CN102544482A - Formula of thermal battery CoS2 cathode material and processing technology - Google Patents
Formula of thermal battery CoS2 cathode material and processing technology Download PDFInfo
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- CN102544482A CN102544482A CN2010105950021A CN201010595002A CN102544482A CN 102544482 A CN102544482 A CN 102544482A CN 2010105950021 A CN2010105950021 A CN 2010105950021A CN 201010595002 A CN201010595002 A CN 201010595002A CN 102544482 A CN102544482 A CN 102544482A
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- thermal cell
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Abstract
The invention discloses a formula of a thermal battery CoS2 cathode material and processing technology. The formula comprises the following components by mass: 70.5%-85% of cobaltous sulfide CoS2, 5%-15% of lithium oxide, 16%-25% of molten salts. The processing technology of the formula comprises the following steps: adding the cathode active substance of the cobaltous sulfide CoS2 material in an enamel disc, putting in a vacuum drying oven, performing high temperature dehydration at 90 DEG C-250 DEG C; performing high temperature sintering of the dehydrated cobaltous sulfide CoS2 at 290 DEG C-500 DEG C under inert gas protection for 4 h-8 h, cooling and sieving, adding 5%-15% of lithium oxide and 16%-25% of molten salts into the cobaltous sulfide CoS2, mixing and sintering at 330 DEG C-500 DEG C for 4 h-6 h, cooling to room temperature, sieving by a 80-mesh sieve so as to prepare the high temperature resistant thermal battery cathode composite material which is bottled to keep in reserve. The invention can improve the security of thermal batteries, and increase the active substance utilization rate.
Description
Technical field
The invention belongs to the thermal cell technical field, particularly relate to a kind of thermal cell positive electrode CoS
2Prescription and treatment process.
Background technology
Thermal cell is a thermally activated battery, and it is to make electrolyte with fused salt, utilizes thermal source to make its fusing and a reserve cell activating.Electrolyte is non-conductive solid at normal temperatures, and battery is through percussion cap or light electric firing head, pyrotechnic heat source in the battery pack of igniting; Make that temperature is instantaneous in the battery pack is elevated to 450 ℃～550 ℃; Electrolyte is melt into the ion conductor that high electricity is led, activation heat battery pack, output electric energy.Advantages such as thermal cell has specific energy and specific power height, environment for use temperature wide (being generally-55 ℃～+ 70 ℃), period of storage long (10～25 years), activationary time short (being generally less than 1.5s), compact conformation, the influence that does not receive installation position, good mechanical performance, need not safeguard.
It is thermal cell that present thermal cell is mainly lithium, generally with the sulfide of transition metal as positive electrode, with lithium alloy as negative material.Ripe at present positive electrode is mainly FeS
2, but the research focus concentrates on CoS
2Positive electrode.FeS
2Shortcoming maximum in thermal cell is used is exactly that its thermal stability is lower, generally in the time of 550 ℃, thermal decomposition will take place, and produces sulphur steam, sulphur steam be easy to negative pole in lithium alloy generation exothermic reaction, thereby produce more heat, cause FeS
2Decompose and quicken, finally cause the battery premature failure.And CoS
2Thermal stability higher, can be up to more than 650 ℃, this is than FeS
2High nearly 100 ℃, be equivalent to enlarge nearly 100 ℃ of effective operation temperature area of thermal cell, this has crucial meaning to specific energy and the working life that improves thermal cell.CoS
2Resistivity be 0.002 Ω cm, far below FeS
217.7 Ω cm, more help reducing the ohmic polarization of electrode, and CoS
2Be vesicular texture, increased CoS
2Specific area, help reducing electrochemical polarization.
Because artificial synthetic CoS
2A large amount of sulphur simple substance is contained on the positive electrode surface; High temperature can produce sulfur vapor, and the air pressure of inside battery is increased, and causes the fail safe existing problems of battery; Therefore can not directly be used for thermal cell, needing could be as the positive electrode of thermal cell through the processing in early stage.
Summary of the invention
The technical problem that the present invention will solve is: a kind of thermal cell CoS is provided
2The prescription of positive electrode and treatment process are through to thermal cell positive electrode cobalt disulfide CoS
2Carry out technology and prescription processing, remove impurity wherein, improve its thermal stability; Eliminate thermal cell and activate the high voltage that moment occurs; Improve the stationarity of output voltage, thus the fail safe that improves thermal cell with improve active material utilization, can produce sulfur vapor to overcome the high temperature that prior art exists; The air pressure of inside battery is increased, cause the deficiencies such as fail safe existing problems of battery.
Thermal cell positive electrode CoS of the present invention
2Prescription: its mass percent consists of: cobalt disulfide CoS
2Be 70.5%～85%, lithia is 5%～15%, and congruent melting salt is 16%～25%.
