CN113437358A - Electrolyte additive and application thereof in rechargeable lithium thionyl chloride battery - Google Patents

Electrolyte additive and application thereof in rechargeable lithium thionyl chloride battery Download PDF

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Publication number
CN113437358A
CN113437358A CN202110811715.5A CN202110811715A CN113437358A CN 113437358 A CN113437358 A CN 113437358A CN 202110811715 A CN202110811715 A CN 202110811715A CN 113437358 A CN113437358 A CN 113437358A
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lithium
electrolyte
additive
thionyl chloride
battery
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崔光磊
李文达
董杉木
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators 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
    • H01M10/0563Liquid materials, e.g. for Li-SOCl2 cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/002Inorganic electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0088Composites
    • H01M2300/0091Composites in the form of mixtures
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention belongs to the technical field of energy materials, and further relates to the field of lithium secondary batteries, in particular to an electrolyte additive and application thereof in a rechargeable lithium thionyl chloride battery. The electrolyte additive of the rechargeable lithium thionyl chloride battery is an iodine simple substance and/or an iodine-based compound; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte. The additive is added into a basic electrolyte for a lithium thionyl chloride battery which takes conductive carbon as a positive electrode material. The introduction of the additive changes the environment of lithium salt in electrolyte, and simultaneously, the additive reacts with thionyl chloride which is an active substance, so that the discharge platform under high current density can be obviously improved, the electrode polarization can be improved, the lithium/thionyl chloride battery can obtain good discharge voltage and discharge capacity, and the voltage hysteresis phenomenon of the lithium/thionyl chloride battery can be obviously improved. Compared with a control sample which is not added, the discharge voltage of the battery using the additive provided by the invention is obviously improved, and the rate capability is improved.

Description

Electrolyte additive and application thereof in rechargeable lithium thionyl chloride battery
Technical Field
The invention belongs to the technical field of energy materials, and further relates to the field of lithium secondary batteries, in particular to an electrolyte additive and application thereof in a rechargeable lithium thionyl chloride battery.
Background
In recent years, lithium ion batteries have been extensively and deeply researched and developed, and due to the advantages of high energy density, long service life, no memory effect and the like, the lithium ion batteries occupy main markets of portable electronic equipment, electric automobiles and the like, and have great prospects in large-scale energy storage markets. But the development of the electric automobile market is severely restricted due to lower energy density and safety. Therefore, the research and development of novel batteries with high energy density, good safety and stable cycle can well meet the challenges of large-scale energy storage and electric automobile market development. Before the invention of secondary lithium ion battery, thionyl chloride (SOCl) was used2) Primary lithium thionyl chloride (Li-SOCl) was developed as an active material, with lithium metal as the negative electrode and conductive carbon as the positive electrode2) The battery system has the advantages of high energy density (600Wh/kg), large specific power, long shelf life (10-20 years), wide working temperature range, stable discharge voltage, high safety and the like, and is widely applied to the fields of oil and gas production, military, electric power metering and directional navigation.
In Li-SOCl2In the battery, SOCl2Also appear as active positive electrode reactants as solvents. In order to increase the conductivity and to facilitate the transport of lithium ions, in SOCl2Adding for example LiAlCl4The electrolyte of (1). The system battery is a high-energy chemical power source, and during discharge, a certain degree of pressure is generated due to sulfur dioxide generation. The discharge reaction mechanism is as follows: 4Li +2SOCl2→4LiCl+S+SO2×, some of the sulphur and sulphur dioxide may be dissolved in excess thionyl chloride electrolyte. Further, during storage, the lithium negative electrode, once in contact with the electrolyte, reacts with thionyl chloride electrolyte to produce LiCl, which is protected by the LiCl film formed thereon. This passivation film is useful for prolonging the storage life of the battery, but causes a voltage hysteresis at the start of discharge, and the voltage hysteresis is particularly significant when the battery is discharged in a low-temperature environment after being stored at a high temperature for a long period of time.
