CN104022307A - Electrolyte as well as preparation method thereof and lithium sulfur battery - Google Patents

Electrolyte as well as preparation method thereof and lithium sulfur battery Download PDF

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Publication number
CN104022307A
CN104022307A CN201410286582.4A CN201410286582A CN104022307A CN 104022307 A CN104022307 A CN 104022307A CN 201410286582 A CN201410286582 A CN 201410286582A CN 104022307 A CN104022307 A CN 104022307A
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China
Prior art keywords
electrolyte
lithium
ether
salt
functional group
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CN201410286582.4A
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Inventor
仰永军
韩鸿波
陈卫
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Dongguan City Kai Xin Battery Material Co Ltd
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Dongguan City Kai Xin Battery Material Co Ltd
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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
    • H01M10/0569—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
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides electrolyte as well as a preparation method thereof and a lithium sulfur battery prepared by the electrolyte. The electrolyte comprises electrolyte lithium salt, a non-aqueous organic solvent and ion liquid containing ether-base functional groups. The ion liquid containing the ether-base functional groups is used as a solvent, so that the vapor pressure of the electrolyte can be remarkably reduced, the flame resistance of the electrolyte is improved, and the solubility and the degree of dissociation of lithium salt in the electrolyte can be improved in the presence of the ether-base functional groups.

