CN108281700A - A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte - Google Patents
A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte Download PDFInfo
- Publication number
- CN108281700A CN108281700A CN201810055479.7A CN201810055479A CN108281700A CN 108281700 A CN108281700 A CN 108281700A CN 201810055479 A CN201810055479 A CN 201810055479A CN 108281700 A CN108281700 A CN 108281700A
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- China
- Prior art keywords
- electrolyte
- lithium
- organic solvent
- functional additive
- 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
-
- 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
-
- 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 present invention disclose a kind of electrolyte and preparation method with using the secondary lithium-sulfur battery of the electrolyte, the electrolyte includes lithium salts, organic solvent and functional additive, a concentration of 0.5 ~ the 5mol/L of lithium salts in the electrolytic solution, the mass percent of functional additive in the electrolytic solution are 0.1 ~ 3%.Lithium salts is added into organic solvent, is configured to electrolyte after stirring evenly, functional additive is added into electrolyte, continues stirring to being uniformly mixed to get to secondary lithium-sulfur battery function electrolyte.Electrolyte of the present invention may participate in solid electrolyte interface using five phenylborine of trifluoro as functional additive（SEI films）Formation, can dissolve LiF, enhance SEI films electric conductivity；Five phenylborine of trifluoro may advantageously facilitate LiPF6Dissociation reaction, adsorb free F‑, to reduce the HF formed due to trace water, reduce corrosion of the HF to electrode material；The capacity attenuation for effectively inhibiting positive electrode in cyclic process, improves the cyclical stability and capacity retention ratio of lithium-sulfur cell.
Description
Technical field
The present invention relates to technical field of lithium batteries, specifically a kind of electrolyte and preparation method with use the two of the electrolyte
Secondary lithium-sulfur cell.
Background technology
In recent years, lithium ion battery lithium ion battery is excellent with mass energy density height and volume energy density height etc. with it
Gesture is widely used in mobile electronic device and electric vehicle field.However, with the rapid development of electric vehicle, it is right
The performance requirement of lithium ion battery also steps up.Lithium-sulfur rechargeable battery energy density is high, is made using sulphur simple substance or sulphur-containing substance
For the lithium-sulfur cell of positive active material, theory is 2600Whkg than energy-1.In addition, lithium-sulfur cell also has Sulphur ressource rich
The advantages that rich, cheap, environment friendly and pollution-free is a kind of very battery with application prospect.
The electrolyte of lithium-sulfur cell mostly uses greatly ether organic solvent now, such as 1,3- dioxolanes and glycol dinitrate
Ether, in ethers electrolyte, the high-valence state polysulfide ion generated in lithium-sulfur cell discharge process is soluble in electrolyte, and high-valence state is poly-
Sulphion diffuses to cathode of lithium and side reaction occurs to generate irreversible lithium sulfide to be the important original for restricting lithium-sulfur cell cycle performance
Cause.The structure of positive electrode is mainly designed for the solution of above-mentioned problem at present to improve performance, and uses nitre
Sour lithium is with obvious effects but ideal not enough as electrolyte cathode additive agent.Positive film for additive is for improving lithium sulphur
Battery performance plays an important role, less for the research of positive film for additive at present.
Invention content
It is an object of the invention to overcome defect of the existing technology, a kind of electrolyte and preparation method and use are provided
The secondary lithium-sulfur battery of the electrolyte, additive may participate in positive electrode solid electrolyte interface (SEI in electrolyte of the present invention
Film) formation, enhance SEI films electric conductivity；The free F of absorption-, to reduce the HF formed due to trace water, reduce HF
Corrosion to electrode material.Improve the cyclical stability and capacity retention ratio of lithium-sulfur cell.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of secondary lithium-sulfur battery function electrolyte, which includes lithium salts, organic solvent and functional additive, described
A concentration of 0.5~the 5mol/L of lithium salts in the electrolytic solution, the mass percent of the functional additive in the electrolytic solution be 0.1~
3%.
Further scheme, the functional additive are five phenylborine of trifluoro, and structural formula is：
The mass percent of functional additive in the electrolytic solution preferably 0.5~1%.
Further scheme, the lithium salts are LiPF6、LiBF4、LiBOB、LiBC2O4F2、LiClO4、LiCF3SO3、LiN
(FSO2)2、LiN(CF3SO2)2One or more of.