It is 36.53% LiBr, 12.05% LiCl and the mixing of 51.42% KBr that the composition of congruent melting salt is measured by percentage to the quality, and this is the mixing of low conductivity congruent melting salt.
It is 0.68% LiF, 42.03% KBr and the mixing of 57.29% LiBr that the composition of congruent melting salt is measured by percentage to the quality, and this is the mixing of high conductivity congruent melting salt.
The composition of congruent melting salt is measured the mixing of the LiF that is 68.44% LiBr, 22% LiCl and 9.56% by percentage to the quality, and this is that the full lithium congruent melting of ternary salt mixes.
Thermal cell positive electrode CoS of the present invention
2The prescription treatment process: with positive active material cobalt disulfide CoS
2Material is put into enamel tray, puts into vacuum drying chamber and carries out 90 ℃～250 ℃ high temperature and dewater; With the positive active material cobalt disulfide CoS after dewatering
2Material carries out 290 ℃～500 ℃ high temperature sintering 4h～8h under inert gas shielding, sieve after the cooling, again at positive active material cobalt disulfide CoS
2Add 5%～15% lithia in the material, 16%～25% congruent melting salt mixes and carries out 330 ℃～500 ℃ sintering 4h～6h, is cooled to room temperature, mills, and crosses 80 mesh sieves, so promptly processes the high temperature heat-resistant battery anode composite material, and it is subsequent use to bottle.This material has thermal stability preferably; Can improve the stationarity of thermal cell output voltage; Wherein lithia plays and suppresses battery activated moment and high-tension effect occurs, and congruent melting salt pair positive electrode active material carries out heat protection, the formation coating effect on the positive active material surface; Can increase the electrochemical reaction contact point, thereby reduce polarization.
The present invention selects different congruent melting salt preparation positive electrodes for use according to the different working situation, improves cobalt disulfide (CoS
2) the positive electrode performance.Low electricity leads that congruent melting salt fusing point is low, conductivity is little, is fit to low current density, long-life thermal cell; High electricity leads that congruent melting salt fusing point is low, conductivity is high, equivalent life thermal cell in being fit to; The full lithium congruent melting of ternary salt fusing point is high, conductivity is high, Li content is high in the fused salt, is fit to big electric current, middle high power type thermal cell.In positive electrode, adding congruent melting salt can be at positive active material CoS
2The surface form the coating effect because positive active material CoS
2Positive active material has porousness, and is also wherein permeable, has thermal shock resistance preferably, and the adding of congruent melting salt can increase the effecting reaction area of positive electrode, reduces polarization, improves the electrical property of battery; Lithia is to eliminate the high voltage that battery activated moment occurs, and has improved the stationarity of output voltage.
Embodiment
Provide embodiments of the invention below:
Prescription of the present invention is made up of following: cobalt disulfide (CoS
2) 70%～80%, lithia 5%～15%, congruent melting salt 15%～25%, each component is by mass percentage.
Embodiment one
A kind of treatment process and prescription of thermal cell positive electrode consist of: with positive active material cobalt disulfide (CoS
2) material puts into enamel tray, put into vacuum drying chamber and carry out 125 ℃ of temperature and dewater.With the positive active material cobalt disulfide (CoS after dewatering
2) material carries out 500 ℃ of high temperature sintering 8h under inert gas shielding, sieve after the cooling, presses cobalt disulfide (CoS again
2) 80%, lithia 5%, congruent melting salt 15% mixes, and carries out 500 ℃ of high temperature sintering 6h, is cooled to room temperature, mills, and crosses 80 mesh sieves, and it is subsequent use to bottle.Wherein the mass percent of congruent melting salt consists of: 68.44% LiBr, 22% LiCl and 9.56% LiF.
Embodiment two
A kind of treatment process and prescription of thermal cell positive electrode consist of: with positive active material cobalt disulfide (CoS
2) material puts into enamel tray, put into vacuum drying chamber and carry out 125 ℃ of high temperature and dewater.With the positive active material cobalt disulfide (CoS after dewatering
2) material carries out 500 ℃ of high temperature sintering 8h under inert gas shielding, sieve after the cooling, presses cobalt disulfide (CoS again
2) 73.5%, lithia 5.5%, congruent melting salt 21% mixes, and carries out 400 ℃ of high temperature sintering 6h, is cooled to room temperature, mills, and crosses 80 mesh sieves, and it is subsequent use to bottle.Wherein the mass percent of congruent melting salt consists of: 36.53% LiBr, 12.05% LiCl and 51.42% KBr.
