CN105261791A - Ultra-temperature high-voltage lithium-ion battery electrolyte and lithium-ion battery using electrolyte - Google Patents
Ultra-temperature high-voltage lithium-ion battery electrolyte and lithium-ion battery using electrolyte Download PDFInfo
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- CN105261791A CN105261791A CN201510768172.8A CN201510768172A CN105261791A CN 105261791 A CN105261791 A CN 105261791A CN 201510768172 A CN201510768172 A CN 201510768172A CN 105261791 A CN105261791 A CN 105261791A
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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
-
- 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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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 ultra-temperature high-voltage lithium-ion battery electrolyte and a lithium-ion battery using the electrolyte. The ultra-temperature high-voltage lithium-ion battery electrolyte comprises non-aqueous organic solvents, lithium hexafluorophosphate, an anaerogenic additive and a low-impedance additive, wherein the non-aqueous organic solvents include a carbonic ester solvent and a high-boiling-point carboxylic ester solvent; the anaerogenic additive is a sultone compound; the low-impedance additive is any one or a mixture of lithium fluorosulfonimide and cyclic sulphate. The ultra-temperature high-voltage lithium-ion battery electrolyte utilizes the carboxylic ester solvent with high boiling point and good wettability to replace some carbonic ester solvents, so that the high-temperature storage performance of the lithium-ion battery can be effectively promoted, and the wettability of the electrolyte about a graphite cathode is improved; through utilizing the lithium-ion battery prepared by the lithium-ion battery electrolyte provided by the invention, the ultra-temperature performance requirement for storage at 85 DEG C under 4.35 V full electric state for 16 hours can be met.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of superelevation warm type high-voltage lithium-ion battery electrolyte and use the lithium ion battery of this electrolyte.
Background technology
Lithium ion battery has that operating voltage is high, specific capacity is large, have extended cycle life, memory-less effect and advantages of environment protection, is widely used in the fields such as number, energy storage, power and militay space flight aviation.The carrier that electrolyte transmits as lithium ion battery intermediate ion, plays vital effect to the performance of lithium ion battery various aspects of performance.
At present, in order to meet the energy density requirement of terminal equipment, realizing mainly through improving active material compacted density and improving charge cutoff current potential, but improving the interface side reaction of positive electrode active materials charge cutoff current potential meeting accelerating electrode and electrolyte.Particularly in high temperature environments, more than 4.35V high-voltage battery ubiquity thickness swelling, internal resistance increase, problem that capability retention is low in long circulation and storage process.The factor of high-voltage battery high-temperature behavior difference is caused to mainly contain: under (1), hot conditions, to exacerbate the catalytic decomposition of transition metal ions to electrolyte, electrolyte decomposition gaseous product directly causes cell thickness to expand, solid product, in both positive and negative polarity interface deposition, increases the internal resistance of cell and pole piece thickness; (2), LiPF
6the HF decomposing generation under hot conditions corrodes positive active material, causes transition metal ions stripping, thus destroys cathode material structure, affects battery performance and plays; (3), the SEI film that formed when initial charge of battery decomposes under the high temperature conditions, and SEI membrane structure is destroyed, and causes that battery impedance rises, capacity reduces.
Therefore, for effectively improving lithium ion battery energy density, be badly in need of developing electrode/electrolyte interface compatibility good, have extended cycle life, the superelevation warm type high-voltage lithium-ion battery electrolyte of high-temperature behavior excellence.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of superelevation warm type high-voltage lithium-ion battery electrolyte and use the lithium ion battery of this electrolyte, prepared lithium ion battery can meet the superhigh temperature performance requirement that the full electric state 85 DEG C of 4.35V stores 16h.
To achieve these goals, the technical solution used in the present invention is:
A kind of superelevation warm type high-voltage lithium-ion battery electrolyte, comprise non-aqueous organic solvent, lithium hexafluoro phosphate, suppression aerogenesis additive and Low ESR additive, it is characterized in that: described non-aqueous organic solvent comprises carbonate solvent and higher boiling point carboxylate solvent, wherein carbonate solvent and higher boiling point carboxylate solvent mass ratio are 50-90:50-10; Described suppression aerogenesis additive is the sultone compounds shown in structural formula I; Any one or two kinds of mixing that described Low ESR additive is the cyclic sulfates shown in fluorine sulfimide lithium and formula II;
In structural formula I and formula II: n, m are the integer of 1 ~ 4, R
1for any one of hydrogen atom, methyl, propyl group and vinyl.
Described sultone compounds is at least one in 1,3-propane sultone, 1,3-propene sultone, Isosorbide-5-Nitrae-butane sultones.