Further scheme, one kind in carbonate based organic solvent or ether organic solvent of the organic solvent or
Two kinds.
Further scheme, the carbonate based organic solvent are ethylene carbonate, vinylene carbonate, fluoro carbonic acid second
One or more of enester, propene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate.
Further scheme, the ether organic solvent are dioxolane, dioxane, glycol dimethyl ether, diethyl two
One or more of diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, ethylene glycol diethyl ether or diethylene glycol diethyl ether.
It is another object of the present invention to provide a kind of preparation methods of electrolyte, which is characterized in that organic solvent
Middle addition lithium salts, electrolyte is configured to after stirring evenly, and then to functional additive is added in electrolyte, continues stirring to mixing
Uniformly, that is, secondary lithium-sulfur battery function electrolyte is prepared.
It is a still further object of the present invention to provide a kind of secondary lithium-sulfur batteries, including above-mentioned electrolyte, the anode used
Material is elemental sulfur, more lithium sulfides, sulfenyl composite material, organic sulfur compound or sulphur carbon polymer etc..
Beneficial effects of the present invention：Electrolyte of the present invention may participate in using five phenylborine of trifluoro as functional additive
The formation of solid electrolyte interface (SEI films) can dissolve LiF, enhance the electric conductivity of SEI films；Five phenylborine of trifluoro has
Conducive to promotion LiPF6Dissociation reaction, adsorb free F-, to reduce the HF formed due to trace water, reduce HF to electrode
The corrosion of material.The capacity attenuation for effectively inhibiting positive electrode in cyclic process, improves the cyclical stability and appearance of lithium-sulfur cell
Measure conservation rate.
Description of the drawings
Fig. 1 is that the electrolyte for being 0.5% by functional additive in blank electrolysis liquid and embodiment 3 assembles the normal of lithium-sulfur cell
Warm cycle performance.
Specific implementation mode
Present invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
By volume 1 in glove box:1 uniformly mixes 1,3- dioxolanes and glycol dimethyl ether, to the mixed solvent
It is middle that double trifluoromethanesulfonimide lithiums are added, it stirs evenly, the electrolyte of a concentration of 1mol/L is made, 1wt% lithium nitrates are added.
Five phenylborine of functional additive trifluoro is added into the electrolyte, obtains function electrolyte, the functional additive accounts for electrolysis
The mass percentage content of liquid gross weight is respectively 0.1%, 0.5%, 1%, 2%, 3%.
Embodiment 2
By volume 1 in glove box:1:1 uniformly mixes fluorinated ethylene carbonate, propene carbonate and ethylene glycol diethyl
Ether, it is 1 that molar ratio, which is added, to the in the mixed solvent:1 LiN (FSO2)2With LiN (CF3SO2)2, stir evenly, be made a concentration of
The electrolyte of 0.5mol/L.Five phenylborine of functional additive trifluoro is added into the electrolyte, obtains function electrolyte, it is described
The mass percentage content that functional additive accounts for electrolyte gross weight is respectively 0.1%, 0.5%, 1%, 2%, 3%.
Embodiment 3
By volume 1 in glove box:1 uniform mixed carbonic acid vinyl acetate and ethyl methyl carbonate, to the mixed solvent
Middle addition LiBC2O4F2, stir evenly, the electrolyte of a concentration of 5mol/L be made.Functional additive three is added into the electrolyte
Five phenylborine of fluorine, obtains function electrolyte, and the mass percentage content that the functional additive accounts for electrolyte gross weight is respectively
0.1%, 0.5%, 1%, 2%, 3%.
Embodiment 4
It is assembled into battery and carries out electrochemical property test
The preparation of positive electrode：Sulphur carbon composite is prepared with heat melting method, sulphur powder and porous carbon are pressed into quality 4:1 places
In ball grinder, 12 hours mixings of ball milling are transferred in corundum boat, 155 DEG C of heat preservations 24 in the tube furnace full of nitrogen atmosphere
Hour, sulphur carbon composite (S/C) is obtained, by S/C:Conductive carbon:PVDF is 8 in mass ratio:1:1 prepares slurry, is coated in aluminium
On foil, pole piece is prepared into after drying.
