CN103928703A - Electrolyte and lithium-sulfur battery with same - Google Patents
Electrolyte and lithium-sulfur battery with same Download PDFInfo
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- CN103928703A CN103928703A CN201410168623.XA CN201410168623A CN103928703A CN 103928703 A CN103928703 A CN 103928703A CN 201410168623 A CN201410168623 A CN 201410168623A CN 103928703 A CN103928703 A CN 103928703A
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- Prior art keywords
- lin
- lithium
- electrolyte
- sulfur cell
- ionic liquid
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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
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- 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
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to electrolyte and a lithium-sulfur battery with the same. The electrolyte comprises LiN(SO2CF3)2, LiN(SO2F)2, and CH3O(CH2CH2O)nCH3, wherein n is 2-4; imidazolyl ionic liquid is EMITFSI or BMITFSI, and contains 0.1-2.0 M of LiN(SO2F)2 and 1-7 M of LiN(SO2CF3); the volume ratio of an ether solvent to the imidazolyl ionic liquid is 0.25:1 to 4:1. The electrolyte can relieve passivation and polarization of the material when being applied to the lithium-sulfur battery, the utilization rate of active substances of the material is improved, and the diffusion of the active substances is restrained to improve the cycle performance of a battery system. The electrochemical characterization performance of the lithium-sulfur battery is improved, and the lithium-sulfur battery has the characteristics of being high in capacity, good in cycle performance, simple, good in reproducibility and the like.
Description
Technical field
The present invention relates to a kind ofly for the electrolyte of lithium-sulfur cell and the lithium-sulfur cell of formation thereof, be specially to adding a kind of lithium-sulfur cell electrolyte assisted electrolysis matter efficiently in traditional electrolyte, further improve the overall performance of battery simultaneously by solvent optimization.
Background technology
Along with social development, the particularly development of electric automobile industry, lithium ion battery is faced with unprecedented challenge.Owing to embedding the restriction of emergence type reaction mechanism, traditional positive electrode is difficult to have further quantum jump aspect energy density, has the more material of high power capacity in order to obtain, and the sulfur electrode based on dissolution-deposition reaction is by extensive concern.
, can there are two electronics transfers when it reacts with lithium in the element that sulphur is a kind of lightweight, nontoxic and reserves are abundant, its theoretical capacity, up to 1675mAh/g, is desirable electrode material of new generation.But the intrinsic active material of this electrode reaction dissolves diffusion and reaction volume expansion has caused low life-span of battery and efficiency for charge-discharge.Electrolyte, as an important composition of battery, is not only effective ion transfer carrier, also by affecting the factor such as interfacial property, intermediate product solubility, lithium-sulfur cell overall performance is had to decisive role.Chinese patent CN1335653A has the solvent burden ratio of different sulphur and polysulfide solubility by adjusting, and is filled with special gas to improve the cyclicity of battery at the cathode of lithium surface desirable solid electrolyte interface of formation in solvent; CN1838469A, CN1495957A and CN1487620A are respectively by regulating structure composition raising capacity and the cycle life of quaternary ammonium salt ionic liquid and imide salts ionic liquid.
Summary of the invention
It is a kind of for the electrolyte of lithium-sulfur cell and the lithium-sulfur cell of formation thereof that the object of the invention is to provide, its feature is for adding lithium-sulfur cell assisted electrolysis matter, and by solvent modified lifting active material utilization and life properties, make for the electrolyte of lithium-sulfur cell and the lithium-sulfur cell of composition thereof.The present invention has that specific capacity is high, cycle life good and discharge and recharge the advantages such as degree of polarization is low.
Electrolyte for lithium-sulfur cell provided by the invention comprises:
LiN(SO
2CF
3)
2
LiN(SO
2F)
2
CH
3o (CH
2cH
2o)
ncH
3, wherein n=2～4;
Imidazolium ionic liquid: 1-methyl-3-butyl imidazole two (trimethyl fluoride sulfonyl) imines (BMITFSI) and 1-methyl-3-ethyl imidazol(e) two (trimethyl fluoride sulfonyl) imines (EMITFSI);
Wherein, LiN (SO
2f)
2concentration range is at 0.1～2.0M, LiN (SO
2cF
3)
2concentration range is 1～7M; The volume ratio of ether solvent and imidazolium ionic liquid is 0.25: 1～4: 1.
The present invention evenly mixes with imidazolium ionic liquid than for example, by ether solvent (, tetraethylene glycol dimethyl ether) by metering volume for the preparation method of the electrolyte of lithium-sulfur cell, quantitatively dissolves in LiN (SO
2f)
2and LiN (SO
2cF
3)
2, the liquid that abundant stirring becomes clear obtain target electrolyte.