Described sultone compounds consumption accounts for 2.0% ~ 8.0% of described electrolyte gross mass.
Described fluorine sulfimide lithium is two trifluoromethanesulfonimide lithium and at least one in two fluorine sulfimide lithium; Its consumption accounts for 0.2% ~ 3.0% of described electrolyte gross mass.
Described cyclic sulfates is at least one in sulfuric acid vinyl ester, sulfuric acid propylene, BDO sulfuric ester, 4-methylsulfuric acid vinyl acetate, 4-propylthio vinyl acetate.
Described cyclic sulfates consumption accounts for 0.5% ~ 2.0% of described electrolyte gross mass.
Described carbonate solvent is at least one in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; Described higher boiling point carboxylate solvent is at least one in n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n propyl propionate, ethyl butyrate.
Described additive also comprise in vinyl ethylene carbonate, fluorinated ethylene carbonate, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether any one and more than; Its consumption accounts for 0.5% ~ 10.0% of described electrolyte gross mass.
A kind of superelevation warm type high-voltage lithium ion batteries, comprise positive pole, negative pole, barrier film and above-described superelevation warm type high-voltage lithium-ion battery electrolyte, described lithium ion cell charging cut-ff voltage is greater than 4.3V and is less than or equal to 4.5V.
The structural formula of the active material of described positive pole is: LiCo
xl
1-xo
2, wherein, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<x≤1.
The invention has the advantages that:
1, the present invention selects carbonic ester and high boiling carboxylate as cosolvent, can effectively promote high-temperature lithium ion battery storge quality; In addition, low viscous carboxylate solvent can improve wettability, the reduction electrode/electrolyte interface impedance of electrolyte to graphite cathode, while liquid measure protected by minimizing battery, improve cycle performance of battery.
2, the sultone compounds that the present invention selects in positive electrode surface film forming, can suppress the stripping of cobalt and the decomposition aerogenesis of electrolyte, effectively promotes battery high-temperature storge quality, reduces thickness swelling and improve battery capacity conservation rate.
3, the additive such as fluorine sulfimide lithium and cyclic sulfates then improves SEI film quality further, increases SEI film thermal stability and reduces its impedance, having good high temperature and take into account cycle characteristics.Use lithium ion battery prepared by lithium-ion battery electrolytes provided by the invention, the superhigh temperature performance requirement that the full electric state 85 DEG C of 4.35V stores 16h can be met.
Embodiment
Be described further the present invention below in conjunction with embodiment, enforcement of the present invention includes but not limited to following execution mode.Any do not depart from content of the present invention change or replace and can be understood by those skilled in the art, all should within protection scope of the present invention.
Embodiment 1
Electrolyte quota step: in the glove box being full of argon gas, by ethylene carbonate, propene carbonate, diethyl carbonate and n propyl propionate are in mass ratio for EC:PC:DEC:PP=2:1:5:2 mixes, add the vinyl ethylene carbonate (VEC) of the 1wt% based on electrolyte total weight, 3wt% fluorinated ethylene carbonate (FEC), 3.5wt%1, 3-propane sultone (1, 3-PS), 0.5wt%1, 3-propene sultone (1, 3-PST), 2wt% adiponitrile (ADN), 0.5wt% sulfuric acid vinyl ester (DTD), the two fluorine sulfimide lithium (LiFSi) of 0.5wt%, the most backward mixed solution slowly adds the lithium hexafluoro phosphate that concentration is 1.0mol/L, the lithium-ion battery electrolytes of embodiment 1 is obtained after stirring.
Lithium-ion battery electrolytes above-mentioned steps prepared injects through fully dry 4.35V graphite/LiCoO
2polymer battery, the amount of electrolyte will ensure the space be full of in battery core, battery one envelope; After normal temperature shelf 24hr, the routine of carrying out initial charge according to the following steps changes into: 0.05C constant current charge 60min, and 0.1C constant current charge is to 3.95V, and 85 DEG C of upper fixture constant temperature toast 4hr, secondary sealing; Then further with the electric current constant-current constant-voltage charging of 0.5C to 4.35V, cut-off current 0.01C, finally carries out partial volume with the electric current constant-current discharge of 0.5C to 3.0V.