Description

A kind of electrolyte and preparation method thereof and a kind of lithium-sulfur cell
Technical field
The present invention relates to electrode material of lithium battery preparation field, be specifically related to a kind of electrolyte and preparation method thereof, and a kind of lithium-sulfur cell that adopts this electrolyte to prepare.
Background technology
Along with the fast development of compact portable formula electronic product equipment and electrokinetic cell, the demand of high energy density cells is increased day by day.Elemental sulfur has higher theoretical specific capacity (1675mAh/g) and specific energy (2600Wh/kg), the more than 5 times of traditional lithium ion battery theoretical energy density, the actual energy density of the lithium-sulfur cell of developing is at present 400～600Wh/kg, is 2～3 times of commercial Li-ion batteries actual energy density.As the elemental sulfur of positive electrode, also there are nature reserves abundant, cheap, advantages of environment protection.
Lithium-sulfur cell system is also the focus of academia's broad research instantly, it is generally acknowledged, the subject matter that lithium-sulfur cell exists is: 1) electronic conductivity of elemental sulfur is lower.2) S producing in charge and discharge process x n-anion has stronger nucleophilie nucleus ability, itself and carbonic ester, LiPF 6between equal solvent or electrolyte, exist to interact, so traditional lithium-ion battery electrolytes is not suitable for lithium-sulfur cell system, 3) polysulfide (Li that produces in charge and discharge process 2s x) (x=4～8) can be dissolved in electrolyte and between positive and negative electrode and shuttle back and forth gradually, thereby causing the loss of positive active material, this is also the key factor that lithium-sulfur cell coulomb efficiency is low, capacity attenuation is fast simultaneously.4) adopt lithium metal as negative pole, in long cyclic process, have the problem of Li dendrite.
In order to solve the above-mentioned problem of lithium-sulfur cell, current work mainly focuses on the structural design of positive electrode, thereby by the peripheral coated polymer of positive pole or with the polysulfide that additive adsorbs formation, reaches the crown_interception to polysulfide.The lithium trifluoromethanesulp,onylimide (LiTFSI) that the large more options chemical stability of lithium-sulfur cell electrolyte system is good and ether (DME and DOL) solvent, but ether solvent has stronger polarity and donicity (DN), dissolubility to polysulfide is larger, in order to suppress the dissolubility of solvent to polysulfide, studies have reported that the concentration that can the improve electrolytic salt (L.Suo that achieves the goal, et al., Nature Communication, 2013).Also there is in addition report to select solid electrolyte can partly suppress generation (X.Liang, et al., the Journal of Power Sources of dendrite, 2011,196,3655), but the conductivity of organic all solid state electrolyte is lower, cause battery to be at room temperature difficult to high current charge-discharge.
Summary of the invention
In view of the existing problem of background technology, the lithium-sulfur cell that the object of the present invention is to provide a kind of electrolyte for lithium-sulfur cell and comprise this electrolyte, this electrolyte can effectively suppress the dissolving of polysulfide in electrolyte, can form stable passivating film on lithium metal surface, and have good fire resistance, these character have guaranteed that lithium-sulfur cell has good cycle performance and security performance.
Another object of the present invention is to provide above-mentioned a kind of lithium-sulfur cell and preparation method thereof.
The present invention is achieved through the following technical solutions:
An electrolyte, the ionic liquid that comprises electrolyte lithium salt, non-aqueous organic solvent He Han ether functional group, the described structural formula containing ether functional group ionic liquid is C +[A] -, cation C wherein +structure be one of following:
R in formula 1, R 2, R 3and R 4identical or not identical, and have a substituting group Wei – (CH at least 2cH 2o) ncH 3, n=1～3 wherein; – (CH 2cH 2o) ncH 3in (n=1～3) group, as n=1 Shi ， – CH 2cH 2oCH 3for methyl ethoxy, as n=2 Shi ， – (CH 2cH 2o) 2cH 3for methyl diethoxy, as n=3 Shi ， – (CH 2cH 2o) 3cH 3for methyl triethoxy; It is described that containing ether functional group ionic liquid, to account for solvent ratios be 5%～100%; The concentration of electrolyte lithium salt in electrolyte is 0.5～7mol/L.
