CN112928331B - Electrolyte for lithium-sulfur battery - Google Patents

Electrolyte for lithium-sulfur battery Download PDF

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CN112928331B
CN112928331B CN202110193868.8A CN202110193868A CN112928331B CN 112928331 B CN112928331 B CN 112928331B CN 202110193868 A CN202110193868 A CN 202110193868A CN 112928331 B CN112928331 B CN 112928331B
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lithium
electrolyte
sulfur battery
sulfur
battery
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CN112928331A (en
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邓丁榕
樊晓红
翁建春
吴启辉
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Jimei University
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Jimei University
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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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to an electrolyte for a lithium-sulfur battery, which comprises a basic component and an additive, wherein the additive comprises one or more of ruthenium terpyridine chloride, cobalt terpyridine chloride, nickel terpyridine chloride and ferric terpyridine chloride. The invention can optimize the reaction electromechanics of the battery, improve the reaction rate, reduce the resistance between the electrode and the electrolyte, and improve the capacity, cycle life and rate capability of the battery. The terpyridine group can be effectively adsorbed on a conductive agent and a carbon material, so that the conductive capacity of the whole electrode is improved, the metal element and the chlorine element can effectively adsorb polysulfide and catalyze the conversion reaction of sulfur, the capacity of the battery is improved, and the shuttle effect of the battery is reduced.

