CN101587957B - Perfluor organic molten salt electrolyte, preparation method and application thereof - Google Patents

Perfluor organic molten salt electrolyte, preparation method and application thereof Download PDF

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Publication number
CN101587957B
CN101587957B CN 200910099794 CN200910099794A CN101587957B CN 101587957 B CN101587957 B CN 101587957B CN 200910099794 CN200910099794 CN 200910099794 CN 200910099794 A CN200910099794 A CN 200910099794A CN 101587957 B CN101587957 B CN 101587957B
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molten salt
salt electrolyte
organic molten
lin
perfluor organic
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CN101587957A (en
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马淳安
屠晓华
褚有群
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a perfluor organic molten salt electrolyte, preparation method and application thereof. The perfluor organic molten salt electrolyte is prepared from LiN(C2F5SO2)2, CF3SO3Na or CF3SO3K, wherein the mole fraction of the LiN(C2F5SO2)2 is 10 to 50%. The preparation method is as follows: respectively weighing the required raw material components based on proportion; fully and evenly mixing the selected raw material components; then heating and fusing the mixture; then evenly milling the mixture after re-cooled so as to obtain the perfluor organic molten salt electrolyte. The molten salt electrolyte of the invention is advantageous in low melting point, wide electrochemical window, excellent thermal stability and electrochemical performance. The invention can be applied to the fields, for example, lithium thermal battery.

Description

A kind of perfluor organic molten salt electrolyte
(1) technical field
The present invention relates to a kind of perfluor organic molten salt electrolyte, especially is the application in the thermal cell at lithium.
(2) technical background
Generally, fused salt comprises more than a kind of salt at least, and generally under molten condition, just is employed.Fused salt has low vapour pressure in wide temperature range, advantages such as low viscosity and good electrical conductivity, and these characteristics have determined fused salt in industrial electrolysis, nuclear power industry and material industry, to have a wide range of applications.
Because the particularity of fused salt performance, it also is widely used in thermal cell.Thermal cell is a kind of reserve type battery, and it utilizes the heating system of battery itself to present nonconducting solid state electrolyte heating and melting ionic conductor and get into a kind of hot activation reserve cell of operating state.Advantages such as it is big that thermal cell possesses power-discharging density, and specific energy and specific power are high, and activationary time is short occupy an important position in military field always.Recently, thermal cell is applied to the interest that the civilian industry field has caused the research worker, and wherein underground heat and oil and gas exploration are considered to wherein the most representative application with thermal cell.Yet because the particularity of civilian industry field applied environment, therefore, the research worker thinks that it is the key that thermal cell is applied to the civilian industry field that the exploitation fusing point is lower than 300 ℃ molten salt electrolyte.
Traditional lithium is thermal cell electrolyte LiCl-KCl, because its fusing point is higher, thereby is difficult to be applied to the civilian industry field.In fact, the electrolyte system of development of new is devoted in existing many research work, in the hope of thermal cell more wide application prospect can be arranged.Patent US20080299447A1 has introduced a series of novel electrolytes systems, but fluoridize owing to this type molten salt electrolyte is based on, chlorination and Bromide develop, so fusing point is still higher.Non-Patent data (P.Masset, J.Power source 160 (2006) 688-697) has been introduced one type of electrolyte system that contains iodized salt, and its fusing point is lower, but very easily deliquescence and oxidation of iodized salt, and also price is very expensive, thereby fail to obtain large development.The nitrate molten salt system possesses lower fusing point than the halide salt system, and cheap, but the nitric acid fused salt has very strong oxidizability, easily with highly active anode material reaction, thus the potential safety hazard that has caused battery to use.
2009 the 2nd phases of chemical industry journal have disclosed inventor's of the present invention achievement in research: " calorifics and the chemical property of novel binary molten salt electrolyte LiTFSI/NaTf ", this article discloses LiN (CF 3SO 2) 2-CF 3SO 3Na binary molten-salt electrolysis plastidome.In addition, Electrochemicaland Solid-State Letters disclosed another achievement in research of inventor 2009 the 4th phases: " Thermal and Electrochemical Performance of Binary MoltenSalt Electrolyte Based on LiTFSI and CF 3SO 3K ".This article discloses LiN (CF 3SO 2) 2-CF 3SO 3K binary molten-salt electrolysis plastidome.Though above-mentioned two molten-salt electrolysis plastidomes can satisfy lithium on overall performance be the needs that thermal cell is used, yet this two individual system is still waiting to improve in thermal stability.The Temperature Distribution of considering actual application environment is very complicated, therefore has certain limitation.
(3) summary of the invention
To binary molten-salt electrolysis plastidome LiN (CF 3SO 2) 2-CF 3SO 3Na and LiN (CF 3SO 2) 2-CF 3SO 3There is the problem of thermal stability aspect in K, the invention provides the perfluor organic molten salt electrolyte of a kind of electrochemical window with low melting point, broad, good thermal stability.
For solving the problems of the technologies described above, the concrete technical scheme that the present invention adopts is following:
A kind of perfluor organic molten salt electrolyte is by LiN (C 2F 5SO 2) 2With CF 3SO 3Na or CF 3SO 3K processes, wherein LiN (C 2F 5SO 2) 2Molar fraction be 10～50%.Further, described LiN (C 2F 5SO 2) 2Molar fraction be preferably 10～40%.
The perfluor organic molten salt electrolyte that the present invention makes also has good thermal stability in the electrochemical window with low melting point, broad, outstanding above the performance.
The present invention also provides a kind of preparation method of described perfluor organic molten salt electrolyte, and concrete preparation method is following: take by weighing the needed raw material component in proportion respectively, selected raw material components is fully mixed; Then, mill after treating to cool off again evenly, promptly obtain described perfluor organic molten salt electrolyte this mixture heating and melting.
Further, preferably before taking by weighing raw material components, with all raw material components intensive dryings.
Perfluor organic molten salt system of the present invention has the electrochemical window of low melting point, high conductivity, broad, good thermal stability and chemical property, widely used characteristics, and can be applicable to lithium is fields such as thermal cell.
Compared with prior art, the present invention has following advantage:
The present invention is through selection and combination to raw material; The perfluor organic molten salt system that makes the present invention make has the electrochemical window of low melting point, broad, good advantages such as thermal stability, can meet lithium and is thermal cell and be applied to civilian industry field electrolyte fusing point and be lower than 300 ℃ requirement.
(4) specific embodiment
With specific embodiment technical scheme of the present invention is further described below, but protection scope of the present invention is not limited thereto:
Embodiment 1:
Take by weighing dried LiN (C respectively 2F 5SO 2) 24g and CF 3SO 3Na 8g fully mixes and mills in grinding alms bowl, then with this mixture heating and melting, mills after treating to cool off again evenly, forms the low-temperature molten salt system.From this mixed fused salt, take by weighing about 10mg and measure its thermal property with PyrisDiamond TG/DTA (Seiko Instruments) thermogravimetric analyzer, recording its fusing point is 195 ℃, and heat decomposition temperature is more than 400 ℃.Its conductivity in the time of 270 ℃ is 34mS/cm, and when temperature was 250 ℃, recording its electrochemical stability window was 4.3V.
Embodiment 2:
Take by weighing dried LiN (C respectively 2F 5SO 2) 25g and CF 3SO 3K 12g fully mixes and mills in grinding alms bowl, then with this mixture heating and melting, mills after treating to cool off again evenly, forms the low-temperature molten salt system.From this mixed fused salt, take by weighing about 10mg and measure its thermal property with PyrisDiamond TG/DTA (Seiko Instruments) thermogravimetric analyzer, recording its fusing point is 182 ℃, and heat decomposition temperature is more than 400 ℃.Its conductivity in the time of 270 ℃ is 38mS/cm, and when temperature was 250 ℃, recording its electrochemical stability window was 4.4V.
Embodiment 3:
Take by weighing dried LiN (C respectively 2F 5SO 2) 210.5g and CF 3SO 3Na 12.5g fully mixes and mills in grinding alms bowl, then with this mixture heating and melting, mills after treating to cool off again evenly, forms the low-temperature molten salt system.From this mixed fused salt, take by weighing about 10mg and measure its thermal property with Pyris Diamond TG/DTA (Seiko Instruments) thermogravimetric analyzer, recording its fusing point is 189 ℃, and heat decomposition temperature is more than 400 ℃.Its conductivity in the time of 270 ℃ is 26mS/cm, and when temperature was 250 ℃, recording its electrochemical stability window was 4.3V.
Embodiment 4:
Take by weighing dried LiN (C respectively 2F 5SO 2) 25g and CF 3SO 3Na 15g fully mixes and mills in grinding alms bowl, then with this mixture heating and melting, mills after treating to cool off again evenly, forms the low-temperature molten salt system.From this mixed fused salt, take by weighing about 10mg and measure its thermal property with PyrisDiamond TG/DTA (Seiko Instruments) thermogravimetric analyzer, recording its fusing point is 201 ℃, and heat decomposition temperature is more than 400 ℃.Its conductivity in the time of 270 ℃ is 38mS/cm, and when temperature was 250 ℃, recording its electrochemical stability window was 4.3V.
Embodiment 5:
Take by weighing dried LiN (C respectively 2F 5SO 2) 211g and CF 3SO 3K 15g fully mixes and mills in grinding alms bowl, then with this mixture heating and melting, mills after treating to cool off again evenly, forms the low-temperature molten salt system.From this mixed fused salt, take by weighing about 10mg and measure its thermal property with PyrisDiamond TG/DTA (Seiko Instruments) thermogravimetric analyzer, recording its fusing point is 178 ℃, and heat decomposition temperature is more than 400 ℃.Its conductivity in the time of 270 ℃ is 30mS/cm, and when temperature was 250 ℃, recording its electrochemical stability window was 4.4V.

