CN110212208A - Electrolyte material for storage thermal battery - Google Patents
Electrolyte material for storage thermal battery Download PDFInfo
- Publication number
- CN110212208A CN110212208A CN201910361512.3A CN201910361512A CN110212208A CN 110212208 A CN110212208 A CN 110212208A CN 201910361512 A CN201910361512 A CN 201910361512A CN 110212208 A CN110212208 A CN 110212208A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- content
- electrolyte material
- lithium
- eutectic salts
- 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.)
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- 239000002001 electrolyte material Substances 0.000 title abstract 6
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 230000005496 eutectics Effects 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims description 40
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 23
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 22
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- -1 lithium fluoride-lithium chloride-lithium bromide-potassium bromide Chemical compound 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 229910013489 LiCl-LiBr-KBr Inorganic materials 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005619 thermoelectricity Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- KBLNJXFYIVRCRS-UHFFFAOYSA-L trilithium chloride fluoride Chemical compound [F-].[Li+].[Cl-].[Li+].[Li+] KBLNJXFYIVRCRS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses an electrolyte material for a storage thermal battery, which adopts an eutectic salt system of quaternary components LiF-LiCl-LiBr-KBr and high-activity MgO or Al2O3The electrolyte material is a binder and is finally prepared into the electrolyte material for the thermal battery with long working time through high-temperature melting, ball-milling and screening and vacuum drying treatment. The invention has simple process, low equipment investment cost and strong practicability. The prepared electrolyte material has the characteristics of low melting point and high ionic conductivity, and a thermal battery developed by adopting the electrolyte material has the characteristic of long working time.
Description
Technical field
It is especially a kind of for storeing the electrolyte of thermal cell the present invention relates to reserve thermoelectricity pool technology.
Background technique
Thermal cell be with the heating system of battery itself nonconducting solid state salt electrolyte heating melting be in from
A kind of hot activation reserve cell of subtype conductor and entrance working condition.Since its electrolyte is in solid-state at normal temperature, do not have
Ion ducting capacity, therefore there is long storage life, while it is with high reliability and stronger environmental suitability.Thermoelectricity
Pond is widely used at present in the weapons such as guided missile, torpedo.
Thermal cell is all to be formed by eutectic salts and binder high-temperature fusion with electrolyte.Wherein the purpose of high-temperature fusion is to make
The fused salt of flowing infiltrates binder, to ensure binder to the retentivity of fused salt.The content of binder is a weight in electrolyte
The physical parameter wanted.By at present in the Li system thermal cell ground for, if the ratio of MgO is too low, it is possible to cause positive and negative
Physical isolation is weak between pole or aggravates electrolyte flow, causes it to ooze out from pile, so that short circuit occur, influences battery
Safety.But if the ratio of MgO is too high, the internal resistance that will lead to battery increases, and influences the working time of battery.Traditional electricity
The mass ratio of Xie Zhizhong MgO is 50% or so.
With the rapid development of Space Science and Technology and missile armament, the thermal cell performance especially working time is proposed higher
It is required that.The outstanding feature of long working time thermal cell is that current density is smaller, usually less than 200mA/cm2, therefore searching has
Compared with the eutectic salts of low melting point (≤440 DEG C), while there is the electrolyte of lower internal resistance to become an important research direction.
Summary of the invention
The technical problems to be solved by the invention, provide a kind of for storeing the electrolyte of thermal cell, are a kind of molten
The lower eutectic salt system of point, and electrolyte internal resistance is reduced by reducing binder ratio.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: it is a kind of for storeing the electrolysis of thermal cell
Material, it is made of quaternary eutectic salts and binder material, and quaternary eutectic salts are lithium fluoride-lithium chloride-lithium bromide-bromination
Potassium system, by weight, quaternary eutectic salt content are 65%~80%, and binder is the MgO or Al of high activity2O3Powder, powder
Specific surface area is not less than 40m2/ g, by weight, binder content are 20%~35%.