Description

Electrolyte for lithium-sulfur battery
Technical Field
The present invention relates to an electrolyte for a lithium-sulfur battery.
Background
With the development of economy and science and technology, the energy structure of human beings is continuously changing towards a clean and sustainable direction. At present, lithium ion batteries with high energy density and long cycle life have become the main power source of consumer electronics products, playing an important role. However, with the development of high specific energy mobile devices, lithium ion batteries have been difficult to meet the current market demand. Compared with the traditional lithium ion battery, the lithium-sulfur battery has the advantages of ultrahigh theoretical specific capacity (1675mAh/g), theoretical energy density (2600Wh/kg), abundant sulfur storage capacity, low price and the like, so the lithium-sulfur battery is considered to be one of novel energy storage systems with development potential, and can be applied to the fields of portable electronic products, power automobiles, large-scale energy storage and the like. However, lithium sulfur batteries still have many problems and challenges, such as elemental S reactant for the battery system8And the final reduction product Li2S2And Li2S has extremely low electronic and ionic conductivity, volume change of electrodes in the charging and discharging processes, and simple substance S8Polysulfide which can be dissolved in electrolyte is generated in the process of charging and discharging of the battery, the polysulfide is easy to shuttle to the negative electrode of the battery and deposits on the surface of metal lithium to cause the defects of irreversible loss of active materials of the battery and the like, and finally, the utilization rate of active materials of the lithium-sulfur battery is low, and the cycling stability of the battery is poor, thereby restricting the development and the application of the lithium-sulfur battery.
Various materials are added into the positive electrode of the lithium-sulfur battery as sulfur framework materials to improve the battery performance. For example, the addition of the carbon material can effectively improve the conductivity of the electrode, and the addition of the oxide material can effectively adsorb polysulfide so as to inhibit the generation of shuttle effect. The addition of a nanoporous material may also provide more room for the volume expansion of sulfur. However, in these methods, a solid-phase material is added to the positive electrode, and the proportion of the active material in the positive electrode tends to be reduced.
Accordingly, the present inventors have made extensive studies to solve the above problems and have made the present invention.
Disclosure of Invention
The invention aims to provide an electrolyte for a lithium-sulfur battery, which can reduce polarization of the lithium-sulfur battery and improve charge-discharge capacity and cycle performance of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrolyte for a lithium-sulfur battery, the electrolyte comprising a base component and an additive, the additive comprising ruthenium (C) terpyridyl chloride30 H24 Cl2 N6Ru), cobalt (C) terpyridyl chloride30 H24 Cl2 N6Co), nickel terpyridyl chloride (C)30H24 Cl2 N6Ni) and iron (C) terpyridyl chloride30 H24 Cl2 N6Fe).
In a preferred embodiment of the present invention, the additive is 0.1 to 5% by mass of the electrolyte.
As a preferable mode of the present invention, the base component includes a nonaqueous organic solvent and a lithium salt, and the mass percentage of the nonaqueous organic solvent in the electrolyte is 80% to 95%.
In a preferred embodiment of the present invention, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide, and lithium nitrate.
In a preferred embodiment of the present invention, the concentration of the lithium salt is 0.1mol/L to 1.0 mol/L.
In a preferred embodiment of the present invention, the non-aqueous organic solvent is one or more of a linear ether solvent and a cyclic ether solvent.
In a preferred embodiment of the present invention, the linear ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or a derivative thereof, and the cyclic ether solvent is 1, 3-dioxolane or a derivative thereof.
In a preferred mode of the invention, the non-aqueous organic solvent is prepared by mixing with calcium hydride under an argon glove box, stirring for removing water for one week, and then performing reduced pressure distillation and purification under the protection of nitrogen or inert gas.
After adopting the scheme, the invention has the beneficial effects that:
one or more of ruthenium terpyridyl chloride, cobalt terpyridyl chloride, nickel terpyridyl chloride and ferric terpyridyl chloride are used as additives of the electrolyte, so that the electrolyte can participate in the charging and discharging process of the lithium-sulfur battery, but does not participate in the battery reaction, and can play a role in changing the dynamics of the electrode process of the battery. The invention can optimize the reaction electromechanics of the battery, improve the reaction rate, reduce the resistance between the electrode and the electrolyte, and improve the capacity, cycle life and rate capability of the battery. The terpyridine group can be effectively adsorbed on a conductive agent and a carbon material, so that the conductivity of the whole electrode is improved, the metal elements and chlorine elements can effectively adsorb polysulfide and catalyze the conversion reaction of sulfur, the capacity of the battery is improved, and the shuttling effect of the battery is reduced.
And secondly, the additive of the electrolyte has good stability and a simple structure, can be well contacted with a discharge product, and reduces the polarization of the battery.
And thirdly, the electrolyte has simple formula and easy preparation, and is beneficial to mass production.
Drawings
Fig. 1 is a charge-discharge curve diagram of a lithium-sulfur battery produced from the electrolyte of example 1.
Fig. 2 is a graph of cycle performance of a lithium sulfur battery fabricated with the electrolyte of example 1.
Fig. 3 is a graph of rate performance of a lithium sulfur battery made with the electrolyte of example 1.
Detailed Description
In order to further explain the technical solution of the present invention, the following detailed description is made with reference to the embodiments.
The lithium-sulfur battery of the invention refers to a battery using lithium as a negative electrode and sulfur or a sulfur compound as a positive electrode.
Example 1
Mixing linear ether solvent (ethylene glycol dimethyl ether) and cyclic ether solvent (1, 3-dioxolane) in a ratio of 1:1, and removing water. Weighing and dissolving conductive lithium salt lithium trifluoromethanesulfonate and lithium nitrate in the solvent according to the proportion of 0.5mol/L respectively under the atmosphere of helium at room temperature, and uniformly stirring to obtain the basic electrolyte. And adding terpyridyl ruthenium chloride into the basic electrolyte, wherein the mass percentage of the terpyridyl ruthenium chloride in the whole electrolyte is 0.1%, so as to obtain the target electrolyte. The lithium sulfur battery was assembled under a helium atmosphere and a battery test was performed. The blank test object was a cell assembled without the base electrolyte added with ruthenium terpyridine chloride. Both properties are shown with reference to fig. 1-3.
Example 2
Mixing linear ether solvent (ethylene glycol dimethyl ether) and cyclic ether solvent (1, 3-dioxolane) in a ratio of 1:5, and removing water. And weighing the conductive lithium salt lithium bistrifluoromethanesulfonimide and the lithium nitrate according to the proportion of 0.3mol/L respectively under the atmosphere of helium at room temperature, dissolving in the solvent, and uniformly stirring to obtain the basic electrolyte. Ruthenium terpyridyl chloride and cobalt terpyridyl chloride are added into the basic electrolyte, and the mass percentage (relative to the whole electrolyte) of the ruthenium terpyridyl chloride and the cobalt terpyridyl chloride is 0.05% and 0.05%, respectively, so that the target electrolyte is obtained. The lithium sulfur battery was assembled under a helium atmosphere and a battery test was performed. The blank test object was a battery assembled with the base electrolyte without additives.
Example 3
Mixing linear ether solvent (ethylene glycol dimethyl ether) and cyclic ether solvent (1, 3-dioxolane) in a ratio of 3:1, and removing water. Weighing and dissolving conductive lithium salt lithium trifluoromethanesulfonate and lithium hexafluorophosphate in the ratio of 0.3mol/L and 0.7mol/L in the solvent respectively under the atmosphere of helium at room temperature, and stirring uniformly to obtain the basic electrolyte. And adding nickel terpyridyl chloride into the basic electrolyte, wherein the mass percentage (relative to the whole electrolyte) is 0.2%, and thus obtaining the target electrolyte. The lithium sulfur battery was assembled under a helium atmosphere and a battery test was performed. The blank test object was a battery assembled without the base electrolyte added with nickel terpyridine chloride.
In the invention, the additive adopts one or more of ruthenium terpyridine chloride, cobalt terpyridine chloride, nickel terpyridine chloride and ferric terpyridine chloride, and the effect similar to that of the embodiment 1 can be achieved.
The product form of the present invention is not limited to the embodiments, and any suitable changes or modifications of the similar ideas by anyone should be considered as not departing from the patent scope of the present invention.