The present invention is with sulfur electrode positive pole, and metal Li sheet is negative pole, assembles according to a conventional method lithium-sulfur cell.
Lithium-sulfur cell assisted electrolysis matter of the present invention is two fluorine sulfimide lithium (LiN (SO
2f)
2), it has than traditional electrolyte bis trifluoromethyl sulfimide lithium (LiN (SO
2cF
3)
2) higher ionic conductivity, be beneficial to optimization active material utilization.By changing LiN (SO
2f)
2and LiN (SO
2cF
3)
2concentration, solvent species and proportioning, can further improve the cycle performance of battery.
Outstanding feature of the present invention is, to containing LiN (SO
2cF
3)
2lithium-sulfur cell electrolyte in add LiN (SO
2f)
2after, 1) this electrolyte system has better permeability, ionic conductivity and lithium ion conductivity, and then raising active material utilization, makes battery system have higher initial capacity; 2) this battery system has more excellent electrode-electric solution liquid interfacial property and can alleviate anodal surperficial insoluble product Li
2s/Li
2s
2for the passivation of material; 3) by regulating solvent burden ratio, weaken the diffusion of active sulfur material in cyclic process and run off, improve the cyclical stability of battery.Therefore the present invention has improved the performance of lithium-sulfur cell system, has capacity high, and cyclicity is good, the feature such as simple and favorable reproducibility.
Brief description of the drawings
Fig. 1 is that embodiment 1,2 and comparative example 1 assemble the cyclic voltammetry curve of battery under 0.1 millivolt of sweep speed per second.
Fig. 2 is that embodiment 1,2 and comparative example 1 assemble the charging and discharging curve of battery under 167 milliamperes of every gram of current densities.
Fig. 3 is that embodiment 1,2 and comparative example 1 assemble the cyclic curve of battery under 167 milliamperes of every gram of current densities.
Embodiment
The present invention can be embodied from following embodiment, but just presented for purposes of illustration, instead of for limiting the present invention.
Embodiment 1
The preparation of sulphur positive pole: the Kynoar (PvDF) of the superfine P electric conducting material of the sublimed sulfur of 55wt.%, 35wt.% and 10wt.% is disperseed in 1-METHYLPYRROLIDONE (NMP) solvent, stir and mix to slurry for 12 hours, be coated on the aluminium collector of carbon-coating coating 60 DEG C of dry circular anode pole pieces that are made as diameter 12mm after 12 hours.
Detesting water anaerobic condition lower-weighing, to obtain volume ratio be that (molecular formula is CH for the tetraethylene glycol dimethyl ether of 3: 2
3o (CH
2cH
2o)
4cH
3) and the mixed solvent of EMITFSI, quantitatively dissolve in 0.8M LiN (SO
2f)
2with 3.2M LiN (SO
2cF
3)
2, the liquid that stirring becomes clear obtain target electrolyte.Sulfur electrode with above-mentioned preparation does positive pole, taking lithium metal as to electrode, is assembled into according to a conventional method half-cell, and assembled battery is carried out to cyclic voltammetric and constant current charge-discharge test at ambient temperature, and voltage range is: 1.0～3.0 volts.Fig. 1 has shown in sweep speed to be the cyclic voltammetric result of sulfur electrode under 0.1 millivolt of condition per second, Fig. 2 has shown the discharge curve of sulfur electrode under 167 milliamperes of every gram of current densities, and Fig. 3 is the cycle life of lithium-sulfur cell under 167 milliamperes of every gram of current densities of assembling.As can be seen from Figure 3, this electrolyte can be realized the high initial discharge specific capacity of 1315mAh/g, and after 50 weeks, Capacitance reserve is more than 79%.
Embodiment 2
Adopt positive pole and the assembling mode identical with embodiment 1, it is the tetraethylene glycol dimethyl ether of 3: 2 and the mixed solvent of EMITFSI that target electrolyte is changed to volume ratio, quantitatively dissolves in 0.6M LiN (SO
2f)
2with 3.4M LiN (SO
2cF
3)
2.Initial capacity is slightly low, is 1103mAh/g, and the specific discharge capacity after 50 weeks is 924mAh/g, and the excellent Capacitance reserve of cycle performance is more than 86%.
Comparative example 1
Adopt positive pole and the assembling mode identical with embodiment 1, it is the tetraethylene glycol dimethyl ether of 3: 2 and the mixed solvent of EMITFSI that target electrolyte is changed to volume ratio, quantitatively dissolves in 4M LiN (SO
2cF
3)
2.Initial capacity is lower is 1042mAh/g, Capacitance reserve 73% after 50 weeks.