Lithium thionyl chloride battery with electrolyte at primaryTherefore, the problems of the lithium thionyl chloride battery can be remarkably improved by improving the electrolyte. In Li-SOCl2In the cell, the use of tetrafluoroborane anion in place of the electrolyte salt can reduce the voltage delay problem. Meanwhile, the introduction of bromine chloride in the electrolyte can greatly change the discharge chemical behavior of the battery and is also beneficial to removing SOCl2Some sulfur formed by reduction (k.m. abraham et al 1988j. electrochem. soc.1352686). In addition, LiGaCl4And Li2O·2GaCl3In Li-SOCl2When used as electrolytes in solution, have been shown to react with LiAlCl4Similar conductivity and solubility, and capacity increased by 60%. Nevertheless, the research on the development of a novel electrolyte additive for a chargeable and dischargeable lithium thionyl chloride battery is almost not available, and the chargeable and dischargeable lithium thionyl chloride battery has a prominent application prospect due to the advantages of high energy density and wide temperature range, so the development of the novel electrolyte additive for the chargeable and dischargeable lithium thionyl chloride battery is of great significance.
Disclosure of Invention
The invention provides an electrolyte additive and application thereof in a rechargeable lithium thionyl chloride battery, aiming at solving the problems of voltage hysteresis, non-charging and the like of the conventional lithium thionyl chloride battery.
In order to achieve the purpose, the invention provides the following technical scheme:
an electrolyte additive of a rechargeable lithium thionyl chloride battery is a simple substance iodine and/or an iodine-based compound; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte, preferably 0.5-5%, and more preferably 0.5-1%.
The purity of the iodine simple substance or iodine-based compound is more than or equal to 98 percent.
The iodine-based compound is one or more of iodine bromide, iodine chloride, iodine fluoride, potassium iodide, lithium iodide, sodium iodide and sulfur iodide.
The preferable additive is one or more of iodine chloride, iodine simple substance, potassium iodide, lithium iodide and sodium iodide.
The electrolyte of the lithium thionyl chloride battery is lithium salt and thionyl chloride.
The final concentration of the lithium salt in the electrolyte is 0.5-3mol/L, and preferably 1-2 mol/L.
The lithium salt is one or more of lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorosulfonate imide, lithium tetrachlorogallate and lithium perchlorate, and preferably one or more of lithium tetrachloroaluminate, lithium tetrachlorogallate and lithium perchlorate. The purity of the lithium salt is more than or equal to 99 percent.
The SOCl2The purity of the product is more than or equal to 99.5 percent.
The application of the additive is applied to the electrolyte of a rechargeable lithium thionyl chloride battery taking a carbon material as a positive electrode.
Preparing the electrolyte:
(1) dissolving required lithium salt in an inorganic solvent to obtain a uniform solution;
(2) and dissolving the additive in the solution, and uniformly stirring to obtain the required electrolyte.
The inorganic solvent is thionyl chloride.
A rechargeable lithium thionyl chloride battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte contains the additive.
The anode material is one or more of graphite, acetylene black, Ketjen black, carbon nano tubes and carbon fibers.
The current collector of the positive electrode in the battery is stainless steel; the negative electrode material is metallic lithium.
Compared with the prior art, the invention has the following advantages:
1. the electrolyte additive is added into the electrolyte of the lithium thionyl chloride battery, so that the content of halogen and halogen compounds in the electrolyte is increased, the voltage hysteresis of the battery can be effectively improved, and the discharge product can be fully decomposed in the charging process due to the existence of iodine simple substance or iodide. In addition, the additive is not lost in the battery cycle process, and meanwhile, the decomposition product and SO are timely mixed2The reactant formed by the action of the substances can be recycled by the batteryThe ring provides conditions, thereby reducing charge and discharge voltage polarization, obtaining excellent cycle performance, and being applied as a secondary lithium ion battery
2. The lithium thionyl chloride battery electrolyte added with the additive is simple in preparation process, short in preparation period, simple in preparation equipment, easy to operate and convenient for large-scale industrial production.