Claims (7)

1. An electrolyte for a lithium-sulfur battery, the electrolyte comprising a base component and an additive, characterized in that: the additive comprises one or more of ruthenium terpyridine chloride, cobalt terpyridine chloride, nickel terpyridine chloride and ferric terpyridine chloride, the basic components comprise a non-aqueous organic solvent and lithium salt, the mass percentage of the non-aqueous organic solvent in the electrolyte is 80-95%, and the non-aqueous organic solvent is one or more of linear ether solvents or annular ether solvents.
2. The electrolyte for a lithium-sulfur battery as defined in claim 1, wherein: the mass percentage of the additive in the electrolyte is 0.1-5%.
3. The electrolyte for a lithium-sulfur battery according to claim 2, wherein: the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonimide and lithium nitrate.
4. The electrolyte for a lithium-sulfur battery according to claim 3, wherein: the concentration of the lithium salt is 0.1mol/L-1.0 mol/L.
5. The electrolyte for a lithium-sulfur battery according to claim 4, wherein: the linear ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or derivatives thereof, and the annular ether solvent is 1, 3-dioxolane or derivatives thereof.
6. The electrolyte for a lithium-sulfur battery according to claim 5, wherein: the non-aqueous organic solvent is prepared by mixing with calcium hydride under an argon glove box, stirring for removing water for one week, and then carrying out reduced pressure distillation and purification under the protection of nitrogen or inert gas.
7. The electrolyte for a lithium-sulfur battery according to any one of claims 1 to 5, wherein: lithium sulfur batteries use lithium as the negative electrode and sulfur or sulfur complexes as the positive electrode.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN102617647A (en) * 2012-02-28 2012-08-01 中山大学 Terpyridyl ruthenium coordination compound, and preparation method and application thereof
CN103201891A (en) * 2010-09-30 2013-07-10 巴斯夫欧洲公司 Additive for electrolytes
CN105304861A (en) * 2014-06-30 2016-02-03 中国科学院大连化学物理研究所 Electrode for lithium-sulfur battery and preparation and application of electrode
CN107516730A (en) * 2016-06-17 2017-12-26 珠海泰坦储能科技有限公司 A kind of preparation of the lithium sulfur battery anode material of phosphoric acid iron and the lithium-sulfur cell containing this positive electrode

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EP2355223B1 (en) * 2010-01-29 2019-04-17 Samsung Electronics Co., Ltd. Redox flow battery including an organic electrolyte soution
WO2013142994A1 (en) * 2012-03-30 2013-10-03 Valorisation-Recherche, Limited Partnership Redox-active ionic liquids
US9947481B2 (en) * 2014-06-19 2018-04-17 Massachusetts Institute Of Technology Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same
CN107665966A (en) * 2016-07-27 2018-02-06 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell
JP2021523547A (en) * 2018-04-30 2021-09-02 ライテン・インコーポレイテッド Lithium-ion batteries and battery materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103201891A (en) * 2010-09-30 2013-07-10 巴斯夫欧洲公司 Additive for electrolytes
CN102617647A (en) * 2012-02-28 2012-08-01 中山大学 Terpyridyl ruthenium coordination compound, and preparation method and application thereof
CN105304861A (en) * 2014-06-30 2016-02-03 中国科学院大连化学物理研究所 Electrode for lithium-sulfur battery and preparation and application of electrode
CN107516730A (en) * 2016-06-17 2017-12-26 珠海泰坦储能科技有限公司 A kind of preparation of the lithium sulfur battery anode material of phosphoric acid iron and the lithium-sulfur cell containing this positive electrode

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