Described R 1, R 2, R 3or R 4when not containing the group of ether, R 1, R 2, R 3or R 4structure Wei – C nh 2n+1, n=1～4; In ether functional group ion liquid compound, anion A-is N[(V 1sO 2) (V 2sO 2)]-, V wherein 1, V 2for CF 3, C 2f 5, C 3f 7, C 4f 9, C 6f 13, C 8f 17, HCF 2oCF 2cF 2cF 2any.
The described electrolyte lithium salt that contains comprises main salt-perfluoroalkyl sulfimide lithium, wherein: the structural formula of perfluoroalkyl sulfimide lithium is LiN[(T 1sO 2) (T 2sO 2)], T 1, T 2for CF 3, C 2f 5, C 3f 7, C 4f 9, C 6f 13, C 8f 17, HCF 2oCF 2cF 2cF 2any.
The concentration of described salt-perfluoroalkyl sulfimide lithium in electrolyte is 0.5～5mol/L, is preferably 0.8～4mol/L.
The described electrolyte lithium salt that contains also comprises auxiliary salt, and described auxiliary salt is at least one of LiDFOB, LiBOB.
The concentration of described auxiliary salt in electrolyte is 0～2mol/L, is preferably 0.1～0.5mol/L.
Described non-aqueous organic solvent comprises ether solvent, and described ether solvent comprises dioxolane, 1, more than one of 3-dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
It is described that containing ether functional group ionic liquid, to account for solvent ratios be 10～60%.
A preparation method of electrolyte, is dissolved into electrolyte lithium salt in the ionic liquid of non-aqueous organic solvent He Han ether functional group, stirs, and makes electrolyte.
A lithium-sulfur cell, comprises electrolyte prepared by positive plate, negative plate, barrier film and the present invention.
The invention has the advantages that:
(1) use, containing the ionic liquid of ether functional group as solvent, can significantly reduce the vapour pressure of electrolyte, improves the fire resistance of electrolyte, and having of ether functional group is beneficial to dissolubility and the degree of dissociation of raising lithium salts in electrolyte.
(2) use ionic liquid as solvent, and suitably improve the concentration of lithium salts, can effectively suppress the dissolubility of polysulfide, improve coulomb efficiency and the capability retention of battery.
(3) when ionic liquid compounded organic solvent is used, can not change on the basis of electrolyte security performance, by regulating the viscosity of ratio regulation and control electrolyte of organic solvent and wettability etc., to meet the multiplying power requirement for electrokinetic cell system.
Embodiment
Below by exemplary embodiment, illustrate the present invention.Should be appreciated that scope of the present invention should not be limited to the scope of embodiment.Any variation or change that does not depart from purport of the present invention can be understood by those skilled in the art.Protection scope of the present invention is determined by the scope of claims.
Embodiment 1
One, the preparation of electrolyte
The preparation of perfluoroalkyl sulfimide lithium list of references (L.Conte, et al., J.Fluorine Chem., 2004,125:243; C.Zhang, et al., Eur.J.Inorg.Chem.2012:3419).Containing the preparation of ether functional group ionic liquid list of references (Z.Zhou, et al., Chem.Eur.J., 2005,11:752).
Two, the preparation of electrolyte
(H in the glove box of argon atmosphere 2o<1ppm), 1M lithium trifluoromethanesulp,onylimide is dissolved into N, N-diethyl-N, in N-bis-(methoxy ethyl) ammonium-trifluoromethanesulp-onyl-onyl imide salt, stir, obtain lithium-sulfur cell electrolyte of the present invention (free acid <5ppm, moisture <10ppm).
Three, the preparation of lithium-sulfur cell
Sulfenyl anode pole piece, barrier film, metal lithium sheet are positioned in battery case, drip the electrolyte that the present embodiment is prepared, after sealing, prepare CR2025 button cell.
Four, the method for testing of electrolyte flame-retardant performance
The mineral wool of the weight such as getting is dipped in electrolyte 10 minutes, then with tweezers, takes out, and near igniter flame, stops 2s, then removes flame, and observe phenomena also records the self-gravitation time, the self-gravitation time 20s with interior be judged to be fire-retardant.
Five, battery performance test
Cycle performance test, the multiplying power discharging and recharging with 0.5/0.5C is carried out charge and discharge cycles test to battery, and cut-ff voltage interval is 1.5～3.0V.Test result is listed in table 2.
Table 1 embodiment 2-13
The test result of table 2 embodiment and comparative example
By above experimental data, show, electrolyte of the present invention has obvious anti-flaming function, and adopts the battery of this electrolyte obviously to have good capability retention.

