CN105742704B - A kind of high-voltage electrolyte containing cyclopentene dintrile and the lithium ion battery using the electrolyte - Google Patents
A kind of high-voltage electrolyte containing cyclopentene dintrile and the lithium ion battery using the electrolyte Download PDFInfo
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- CN105742704B CN105742704B CN201610155992.4A CN201610155992A CN105742704B CN 105742704 B CN105742704 B CN 105742704B CN 201610155992 A CN201610155992 A CN 201610155992A CN 105742704 B CN105742704 B CN 105742704B
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- cyclopentene
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- dintrile
- carbonate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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 the lithium ion batteries of a kind of high-voltage electrolyte containing cyclopentene dintrile and the use electrolyte, it is characterized in that, the high-voltage electrolyte is by electrolyte lithium salt, non-aqueous organic solvent and additive composition, the additive includes fluorinated ethylene carbonate and cyclopentene dinitrile compound, itrile group functional group CN in the cyclopentene dinitrile compound, complexing can occur with transition metal ions in positive electrode active materials, electrolyte is reduced to be catalytically decomposed and inhibit digestion of metallic ion, stablize high-voltage anode active material crystal structure, so as to improve high-voltage battery cycle performance and high-temperature behavior.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of high-voltage electrolyte containing cyclopentene dintrile and makes
With the lithium ion battery of the electrolyte.
Background technology
With being increasingly enhanced for people's environmental consciousness, the uses of the traditional galvanic batteries such as lead-acid battery and Ni-MH battery increasingly by
To limitation.Lithium ion battery has many advantages, such as that voltage is high, environmentally friendly and memory-less effect bigger than energy, is widely used in digital, army
The fields such as work, energy storage and power.Develop to miniaturization, multifunction direction to meet Portable mobile electronic device, terminal
Consumer requires the energy density of lithium rechargeable battery higher and higher.
Currently, in order to improve lithium ion battery energy density, mainly by selecting the positive and negative anodes of high power capacity, high-pressure solid active
Material and raising positive electrode active materials charge cutoff current potential.But its oxygen can be improved by improving positive electrode active materials charge cutoff current potential
Change activity, aggravates the oxygenolysis of electrolyte, cracking battery comprehensive performance；It increases, hold when lithium ion battery faces environment temperature
When the conditions of high temperature such as continuous electric discharge fever, active material structure destruction and a large amount of aerogenesis of battery are more accelerated, and then set off an explosion, fire
The safety accidents such as burning.Electrolyte is one of four big critical material of lithium ion battery, is that lithium ion battery obtains long-life, high safety
Guarantee, the electrolyte for developing electrode/electrolyte interface compatibility is good, high temperature and cycle performance are excellent is to improve lithium ion battery
One of the key of energy density and security performance.
Studies have shown that fluorinated ethylene carbonate FEC has good filming performance and oxidative resistance, it is added in electrolyte
Cycle performance of battery can be effectively improved.But FEC is easy to decompose under the high temperature conditions, decomposition product HF can destroy positive electrode
Crystal structure leads to digestion of metallic ion in active material, accelerates electrolyte decomposition aerogenesis and deterioration battery high-temperature storge quality.
For this deficiency, method commonplace at present is to add the saturated fats nitrile objects such as succinonitrile, adiponitrile in the electrolytic solution
Matter (such as application number CN201110157665), can inhibit high temperature aerogenesis caused by fluorinated ethylene carbonate to a certain extent.So
And saturated fat nitrile cannot form a film in electrode surface, mainly by electric field action physical absorption in positive electrode surface gold is complexed
Belong to ion, suction-operated is weaker, fails effective absorbed portion and is easy embedded cathode, destroys graphite laminate structure.
Invention content
The present invention is directed to background above technology and existing deficiency, provides a kind of high voltage electrolysis containing cyclopentene dintrile
Liquid and the lithium ion battery for using the electrolyte, to improve high-voltage battery cycle performance and high-temperature behavior.
