CN116207340A - Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof - Google Patents

Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof Download PDF

Info

Publication number
CN116207340A
CN116207340A CN202310055182.1A CN202310055182A CN116207340A CN 116207340 A CN116207340 A CN 116207340A CN 202310055182 A CN202310055182 A CN 202310055182A CN 116207340 A CN116207340 A CN 116207340A
Authority
CN
China
Prior art keywords
electrolyte
lithium
thionyl chloride
chloride battery
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310055182.1A
Other languages
Chinese (zh)
Inventor
毕惠婷
朱登霞
王超龙
朱君江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Textile University
Original Assignee
Wuhan Textile University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Textile University filed Critical Wuhan Textile University
Publication of CN116207340A publication Critical patent/CN116207340A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • 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
    • H01M2300/002—Inorganic 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 invention belongs to the technical field of lithium batteries, and particularly relates to an electrolyte for a rechargeable lithium thionyl chloride battery, and a preparation method and application thereof. The method takes a porous carbon film as an anode active material reaction carrier, lithium metal as a cathode and a glass fiber film as a diaphragm. By dissolving AlCl in 3 SOCl of (C) 2 The lithium metal-fluoride additive is added into the solution to form a lithium metal-fluoride doped lithium metal-chloride solid electrolyte interface with excellent stabilizing effect on a lithium negative electrode, so that the reversibility of the reaction of the battery reactor at the positive electrode side is realized, the primary battery with high specific energy and excellent low-temperature performance, namely lithium thionyl chloride, has the capability of secondary charge and discharge, and provides a new solution for the requirement of military equipment on secondary energy.