In the quaternary eutectic salts, in mole percent, the content of lithium fluoride is 6%~22%, the content of lithium chloride
It is 18%~22%, the content of lithium bromide is 46%~57%, and the content of potassium bromide is 1%~30%.
It is preferred that in mole percent, the content of lithium fluoride is 6%~15%, lithium chloride in the quaternary eutectic salts
Content is 18%~21%, and the content of lithium bromide is 46%~54%, and the content of potassium bromide is 10%~30%.
The quaternary eutectic salts fusing point is between 380 DEG C~440 DEG C.
The beneficial effects of the present invention are: electrolyte of the invention has the characteristics that fusing point is lower, internal resistance is lesser, use
The thermal cell of this kind of electrolyte development has the characteristics that longevity of service.
Detailed description of the invention:
Fig. 1 is the SEM figure of high activity MgO material mentioned by the present invention.
Fig. 2 is high activity Al mentioned by the present invention2O3The SEM of material schemes.
Fig. 3 is to use electrolyte of the present invention (LiF-LiCl-LiBr-KBr/MgO is binder) and the full lithium electrolysis of ternary
The thermal cell discharge performance of matter (LiF-LiCl-LiBr/MgO is binder) compares figure.
Specific embodiment
It is described in detail further to disclose invention, features and effects of the invention especially exemplified by following instance
It is as follows.Embodiments of the present invention are not limited thereto.
As shown in Figure 1, 2, the electrolyte for being used to store thermal cell of the invention, it is by quaternary eutectic salts and bonding
Agent material composition, quaternary eutectic salts are lithium fluoride-lithium chloride-lithium bromide-potassium bromide system, and by weight, quaternary eutectic salts contain
Amount is 65%~80%, and binder is the MgO or Al of high activity2O3Powder, powder specific-surface area detection are not less than 40m2/ g, with weight
Meter, binder content are 20%~35%.
In the quaternary eutectic salts, in mole percent, the content of lithium fluoride is 6%~22%, the content of lithium chloride
It is 18%~22%, the content of lithium bromide is 46%~57%, and the content of potassium bromide is 1%~30%.
It is preferred that in mole percent, the content of lithium fluoride is 6%~15%, lithium chloride in the quaternary eutectic salts
Content is 18%~21%, and the content of lithium bromide is 46%~54%, and the content of potassium bromide is 10%~30%.
The quaternary eutectic salts fusing point is between 380 DEG C~440 DEG C.
The present invention adds KBr in LiF-LiCl-LiBr ternary eutectic salt system to reduce the fusing point of eutectic salts；It selects simultaneously
Select the MgO and Al of high-specific surface area2O3The dosage for reducing binder, reduces the internal resistance of electrolyte.LiF-LiCl-LiBr-KBr tetra-
First eutectic salt system, and add the MgO or Al of high-specific surface area2O3As the electrolyte of binder, the electrolyte not only fusing point
It is low, and ionic conductivity is high.In order to guarantee the safety of battery, MgO or Al is added in eutectic salts2O3As binder, glue
The specific surface area of knot agent powder should at least reach 40m2/g。
Embodiment 1
Reagent 5.2g LiF, 9.35g LiCl, 49.59g LiBr, 1.19g KBr are uniformly mixed and added in ceramic crucible
Then melt rapid cooling to room temperature, crushing grinding and 60 meshes excessively are obtained eutectic salt fines to 500 DEG C of melt process 4h by heat
Body.By active MgO powder, (specific surface area is tested as 43m2/ g) it is heat-treated at 500 DEG C after 4h and is sufficiently mixed with quaternary eutectic salts
It closes, wherein the mass ratio of MgO is 31%, and mixed powder melt process 4h at 500 DEG C is then chilled to room temperature, cracker
Cross 60 meshes after mill and obtain electrolyte powder, electrolyte powder is subsequent to be dried in vacuo 6h under conditions of 300 DEG C, packing to
With.
Fusing point test is carried out to the electrolyte, electrolyte fusing point is 440 DEG C.
Embodiment 2
Reagent 3.9g LiF, 8.92g LiCl, 46.98g LiBr, 11.9g KBr are uniformly mixed and added in ceramic crucible
Then melt rapid cooling to room temperature, crushing grinding and 60 meshes excessively are obtained eutectic salt fines to 500 DEG C of melt process 4h by heat
Body.By active Al2O3(specific surface area test is 44m to powder2/ g) it is heat-treated at 500 DEG C after 4h and is sufficiently mixed with quaternary eutectic salts
It closes, wherein Al2O3Mass ratio be 31%, mixed powder melt process 4h at 500 DEG C is then chilled to room temperature, cracker
Cross 60 meshes after mill and obtain electrolyte powder, electrolyte powder is subsequent to be dried in vacuo 6h under conditions of 300 DEG C, packing to
With.
Fusing point test is carried out to the electrolyte, electrolyte fusing point is 420 DEG C.
Embodiment 3
Reagent 2.6g LiF, 8.5g LiCl, 43.50g LiBr, 23.8g KBr are uniformly mixed and added in ceramic crucible
Then melt rapid cooling to room temperature, crushing grinding and 60 meshes excessively are obtained eutectic salt fines to 500 DEG C of melt process 4h by heat
Body.By active MgO powder, (specific surface area is tested as 46m2/ g) it is heat-treated at 500 DEG C after 4h and is sufficiently mixed with quaternary eutectic salts
It closes, wherein the mass ratio of MgO is 32%, and mixed powder melt process 4h at 500 DEG C is then chilled to room temperature, cracker
Cross 60 meshes after mill and obtain electrolyte powder, electrolyte powder is subsequent to be dried in vacuo 6h under conditions of 300 DEG C, packing to
With.
Fusing point test is carried out to the electrolyte, electrolyte fusing point is 400 DEG C.
Embodiment 4
Reagent 1.56g LiF, 7.65g LiCl, 40.02g LiBr, 35.7g KBr are uniformly mixed in ceramic crucible
500 DEG C of melt process 4h are heated to, melt rapid cooling to room temperature, crushing grinding and 60 meshes excessively are then obtained into eutectic salt fines
Body.By active MgO powder, (specific surface area is tested as 46m2/ g) it is heat-treated at 500 DEG C after 4h and is sufficiently mixed with quaternary eutectic salts
It closes, wherein the mass ratio of MgO is 32%, and mixed powder melt process 4h at 500 DEG C is then chilled to room temperature, cracker
Cross 60 meshes after mill and obtain electrolyte powder, electrolyte powder is subsequent to be dried in vacuo 6h under conditions of 300 DEG C, packing to
With.
Fusing point test is carried out to the electrolyte, electrolyte fusing point is 380 DEG C.
Test example
As shown in figure 3, LiB alloy is as cathode, and MS is as anode compacting using the electrolyte matched in case study on implementation 4
The single battery of Φ 54mm.It is monomer series-connected by 15, and be fitted into the Stainless Steel Shell of Φ 67mm and discharge, constant current 2.3A
(100mA/cm2), every the pulse of 150s output 35A, lower work threshold voltage is 25V, and the working time is up to 1250s or more.Together
Shi Caiyong traditional LiF-LiCl-LiBr system electrolyte, other parameters are constant, do same single battery, battery discharge machine
Make identical, battery working time 1050s.Simultaneously by being compared discovery to discharge curve pulse voltage, in previous work
Stage, the anti-pulse ability of two kinds of electrolyte are suitable.
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent model of the invention only cannot be limited with the present embodiment
It encloses, i.e., same changes or modifications made by all disclosed spirit are still fallen in the scope of the patents of the invention.
Claims (4)
1. a kind of for storeing the electrolyte of thermal cell, which is characterized in that it is by quaternary eutectic salts and binder material
Composition, quaternary eutectic salts are lithium fluoride-lithium chloride-lithium bromide-potassium bromide system, and by weight, quaternary eutectic salt content is
65%~80%, binder is the MgO or Al of high activity2O3Powder, powder specific-surface area detection are not less than 40m2/ g glues by weight
Tying agent content is 20%~35%.
2. according to claim 1 for storeing the electrolyte of thermal cell, which is characterized in that the quaternary eutectic salts
In, in mole percent, the content of lithium fluoride is 6%~22%, and the content of lithium chloride is 18%~22%, and lithium bromide contains
Amount is 46%~57%, and the content of potassium bromide is 1%~30%.
3. according to claim 2 for storeing the electrolyte of thermal cell, which is characterized in that the quaternary eutectic salts
In, in mole percent, the content of lithium fluoride is 6%~15%, and the content of lithium chloride is 18%~21%, and lithium bromide contains
Amount is 46%~54%, and the content of potassium bromide is 10%~30%.
4. according to claim 1 for storeing the electrolyte of thermal cell described in -3 any one, which is characterized in that the quaternary
Eutectic salts fusing point is between 380 DEG C~440 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910361512.3A CN110212208A (en) | 2019-04-30 | 2019-04-30 | Electrolyte material for storage thermal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910361512.3A CN110212208A (en) | 2019-04-30 | 2019-04-30 | Electrolyte material for storage thermal battery |
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| Publication Number | Publication Date |
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| CN110212208A true CN110212208A (en) | 2019-09-06 |
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| CN201910361512.3A Pending CN110212208A (en) | 2019-04-30 | 2019-04-30 | Electrolyte material for storage thermal battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129535A (en) * | 2019-11-25 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Electrolyte material for thermal battery, preparation method and application |
| CN111725534A (en) * | 2020-07-14 | 2020-09-29 | 中国电子科技集团公司第十八研究所 | Thermal battery capable of resisting high temperature environment of 500 DEG C |
| CN112687947A (en) * | 2020-12-26 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | High-pressure-resistant and decomposition-resistant electrolyte for thermal battery and preparation method thereof |
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| CN101471446A (en) * | 2007-12-26 | 2009-07-01 | 北京有色金属研究总院 | Low-melting-point high-conductivity molten salt electrolyte and preparation method thereof |
| CN105703002A (en) * | 2014-11-27 | 2016-06-22 | 中国电子科技集团公司第十八研究所 | Electrolyte material for thermal battery and preparation method for electrolyte material |
| CN105789653A (en) * | 2016-04-13 | 2016-07-20 | 武汉理工大学 | Preparation method of thermal battery electrolyte containing hollow magnesia powder |
| CN107611389A (en) * | 2017-08-31 | 2018-01-19 | 上海空间电源研究所 | A kind of thermal cell aoxidizes copper-based composite positive pole and its production and use |
-
2019
- 2019-04-30 CN CN201910361512.3A patent/CN110212208A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101471446A (en) * | 2007-12-26 | 2009-07-01 | 北京有色金属研究总院 | Low-melting-point high-conductivity molten salt electrolyte and preparation method thereof |
| CN105703002A (en) * | 2014-11-27 | 2016-06-22 | 中国电子科技集团公司第十八研究所 | Electrolyte material for thermal battery and preparation method for electrolyte material |
| CN105789653A (en) * | 2016-04-13 | 2016-07-20 | 武汉理工大学 | Preparation method of thermal battery electrolyte containing hollow magnesia powder |
| CN107611389A (en) * | 2017-08-31 | 2018-01-19 | 上海空间电源研究所 | A kind of thermal cell aoxidizes copper-based composite positive pole and its production and use |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129535A (en) * | 2019-11-25 | 2020-05-08 | 中国电子科技集团公司第十八研究所 | Electrolyte material for thermal battery, preparation method and application |
| CN111725534A (en) * | 2020-07-14 | 2020-09-29 | 中国电子科技集团公司第十八研究所 | Thermal battery capable of resisting high temperature environment of 500 DEG C |
| CN112687947A (en) * | 2020-12-26 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | High-pressure-resistant and decomposition-resistant electrolyte for thermal battery and preparation method thereof |
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