Embodiment three
A kind of treatment process and prescription of thermal cell positive electrode consist of: with positive active material cobalt disulfide (CoS
2) material puts into enamel tray, put into vacuum drying chamber and carry out 125 ℃ of high temperature and dewater.With the positive active material cobalt disulfide (CoS after dewatering
2) material carries out 500 ℃ of high temperature sintering 8h under inert gas shielding, sieve after the cooling, presses cobalt disulfide (CoS again
2) 75%, lithia 5%, congruent melting salt 20% mixes, and carries out 360 ℃ of high temperature sintering 6h, is cooled to room temperature, mills, and crosses 80 mesh sieves, and it is subsequent use to bottle.Wherein the mass percent of congruent melting salt consists of: 0.68% LiF, 42.03% KBr and 57.29% LiBr.
Claims (5)
1. thermal cell positive electrode CoS
2Prescription, it is characterized in that: its mass percent consists of: cobalt disulfide CoS
2Be 70.5%～85%, lithia is 5%～15%, and congruent melting salt is 16%～25%.
2. thermal cell positive electrode CoS according to claim 1
2Prescription, it is characterized in that: it is 36.53% LiBr, 12.05% LiCl and the mixing of 51.42% KBr that the composition of congruent melting salt is measured by percentage to the quality.
3. thermal cell positive electrode CoS according to claim 1
2Prescription, it is characterized in that: it is 0.68% LiF, 42.03% KBr and the mixing of 57.29% LiBr that the composition of congruent melting salt is measured by percentage to the quality.
4. thermal cell positive electrode CoS according to claim 1
2Prescription, it is characterized in that: the composition of congruent melting salt is measured the mixing of the LiF that is 68.44% LiBr, 22% LiCl and 9.56% by percentage to the quality.
5. thermal cell positive electrode CoS as claimed in claim 1
2The treatment process of prescription, it is characterized in that: with positive active material cobalt disulfide CoS
2Material is put into enamel tray, puts into vacuum drying chamber and carries out 90 ℃～250 ℃ high temperature and dewater; With the positive active material cobalt disulfide CoS after dewatering
2Material carries out 290 ℃～500 ℃ high temperature sintering 4h～8h under inert gas shielding, sieve after the cooling, again at positive active material cobalt disulfide CoS
2Add 5%～15% lithia in the material, 16%～25% congruent melting salt mixes and carries out 330 ℃～500 ℃ sintering 4h～6h, is cooled to room temperature, mills, and crosses 80 mesh sieves, promptly processes the high temperature heat-resistant battery anode composite material.
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| CN2010105950021A CN102544482A (en) | 2010-12-20 | 2010-12-20 | Formula of thermal battery CoS2 cathode material and processing technology |
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|---|---|---|---|
| CN2010105950021A CN102544482A (en) | 2010-12-20 | 2010-12-20 | Formula of thermal battery CoS2 cathode material and processing technology |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140485A (en) * | 2015-08-26 | 2015-12-09 | 上海空间电源研究所 | Composite cathode material for thermal battery and preparation method of composite cathode material |
| CN106207085A (en) * | 2015-05-06 | 2016-12-07 | 上海空间电源研究所 | A kind of thermal cell method for preparing anode material and the thermal cell utilizing it to prepare |
| CN107565105A (en) * | 2017-07-25 | 2018-01-09 | 北京理工大学 | A kind of long life thermal battery composite positive pole and preparation method thereof |
| CN107732268A (en) * | 2017-11-23 | 2018-02-23 | 上海空间电源研究所 | A kind of cell of carrier rocket thermal cell |
| CN109052488A (en) * | 2018-09-05 | 2018-12-21 | 中国工程物理研究院电子工程研究所 | A kind of cobalt disulfide material and its preparation method and application with high-storage stability |
| CN109494362A (en) * | 2018-10-31 | 2019-03-19 | 贵州梅岭电源有限公司 | A kind of thermal cell positive electrode and preparation method thereof |
| CN113594401A (en) * | 2021-07-30 | 2021-11-02 | 沈阳理工大学 | Preparation method of thermal battery thin film anode |
| CN114068874A (en) * | 2021-11-16 | 2022-02-18 | 中国电子科技集团公司第十八研究所 | High-temperature-resistant composite cathode material for thermal battery and preparation method thereof |
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| CN107565105B (en) * | 2017-07-25 | 2021-02-26 | 北京理工大学 | Composite cathode material for long-life thermal battery and preparation method thereof |
| CN107732268A (en) * | 2017-11-23 | 2018-02-23 | 上海空间电源研究所 | A kind of cell of carrier rocket thermal cell |
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| CN109494362A (en) * | 2018-10-31 | 2019-03-19 | 贵州梅岭电源有限公司 | A kind of thermal cell positive electrode and preparation method thereof |
| CN113594401A (en) * | 2021-07-30 | 2021-11-02 | 沈阳理工大学 | Preparation method of thermal battery thin film anode |
| CN114068874A (en) * | 2021-11-16 | 2022-02-18 | 中国电子科技集团公司第十八研究所 | High-temperature-resistant composite cathode material for thermal battery and preparation method thereof |
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Application publication date: 20120704 |