Description

Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an electrolyte for a rechargeable lithium thionyl chloride battery, and a preparation method and application thereof, so that a lithium thionyl chloride battery system which is used as a primary battery for a long time has the capability of secondary charge and discharge.
Background
The lithium thionyl chloride battery is a typical nonaqueous inorganic electrolyte battery, which uses metallic lithium as a negative electrode, a porous carbon film as a positive electrode, a glass fiber film as a diaphragm, and anhydrous aluminum lithium tetrachloride (LiAlCl) 4 ) SOCl of (C) 2 The solution is an electrolyte in which SOCl 2 Both as solvent and as positive electrode active material. As a battery system (up to 500 Wh/kg) with the highest specific energy in commercial lithium primary batteries, the lithium thionyl chloride battery also has the advantages of low self-discharge rate, long storage life and maintenance-free continuous operation for 5-10 years. In addition, li/SOCl 2 The non-aqueous battery has good low-temperature performance, and the battery still has good electrical performance in the range of-40 ℃ to +80 ℃, especially in the low-temperature environment of-40 ℃. Based on the advantages, the system battery is mainly used in the military field, such as intelligent aerial shells, underwater vehicles, communication equipment and the like.
For a long time, research on lithium thionyl chloride batteries by research institutions at home and abroad is mostly focused on battery voltage hysteresis, safety, power characteristics, electrocatalysis, porous carbon anodes, and the directions of battery structural design, electrolyte preparation and the like are also relevant to part of battery research institutions, but researches on the possibility of secondary charge and discharge of the primary batteries are rarely reported. The existing lithium thionyl chloride batteries are all disposable in the form of lithium primary batteries, and no chargeable and dischargeable Li/SOCl exists 2 And a battery.
Disclosure of Invention
Aiming at the defects existing in the prior art, the lithium metal-fluoride doped lithium metal-chloride solid electrolyte interface with excellent stabilizing effect on a lithium negative electrode is formed at the interface of the electrode electrolyte by matching a lithium salt and a specific lithium-fluoride additive in the lithium thionyl chloride battery electrolyte, and the reversibility of a redox couple of the battery is realized for the first timeLi/SOCl as a primary battery system for a long time 2 The battery has the capability of secondary charge and discharge and has the potential of becoming a new secondary battery system.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
electrolyte for rechargeable lithium thionyl chloride battery, wherein the electrolyte contains AlCl 3 SOCl and lithium-fluoride additive 2 An electrolyte, wherein the lithium-fluoride additive is at least one of LiTFSI and LiFSI;
further, alCl in the electrolyte 3 The concentration of the lithium-fluoride additive is 3-4 mol/L, and the weight ratio of the total amount of the lithium-fluoride additive to the electrolyte is (1-4)%.
Further, the lithium-fluoride additive is LiTFSI and LiFSI respectively accounting for 2% of the electrolyte by weight.
The invention also provides a preparation method of the electrolyte for the rechargeable lithium thionyl chloride battery, which comprises the following specific steps:
SOCl is put into 2 Electrolyte (the electrolyte contains LiAlCl with a certain concentration) 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the electrolyte contains 1.5mol/L LiAlCl 4 ) After two distillations are carried out to remove water, part of AlCl is added into the mixture 3 After dissolution, add the rest AlCl 3 And lithium-fluoride additive, heating, stirring and dissolving to obtain the product containing AlCl 3 SOCl and lithium-fluoride additive 2 And (3) an electrolyte. The invention also provides application of the electrolyte for the rechargeable lithium thionyl chloride battery in preparation of the rechargeable lithium thionyl chloride battery.
The invention also provides application of the electrolyte for the rechargeable lithium thionyl chloride battery, which is obtained by the preparation method, in preparation of the rechargeable lithium thionyl chloride battery.
Furthermore, in the application, porous carbon is used as a positive electrode, lithium metal is used as a negative electrode, a glass fiber membrane is used as a diaphragm, and the electrolyte prepared by the method is used as an auxiliary material to prepare the required rechargeable lithium thionyl chloride battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) By at SOCl 2 AlCl with a certain concentration is matched in electrolyte 3 And a lithium-fluoride additive that helps to form a stable solid electrolyte interface, a lithium metal-fluoride doped lithium metal-chloride solid electrolyte interface having excellent stabilization to a lithium anode being formed at the electrode electrolyte interface.
(2) Realizes the reversibility of the battery reaction pair at the positive electrode side, so that the battery can be used as Li/SOCl of a primary battery for a long time 2 The system battery has the capability of secondary charge and discharge, and becomes a potential new secondary battery system.
Drawings
FIG. 1 shows a rechargeable buckle Li/SOCl according to example 1 2 The battery charge-discharge cycle performance, wherein the curve shown by the inverted triangle is coulomb efficiency, and the curve shown by the square is discharge capacity;
FIG. 2 shows a rechargeable buckle Li/SOCl according to example 1 2 Charge-discharge curve of the battery.
Detailed Description
The technical scheme of the invention is further explained below by combining specific embodiments.
The invention takes a porous carbon film as a positive active material reaction carrier, lithium metal as a negative electrode, a glass fiber film as a diaphragm, and AlCl is dissolved in the porous carbon film 3 SOCl of (C) 2 The addition of lithium metal-fluoride additives to the (both electrolyte and active material) solution forms a lithium metal-fluoride doped lithium metal-chloride solid electrolyte interface with excellent stabilization to the lithium anode and achieves reversibility of the reaction pair.
The above lithium-fluoride additives are LiTFSI and LiFSI that help to form a stable solid electrolyte interface.
AlCl in the electrolyte 3 The combination mode of the additive is AlCl 3 And LiTFSI, alCl 3 And LiFSI, alCl 3 One of +LiTFSI+LiFSI; SOCl 2 AlCl in electrolyte 3 The concentration range of the electrolyte is 3-4 mol/L, and the content of additives LiTFSI and LiFSI in the electrolyte is less than or equal to 2wt%.
Example 1: a rechargeable lithium thionyl chloride battery prepared by the method comprising:
commercial SOCl 2 Electrolyte (1.5 mol/L LiAlCl) 4 SOCl of (C) 2 Solution) is distilled twice to remove water, and the water is distilled twice according to the stoichiometric ratio (reaction relation is: alCl 3 React with LiCl which is a discharge product of a lithium sub-battery to generate LiAlCl 4 Reaction to AlCl 3 Excess to ensure reaction completion) AlCl is added thereto 3 And additives, in this embodiment, an appropriate amount of AlCl is dissolved in the solution 3 (0.8-1.6 mol/L, 1.2mol/L in the embodiment), and adding residual AlCl after complete dissolution 3 And a proper amount of additives of lithium bis (trifluoromethanesulfonyl) imide LiTFSI and lithium bis (fluorosulfonyl) imide LiSSI, heating, stirring and dissolving to prepare the catalyst containing 4mol/L AlCl 3 SOCl (in terms of aluminum) 2 And the content of LiTFSI and LiFSI additives in the electrolyte is 2wt%.
The porous carbon anode is prepared by ball milling pulping, emulsifying dispersing, rolling and foaming by taking acetylene black as a conductive agent, polytetrafluoroethylene emulsion as a binder and ammonium bicarbonate as a foaming agent (the step is a common technology in the field, the weight ratio of the acetylene black to the polytetrafluoroethylene to the ammonium bicarbonate is 95:5:5 in the embodiment), lithium metal is taken as a negative electrode, a glass fiber membrane is taken as a diaphragm, the electrolyte prepared by the above is supplemented, and the rechargeable Li/SOCl is prepared according to the button cell process 2 Button cell and charge and discharge cycles with a current density of 100mA/g showed: this rechargeable Li/SOCl during 20 cycles 2 The charge and discharge efficiency of the battery can reach more than 90%, the energy density can be stabilized at 420-440 mAh/g, and the battery has the potential of becoming a new secondary battery.
Comparative example: the commercial lithium/thionyl chloride battery electrolyte uses thionyl chloride solution of aluminum trichloride as electrolyte, thionyl chloride is both solvent and positive electrode active material, electrolyte salt is aluminum trichloride, and Li/SOCl is prepared after replacing the electrolyte with the commercial lithium/thionyl chloride battery electrolyte of comparative example according to the method 2 Button cell, which is primary cell, cannot be charged or discharged。

