CN109301325A - A kind of lithium-sulfur cell electrolyte - Google Patents
A kind of lithium-sulfur cell electrolyte Download PDFInfo
- Publication number
- CN109301325A CN109301325A CN201811060488.1A CN201811060488A CN109301325A CN 109301325 A CN109301325 A CN 109301325A CN 201811060488 A CN201811060488 A CN 201811060488A CN 109301325 A CN109301325 A CN 109301325A
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- China
- Prior art keywords
- lithium
- sulfur cell
- cell electrolyte
- electrolyte
- organic solvent
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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
-
- 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
-
- 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 relates to a kind of new lithium-sulfur cell electrolyte, including organic solvent, lithium salts and active additive, which is thionyl chloride (volume fraction 0.5%-10%).The concentration of the lithium salts is 0.1-2mol/L；The organic solvent is carbonates；The present invention can effectively generate the stability that negative electrode material protective film improves structure, significantly improve the performance of battery, improve its safety and improve the energy density of battery.
Description
Technical field
The present invention relates to a kind of new lithium-sulfur cell electrolyte.
Background technique
With the extensive use of portable electronic product become increasingly popular with new-energy automobile, people are for electrochmical power source
More stringent requirements are proposed for chemical property and security performance.Compared with traditional lithium ion battery, lithium-sulfur cell has because of it
Higher theoretical specific capacity and it is environmentally friendly the advantages that, get more and more people's extensive concerning recently.
However there is also many problems in actual application for lithium-sulfur cell.Wherein well-known is lithium-sulfur cell
Electric discharge intermediate product be high price more lithium sulfides, these readily soluble high price polysulfides are diffused into cathode of lithium, and and lithium metal
Reaction generates the polysulfide (Li of low price2S、Li2S2), these insoluble low price polysulfides largely deposit on cathode of lithium surface,
It further reduced the utilization rate of active material.The corrosion that cathode of lithium can also be caused simultaneously, reduces its chemical property.It is above-mentioned to ask
Topic is to limit the widely applied major reason of lithium-sulfur cell.To solve the above-mentioned problems, more and more researchers are by sight
It has focused in cathode of lithium protection.For example, cathode of lithium surface formed one layer of SEI protective film, come prevent cathode of lithium corrosion and
The deposition of low price polysulfide, and then improve the chemical property of battery.
Electrolyte is the important component of lithium-sulfur cell, it has the chemical property and security performance of battery very big
Influence.Research shows that a kind of SEI guarantor can be generated on cathode of lithium by adding one or more active additives in the electrolytic solution
Cuticula, this will substantially improve the chemical property of battery.
So far, it there are no report of the thionyl chloride as the active additive of the electrolyte of lithium-sulfur cell.
Summary of the invention
The object of the present invention is to provide a kind of new lithium-sulfur cell electrolyte and preparation method thereof.The present invention is into electrolyte
Suitable thionyl chloride is added as active additive, stable SEI protective film can be formed in electrochemical process, and improve
The utilization rate of sulphur anode, the i.e. electrolyte can form one layer of SEI protective film on cathode of lithium surface and improve lithium-sulfur cell cyclicity
Can and security performance experiments have shown that this electrolyte can also significantly improve the utilization rate of sulphur anode increase additional capacity.
Lithium-sulfur cell electrolyte provided by the invention is made of organic solvent, lithium salts, active additive.The lithium salts is
LiPF6、LiBF4、LiCH3SO3、LiCF3SO3、LiAsF6、LiClO4、LiBOB、LiN(CF3SO2)2One or more of, it is excellent
Select LiPF6With LiN (CF3SO2)2。
The concentration of the lithium salts is 0.1-2mol/L；It is preferred that 0.5-1.5 mol/L.
The organic solvent is dimethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, propionic acid first
It is ester, ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, dimethoxymethane, 1,2- dimethoxy, two sweet
One or more of diethylene glycol dimethyl ether, tetrahydrofuran, 2- methyltetrahydrofuran, 1,3- dioxolanes；It is preferred that carbonates
Solvent.
The active additive is thionyl chloride, molecular formula SOCl2, the volume fraction of the additive is 0.5%-10%,
It is preferably in a proportion of 1.0-3.0%.
The present invention provides a kind of preparation method of new lithium-sulfur cell electrolyte the following steps are included:
1) lithium salts is added into organic solvent at room temperature according to metering, stirs to dissolve；
2) thionyl chloride additive is added into the mixture that step 1) obtains, stirs to dissolve.
The present invention provides a kind of new lithium-sulfur cell electrolyte, which can significantly improve lithium-sulfur cell electrochemistry
The electrolyte of performance.Compared with prior art, the invention has the characteristics that:
1) material used in the present invention is commercially available gained, easy to operate, low production cost, and chemical property is steady
It is fixed, it is convenient for large-scale industrial production.