Drawings
Fig. 1 is a charge-discharge curve diagram of an additive-free electrolyte according to an embodiment of the present invention.
FIG. 2 is a graph showing the charging and discharging curves of the electrolyte with additive according to the embodiment of the present invention.
FIG. 3 is a graph of charge and discharge curves at different currents for electrolytes without additives according to embodiments of the present invention.
FIG. 4 is a graph of charge and discharge curves at different currents for electrolytes with additives according to embodiments of the present invention.
Fig. 5 is a cycle diagram of a corresponding battery with additive-free electrolyte according to an embodiment of the present invention.
Fig. 6 is a cycle diagram of a battery incorporating an additive electrolyte according to an embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
The reagents adopted in the following embodiments are all commercial products, wherein the purity of the iodine simple substance or iodine-based compound is more than or equal to 98 percent; the purity of the lithium salt is more than or equal to 99 percent; SOCl2The purity of the product is more than or equal to 99.5 percent.
Example 1
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium plate as a counter electrode in a conventional manner, and assembled with the above electrolyte to form a battery as a control, and tested for electrochemical performance (fig. 1, 3 and 5).
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain a mixed solution, and then adding an iodine simple substance with the mass of 0.5% into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium plate as a counter electrode in a conventional manner, and assembled with the above electrolyte to form a battery as a control, and tested for electrochemical performance (fig. 2, 4 and 6).
And (3) carrying out electrochemical performance test on the batteries of the obtained experimental group and the control group:
as can be seen from fig. 1-2, the introduction of the additive promotes the amount of sulfuryl chloride formed by the reaction of the decomposition products chlorine and sulfur dioxide, thereby increasing the discharge voltage of the battery and increasing the energy density of the battery. Meanwhile, after the additive is introduced, the electrochemical reaction kinetics is improved due to the catalytic property of iodine-containing substances, and the introduction of the additive can improve the rate performance of the battery and is beneficial to the high-power work of the battery as can be seen from figures 3-4. The introduction of the additive can enable chemical reaction behind electrochemistry to be carried out rapidly and efficiently, so that reactants and products can be carried out reversibly in an efficient manner in the whole process, the cycling stability of the battery is improved, the service life of the battery is prolonged, and the retention rate of the cycling capacity can reach 99 percent after 100 cycles (figures 5-6).
Example 2
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirring for 40 hours to obtain a mixed solution, and then adding an iodine simple substance with the mass of 1% into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 98% after 100 cycles.
Example 3
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirred for 40 hours to obtain a mixed solution, and then potassium iodide of which the mass is 1% is added to the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 98% after 100 cycles.
Example 4
Control group battery:
(1) preparing an electrolyte:
20g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
20g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirring for 40 hours to obtain a mixed solution, and then adding iodine bromide with the mass of 0.1% into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
Example 5
Control group battery:
(1) preparing an electrolyte:
30g of tetrachloroLithium aluminate is added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirred for 40 hours to obtain a mixed solution, and then iodine chloride accounting for 5 percent of the mass of the mixed solution is added into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
Example 6
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Post-agitationAnd obtaining a mixed solution after 40 hours, and adding iodine fluoride with the mass percent of 2% into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
Example 7
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirring for 40h to obtain a mixed solution, and then adding iodine chloride accounting for 0.5 percent of the mass of the mixed solution and lithium iodide accounting for 0.5 percent of the mass of the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
Example 8
Control group battery:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
In a conventional manner, ketjen black material was knife-coated on a stainless steel foil as a working electrode and a metal lithium plate as a counter electrode, and a battery was assembled with the above electrolyte as a control, and its electrochemical performance was tested.
