery electrolyte, preparation method and application of electrolyte |
| CN104934638A (en) * | 2015-04-24 | 2015-09-23 | 江苏华盛精化工有限责任公司 | High-voltage electrolyte for lithium ion battery |
| CN105428719B (en) * | 2015-12-31 | 2018-12-18 | 石家庄圣泰化工有限公司 | Wide temperature lithium-ion battery electrolytes of high voltage and preparation method and application |
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| JP6712588B2 (en) | 2020-06-24 |
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