2) present invention is mixed using simple agitation to prepare required electrolyte, suitable by adding into organic electrolyte
Thionyl chloride can effectively generate the stability that negative electrode material protective film improves structure, electricity of the electrolyte to lithium-sulfur cell
Chemical reaction also has apparent facilitation.
3) present invention is only by adding relatively small number of thionyl chloride, so that it may significantly improve the performance of battery.While by
Relatively small number of thionyl chloride is only added in us, avoiding problems a large amount of due to thionyl chloride in electrochemical reaction process
It decomposes and causes volume excessively to expand and the problems such as structural breakdown.On the other hand, the decomposition product meeting of thionyl chloride and lithium metal
It reacts to form a kind of SEI protective film, its safety can be improved, while the sulphur generated can be further improved the energy of battery
Metric density.
Detailed description of the invention
Fig. 1 is all discharge curves of head of the assembled lithium-sulfur cell of the embodiment of the present invention 1 in different electrolytes.
Fig. 2 is all discharge curves of head of the assembled lithium-sulfur cell of the embodiment of the present invention 2 in different electrolytes.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1:
Materials synthesis: example 6:4 in mass ratio weighs sulphur simple substance (sublimed sulfur, 99%, Sinopharm Chemical Reagent Co., Ltd.) and lives
Property carbon (LITHIUM BATTERY, Jiangsu Xian Feng Nono-material Science & Technology Ltd.) be transferred in ball grinder, a small amount of ethyl alcohol (analysis pure) is added
With 300r/min wet ball grinding 3h, sample after ball milling is placed in 60 DEG C of baking ovens dry 6h, is then transferred to the sample after drying
In the reaction kettle of polytetrafluoroethylene (PTFE).In Muffle furnace (DZ47-60, Hefei Ke Jing Materials Technology Ltd.), with 2 DEG C/min
Speed be warming up to 155 DEG C of constant temperature 12h, be cooled to room temperature the sample for obtaining prepared sulfur-bearing 60%.
The preparation of electrode material: by prepared active material, super conductive black and binder (Kynoar,
PVDF after) ratio with mass ratio for 7:2:1 weighs, after being sufficiently mixed with mortar, suitable n-methyl-2-pyrrolidone is added
(NMP), uniform sizing material is obtained after stirring 12 h.Obtained slurry is coated uniformly on aluminium foil (collector) with applicator,
12 h are dried in 60 DEG C of vacuum drying oven, and the circular electric pole piece that diameter is 10 mm is prepared into after oil pressure.
The assembling of battery: experimental result is had an impact as far as possible to avoid and testing irrelevant factor, will first be cleaned up
The baking oven that 60 DEG C of temperature are placed in after button cell, all materials such as good electrode slice of punching press and tool cleaning is dried
6 h or so are handled, then rapidly by the pole piece weighing after drying, are immediately put into glove box together with other tools, gloves
The water oxygen value of case is below 5 ppm.Using metal lithium sheet as cathode, prepared composite electrode piece is as anode, copper foil
As negative current collector, diaphragm model Celgard 2325,1M lithium hexafluoro phosphate (LiPF6) electrolyte (acrylic carbonic acid
Ester: vinylcarbonates: dimethyl carbonate=1:4:5, volume ratio) and thionyl chloride additive according to volume ratio 98:2 carry out
Mixing, as electrolyte used in this experiment.After being completed button cell, after above-mentioned 6 h of battery standing being completed,
In 1.4-3.0 V voltage windows, 80 mA g-1Under current density, electrochemistry is carried out on blue electrical testing instrument (CT2001A)
The test of performance, first week discharge capacity is close to 2700 mAh g-1。
Example 2:
The preparation of electrode material: by prepared active material, super conductive black and binder (Kynoar,
PVDF after) ratio with mass ratio for 5:4:1 weighs, after being sufficiently mixed with mortar, suitable n-methyl-2-pyrrolidone is added
(NMP), uniform sizing material is obtained after stirring 12 h.Obtained slurry is coated uniformly on aluminium foil (collector) with applicator,
12 h are dried in 60 DEG C of vacuum drying oven, and the circular electric pole piece that diameter is 10 mm is prepared into after oil pressure.
The assembling of battery: experimental result is had an impact as far as possible to avoid and testing irrelevant factor, will first be cleaned up
The baking oven that 60 DEG C of temperature are placed in after button cell, all materials such as good electrode slice of punching press and tool cleaning is dried
6 h or so are handled, then rapidly by the pole piece weighing after drying, are immediately put into glove box together with other tools, gloves
The water oxygen value of case is below 5 ppm.Using metal lithium sheet as cathode, prepared composite electrode piece is as anode, copper foil
As negative current collector, diaphragm model Celgard 2325,1M lithium hexafluoro phosphate (LiPF6) electrolyte (acrylic carbonic acid
Ester: vinylcarbonates: dimethyl carbonate=1:4:5, volume ratio) and thionyl chloride additive according to volume ratio 98:2 carry out
Mixing, as electrolyte used in this experiment.After being completed button cell, after above-mentioned 6 h of battery standing being completed,
In 1.4-3.0 V voltage windows, 80 mA g-1Under current density, electrochemistry is carried out on blue electrical testing instrument (CT2001A)
The test of performance, first week discharge capacity is close to 1800 mAh g-1。
Claims (10)
1. a kind of lithium-sulfur cell electrolyte, is made of, it is characterised in that: electrolyte lithium salt organic solvent, lithium salts, active additive
Molar concentration is 0.1-2.0 mol/L, and the volume accounting in organic solvent of active additive is 0.5 %-10 %, remaining is
Organic solvent.
2. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the active additive is thionyl chloride.
3. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the organic solvent is dimethyl carbonate, second
Sour methyl esters, ethyl acetate, propyl acetate, ethyl propionate, methyl propionate, ethylene carbonate, propene carbonate, diethyl carbonate,
Methyl ethyl carbonate, dimethoxymethane, 1,2- dimethoxy, diethylene glycol dimethyl ether, tetrahydrofuran, 2- methyltetrahydrofuran, 1,
One or more of 3- dioxolanes.
4. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the lithium salts be LiPF6, LiBF4,
LiCH3SO3, LiCF3SO3, LiAsF6, LiClO4, LiBOB, LiN (CF3SO2) one or more of 2.
5. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the volume fraction of the additive is 1.0-
3.0%。
6. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the lithium salts is LiPF6 or LiN
(CF3SO2)2。
7. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the concentration of the lithium salts is 0.5-1.5
mol/L。
8. lithium-sulfur cell electrolyte as described in claim 1, it is characterised in that the organic solvent is carbonate-based solvent.
9. the lithium-sulfur cell of any lithium-sulfur cell electrolyte assembling of claim 1-8.
10. lithium-sulfur cell as described in claim 1, it is characterised in that the lithium-sulfur cell is button cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811060488.1A CN109301325A (en) | 2018-09-12 | 2018-09-12 | A kind of lithium-sulfur cell electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811060488.1A CN109301325A (en) | 2018-09-12 | 2018-09-12 | A kind of lithium-sulfur cell electrolyte |
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| CN201811060488.1A Pending CN109301325A (en) | 2018-09-12 | 2018-09-12 | A kind of lithium-sulfur cell electrolyte |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176622A (en) * | 2019-05-15 | 2019-08-27 | 华南理工大学 | A kind of lithium metal secondary battery electrolyte and the preparation method and application thereof |
| CN112117492A (en) * | 2020-10-16 | 2020-12-22 | 江苏师范大学 | Organic ester electrolyte additive, electrolyte containing additive, lithium metal battery and application |
| CN112242571A (en) * | 2020-10-16 | 2021-01-19 | 江苏师范大学 | Electrolyte for protecting zinc ion battery electrode and zinc ion battery |
Citations (3)
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| US3891458A (en) * | 1973-11-15 | 1975-06-24 | Electrochimica Corp | Electric current producing galvanic cell |
| CN104716381A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for protecting negative electrode of lithium sulfur battery |
| CN108110321A (en) * | 2017-12-27 | 2018-06-01 | 河南省法恩莱特新能源科技有限公司 | A kind of lithium battery high-voltage electrolyte |
-
2018
- 2018-09-12 CN CN201811060488.1A patent/CN109301325A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3891458A (en) * | 1973-11-15 | 1975-06-24 | Electrochimica Corp | Electric current producing galvanic cell |
| CN104716381A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for protecting negative electrode of lithium sulfur battery |
| CN108110321A (en) * | 2017-12-27 | 2018-06-01 | 河南省法恩莱特新能源科技有限公司 | A kind of lithium battery high-voltage electrolyte |
Non-Patent Citations (2)
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| 刘思思: "二次锂电池锂基负极与电解质界面研究", 《中国博士学位论文全文数据库（电子期刊）》 * |
| 陈龙: "负载ZnS的介孔碳复合硫正极材料的制备及性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176622A (en) * | 2019-05-15 | 2019-08-27 | 华南理工大学 | A kind of lithium metal secondary battery electrolyte and the preparation method and application thereof |
| CN110176622B (en) * | 2019-05-15 | 2022-05-24 | 华南理工大学 | Lithium metal secondary battery electrolyte and preparation method and application thereof |
| CN112117492A (en) * | 2020-10-16 | 2020-12-22 | 江苏师范大学 | Organic ester electrolyte additive, electrolyte containing additive, lithium metal battery and application |
| CN112242571A (en) * | 2020-10-16 | 2021-01-19 | 江苏师范大学 | Electrolyte for protecting zinc ion battery electrode and zinc ion battery |
| CN112242571B (en) * | 2020-10-16 | 2022-03-11 | 江苏师范大学 | Electrolyte for protecting zinc ion battery electrode and zinc ion battery |
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Application publication date: 20190201 |