Experimental battery pack:
(1) preparing an electrolyte:
30g of lithium tetrachloroaluminate are added to 100mL of rectified and purified SOCl2And then stirring for 40h to obtain a mixed solution, and then adding iodine chloride accounting for 0.5 percent of the mass of the mixed solution and lithium iodide accounting for 0.5 percent of the mass of the mixed solution. Obtaining the electrolyte;
(2) battery assembly
In a conventional manner, ketjen black material was knife-coated on a stainless steel foil as a working electrode and a metal lithium plate as a counter electrode, and a battery was assembled with the above electrolyte as a control, and its electrochemical performance was tested.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
Example 9
Control group battery:
(1) preparing an electrolyte:
20g of lithium tetrachlorogallate and 10g of lithium tetrachloroaluminate were added to 100mL of rectified and purified SOCl2Then stirring for 40h to obtain electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
Experimental battery pack:
(1) preparing an electrolyte:
20g of lithium tetrachlorogallate and 10g of lithium tetrachloroaluminate were added to 100mL of rectified and purified SOCl2And then stirring for 40 hours to obtain a mixed solution, and then adding an iodine simple substance with the mass of 1% into the mixed solution. Obtaining the electrolyte;
(2) battery assembly
Acetylene black material was knife coated onto stainless steel foil as a working electrode and a metal lithium sheet as a counter electrode in a conventional manner, and a battery was assembled with the above electrolyte as a control and tested for electrochemical performance.
When the electrochemical performance test is carried out on the batteries of the obtained experimental group and the control group, the discharge voltage of the experimental group is obviously improved relative to the discharge voltage of the control group, the multiplying power performance is improved, the cycling stability of the experimental group is also greatly improved, and the retention rate of the cycling capacity can reach 97 percent after 100 cycles.
The introduction of the additive changes the lithium salt in the electrolyte environment, and simultaneously reacts with the active substance thionyl chloride, so that the discharge platform under high current density can be obviously improved, the electrode polarization can be improved, the lithium/thionyl chloride battery can obtain good discharge voltage and discharge capacity, and the voltage hysteresis phenomenon of the lithium/thionyl chloride battery can be obviously improved. Compared with a control sample which is not added, the discharge voltage of the battery using the additive provided by the invention is obviously improved, the rate capability is improved, the cycling stability is also greatly improved, and the retention rate of the cycling capacity can reach more than 97% after 100 cycles.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. An electrolyte additive, characterized in that: the electrolyte additive of the rechargeable lithium thionyl chloride battery is an iodine simple substance and/or an iodine-based compound; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte.
2. The electrolyte additive as claimed in claim 1, wherein: the iodine-based compound is one or more of iodine bromide, iodine chloride, iodine fluoride, potassium iodide, lithium iodide, sodium iodide and sulfur iodide.
3. The electrolyte additive as claimed in claim 1 or 2, wherein: the electrolyte of the lithium thionyl chloride battery is lithium salt and thionyl chloride.
4. The electrolyte additive as claimed in claim 3, wherein: the final concentration of the lithium salt in the electrolyte is 0.5-3 mol/L.
5. The electrolyte additive as claimed in claim 4, wherein: the lithium salt comprises one or more of lithium tetrachloroaluminate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethylsulfonate, lithium difluorosulfonate, lithium tetrachlorogallate and lithium perchlorate.
6. Use according to claim 1, characterized in that: the additive is applied to the electrolyte of a rechargeable lithium thionyl chloride battery taking a carbon material as a positive electrode.
7. Use according to claim 6, characterized in that: preparing the electrolyte:
(1) dissolving required lithium salt in an inorganic solvent to obtain a uniform solution;
(2) dissolving the additive of claim 1 in the solution, and stirring to obtain the desired electrolyte.
8. A rechargeable lithium thionyl chloride battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the electrolyte contains the additive according to claim 1.
9. A rechargeable lithium thionyl chloride cell as claimed in claim 8, wherein: the anode material is one or more of graphite, acetylene black, Ketjen black, carbon nano tubes and carbon fibers.
10. A rechargeable lithium thionyl chloride cell as claimed in claim 8, wherein: the current collector of the positive electrode in the battery is stainless steel; the negative electrode material is metallic lithium.
CN202110811715.5A 2021-07-19 2021-07-19 Electrolyte additive and application thereof in rechargeable lithium thionyl chloride battery Pending CN113437358A (en)

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