CN103337657A - Novel sulfate solvent for lithium ion secondary battery - Google Patents
Novel sulfate solvent for lithium ion secondary battery Download PDFInfo
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- CN103337657A CN103337657A CN2013102676813A CN201310267681A CN103337657A CN 103337657 A CN103337657 A CN 103337657A CN 2013102676813 A CN2013102676813 A CN 2013102676813A CN 201310267681 A CN201310267681 A CN 201310267681A CN 103337657 A CN103337657 A CN 103337657A
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- solvent
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a novel solvent which can be used for an electrolyte of a lithium secondary cell. The solvent is structurally characterized by being a sulfate compound and a derivative thereof, and the condensed structural formula is R1OSO2OR2, wherein R1 and R2 can be symmetric or asymmetric; R1 or R2 is an alkyl (but not virulent dimethyl sulfate), an ether chain, an aryl group, a halogenated alkyl group, a halogenated ether or a halogenated aryl group; the halogen is F, Cl or Br; the halogenation is partial or complete substitution. By using and containing the solvent, the high-temperature and low-temperature range of the electrolyte can be widened, and more choices can be provided for the solvent for a lithium ion battery; and the performance of a lithium ion battery, such as specific capacity, circularity and the like, can be affected less.
Description
Technical field
The present invention relates to a kind of secondary lithium batteries novel dissolvent.Relating to a kind of sulfate compound or derivative particularly is the electrolyte of solvent, belongs to the technical field of electrochemistry and chemical power source product.
Background technology
Lithium ion battery because have operating voltage height, specific capacity height, advantage such as quality is light, self-discharge rate is low, environmental pollution is little, be widely used, in recent years, particularly in pure electric vehicle EV and hybrid-power electric vehicle HEV field, receive publicity especially.Solvent is the important component part of lithium-ion battery electrolytes, and the physics and chemistry of solvent and electrochemical properties affect the performance of battery to a great extent.Solvent commonly used is the carbonates solvent in the lithium-ion battery electrolytes at present, comprises linear carbonate (DMC, DEC and EMC) and cyclic carbonate (EC, PC).The combination excellent combination property of linear carbonate and cyclic carbonate: operating temperature range is wideer, conductivity is high, electrochemical window is wide, and it is good to the most important thing is the electrochemistry compatibility of both positive and negative polarity.But also show the some shortcomings part in actual applications, low as the boiling point of linear carbonate, vapour pressure is high, particularly flash-point low (on average about 30 ℃) very easily burns; Performance under some occasions (low temperature, high working voltage cathode material) remains further to be improved.Some other common solvent has ether solvent, acetates solvent, phosphoric acid ester solvent, sulfone class, nitrile and ionic liquid etc., and these solvents respectively have pluses and minuses.Ether solvent such as DME fusing point are lower, solvability can provide higher conductivity by force, but cathode stabilization is not enough, and oxidation resistance is relatively poor; Acetates solvent fusing point is very low, can improve the cryogenic property of electrolyte, but not enough to the compatibility of graphite cathode; The phosphoric acid ester solvent comes into one's own because of incombustible advantage, but the poor compatibility on graphite cathode is restricting its application; Sulfone class and nitrile solvents cathode stabilization are very high, but viscosity is big, and wetting capacity is poor, and particularly the compatibility to graphite cathode has much room for improvement; Ionic liquid is non-volatile substantially and do not fire, cathode stabilization height, but viscosity of il is big, fusing point is high, and particularly conductivity is lower and limited its application under the low temperature environment.These solvents exist advantage aspect some of chemical property, compatible not enough to negative or positive electrode, though by using some additives to improve, but combination property is still lower.By these solvents and carbonates solvent are used, optimum organization and the suitable ratio of selection, can improve the performance (low temperature, burning, anti-oxidant etc.) of carbonic ester electrolyte aspect to a certain extent, and don't influence is to the compatibility of positive and negative pole material.Certainly, except the existing solvent of optimum organization, the exploration of novel dissolvent also is necessary.The searching of novel dissolvent mainly contains two aspects: one side is to improve on the basis of the carbonats compound of excellent combination property, improve performance in a certain respect, as introduce fluorine-containing carbonate products and improve non-oxidizability, or introduce and contain silica-based compound and improve first all reversible capacities etc.; On the other hand, seek novel non-carbonates solvent, as sydnone etc.The work of seeking novel non-carbonates solvent is a challenging job, not only to make these novel dissolvents satisfy requirement on electrolyte physics and chemistry and the electrochemistry, and compare and to have some particularity (as high low temperature, fire-retardant, anti-oxidant etc.) with conventional carbonates solvent.Yet the difficulty and hope coexistence to the exploration of novel dissolvent, may make us expand lithium ion battery with the visual field of organic solvent system, also can provide the necessary knowledge accumulation for additive or the cosolvent of seeking specific function.