1) normal-temperature circulating performance test: at 25 DEG C, the battery 1C constant current constant voltage after changing into is charged to 4.35V, cut-off current 0.01C, then uses 1C constant-current discharge to 3.0V.The conservation rate of the 500th circulation volume is calculated, internal resistance growth rate and thickness swelling after charge/discharge 500 circulations.Computing formula is as follows:
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/cyclic discharge capacity first) × 100%th;
Thickness × 100% before 500th circulation thickness swelling (%)=(after the 500th circulation the front thickness of thickness-circulation)/circulation;
Internal resistance × 100% before 500th circulation internal resistance growth rate (%)=(after the 500th circulation internal resistance before internal resistance-circulation)/circulation;
2) high-temperature storage performance: the battery after changing into is charged to 4.35V with 1C constant current constant voltage at 25 DEG C, cut-off current 0.01C, measure initial battery thickness, record initial discharge capacity, then in 85 DEG C of insulating boxs, 16hr is stored, storage terminates the hot thickness of rear test battery, calculates the hot thickness swelling of battery; Measure the maintenance capacity of battery afterwards with 1C electric current constant-current discharge to 3.0V, recover capacity with 1C discharge and recharge one-shot measurement.Computing formula is as follows:
The hot thickness swelling of battery (%)=(hot thickness-original depth)/original depth × 100%;
Battery capacity conservation rate (%)=maintenance capacity/initial capacity × 100%;
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
Embodiment 2 ~ 10
In embodiment 2 ~ 10, except electrolyte solvent and additive composition and content press that table 1 is shown and added, other is all identical with embodiment 1.Table 1 is each constituent content table of electrolyte of embodiment 1 ~ 10:
Comparative example 1 ~ 5
In comparative example 1 ~ 5, except electrolyte solvent and additive composition and content press that table 2 is shown and added, other is all identical with embodiment 1.Table 2 is each constituent content table of electrolyte of comparative example 1 ~ 5:
In above-mentioned table 1 and table 2, it is as follows that corresponding title write a Chinese character in simplified form in each chemical substance letter:
EC (ethylene carbonate), PC (propene carbonate), DEC (diethyl carbonate), EMC (methyl ethyl carbonate), PP (n propyl propionate), BA (n-butyl acetate), IBA (isobutyl acetate), EB (ethyl butyrate), PS (1, 3-propane sultone), BS (1, 4-butane sultones), PST (1, 3-propene sultone), DTD (sulfuric acid vinyl ester), PCS (sulfuric acid propylene), LiFSi (two fluorine sulfimide lithium), LiTFSi (two trifluoromethanesulfonimide lithium), VEC (vinyl ethylene carbonate), FEC (fluorinated ethylene carbonate), AND (adiponitrile).
The performance comparison of embodiment 1 ~ 10 and comparative example 1 ~ 5
Table 3 is the performance comparison table of embodiment 1 ~ 10 and comparative example 1 ~ 5:
By comparative example 3 and each embodiment more known, the present invention selects high boiling carboxylate as cosolvent, can effectively promote high-temperature lithium ion battery storge quality and cycle performance, improve the capability retention in battery 85 DEG C of high-temperature storage 16hr and cyclic process, suppress thickness swelling.
By comparative example 4 and each embodiment more known, sultone compounds effectively can promote battery high-temperature storge quality, reduce thickness swelling improve battery capacity conservation rate.
Compared by comparative example 1 and comparative example 3, comparative example 2 and comparative example 4 compares, comparative example 5 and each embodiment more known, add the Low ESR additive such as fluorine sulfimide lithium and cyclic sulfates in the electrolytic solution, cycle performance of battery and high-temperature storage performance can be improved further.
Above-mentioned each comparative example and each embodiment Integrated comparative known, for meeting the superhigh temperature performance of 4.35V cycle performance and 85 DEG C of high-temperature storage 16hr, higher boiling point carboxylate solvent in electrolyte system, suppress aerogenesis additive and Low ESR additive three kinds of function ingredients to complement each other, indispensable.
Be more than illustrating for section Example of the present invention, not for limiting the scope of the claims of the present invention, all change or replacements not departing from content of the present invention, all should within protection scope of the present invention.
Claims (10)
1. a superelevation warm type high-voltage lithium-ion battery electrolyte, comprise non-aqueous organic solvent, lithium hexafluoro phosphate, suppression aerogenesis additive and Low ESR additive, it is characterized in that: described non-aqueous organic solvent comprises carbonate solvent and higher boiling point carboxylate solvent, wherein carbonate solvent and higher boiling point carboxylate solvent mass ratio are 50-90:50-10; Described suppression aerogenesis additive is the sultone compounds shown in structural formula I; Any one or two kinds of mixing that described Low ESR additive is the cyclic sulfates shown in fluorine sulfimide lithium and formula II;
Formula I Formula II
In structural formula I and formula II: n, m are the integer of 1 ~ 4, R
1for any one of hydrogen atom, methyl, propyl group and vinyl.
2. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, is characterized in that, described sultone compounds is at least one in 1,3-propane sultone, 1,3-propene sultone, Isosorbide-5-Nitrae-butane sultones.
3. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, is characterized in that, described sultone compounds consumption accounts for 2.0% ~ 8.0% of described electrolyte gross mass.
4. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, is characterized in that, described fluorine sulfimide lithium is two trifluoromethanesulfonimide lithium and at least one in two fluorine sulfimide lithium; Its consumption accounts for 0.2% ~ 3.0% of described electrolyte gross mass.
5. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, it is characterized in that, described cyclic sulfates is at least one in sulfuric acid vinyl ester, sulfuric acid propylene, BDO sulfuric ester, 4-methylsulfuric acid vinyl acetate, 4-propylthio vinyl acetate.
6. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, is characterized in that, described cyclic sulfates consumption accounts for 0.5% ~ 2.0% of described electrolyte gross mass.
7. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, is characterized in that, described carbonate solvent is at least one in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; Described higher boiling point carboxylate solvent is at least one in n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n propyl propionate, ethyl butyrate.
8. superelevation warm type high-voltage lithium-ion battery electrolyte according to claim 1, it is characterized in that, described additive also comprise in vinyl ethylene carbonate, fluorinated ethylene carbonate, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether any one and more than; Its consumption accounts for 0.5% ~ 10.0% of described electrolyte gross mass.
9. a superelevation warm type high-voltage lithium ion batteries, comprise positive pole, negative pole, barrier film and the superelevation warm type high-voltage lithium-ion battery electrolyte described in claim 1 to 8 any one, it is characterized in that, described lithium ion cell charging cut-ff voltage is greater than 4.3V and is less than or equal to 4.5V.
10. superelevation warm type high-voltage lithium ion batteries according to claim 9, is characterized in that, the structural formula of the active material of described positive pole is: LiCo
xl
1-xo
2, wherein, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0<x≤1.
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Cited By (9)
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|---|---|---|---|---|
| CN105576283A (en) * | 2016-02-03 | 2016-05-11 | 东莞市凯欣电池材料有限公司 | High voltage electrolyte considering high and low temperature performance and lithium ion battery using the electrolyte |
| CN106025356A (en) * | 2016-06-23 | 2016-10-12 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
| CN106410273A (en) * | 2016-06-23 | 2017-02-15 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery containing same |
| CN107845832A (en) * | 2017-10-27 | 2018-03-27 | 山东大学 | A kind of non-flammable lithium-ion battery electrolytes of Low ESR and preparation method thereof |
| CN107978461A (en) * | 2017-11-22 | 2018-05-01 | 山东大学 | A kind of Low ESR flame retardant super capacitor electrolyzing solution and preparation method thereof |
| CN109546219A (en) * | 2018-12-19 | 2019-03-29 | 珠海光宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte |
| CN109687021A (en) * | 2018-12-18 | 2019-04-26 | 东莞市杉杉电池材料有限公司 | A kind of high temp resistance lithium ion cell nonaqueous electrolytic solution |
| EP3419097A4 (en) * | 2017-01-20 | 2019-07-17 | LG Chem, Ltd. | Non-aqueous electrolyte for lithium secondary battery, and lithium secondary battery comprising same |
| WO2021135923A1 (en) * | 2019-12-31 | 2021-07-08 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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| CN105576283A (en) * | 2016-02-03 | 2016-05-11 | 东莞市凯欣电池材料有限公司 | High voltage electrolyte considering high and low temperature performance and lithium ion battery using the electrolyte |
| CN106410273B (en) * | 2016-06-23 | 2019-04-26 | 宁德新能源科技有限公司 | A kind of electrolyte and the lithium ion battery containing the electrolyte |
| CN106025356A (en) * | 2016-06-23 | 2016-10-12 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
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| CN107845832A (en) * | 2017-10-27 | 2018-03-27 | 山东大学 | A kind of non-flammable lithium-ion battery electrolytes of Low ESR and preparation method thereof |
| CN107978461B (en) * | 2017-11-22 | 2020-08-04 | 山东大学 | Low-impedance flame-retardant supercapacitor electrolyte and preparation method thereof |
| CN107978461A (en) * | 2017-11-22 | 2018-05-01 | 山东大学 | A kind of Low ESR flame retardant super capacitor electrolyzing solution and preparation method thereof |
| CN109687021A (en) * | 2018-12-18 | 2019-04-26 | 东莞市杉杉电池材料有限公司 | A kind of high temp resistance lithium ion cell nonaqueous electrolytic solution |
| CN109546219A (en) * | 2018-12-19 | 2019-03-29 | 珠海光宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery using the electrolyte |
| WO2021135923A1 (en) * | 2019-12-31 | 2021-07-08 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN113130971A (en) * | 2019-12-31 | 2021-07-16 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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