Claims (8)
1. for an electrolyte for lithium-sulfur cell, this electrolyte comprises:
LiN(SO
2CF
3)
2
LiN(SO
2F)
2
CH
3o (CH
2cH
2o)
ncH
3, wherein n=2～4;
Imidazolium ionic liquid EMITFSI or BMITFSI.
2. the electrolyte for lithium-sulfur cell according to claim 1, is characterized in that described LiN (SO
2f)
2concentration range is at 0.1～2.0M; LiN (SO
2cF
3)
2concentration range is 1～7M.
3. the electrolyte for lithium-sulfur cell according to claim 1, is characterized in that described ether solvent CH
3o (CH
2cH
2o)
ncH
3with the volume ratio of imidazolium ionic liquid be: 0.25: 1～4: 1.
4. the electrolyte for lithium-sulfur cell according to claim 1, is characterized in that described LiN (SO
2f)
2concentration be 0.8M LiN (SO
2f)
2.
5. the electrolyte for lithium-sulfur cell according to claim 1, is characterized in that described LiN (SO
2cF
3)
2concentration be 3.2M.
6. for an electrolyte for lithium-sulfur cell, this electrolyte comprises:
LiN(SO
2CF
3)
2
LiN(SO
2F)
2
CH
3o (CH
2cH2O)
ncH
3, wherein n=4;
Imidazolium ionic liquid EMITFSI
Wherein, LiN (SO
2f)
20.8M, LiN (SO
2cF
3)
23.2M;
The volume ratio of ether solvent and imidazolium ionic liquid is 3: 2.
7. the preparation method of the electrolyte for lithium-sulfur cell claimed in claim 1, it is characterized in that through step be: evenly mix with imidazolium ionic liquid than by ether solvent by metering volume, quantitatively dissolve in LiN (SO
2f)
2and LiN (SO
2cF
3)
2, the liquid that abundant stirring becomes clear obtain target electrolyte.
8. for a lithium-sulfur cell, it is characterized in that with sulfur electrode positive pole, metal Li sheet is negative pole, is assembled into according to a conventional method lithium-sulfur cell taking the arbitrary described electrolyte of claim 1-6 as electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168623.XA CN103928703A (en) | 2014-04-23 | 2014-04-23 | Electrolyte and lithium-sulfur battery with same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168623.XA CN103928703A (en) | 2014-04-23 | 2014-04-23 | Electrolyte and lithium-sulfur battery with same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103928703A true CN103928703A (en) | 2014-07-16 |
Family
ID=51146842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410168623.XA Pending CN103928703A (en) | 2014-04-23 | 2014-04-23 | Electrolyte and lithium-sulfur battery with same |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110752407A (en) * | 2018-07-23 | 2020-02-04 | 张家港市国泰华荣化工新材料有限公司 | Lithium-sulfur battery electrolyte and lithium-sulfur battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102138235A (en) * | 2008-08-29 | 2011-07-27 | 法国原子能及替代能源委员会 | Lithium-ion rechargeable accumulators including an ionic liquid electrolyte |
| CN102199846A (en) * | 2011-04-29 | 2011-09-28 | 华南师范大学 | Porous polymer electrolyte supporting membrane material, preparation method thereof and application thereof |
| CN102280664A (en) * | 2010-06-09 | 2011-12-14 | 中国科学院物理研究所 | Electrolyte and secondary lithium battery and capacitor containing electrolyte |
-
2014
- 2014-04-23 CN CN201410168623.XA patent/CN103928703A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102138235A (en) * | 2008-08-29 | 2011-07-27 | 法国原子能及替代能源委员会 | Lithium-ion rechargeable accumulators including an ionic liquid electrolyte |
| CN102280664A (en) * | 2010-06-09 | 2011-12-14 | 中国科学院物理研究所 | Electrolyte and secondary lithium battery and capacitor containing electrolyte |
| CN102199846A (en) * | 2011-04-29 | 2011-09-28 | 华南师范大学 | Porous polymer electrolyte supporting membrane material, preparation method thereof and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110752407A (en) * | 2018-07-23 | 2020-02-04 | 张家港市国泰华荣化工新材料有限公司 | Lithium-sulfur battery electrolyte and lithium-sulfur battery |
| CN110752407B (en) * | 2018-07-23 | 2021-05-25 | 张家港市国泰华荣化工新材料有限公司 | Lithium-sulfur battery electrolyte and lithium-sulfur battery |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140716 |
|
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