To achieve the goals above, the present invention is achieved through the following technical solutions：
A kind of high-voltage electrolyte containing cyclopentene dintrile, by electrolyte lithium salt, non-aqueous organic solvent and additive group
At the additive includes fluorinated ethylene carbonate and at least one cyclopentene dinitrile compound, structure as shown in structural formula I
Formulas I is：
Structural formula I
Wherein m, n are respectively 0~3 integer.
The cyclopentene dinitrile compound as shown in structural formula I be 3- cyclopentene -1,1- dimethoxy nitriles, cyclopentene -1 3-,
1- diacetonitriles, two propionitrile of 3- cyclopentene -1,1- or 3- cyclopentene -1,1- dibutyronitriles it is any.
The mass percent of the cyclopentene dinitrile compound in the electrolytic solution is 0.1%~5.0%.
The mass percent of the fluorinated ethylene carbonate in the electrolytic solution is 0.5%~10.0%.
The electrolyte lithium salt is three kinds of lithium hexafluoro phosphate, double fluorine sulfimide lithiums, double trifluoromethanesulfonimide lithiums changes
Close object in molar ratio 1:0~0.2:0~0.2 combination.
The non-aqueous organic solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic acid two
Two or more in ethyl ester, methyl propyl carbonate, ethyl propionate, propyl propionate.
The additive further includes vinylene carbonate, 1,3- propane sultones, one kind in sulfuric acid vinyl ester or several
Kind, and the mass percent of above-mentioned each additive in the electrolytic solution is respectively 0.1%~5.0%.
A kind of high-voltage lithium ion batteries, including anode, cathode, isolation film and above-described containing cyclopentene dintrile
High-voltage electrolyte, the structural formula of active material used by the anode are：LiCoxL1-xO2, wherein L Al, Sr, Mg,
Ti, Ca, Zr, Zn, Si or Fe, 0<X≤1, the lithium ion battery charge cutoff voltage are less than 4.5V more than 4.3V.
The advantage of the invention is that：
1, fluorinated ethylene carbonate as one of functional additive in the present invention can be with good filming performance
Fine and close flexible and low-impedance SEI films are formed in negative terminal surface；FEC can enhance electrolyte oxidative resistance and reduce electrolysis simultaneously
Liquid surface tension ensure that high-voltage anode material and the good interface compatibility of electrolyte, the high-voltage battery of preparation have
Excellent cycle performance.
2, two cyclopentene dinitrile compound as functional additive in the present invention, itrile group functional group-CN, can with just
Complexing occurs for transition metal ions in the active material of pole, reduces electrolyte and is catalytically decomposed and inhibits digestion of metallic ion, surely
High-voltage anode active material crystal structure is determined, so as to improve high-voltage battery cycle performance and high-temperature behavior.
3, more conventional saturated fat nitrile is compared, in positive electrode surface voltolisation may occur for the double bond functional group in cyclopentene dintrile
Close reaction, itrile group functional group by chemisorption in positive electrode surface, to Co3+Equal complexing of metal ion effect is stronger, and then more
It is effectively improved high-voltage battery cycle and high-temperature behavior.
Specific implementation mode
Below by exemplary embodiment, the present invention will be further elaborated；But the scope of the present invention should not limit to
In the range of embodiment, any variation or change without departing from present subject matter can be understood by the person skilled in the art,
All within protection scope of the present invention.
Embodiment 1
Electrolyte quota step：In the glove box full of argon gas, by ethylene carbonate, diethyl carbonate, methyl ethyl carbonate
Ester is EC in mass ratio：DEC：EMC=1：1：1 is mixed, and is then slowly added to a concentration of 1.0mol/L's to mixed solution
Lithium hexafluoro phosphate and the bis- fluorine sulfimide lithiums of 0.1mol/L, are eventually adding the fluoro carbonic acid second based on electrolyte total weight 3wt%
Enester, 0.5wt%3- cyclopentene -1,1- diacetonitrile, 3wt%1,3- propane sultones obtain embodiment 1 after stirring evenly
Lithium-ion battery electrolytes.
