CN102544536A - Electrolyte for thermal battery and provided with 4-component inorganic fused salt - Google Patents
Electrolyte for thermal battery and provided with 4-component inorganic fused salt Download PDFInfo
- Publication number
- CN102544536A CN102544536A CN2010106049297A CN201010604929A CN102544536A CN 102544536 A CN102544536 A CN 102544536A CN 2010106049297 A CN2010106049297 A CN 2010106049297A CN 201010604929 A CN201010604929 A CN 201010604929A CN 102544536 A CN102544536 A CN 102544536A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- fused salt
- inorganic fused
- licl
- constituent element
- 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.)
- Pending
Links
Images
Classifications
-
- Y02E60/12—
Landscapes
- Conductive Materials (AREA)
Abstract
The invention relates to electrolyte for a thermal battery and provided with 4-component inorganic fused salt, which comprises the following components by mass: 20% to 25% of LiBr, 12% to 18% of KBr, 25% to 30% of CsBr and 27% to 43% of LiI. The electrolyte is 60-mesh powder. The 4-component inorganic fused salt electrolyte LiBr-KBr-CsBr-LiI is adopted, the melting point is only 236.4 DEG C which is 115.0 DEG C lower than that of the traditional 2-component inorganic fused salt electrolyte KCl-LiCl, the melting heat is only 32.3 J/g which is 11.0% of that of the traditional 2-component inorganic fused salt electrolyte KCl-LiCl, the conductivity is larger than 0.1S/cm, the effective working temperature range of the thermal battery can be expanded from 400-600 DEG C to 250-600 DEG C, and the effective temperature range increases by 150 DEG C.
Description
Technical field
The invention belongs to technical field of electrochemistry, particularly relate to a kind of thermal cell and use electrolyte with four constituent element inorganic fused salts.
Background technology
Thermal cell be with solid-solid inorganic salt as the electrolytical primary cell of stocking, have the advantages that stability and reliability height and storage life are grown.Under the room temperature, the solid-solid inorganic salt electrolyte is non-conductive, and the inorganic salts electrolyte that is molten condition after the material-to-be-heated heating has high ionic conductivity, and at this moment, cell just can outwards have been exported energy.
After the activation, the electrical property characteristic of thermal cell depends on the electrochemical system of cell, and the Several Factors such as structure of battery.In a single day thermal cell is activated, as long as electrolyte keeps molten condition, thermal cell is just in running order, till participation reactive activity material is exhausted.In addition on the one hand, even active material is excessive, but because the lost electrolyte that causes of thermal cell internal heat solidifies again, thermal cell also can quit work.
Therefore, after activation, guarantee that thermal cell can operate as normal just must possess following two primary conditions: the battery cell electrode material that (1) is suitable and enough negative poles and positive electrode quantity; (2) shape of entire cell, and the type of wherein used heat-barrier material and quantity.
Thermal cell is custom-designed for satisfying concrete electrical property.These concrete performances not only comprise output voltage, output current, the working life after the activation, activationary time etc.; Also comprise storage environmental condition, activate working environment, mount method, battery surface temperature, active mode and activation energy or the like.Along with the difference of thermal cell electrical characteristics demand, thermal cell uses molten salt electrolyte to be very different.
Serge Schoeffert had studied thermal cell modeling (Serge Schoeffert " Thermalbatteries modeling, self-discharge and self-heating " in 2005; Journal of PowerSources 142 (2005) 361-369).KCl-LiCl and LiF-LiCl-LiBr inorganic fused salt electrolyte have mainly been used in this research, and purpose is to solve self discharge and from heating problems.