The assembling and test of battery：It is diaphragm with celgard2400, lithium metal is cathode, and electrolyte is work(in embodiment 3
Can additive be 0.5% electrolyte and blank electrolysis liquid, sulphur carbon anode be assembled into 2016 button cells, 1.0~3.0V it
Between carry out charge-discharge test, with AC impedance of the CHI604D electrochemical workstations test battery under open-circuit voltage.
The normal temperature circulation of button cell is as shown in Figure 1, be added after 0.5% functional additive, cyclical stability is apparent
It improves, capacity retention ratio is higher.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementation cases here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (8)
1. a kind of electrolyte, which is characterized in that the electrolyte includes lithium salts, organic solvent and functional additive, and the lithium salts exists
A concentration of 0.5~5mol/L in electrolyte, the mass percent of the functional additive in the electrolytic solution are 0.1~3%.
2. electrolyte according to claim 1, which is characterized in that the functional additive is five phenylborine of trifluoro,
Structural formula is：
The mass percent of functional additive in the electrolytic solution preferably 0.5~1%.
3. electrolyte according to claim 1, which is characterized in that the lithium salts is LiPF6、LiBF4、LiBOB、
LiBC2O4F2、LiClO4、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2One or more of.
4. electrolyte according to claim 1, which is characterized in that the organic solvent is selected from carbonate based organic solvent
Or one or both of ether organic solvent.
5. electrolyte according to claim 4, which is characterized in that the carbonate based organic solvent is ethylene carbonate
Ester, vinylene carbonate, fluorinated ethylene carbonate, propene carbonate, ethyl methyl carbonate, dimethyl carbonate, carbonic acid diethyl
One or more of ester.
6. electrolyte according to claim 4, which is characterized in that the ether organic solvent is dioxolane, dioxy
Six rings, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, ethylene glycol diethyl ether or diethylene glycol diethyl ether
One or more of.
7. the preparation method of electrolyte as described in claim 1, which is characterized in that lithium salts is added into organic solvent, stirs
It is configured to electrolyte after uniformly, then to functional additive is added in electrolyte, continues stirring to being uniformly mixed, that is, is prepared
Secondary lithium-sulfur battery function electrolyte.
8. a kind of secondary lithium-sulfur battery, which is characterized in that comprising the electrolyte described in any one of claim 1-4, use
Positive electrode be elemental sulfur, more lithium sulfides, sulfenyl composite material, organic sulfur compound or sulphur carbon polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810055479.7A CN108281700A (en) | 2018-01-19 | 2018-01-19 | A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810055479.7A CN108281700A (en) | 2018-01-19 | 2018-01-19 | A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN108281700A true CN108281700A (en) | 2018-07-13 |
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| CN201810055479.7A Withdrawn CN108281700A (en) | 2018-01-19 | 2018-01-19 | A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987803A (en) * | 2018-07-17 | 2018-12-11 | 四川华昆能源有限责任公司 | A kind of lithium an- ode film forming electrolyte and its additive for lithium-sulfur cell |
| CN109004272A (en) * | 2018-07-20 | 2018-12-14 | 珠海格力电器股份有限公司 | A kind of electrolyte mixed solvent and lithium ion battery |
| CN110137573A (en) * | 2019-05-31 | 2019-08-16 | 中国科学院金属研究所 | It is a kind of using lithium metal as the electrolyte for lithium secondary batteries of cathode |
| CN110247052A (en) * | 2019-06-14 | 2019-09-17 | 中国科学技术大学 | Metal fluoride nano particle additive, preparation method and the battery comprising it |
-
2018
- 2018-01-19 CN CN201810055479.7A patent/CN108281700A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987803A (en) * | 2018-07-17 | 2018-12-11 | 四川华昆能源有限责任公司 | A kind of lithium an- ode film forming electrolyte and its additive for lithium-sulfur cell |
| CN109004272A (en) * | 2018-07-20 | 2018-12-14 | 珠海格力电器股份有限公司 | A kind of electrolyte mixed solvent and lithium ion battery |
| CN110137573A (en) * | 2019-05-31 | 2019-08-16 | 中国科学院金属研究所 | It is a kind of using lithium metal as the electrolyte for lithium secondary batteries of cathode |
| CN110247052A (en) * | 2019-06-14 | 2019-09-17 | 中国科学技术大学 | Metal fluoride nano particle additive, preparation method and the battery comprising it |
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Application publication date: 20180713 |
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