Summary of the invention
Technical problem to be solved by this invention provides a kind of novel secondary lithium batteries solvent.
Purpose of the present invention is achieved through the following technical solutions: a kind of secondary lithium batteries solvent, and it is sulfuric acid ester compound and derivative thereof, structural formula is:
R in the formula
1And R
2Can be symmetry or asymmetric, R
1Or R
2Be alkyl (but not adopting hypertoxic dimethyl suflfate), ether chain, aryl, haloalkyl, halogen ether, halogenated aryl, wherein, halo is partly or entirely to replace.
Solvent form of the present invention is liquid.
The sulfuric acid ester compound that the present invention is above-mentioned separately or mix as the solvent in the electrolyte of lithium-ion secondary battery.If mix use in the electrolyte other solvents can select in linear carbonate (dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC etc.) and the cyclic carbonate (ethylene carbonate EC, propene carbonate PC, gamma-butyrolacton GBL etc.) one or more for use.Solvent can also extend to ether solvent such as glycol dimethyl ether DME, 1,3-dioxolane DOL and tetrahydrofuran THF etc.Available lithium salts is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, at least a among LiBOB and the LiTFSI, the concentration of lithium salts is 0.5-2M.
The present invention is to the evaluation of lithium secondary battery charge-discharge performance: use the electrolyte of solvent preparation as mentioned above to assemble 2016 button cells: MCMB/Li, LiFePO respectively
4/ Li.
Beneficial effect of the present invention is: containing solvent of the present invention has lower fusing point, for lithium-ion battery electrolytes provides more choices with solvent, and uses solvent of the present invention less to performance such as the influences such as specific capacity, cyclicity of lithium ion battery.
Description of drawings
Accompanying drawing 1: the structure chart of the used sulfuric acid ester compound of the present invention.
Accompanying drawing 2: the DSC curve of the embodiment of the invention 1---dibutyl sulfate
Accompanying drawing 3: the embodiment of the invention 2,3 and comparative example 1---use contains the electrolyte of described dibutyl sulfate solvent and the charge-discharge performance figure of the button cell that blank electrolysis liquid is assembled.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but these embodiment do not constitute any limitation of the invention.
In being full of the glove box of argon gas, use sulfuric acid ester solvent preparation electrolyte of the present invention, employed lithium salts is LiTFSI, the concentration of LiTFSI in electrolyte is 1M, and employed sulfuric acid ester compound is dibutyl sulfate, and concrete structure is as follows:
This dibutyl sulfate has low fusing point, as shown in Figure 2, is about-41 ℃, can widen lithium ion battery low-temperature electrolytic liquid system choice of Solvent.
Assembling MCMB/Li 2016 button cells in being full of the glove box of argon gas, the electrolyte that uses embodiment 1 described novel dissolvent to prepare, the charging/discharging voltage interval is 0～3 V, current density is 40 mA/g.Test result by accompanying drawing 3 as seen, for the MCMB negative pole, first all charge ratio capacity are that the first all coulombic efficiencies of 349 mAh/g(are 75%), the charge ratio capacity is 332 mAh/g after 100 weeks of circulation, capability retention is 95%, the electrolyte of employed novel dissolvent preparation has close performance with comparative example 1 blank electrolysis liquid, illustrates to use the electrolyte anticathode of described novel dissolvent to have excellent compatibility.
Embodiment 3
In being full of the glove box of argon gas, assemble LiFePO
4/ Li 2016 button cells, the electrolyte that uses embodiment 1 described novel dissolvent to prepare, the charging/discharging voltage interval is 3～4V, current density is 40 mA/g.Test result by accompanying drawing 3 as seen, for LiFePO
4Positive pole, first all specific discharge capacities are that the first all coulombic efficiencies of 134 mAh/g(are 88%), specific discharge capacity is 132 mAh/g after 100 weeks of circulation, capacity does not have decay substantially, illustrates that the electrolyte that uses described novel dissolvent preparation is to LiFePO
4Anodal performance does not have much affect.
