CN102683749A - Non-aqueous electrolyte of high-voltage lithium ion battery - Google Patents
Non-aqueous electrolyte of high-voltage lithium ion battery Download PDFInfo
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- CN102683749A CN102683749A CN2012101228054A CN201210122805A CN102683749A CN 102683749 A CN102683749 A CN 102683749A CN 2012101228054 A CN2012101228054 A CN 2012101228054A CN 201210122805 A CN201210122805 A CN 201210122805A CN 102683749 A CN102683749 A CN 102683749A
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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 non-aqueous electrolyte of a high-voltage lithium ion battery. The non-aqueous electrolyte is functional electrolyte obtained by replacing a conventional carbonic acid esters solvent with a fluorinated solvent. Volume ratio of the fluorinated solvent in a non-aqueous electrolyte solvent is 7-100%. The non-aqueous electrolyte has the advantages of being resistant to high voltage, high in lithium salt dissolution, non-toxic, good in compatibility with a graphite cathode, cheap in material price and the like. Simultaneously, the non-aqueous electrolyte of the high-voltage lithium ion battery is simple in preparation process and wide in application prospects.
Description
Technical field:
The present invention relates to the lithium-ion battery electrolytes field, particularly a kind of high-voltage lithium ion batteries nonaqueous electrolytic solution.
Background technology:
Operating voltage height, energy density big (in light weight), self-discharge rate are low because of having for lithium rechargeable battery, memory-less effect, have extended cycle life and advantage such as pollution-free; Extensive use daily life every field; Little of various portable electric appts, arrive the zero discharge electric motor car greatly.The principal element of decision lithium ion battery energy density, power density and cost is a positive electrode; Energy density is the comprehensive embodiment of voltage and capacity; Seem particularly important so have high voltage and jumbo cell positive material simultaneously, can satisfy the littler lighter development trend of following battery.The anode material for lithium-ion batteries that uses at present is like LiCoO
2, LiMn
2O
4And LiFePO
4Operating voltage all be lower than 4V, with LiNi
0.5Mn
1.5O
4And LiCoPO
4The discharge voltage that Deng material is the high-voltage anode material of representative can be up to about 5V; These high voltage materials are used for output voltage and the power density that lithium ion battery can improve battery; Further widen the scope of application of lithium ion battery on high-power electrical equipment (especially electric automobile), thereby receive researcher's extensive concern in the industry.The liquid electrolyte of commercialization lithium ion battery mainly is based on the carbonate group electrolyte of ethylene carbonate (EC) at present; But when system voltage is higher than 4.5V; Thereby conventional carbonate group electrolyte solvent can take place to decompose and cause the entire cell performance decrease; Can not substitute the carbonates solvent fully and still have other novel dissolvent in the face of this problem; Thereby the test that causes present high voltage material is still based on the electrolyte solvent system of routine, like EC/EMC/DMC, EC/DEC, EC/DMC and EC/EMC etc.
In order to satisfy the needs of lithium ion battery high-energy, high safety performance, the exploitation of novel dissolvent system is necessary.To novel high voltage dicyandiamide solution except high voltage withstanding, to the requirements such as lithium salts dissolving is high, nontoxic, the more important thing is require dicyandiamide solution and battery plus-negative plate particularly the compatibility of graphite cathode to get well.Nitrile compounds, sulfone compound and ionic liquid are as satisfying the research object that the high voltage material uses electrolyte solvent.Wherein ionic liquid have Heat stability is good, non-volatile, do not burn, advantage such as conductivity is high, electrochemical window is wide, but because its raw material is more expensive, cost is higher, the large-scale commercial applications possibility of its application is also very little; Nitrile solvents and sulfone kind solvent and graphite cathode compatibility can not show a candle to conventional carbonates solvent, can substitute the carbonate group solvent fully thereby cause still not having at present novel dissolvent.Therefore, the modification work of on conventional carbonate solvent basis, carrying out electrolyte will be the main direction of present high voltage electrolyte research.
Summary of the invention:
The invention discloses a kind of nonaqueous electrolytic solution of high-voltage lithium ion batteries, on conventional carbonate solvent basis, carry out the modification of electrolyte, adopt fluorinated solvents to substitute conventional carbonates solvent and a kind of high voltage withstanding electrolyte processed.Advantages such as it is high voltage withstanding, high, nontoxic to the lithium salts dissolving that nonaqueous electrolytic solution of the present invention has, and good with the compatibility of graphite cathode, and material price is cheap.