Claims (7)

1. Electrolyte for rechargeable lithium thionyl chloride battery, wherein the electrolyte contains AlCl 3 SOCl and lithium-fluoride additive 2 And the lithium-fluoride additive is at least one of LiTFSI and LiFSI.
2. The electrolyte for a rechargeable lithium thionyl chloride battery according to claim 1, wherein AlCl in the electrolyte 3 The concentration of the lithium-fluoride additive is 3-4 mol/L, and the weight ratio of the total amount of the lithium-fluoride additive to the electrolyte is (1-4)%.
3. The electrolyte for a rechargeable lithium thionyl chloride battery according to claim 1, wherein the lithium-fluoride additive is LiTFSI and LiFSI, respectively, in an amount of 2% by weight of the electrolyte.
4. A method for preparing the electrolyte for a rechargeable lithium thionyl chloride battery according to any one of claims 1 to 3, comprising the following specific steps:
will contain LiAlCl 4 SOCl of (C) 2 After the electrolyte is dehydrated, a part of AlCl is added into the electrolyte 3 After dissolution, add the rest AlCl 3 And lithium-fluoride additive, heating, stirring and dissolving to obtain the product containing AlCl 3 SOCl and lithium-fluoride additive 2 And (3) an electrolyte.
5. Use of the electrolyte for rechargeable lithium thionyl chloride battery according to any one of claims 1 to 3 for the preparation of rechargeable lithium thionyl chloride battery.
6. Use of the electrolyte for rechargeable lithium thionyl chloride battery obtained by the preparation method of claim 4 for preparing rechargeable lithium thionyl chloride battery.
7. The use according to claim 5 or 6, wherein in the use, the electrolyte for rechargeable lithium thionyl chloride battery or the electrolyte obtained by the preparation method according to claim 4 is used as a positive electrode, lithium metal as a negative electrode, and glass fiber membrane as a separator, and the electrolyte for rechargeable lithium thionyl chloride battery according to any one of claims 1 to 3 is used as an auxiliary material to prepare the desired rechargeable lithium thionyl chloride battery.
CN202310055182.1A 2022-10-28 2023-01-13 Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof Pending CN116207340A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2022113391756 2022-10-28
CN202211339175 2022-10-28

Publications (1)

Publication Number Publication Date
CN116207340A true CN116207340A (en) 2023-06-02

Family

ID=86518433

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310055182.1A Pending CN116207340A (en) 2022-10-28 2023-01-13 Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116207340A (en)

Similar Documents

Publication Publication Date Title
US11177507B2 (en) Electrolyte for lithium secondary battery and lithium secondary battery including the same
CN106159325B (en) A kind of low temperature electrolyte for lithium ion battery and low-temperature lithium ion battery
CN109088099A (en) A kind of sulphonyl class electrolysis additive for taking into account high temperature performance and the electrolyte containing the additive
JP2000138072A (en) Nonaqueous electrolyte secondary battery
US20230327210A1 (en) Battery electrolytic solution, secondary battery, and terminal
KR20180124722A (en) Electrolyte system and lithium metal battery comprising the same
WO2019095717A1 (en) Lithium primary cell
CN113871714A (en) Electrolyte of sodium ion battery and application
CN112271334B (en) Cathode film-forming additive for magnesium metal battery with metal magnesium as cathode material and application thereof
CN108832180A (en) A kind of lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte
CN114400321A (en) Low-temperature charge-discharge lithium ion battery and negative electrode material thereof
CN116207340A (en) Electrolyte for rechargeable lithium thionyl chloride battery, and preparation method and application thereof
CN114284559A (en) Electrolyte containing additive and lithium metal secondary battery
CN114204119A (en) Lithium-sulfur battery electrolyte containing mixed lithium salt of low-polarity ethers
KR102046538B1 (en) Electrolyte system and lithium metal battery comprising the same
KR102063821B1 (en) Electrolyte system and lithium metal battery comprising the same
CN105655516A (en) Lithium titanate base lithium secondary battery capable of avoiding gas expansion
CN115051030B (en) Battery electrolyte and lithium ion battery
CN108987803A (en) A kind of lithium an- ode film forming electrolyte and its additive for lithium-sulfur cell
CN110556581A (en) Concentrated electrolyte system suitable for potassium ion battery
KR102536141B1 (en) Electrolyte system for lithium metal battery and lithium metal battery comprising the same
CN115472914B (en) Electrolyte of lithium-sulfur battery with high sulfur surface loading and lithium-sulfur battery with high sulfur surface loading
US20240006653A1 (en) Rechargeable battery with hybrid cathode comprising conversion and intercalation active materials
US10818972B2 (en) Electrolyte solution for lithium secondary battery
JP2548574B2 (en) Electrolyte for lithium battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination