CN107123819A - A kind of slim thermal cell spacer and preparation method thereof - Google Patents
A kind of slim thermal cell spacer and preparation method thereof Download PDFInfo
- Publication number
- CN107123819A CN107123819A CN201710296539.XA CN201710296539A CN107123819A CN 107123819 A CN107123819 A CN 107123819A CN 201710296539 A CN201710296539 A CN 201710296539A CN 107123819 A CN107123819 A CN 107123819A
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- Prior art keywords
- thermal cell
- spacer
- preparation
- slim
- electrolyte
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Abstract
The present invention relates to a kind of slim thermal cell spacer and preparation method thereof.This method prepares thermal cell spacer using the method for electrolyte fuse salt impregnation matrix, make it that the molten salt electrolyte of easily moisture absorption dissolving is prepared into spacer, this method does not need harsh operating environment, reproducible, cost is low, and the spacer of different-thickness can be prepared as needed；Meanwhile, thermal cell spacer prepared by the present invention is more thinned, and spacer thickness is adjustable in 150 350 μ ms, effectively shortens the activationary time of thermal cell, and effectively improves its high power discharge ability.
Description
Technical field
It is more particularly to a kind of to be prepared using electrolyte fuse salt impregnation matrix the invention belongs to thermal cell preparing technical field
The process of slim thermal battery spacer.
Background technology
Thermal cell is to heat the hot activation for being melt into ionic conductor and entering working condition by solid-state salt electrolyte
Redundant electrical power；Thermal cell is because with high power discharge, high-energy-density, high-specific-power, use environment temperature be wide, storage time
The features such as length, activation rapid reliably, compact conformation, and it is very good as modern weapons (guided missile, torpedo, strategic arms etc.)
Power supply, occupies highly important status in Military Power.
At present, lithium system thermal cell is the leading products of thermal cell, can simply be regarded as by positive pole, molten salt electrolyte
With negative pole composition, when operating temperature is higher than electrolyte fuse salt fusing point, electrolyte just melts, flowed, and battery is activated；But
It is that the flowing of electrolyte produces electrical noise, accelerates self discharge, battery short circuit is caused when serious, cell discharge performance is produced negative
Face rings；Therefore the crucial ring that spacer is constituted as thermal cell, directly affects working life and security performance of battery etc.
Characteristic.
At present, in order to restrain the flowing of electrolyte, generally added using the big chemically inert material (such as MgO) of specific surface area
It is added in electrolyte to suppress the flowing of electrolyte；But the spacer diameter dimension for using this method to prepare has been limited, this
Internal resistance is larger in class thermal cell discharge process, and high power discharge ability is not good.
Also, the preferable electrolyte of thermal cell, must both possess preferable electronic isolation to isolate positive and negative pole material, again
Stable ion transmission channel can be provided；In view of condition of work and the negative material extremely strong corruption at high temperature of thermal cell high temperature
Corrosion, to ensure that the isolated material in the operation of battery-efficient safety, thermal battery electrolyte must use good insulating, chemistry steady
The qualitative and strong material of heat endurance；But, existing thermal battery electrolyte material is typically by magnesia (MgO) and electrolyte
Salt lithium chloride, potassium chloride mix progress powder tabletting and formed according to a certain percentage, and subject matter is that powder self-supporting is poor, its
Mechanical strength is poor, and shrinkage and bendability, which are easily affected, during high temperature causes battery short circuit, therefore thickness can not be too thin, from
And battery volume is increased, seriously limit the development of thermal cell miniaturization.Simultaneously in its discharge process of such thermal cell, electrolysis
Matter slip is changed greatly so that the polarization resistance change of battery greatly, causes its power-performance poor.
Meanwhile, the electrolytic salt easily moisture absorption dissolves, therefore, and domestic and international thermal cell spacer uses pressed powder technique system
It is standby, but because powder self-supporting is poor, cause spacer can not too thin, diameter the problems such as can not be molded greatly very much, into thermal cell
The bottleneck of miniaturization, therefore, slim thermal battery spacer turn into following thermal cell miniaturization urgent need to resolve major issue it
One.
The content of the invention
It is an object of the invention to provide a kind of slim thermal cell spacer and preparation method thereof, the thermal cell spacer is more
Slimming, stability is good, while the spacer can effectively shorten the activationary time of thermal cell, improves its high power discharge energy
Power.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation side of slim thermal cell spacer is provided
Method, comprises the following steps：
(1) electrolyte fuse salt is prepared；
(2) matrix is placed in the electrolyte fuse salt and infiltrates a period of time, taken out, then post-treated, cooling and pressure
System, is made slim thermal cell spacer.
Beneficial effects of the present invention are：Thermal cell isolation is prepared by using the method for electrolyte fuse salt impregnation matrix
Piece so that the electrolytic salt of easily moisture absorption dissolving is prepared into spacer and is possibly realized, and the inventive method does not need harsh operation
Environment, reproducible, cost is low, and the spacer of different-thickness can be prepared as needed, is that current high power thermal cell is preferable
Isolated material preparation method.
Meanwhile, thermal cell spacer prepared by the present invention is more thinned, and spacer thickness can in 150-350 μ ms
Adjust, effectively shorten the activationary time of thermal cell, and effectively improve its high power discharge ability.
Also, the present invention uses dipping method can be with independently prepared certain thickness spacer, then by thermal cell positive plate
It is assembled into slimming single cell of thermo battery together with negative plate, it is simple to operate, it is easy to large-scale production.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement：
Further, the specific preparation process of the step (1) is：
Taking electrolyte salt, is heated and is warming up to 400-500 DEG C, heating rate is 5-10 DEG C/min, obtains electrolyte and melts
Melt salt.
Using having the beneficial effect that for above-mentioned further technical scheme：It is molten that the above method can make dipping obtain optimal electrolyte
Melt the spacer of salt content.
Further, the electrolytic salt is KCl and LiCl mixture or LiCl, LiBr and KBr mixture；In KCl
In LiCl mixture, KCl mass percent is 30-60%, and LiCl mass percent is 40-70%；LiCl,
In LiBr and KBr mixture, LiCl mass percent is 5-15%, and LiBr mass percent is 30-45%, KBr's
Mass percent is 40-60%.
Further, in the step (2), dip time of the matrix in electrolyte fuse salt is 10-30min；
Further, described matrix thickness is 100-200 μm, and hole size is 0.5-2.0 μm.
Using having the beneficial effect that for above-mentioned further technical scheme：The condition can effectively ensure that the microcellular structure of matrix can
More to load electrolyte fuse salt.
Further, described matrix is glass fibre or metal-oxide film.
Further, in step (2), the detailed process of post processing is：It is not more than in humidity in 3% environment, at infiltration
The spacer of reason is placed at 350-400 DEG C, is handled 10-30min, is cooled to room temperature.
Further, in step (2), the detailed process of the compacting is：It is not more than in humidity under conditions of 3%, will be through dry
Thermal cell spacer after dry solidification is made in suppressing 5s-1min under 2-15Mpa.
The slim thermal battery spacer prepared using the preparation method of above-mentioned slim thermal cell spacer, the thermoelectricity
Pond spacer internal resistance is small and is conducive to improving high power discharge ability.
Beneficial effects of the present invention are：
1) matrix is directly infiltrated in electrolyte fuse salt, not had in preparation process by thermal cell spacer of the invention
Have any chemically inert material of addition, the preparation of the slim spacer of major diameter can be achieved, meanwhile, using the present invention thermal cell every
From piece thermal cell in discharge process internal resistance it is small, high power discharge ability effectively improves.
2) slim thermal cell spacer good environmental adaptability prepared by the present invention, can be in the extreme ring such as high overload, HI high impact
Used under border；Compared with the use powder of same specification suppresses the thermal cell of spacer, the spacer prepared using the inventive method
Thermal cell rate of activation fast more than 10%, good power solution is provided for special weapon equipment list, thermoelectricity is expanded
The use scope in pond.
3) present invention loads electricity by using special high temperature resistant matrix material (glass fibre membrane or metal oxide film)
Solve matter salt so that the thermal cell internal resistance of preparation is small, and high power discharge performance is improved, while being also beneficial to further carry from now on
Hyperpyrexia automatic battery produces degree.
4) instant invention overcomes many drawbacks that conventional powder tablet forming technique is brought, it is not necessary to high-precision compression mold and
Substantial amounts of labour, can easily realize the preparation of large area and irregular shape spacer, can effectively reduce cell
Volume, is particularly suitable for the research of thermal cell miniaturization.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1：
A kind of preparation method of slim thermal cell spacer, comprises the following steps：
(1) electrolyte fuse salt is prepared：In natural environment, electrolytic salt is put in crucible, then is transferred in Muffle furnace,
400 DEG C are warming up to, heating rate is 5 DEG C/min, obtains electrolyte fuse salt；
Wherein, electrolytic salt is KCl and LiCl mixture, and KCl mass percent is 40%, LiCl quality percentage
Than for 60%.
(2) in natural environment, using glass fibre as load matrix, it is impregnated in electrolyte fuse salt, protects
10min is held, then takes out and obtains spacer；The matrix thickness of glass fibre is 100 μm, and hole size is 1.0 μm；
(3) it is not more than in humidity in 3% environment, spacer, which is transferred in 400 DEG C of Muffle furnaces, to be continued to heat 10min,
Carry out naturally cooling to room temperature again；
(4) it is not more than in humidity in 3% environment, the thermal cell spacer after cooling treatment is suppressed under 5Mpa
30s, obtains slim thermal cell spacer.
Embodiment 2：
A kind of preparation method of slim thermal cell spacer, comprises the following steps：
(1) electrolyte fuse salt is prepared：In natural environment, electrolytic salt is put in crucible, then is transferred in Muffle furnace,
500 DEG C are warming up to, heating rate is 10 DEG C/min, obtains electrolyte fuse salt；
Wherein, electrolytic salt is LiCl, LiBr and KBr mixture, and LiCl mass percent is 5%, LiBr matter
It is 55% to measure the mass percent that percentage is 40%, KBr；
(2) in natural environment, using glass fibre as load matrix, it is impregnated in electrolyte fuse salt, protects
20min is held, then takes out and obtains spacer；The matrix thickness of glass fibre is 200 μm, and hole size is 2.0 μm；
(3) it is not more than in humidity in 3% environment, spacer, which is transferred in 350 DEG C of Muffle furnaces, to be continued to heat 30min,
Carry out naturally cooling to room temperature again；
(4) it is not more than in humidity in 3% environment, the thermal cell spacer after cooling treatment is suppressed under 15Mpa
1min, obtains slim thermal cell spacer.
Embodiment 3：
A kind of preparation method of slim thermal cell spacer, comprises the following steps：
(1) electrolyte fuse salt is prepared：In natural environment, electrolytic salt is put in crucible, then is transferred in Muffle furnace,
450 DEG C are warming up to, heating rate is 8 DEG C/min, obtains electrolyte fuse salt；
Wherein, electrolytic salt is KCl and LiCl mixture, and KCl mass percent is 60%, LiCl quality percentage
Than for 40%；
(2) in natural environment, using metal-oxide film as load matrix, it is impregnated in electrolyte fuse salt
In, 30min is kept, then takes out and obtains spacer；The thickness of metal-oxide film is 110 μm, and hole size is 0.8 μm；
(3) it is not more than in humidity in 3% environment, spacer, which is transferred in 380 DEG C of Muffle furnaces, to be continued to heat 20min,
Carry out naturally cooling to room temperature again；
(4) it is not more than in humidity in 3% environment, the thermal cell spacer after cooling treatment is suppressed under 10Mpa
40s, obtains slim thermal cell spacer.
Embodiment 4：
A kind of preparation method of slim thermal cell spacer, comprises the following steps：
(1) electrolyte fuse salt is prepared：In natural environment, electrolytic salt is put in crucible, then is transferred in Muffle furnace,
420 DEG C are warming up to, heating rate is 6 DEG C/min, obtains electrolyte fuse salt；
Wherein, electrolytic salt is LiCl, LiBr and KBr mixture, and LiCl mass percent is 15%, LiBr matter
It is 50% to measure the mass percent that percentage is 35%, KBr；
(2) in natural environment, using metal-oxide film as load matrix, it is impregnated in electrolyte fuse salt
In, 15min is kept, then takes out and obtains spacer；The thickness of metal-oxide film is 160 μm, and hole size is 1.5 μm；
(3) it is not more than in humidity in 3% environment, spacer, which is transferred in 350 DEG C of Muffle furnaces, to be continued to heat 15min,
Carry out naturally cooling to room temperature again；
(4) it is not more than in humidity in 3% environment, the thermal cell spacer after cooling treatment is suppressed under 8Mpa
35s, obtains slim thermal cell spacer.
Comparative example 1：
It is not more than in humidity in 3% environment, electrolytic salt (KCl and LiCl mixture) and magnesia (MgO) is pressed
According to mass ratio 6:4 ratios are mixed, and the mass percent that KCl mass percent is 40%, LiCl in electrolyte is 60%, according to
Pressed powder technique is prepared into electrolyte sheet.
Using ferrous disulfide as negative electrode, Li-Si alloy is assembled as anode using comparative example and embodiment 1-5 spacer
Into cell, discharge performance test is carried out, test result is as shown in table 1：
Monomer cell discharge performance under the different current densities of table 1
It can be seen that, the average internal resistance of single cell of thermo battery of the spacer assembling prepared by 1-4 of the embodiment of the present invention is less than pair
The single cell of thermo battery of ratio magnesia tabletting mode spacer assembling, high power discharge performance effectively improves；Also,
The result of table 1 confirms that in current density be 125mA/cm2And 1000mA/cm2The thermal cell of spacer assembling prepared by embodiment 1-4
The high 0.055V of single cell of thermo battery that cell average voltage is assembled than comparative example magnesia tabletting mode spacer respectively
And 0.107V.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of slim thermal cell spacer, it is characterized in that, comprise the following steps：
(1) electrolyte fuse salt is prepared；
(2) matrix is placed in the electrolyte fuse salt and infiltrates a period of time, taken out, then post-treated, cooling and compacting, system
Obtain slim thermal cell spacer.
2. the preparation method of slim thermal cell spacer according to claim 1, it is characterized in that, the tool of the step (1)
Production procedure is：
Taking electrolyte salt, is heated and is warming up to 400-500 DEG C, heating rate is 5-10 DEG C/min, obtains electrolyte fuse salt.
3. the preparation method of slim thermal cell spacer according to claim 2, it is characterized in that, the electrolytic salt is
KCl and LiCl mixture or LiCl, LiBr and KBr mixture；In KCl and LiCl mixture, KCl quality percentage
It is 40-70% than the mass percent for 30-60%, LiCl；In LiCl, LiBr and KBr mixture, LiCl quality hundred
Divide than being 5-15%, LiBr mass percent is 30-45%, and KBr mass percent is 40-60%.
4. the preparation method of slim thermal cell spacer according to claim 1, it is characterized in that, in the step (2), base
Dip time of the body in electrolyte fuse salt is 10-30min.
5. the preparation method of the slim thermal cell spacer according to claim 1 or 4, it is characterized in that, described matrix thickness
For 100-200 μm, hole size is 0.5-2.0 μm.
6. the preparation method of slim thermal cell spacer according to claim 5, it is characterized in that, described matrix is glass fibers
Dimension or metal-oxide film.
7. the preparation method of slim thermal cell spacer according to claim 1, it is characterized in that, in step (2), post processing
Detailed process be：It is not more than in humidity in 3% environment, the spacer for infiltrating processing is placed at 350-400 DEG C, handles
10-30min, is cooled to room temperature.
8. the preparation method of slim thermal cell spacer according to claim 1, it is characterized in that, in step (2), the pressure
The detailed process of system is：It is not more than in humidity under conditions of 3%, by the thermal cell spacer after cooling treatment in 2-15Mpa
Lower compacting 5s-1min, is made.
9. the slim thermoelectricity prepared using the preparation method of the slim focus pond spacer described in claim any one of 1-8
Pond spacer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710296539.XA CN107123819B (en) | 2017-04-28 | 2017-04-28 | A kind of slim thermal cell spacer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710296539.XA CN107123819B (en) | 2017-04-28 | 2017-04-28 | A kind of slim thermal cell spacer and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN107123819A true CN107123819A (en) | 2017-09-01 |
| CN107123819B CN107123819B (en) | 2019-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710296539.XA Expired - Fee Related CN107123819B (en) | 2017-04-28 | 2017-04-28 | A kind of slim thermal cell spacer and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115020911A (en) * | 2022-07-12 | 2022-09-06 | 贵州梅岭电源有限公司 | Isolating ring for thermal battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189827A (en) * | 1978-11-03 | 1980-02-26 | The United States Of America As Represented By The United States Department Of Energy | Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl4) to promote electrolyte wetting |
| US20030228520A1 (en) * | 2002-06-06 | 2003-12-11 | Kaun Thomas D. | Process for manufacturing thermal battery with thin fiber separator |
| CN106450366A (en) * | 2016-10-19 | 2017-02-22 | 上海空间电源研究所 | Ultra-thin unit cell for thermal battery and preparation method thereof |
-
2017
- 2017-04-28 CN CN201710296539.XA patent/CN107123819B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189827A (en) * | 1978-11-03 | 1980-02-26 | The United States Of America As Represented By The United States Department Of Energy | Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl4) to promote electrolyte wetting |
| US20030228520A1 (en) * | 2002-06-06 | 2003-12-11 | Kaun Thomas D. | Process for manufacturing thermal battery with thin fiber separator |
| CN106450366A (en) * | 2016-10-19 | 2017-02-22 | 上海空间电源研究所 | Ultra-thin unit cell for thermal battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAE-WON CHEONG等: "Surface modified ceramic fiber separators for thermal batteries", 《JOURNAL OF CERAMIC PROCESSING RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115020911A (en) * | 2022-07-12 | 2022-09-06 | 贵州梅岭电源有限公司 | Isolating ring for thermal battery |
| CN115020911B (en) * | 2022-07-12 | 2024-03-29 | 贵州梅岭电源有限公司 | Isolating ring for thermal battery |
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| Publication number | Publication date |
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| CN107123819B (en) | 2019-06-11 |
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Granted publication date: 20190611 Termination date: 20200428 |