The lithium-ion battery electrolytes injection that above-mentioned steps are prepared is by fully dry 4.40V graphite/LiCoO2It is poly-
Close object battery in, battery by 45 DEG C shelve for 24 hours, chemical conversion, fixture high-temperature baking, secondary sealing and routine partial volume after carry out 3.0V
85 DEG C/6H storage the tests of~4.40V 1C cyclic charging and discharging tests and the full electric states of 4.40V.
1) 1C cyclic charging and discharging tests：At 25 DEG C, the battery after chemical conversion is charged to 4.40V by 1C constant current constant voltages, is ended
Then electric current 0.02C presses 1C constant-current discharges to 3.0V.The 500th cycle circulation volume is calculated after 500 cycles of charge/discharge to keep
Rate.Calculation formula is as follows：
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/for the first time cyclic discharge capacity) ×
100%；
2) 85 DEG C/6H of the full electric states of 4.40V storage tests：At room temperature by battery by 0.5C charge and discharge it is primary, cut-off current
0.02C records initial capacity.It is full of again by 0.5C constant current constant voltages, tests initial battery thickness；Full electric state battery is placed in 85 DEG C
It is stored 6 hours in the climatic chamber of 85% humidity, tests the hot thickness of battery, calculate hot expansion；Battery normal temperature shelf 6 hours
After test cold thickness, voltage, internal resistance, be discharged to 3.0V by 0.5C, record residual capacity, calculate battery capacity surplus ratio：
The hot expansion rate of battery (%)=(hot thickness-original depth)/original depth × 100%；
Battery capacity surplus ratio (%)=residual capacity/initial capacity × 100%；
Embodiment 2~8
It is other same as Example 1 other than each component content of electrolyte is by addition shown in table 1 in embodiment 2~8.
Table 1 is each component content table of electrolyte and battery performance test result of Examples 1 to 8：
Table 1：
In above-mentioned table 1, it is as follows that each chemical substance letter writes a Chinese character in simplified form corresponding title：
EC (ethylene carbonate), DEC (diethyl carbonate), EMC (methyl ethyl carbonate), PP (n propyl propionate), LiFSI
(double fluorine sulfimide lithiums), LiTFSI (double trifluoromethanesulfonimide lithiums), FEC (fluorinated ethylene carbonate), PS (1,3- propane
Sultones), DTD (sulfuric acid vinyl ester).
In conclusion collaboration of the present invention by fluorinated ethylene carbonate and cyclopentene dintrile with good filming performance
Effect improves electrode/electrolyte interface compatibility in battery plus-negative plate surface filming, reduces interface side reaction, improves high electricity
Piezoelectric battery cycle performance and high-temperature behavior.Compared to more conventional saturated fat nitrile, the passing through of itrile group functional group in cyclopentene dintrile
Be adsorbed in positive electrode surface, to Co3+Equal complexing of metal ion effect is stronger, so more efficient improvements high-voltage battery cycle with
High-temperature behavior.
Claims (7)
1. a kind of high-voltage electrolyte containing cyclopentene dintrile, is made of electrolyte lithium salt, non-aqueous organic solvent and additive,
It is characterized in that, the additive includes fluorinated ethylene carbonate and at least one cyclopentene dinitrile compound, the ring penta
Alkene dinitrile compound is 3- cyclopentene -1,1- dimethoxy nitriles, 3- cyclopentene -1,1- diacetonitriles, two propionitrile of 3- cyclopentene -1,1- or 3-
Cyclopentene -1,1- dibutyronitriles it is any；The mass percent of the cyclopentene dinitrile compound in the electrolytic solution be 0.1%~
5.0%.
2. the high-voltage electrolyte according to claim 1 containing cyclopentene dintrile, which is characterized in that the fluoro carbonic acid
The mass percent of vinyl acetate in the electrolytic solution is 0.5%~10.0%.
3. the high-voltage electrolyte according to claim 1 containing cyclopentene dintrile, which is characterized in that the electrolyte lithium
Salt is lithium hexafluoro phosphate, double fluorine sulfimide lithiums, three kinds of compounds of double trifluoromethanesulfonimide lithiums in molar ratio 1:0~0.2:
0~0.2 combination.