Claims (5)

1. perfluor organic molten salt electrolyte is by LiN (C 2F 5SO 2) 2With CF 3SO 3Na or CF 3SO 3K processes, wherein LiN (C 2F 5SO 2) 2Molar fraction be 10～50%.
2. perfluor organic molten salt electrolyte as claimed in claim 1 is characterized in that described LiN (C 2F 5SO 2) 2Molar fraction be 10～40%.
3. the preparation method of a perfluor organic molten salt electrolyte as claimed in claim 1 is characterized in that described perfluor organic molten salt electrolyte is by LiN (C 2F 5SO 2) 2With CF 3SO 3Na or CF 3SO 3K processes, wherein LiN (C 2F 5SO 2) 2Molar fraction be 10～50%; Concrete preparation method is following: take by weighing the needed raw material component in proportion respectively, selected raw material components is fully mixed; Then, mill after treating to cool off again evenly, promptly obtain described perfluor organic molten salt electrolyte this mixture heating and melting.
4. the preparation method of perfluor organic molten salt electrolyte as claimed in claim 3 is characterized in that before taking by weighing raw material components, with all raw material components intensive dryings.
5. perfluor organic molten salt electrolyte as claimed in claim 1 is the application in the thermal cell at lithium.
CN 200910099794 2009-06-15 2009-06-15 Perfluor organic molten salt electrolyte, preparation method and application thereof Expired - Fee Related CN101587957B (en)

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