The present invention based on theoretical foundation is: 1) Fig. 1 has provided and has contained 1M LiPF
6The LSV curve of conventional carbonates solvent on the Pt electrode, can find out the following DMC > of anti-oxidant strong and weak order of conventional carbonates solvent; DEC>PC>Therefore EMC, aspect the selection of cosolvent, preferentially selects DMC; 2) because fluorine atom has strong negative and low pole, cause fluorinated solvents to have higher electrochemical stability.Fluorinated solvents is used in the lithium ion battery liquid electrolyte as cosolvent or additive mostly at present, improves the security performance of battery effectively, improves the oxidation resistance of electrolyte.Fluorinated ethylene carbonate (FEC) HOMO energy is-12.33eV that far below non-fluoro carbonate solvents such as EC, its oxidizing potential on the Pt electrode is higher than non-fluoro carbonate solvents such as EC far away.It is thus clear that with fluorinated solvents particularly fluoro carbonates solvent will be the optimal selection that improves the electrolyte oxidation resistance at present.3) because lithium salts LiPF
6Dissolubility Deng in fluorinated solvents is relatively poor, and the present invention uses fluorinated solvents partly to substitute conventional carbonates solvent, and its volume ratio in the nonaqueous electrolytic solution dicyandiamide solution is 7 ~ 100%, and volumn concentration is 10 ~ 30% according to qualifications.
Concrete technical scheme of the present invention is:
A kind of nonaqueous electrolytic solution of high-voltage lithium ion batteries; It is characterized in that: adopt fluorinated solvents to substitute conventional carbonates solvent in the common electrolyte and a kind of functional electrolysis liquid that obtains, the percent by volume of described fluorinated solvents in the nonaqueous electrolytic solution dicyandiamide solution is 7% ~ 100%.
The nonaqueous electrolytic solution of described high-voltage lithium ion batteries is characterized in that: the percent by volume of described fluorinated solvents in the nonaqueous electrolytic solution solvent is 10% ~ 30%.
The nonaqueous electrolytic solution of described high-voltage lithium ion batteries is characterized in that: described fluorinated solvents is one or more in the fluoro carbonic ester.
The nonaqueous electrolytic solution of described high-voltage lithium ion batteries is characterized in that: described fluoro carbonic ester is a fluorinated ethylene carbonate.
The nonaqueous electrolytic solution of described high-voltage lithium ion batteries is characterized in that: described nonaqueous electrolytic solution dicyandiamide solution is the EC/DMC/FEC ternary solvent system.
Prepare and get according to the conventional preparation method of the nonaqueous electrolytic solution of lithium ion battery.
The present invention has following advantage with respect to prior art: high-voltage lithium ion batteries electrolyte of the present invention is on the basis of existing carbonate group electrolyte, to obtain; Gained high voltage electrolyte obtains the characteristic of the high pressure of anti-4.9V when keeping existing electrolyte correlation properties; And the preparation method is simple, has application promise in clinical practice.
Description of drawings:
Fig. 1 is for containing 1M LiPF
6The LSV curve of conventional carbonates solvent on the Pt electrode;
Fig. 2 is using the 0.5C charge-discharge performance curve of different electrolytes (discharging and recharging the interval 3.5V-4.95V that is) for high voltage spinelle nickel manganese material to the lithium metal half-cell.
Embodiment:
Below in conjunction with embodiment the present invention is described in further detail, but execution mode of the present invention is not limited thereto.
Embodiment 1:
Ethylene carbonate (EC), fluorinated ethylene carbonate (FEC) and cosolvent dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) are mixed, and volume ratio is EC:FEC:EMC:DMC=0.5:0.5:1:1, and dewatering through removal of impurities obtains non-aqueous solvent system after the purification procedures; The LiPF6 gradation is added nonaqueous solvents, and controlled concentration is 1mol/L, stirs and promptly arrives high voltage electrolyte.
With LiNi0.5Mn1.5O4 is positive electrode, forms 2016 button cells with metal lithium sheet, adds gained high voltage electrolyte.At room temperature on Land charge-discharge test appearance, between 4.95V battery is discharged and recharged activation at 3.5V, carry out charge and discharge cycles with 1/2C subsequently with 1/10C.The battery capacity conservation rate that circulates after 50 times is 91.7%, explains that the high voltage electrolyte of present embodiment preparation makes the cycle life of high-voltage battery be improved.
Embodiment 2:
Use with embodiment 1 identical method and prepared the high voltage electrolyte of dicyandiamide solution as EC:FEC:DMC=1:2:7 (volume ratio); Tested the cycle performance of LiNi0.5Mn1.5O4//Li button cell through embodiment 1 identical test condition; The result shows that the battery capacity conservation rate after the 0.5C circulation 50 times is 97.2%, explain that the high voltage electrolyte that present embodiment prepares makes the cycle life of high-voltage battery be further enhanced.