Embodiment 4
Selected novel dissolvent is that R is the compound of butyl (Bu-) in the structure shown in the accompanying drawing 1, i.e. dibutyl sulfate is as follows:
The synthetic route of dibutyl sulfate is as follows:
Experimental procedure: 1) dibutyl sulfite is synthetic: in 500 mL there-necked flasks constant pressure funnel is installed successively, the rubber stopper of the spherical condensating tube of band fluid-tight and band thermometer, the afterbody of fluid-tight connects acid device for absorbing tail gas, taking by weighing 163.0 g (2.2 mol) n-butanol earlier joins in the there-necked flask, take by weighing 118.9 g (1 mol) thionyl chloride then and place constant pressure funnel, slowly splash into thionyl chloride in 2 hours, after splashing into half, there-necked flask is placed ice-water bath, reaction temperature is maintained about 30 ℃, after dripping off thionyl chloride, slowly be heated to and keep 30 min about 80 ℃, revolve to steam and remove the intact thionyl chloride of unreacted, the decompression distillation of remaining liq water pump obtains cut 54.1 g of 120 ~ 121 ℃ (~ 20 mmHg), productive rate 35%, this cut are not identified and are directly used in next step reaction.
2) dibutyl sulfate is synthetic: the same as above device of installing, with twice synthetic dibutyl sulfite totally 103.9 g (about 0.54 mol) place there-necked flask, and place ice-water bath, other takes by weighing 36.1 g (0.27 mol) sulfonic acid chloride in constant pressure funnel, drip off in 30 min, be heated to chloro-normal butane after dripping off and reflux, reaction 4-5 h steams chloro-normal butane, remaining liquid is washed till neutrality with aqueous sodium carbonate, static separatory, tell organic phase after, use anhydrous MgSO
4And the NaH drying, to topple over the stillness of night, 90 ℃ of (＜3.5 mmHg) colourless liquid 9.7 g are collected in the oil pump decompression distillation, fail calculated yield, the product warp because also containing large-tonnage product in the front-end volatiles
1H NMR nuclear-magnetism is identified, and is consistent with bibliographical information.
1H?NMR?(300?MHz,?CDCl
3)?δ/ppm:?4.26?(t,?2H,?-O
CH 2 CH
2-),?1.70-1.79?(m,?2H,?-OCH
2 CH 2 -),?1.41-1.51?(m,?2H,?-
CH 2 CH
3),?0.96?(t,?3H,?-CH
2 CH 3 )。
The comparative example 1
Assembling MCMB/Li 2016 button cells use 1mol/L LiPF in being full of the glove box of argon gas
6DMC/EC/EMC 1:1:1(volume ratio) be blank electrolysis liquid, the charging/discharging voltage interval is 0～3 V, and current density is 40 mA/g.
Claims (3)
1. a lithium rechargeable battery is characterized in that with novel sulfuric ester solvent, and described solvent is sulfuric acid ester compound and derivative thereof, and structural formula is:
R in the formula
1And R
2Can be symmetry or asymmetric, R
1Or R
2Be alkyl (but not adopting hypertoxic dimethyl suflfate), ether chain, aryl, haloalkyl, halogen ether, halogenated aryl, wherein, halo is partly or entirely to replace.
2. a kind of lithium rechargeable battery is characterized in that with novel sulfuric ester solvent described solvent is used alone as the solvent of lithium-ion battery electrolytes according to claim 1, but does not get rid of as cosolvent or additive.
3. a kind of lithium rechargeable battery is characterized in that with novel sulfuric ester solvent according to claim 1, and the lithium salts of selecting for use in the electrolyte is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, at least a among LiBOB or the LiTFSI, the concentration of lithium salts is 0.5-2M.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102676813A CN103337657A (en) | 2013-06-28 | 2013-06-28 | Novel sulfate solvent for lithium ion secondary battery |
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|---|---|---|---|
| CN2013102676813A CN103337657A (en) | 2013-06-28 | 2013-06-28 | Novel sulfate solvent for lithium ion secondary battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359368A (en) * | 2017-06-22 | 2017-11-17 | 武汉大学 | A kind of lithium battery electrolytes based on sulfuric acid ester additive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW432733B (en) * | 1997-10-02 | 2001-05-01 | Basf Ag | Esters as solvents in electrolyte systems for Li-ion storage cells |
-
2013
- 2013-06-28 CN CN2013102676813A patent/CN103337657A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW432733B (en) * | 1997-10-02 | 2001-05-01 | Basf Ag | Esters as solvents in electrolyte systems for Li-ion storage cells |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359368A (en) * | 2017-06-22 | 2017-11-17 | 武汉大学 | A kind of lithium battery electrolytes based on sulfuric acid ester additive |
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