4. the high-voltage electrolyte according to claim 1 containing cyclopentene dintrile, which is characterized in that described non-aqueous organic
Solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, propionic acid
Two or more in ethyl ester, propyl propionate.
5. the high-voltage electrolyte according to claim 1 containing cyclopentene dintrile, the additive further includes carbonic acid Asia
One or more of vinyl acetate, 1,3- propane sultones, sulfuric acid vinyl ester, and the matter of above-mentioned each additive in the electrolytic solution
Amount percentage is respectively 0.1%~5.0%.
6. a kind of high-voltage lithium ion batteries, including containing described in anode, cathode, isolation film and claim 1 to 5 any one
There is the high-voltage electrolyte of cyclopentene dintrile.
7. high-voltage lithium ion batteries according to claim 6, active material configuration formula is used by the anode：
LiCoxL1-xO2, wherein L Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<X≤1, the lithium ion battery charge cutoff electricity
Pressure is less than 4.5V more than 4.3V.
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| CN106410276B (en) * | 2016-09-21 | 2019-04-19 | 珠海光宇电池有限公司 | A kind of nonaqueous electrolytic solution and the lithium ion battery including the nonaqueous electrolytic solution |
| EP3373375A1 (en) * | 2017-03-08 | 2018-09-12 | Basf Se | Use of aliphatic dinitriles in electrochemical cells for reducing metal leaching |
| CN109216764B (en) | 2017-07-05 | 2020-09-15 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical device |
| CN110945705B (en) * | 2017-07-27 | 2023-05-09 | 株式会社村田制作所 | Electrolyte for secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device |
| CN108767318A (en) * | 2018-05-24 | 2018-11-06 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium salt electrolyte containing additive |
| CN109659620B (en) * | 2019-01-25 | 2022-09-16 | 欣旺达电动汽车电池有限公司 | Electrolyte and secondary battery |
| CN112635823A (en) * | 2019-09-24 | 2021-04-09 | 东莞市杉杉电池材料有限公司 | High-voltage lithium cobalt oxide lithium ion battery electrolyte and lithium ion battery |
| CN111129664A (en) * | 2019-12-20 | 2020-05-08 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte and lithium ion battery thereof |
| CN113972396A (en) * | 2020-07-24 | 2022-01-25 | 浙江蓝天环保高科技股份有限公司 | Electrolyte containing nitrile additive and lithium ion battery |
| CN113851722A (en) * | 2021-08-09 | 2021-12-28 | 杉杉新材料（衢州）有限公司 | Non-aqueous electrolyte of lithium ion battery containing cyano-group cyclic unsaturated hydrocarbon compound and lithium ion battery |
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| WO2006025262A1 (en) * | 2004-08-30 | 2006-03-09 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical information recording medium |
| CN107658494A (en) * | 2006-12-06 | 2018-02-02 | 三菱化学株式会社 | Non-aqueous electrolyte and nonaqueous electrolyte secondary battery |
| CN103441303A (en) * | 2013-08-29 | 2013-12-11 | 嘉德力电源科技（苏州）有限公司 | Electrolyte for 4.5 V lithium ion battery |
| CN104979589A (en) * | 2015-07-23 | 2015-10-14 | 东莞市凯欣电池材料有限公司 | High-voltage electrolyte and lithium ion battery using electrolyte |
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Address after: 523000 Guangdong province Dongguan city Dongguan Ecological Industrial Park Xingye Road Applicant after: Dongguan City Kai Xin battery material Co., Ltd Address before: 523000 Guangdong province Dongguan City Chashan Town Ecological Industrial Park Industrial Road Applicant before: Dongguan City Kai Xin battery material Co., Ltd |
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Effective date of registration: 20190329 Address after: 510000 No. 8 Kangda Road, Dongcheng District, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Tianci High-Tech Material Co., Ltd. Address before: 523000 Dongguan Eco-Industrial Park, Dongguan City, Guangdong Province Patentee before: Dongguan City Kai Xin battery material Co., Ltd |