The comparative example:
Use with embodiment 1 identical method and prepared the conventional electrolysis liquid of dicyandiamide solution as EC:EMC:DMC=1:1:1 (volume ratio); Tested the cycle performance of LiNi0.5Mn1.5O4//Li button cell through embodiment 1 identical test condition; The result shows the battery capacity decay most 82.6% after the 0.5C circulation 50 times; It is thus clear that it is not good not contain the button cell cycle performance of common electrolyte preparation of fluoro solvent, capacity attenuation is very fast.
Fig. 2 has provided button cell charge-discharge performance curve chart in the foregoing description.
The foregoing description is a preferred implementation of the present invention; But execution mode of the present invention is not restricted to the described embodiments; Other are any not to deviate from change, modification, combination, the simplification of being made under spirit of the present invention and the principle; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the nonaqueous electrolytic solution of a high-voltage lithium ion batteries; It is characterized in that: adopt fluorinated solvents to substitute conventional carbonates solvent in the common electrolyte and a kind of functional electrolysis liquid that obtains, the percent by volume of described fluorinated solvents in the nonaqueous electrolytic solution dicyandiamide solution is 7% ~ 100%.
2. the nonaqueous electrolytic solution of high-voltage lithium ion batteries according to claim 1, it is characterized in that: the percent by volume of described fluorinated solvents in the nonaqueous electrolytic solution solvent is 10% ~ 30%.
3. the nonaqueous electrolytic solution of high-voltage lithium ion batteries according to claim 1, it is characterized in that: described fluorinated solvents is one or more in the fluoro carbonic ester.
4. the nonaqueous electrolytic solution of high-voltage lithium ion batteries according to claim 3, it is characterized in that: described fluoro carbonic ester is a fluorinated ethylene carbonate.
5. the nonaqueous electrolytic solution of high-voltage lithium ion batteries according to claim 1, it is characterized in that: described nonaqueous electrolytic solution dicyandiamide solution is the EC/DMC/FEC ternary solvent system.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545552A (en) * | 2013-10-14 | 2014-01-29 | 合肥国轩高科动力能源股份公司 | Electrolyte suitable for high-voltage lithium ion battery |
| CN104282944A (en) * | 2014-10-30 | 2015-01-14 | 上海动力储能电池系统工程技术有限公司 | High-voltage electrolyte for lithium ion battery and application of high-voltage electrolyte |
| CN110998954A (en) * | 2017-11-28 | 2020-04-10 | 株式会社Lg化学 | Polymer electrolyte for secondary battery and secondary battery including the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007142121A1 (en) * | 2006-06-02 | 2007-12-13 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| CN102035023A (en) * | 2009-09-28 | 2011-04-27 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102244296A (en) * | 2011-06-14 | 2011-11-16 | 东莞新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
-
2012
- 2012-04-24 CN CN2012101228054A patent/CN102683749A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007142121A1 (en) * | 2006-06-02 | 2007-12-13 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| CN102035023A (en) * | 2009-09-28 | 2011-04-27 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102244296A (en) * | 2011-06-14 | 2011-11-16 | 东莞新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545552A (en) * | 2013-10-14 | 2014-01-29 | 合肥国轩高科动力能源股份公司 | Electrolyte suitable for high-voltage lithium ion battery |
| CN103545552B (en) * | 2013-10-14 | 2016-03-09 | 合肥国轩高科动力能源有限公司 | Be suitable for the electrolyte of high-voltage lithium ion batteries |
| CN104282944A (en) * | 2014-10-30 | 2015-01-14 | 上海动力储能电池系统工程技术有限公司 | High-voltage electrolyte for lithium ion battery and application of high-voltage electrolyte |
| CN110998954A (en) * | 2017-11-28 | 2020-04-10 | 株式会社Lg化学 | Polymer electrolyte for secondary battery and secondary battery including the same |
| US11670800B2 (en) | 2017-11-28 | 2023-06-06 | Lg Energy Solution, Ltd. | Polymer electrolyte for secondary battery and secondary battery including the same |
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Address after: 230011, No. 7 D Road, Yaohai Industrial Park, Hefei, Anhui, China Applicant after: Hefei Guoxuan High-Tech Power Energy Co., Ltd. Address before: 230011, No. 7 D Road, Yaohai Industrial Park, Hefei, Anhui, China Applicant before: Hefei Guoxuan High-Tech Power Energy Co., Ltd. |
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Application publication date: 20120919 |