Claims (10)

1. an electrolyte, the ionic liquid that comprises electrolyte lithium salt, non-aqueous organic solvent He Han ether functional group, the described structural formula containing ether functional group ionic liquid is C +[A] -, cation C wherein +structure be one of following:
R in formula 1, R 2, R 3and R 4identical or not identical, and have a substituting group Wei – (CH at least 2cH 2o) ncH 3, n=1～3 wherein; – (CH 2cH 2o) ncH 3in (n=1～3) group, as n=1 Shi ， – CH 2cH 2oCH 3for methyl ethoxy, as n=2 Shi ， – (CH 2cH 2o) 2cH 3for methyl diethoxy, as n=3 Shi ， – (CH 2cH 2o) 3cH 3for methyl triethoxy; It is described that containing ether functional group ionic liquid, to account for solvent ratios be 5%～100%; The concentration of electrolyte lithium salt in electrolyte is 0.5～7mol/L.
2. electrolyte according to claim 1, described R 1, R 2, R 3or R 4when not containing the group of ether, R 1, R 2, R 3or R 4structure Wei – C nh 2n+1, n=1～4; Anion A in ether functional group ion liquid compound -for N[(V 1sO 2) (V 2sO 2)]-, V wherein 1, V 2for CF 3, C 2f 5, C 3f 7, C 4f 9, C 6f 13, C 8f 17, HCF 2oCF 2cF 2cF 2any.
3. electrolyte according to claim 1, describedly comprises main salt-perfluoroalkyl sulfimide lithium containing electrolyte lithium salt, wherein: the structural formula of perfluoroalkyl sulfimide lithium is LiN[(T 1sO 2) (T 2sO 2)], T 1, T 2for CF 3, C 2f 5, C 3f 7, C 4f 9, C 6f 13, C 8f 17, HCF 2oCF 2cF 2cF 2any.
4. electrolyte according to claim 3, the concentration of described salt-perfluoroalkyl sulfimide lithium in electrolyte is 0.5～5mol/L, is preferably 0.8～4mol/L.
5. electrolyte according to claim 3, describedly also comprises auxiliary salt containing electrolyte lithium salt, and described auxiliary salt is at least one of LiDFOB, LiBOB.
6. electrolyte according to claim 5, the concentration of described auxiliary salt in electrolyte is 0～2mol/L, is preferably 0.1～0.5mol/L.
7. electrolyte according to claim 1, described non-aqueous organic solvent comprises ether solvent, described ether solvent comprises dioxolane, 1, more than one of 3-dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether.
8. electrolyte according to claim 1, described containing ether functional group ionic liquid, to account for solvent ratios be 10～60%.
9. a preparation method of electrolyte, is dissolved into electrolyte lithium salt in the ionic liquid of non-aqueous organic solvent He Han ether functional group, stirs, and makes the electrolyte of claim 1-8 described in any.
10. a lithium-sulfur cell, comprises positive plate, negative plate, barrier film and the claim 1-9 electrolyte described in any.
CN201410286582.4A 2014-06-24 2014-06-24 Electrolyte as well as preparation method thereof and lithium sulfur battery Pending CN104022307A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105449275A (en) * 2015-11-16 2016-03-30 深圳市沃特玛电池有限公司 Lithium ion battery electrolyte and lithium ion battery
CN112174894A (en) * 2019-07-04 2021-01-05 天津工业大学 Preparation and application of imidazole ionic liquid containing fluorine ether group
CN114628821A (en) * 2022-03-25 2022-06-14 中国电子科技集团公司第十八研究所 Preparation method of high-specific-energy organic electrolyte applied to lithium-sulfur hexafluoride battery and electrolyte
CN115286522A (en) * 2022-08-22 2022-11-04 浙江大学 Ionic liquid and preparation method and application thereof

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CN1682320A (en) * 2002-09-20 2005-10-12 日清纺织株式会社 Nonaqueous electrolyte, electrical double layer capacitors, and nonaqueous electrolyte secondary cells
CN101284791A (en) * 2001-03-26 2008-10-15 日清纺织株式会社 Electrolytic solution for storage device, and electric double layer capacitor
CN102037600A (en) * 2008-05-19 2011-04-27 日本电气株式会社 Secondary battery
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
CN102754268A (en) * 2010-02-12 2012-10-24 三菱化学株式会社 Nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery
CN104756301A (en) * 2013-08-27 2015-07-01 松下电器产业株式会社 Electrochemical energy storage device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101284791A (en) * 2001-03-26 2008-10-15 日清纺织株式会社 Electrolytic solution for storage device, and electric double layer capacitor
CN1682320A (en) * 2002-09-20 2005-10-12 日清纺织株式会社 Nonaqueous electrolyte, electrical double layer capacitors, and nonaqueous electrolyte secondary cells
CN102037600A (en) * 2008-05-19 2011-04-27 日本电气株式会社 Secondary battery
CN102754268A (en) * 2010-02-12 2012-10-24 三菱化学株式会社 Nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery
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
CN104756301A (en) * 2013-08-27 2015-07-01 松下电器产业株式会社 Electrochemical energy storage device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105449275A (en) * 2015-11-16 2016-03-30 深圳市沃特玛电池有限公司 Lithium ion battery electrolyte and lithium ion battery
CN112174894A (en) * 2019-07-04 2021-01-05 天津工业大学 Preparation and application of imidazole ionic liquid containing fluorine ether group
CN114628821A (en) * 2022-03-25 2022-06-14 中国电子科技集团公司第十八研究所 Preparation method of high-specific-energy organic electrolyte applied to lithium-sulfur hexafluoride battery and electrolyte
CN115286522A (en) * 2022-08-22 2022-11-04 浙江大学 Ionic liquid and preparation method and application thereof

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