Patrick Masset had studied the thermal cell electrolyte (PatrickMasset based on iodide in 2006; " Iodied-based electrolytes:A promising alternative for thermalbatteries "; Journal of Power Sources 160 (2006) 688-697).This report has mainly been studied two constituent elements, three constituent elements and four constituent element inorganic fused salt electrolyte.The two constituent element electrolyte that are studied mainly contain: fusing point is 354 ℃ 55.2%KCl-44.8%LiCl, and fusing point is 260 ℃ 58.2%LiI-41.8%KI, and fusing point is 368 ℃ 14.4%LiCl-85.6%.The three constituent element electrolyte that are studied mainly contain: fusing point is 443 ℃ 9.6%LiF-22%LiCl-68.4%LiBr; Fusing point is 312 ℃ 0.67%LiF-53.5%LiBr-45.83%KBr; Fusing point is 312 ℃ 0.81%LiF-56%LiBr-43.18%KBr; Fusing point is 341 ℃ 3.2%LiF-13%LiCl-83.8%LiI, and fusing point is 265 ℃ 2.6%LiCl-57.3%LiI-40.1%KI.The four constituent element electrolyte that are studied are that fusing point is 360 ℃ 4.9%LiF-11.2%LiCl-34.9%LiBr-49%LiI.
Obviously, can confirm to use the electrolytical thermal cell exemplary operation of KCl-LiCl inorganic fused salt temperature range through document comparison research is 400 ℃～600 ℃; Using the electrolytical thermal cell exemplary operation of LiF-LiCl-LiBr inorganic fused salt temperature range is 500 ℃～600 ℃.These two kinds of electrolyte working temperature upper limits can not surpass the decomposition temperature of positive electrode, and therefore in fact effective operation temperature area of thermal cell is very narrow, has seriously limited the raising of battery discharge time and specific energy and specific power.In addition, under the acting in conjunction of dynamic mechanical loads such as high temperature and radial centrifugal force, contained lithium metal or alloy and liquefaction thereof in the thermal cell lithium alloy negative material and be thrown out of cause the thermal cell short circuit, burn, and injure the safety of single unit system.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art; Provide a kind of thermal cell to use electrolyte with four constituent element inorganic fused salts; This electrolyte has that fusing point is low, conductivity is high, widens battery operated warm area, raising battery specific energy and application safety performance, and the characteristics that prolong battery service life.
The thermal cell that the present invention has four constituent element inorganic fused salts adopts following technical scheme with electrolyte:
A kind of thermal cell with four constituent element inorganic fused salts is used electrolyte, comprises LiBr, KBr, and CsBr and LiI, said mass percentage content: LiBr are 20%～25%, and KBr is 12%～18%, and CsBr is 25%～30%, and LiI is 27%～43%.
And said electrolyte is 60 order powder.
Advantage that the present invention has and good effect:
The present invention adopts four constituent element inorganic fused salt electrolyte LiBr-KBr-CsBr-LiI, and fusing point only is 236.4 ℃, low 115.0 ℃ than two traditional constituent element inorganic fused salt electrolyte KCl-LiCl; Its melting heat has only 32.3J/g, has only 11.0% of traditional two constituent element inorganic fused salt electrolyte KCl-LiCl; Conductivity is greater than 0.1S/cm; Effective operation temperature area that can make thermal cell expands to 250 ℃～600 ℃ from 400 ℃-600 ℃, and effectively warm area has increased by 150 ℃.
Description of drawings
Fig. 1 has the thermal cell of four constituent element inorganic fused salts with electrolysis Mass Thermal Analysis curve chart for the present invention;
Fig. 2 has the thermal cell of four constituent element inorganic fused salts with electrolytic conductivity-temperature relation curve chart for the present invention;
Fig. 3 is two constituent element inorganic fused salt electrolyte KCl-LiCl thermal analysis curve figure in the prior art;
Fig. 4 is two constituent element inorganic fused salt electrolyte KCl-LiCl conductivity-temperature relation curve charts in the prior art.
Embodiment
Below in conjunction with accompanying drawing and through specific embodiment the present invention is made further detailed description, following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
LiCl among the present invention, LiBr, KBr, CsBr and LiI are the pure medicines of the analysis of chemicals market purchasing, use precision as five kinds of medicines of the electronic scale of 0.001g or the required composition of equivalent weighing utensil weighing and put into the general chemistry porcelain crucible; Main preparation methods is to put into the conventional, electric-resistance crucible furnace that operation temperature area can reach 1000 ℃ to the chemical porcelain crucible that fills the good medicine of weighing; In argon gas or nitrogen atmosphere, cure; Sintering temperature is in 500 ℃～600 ℃ scopes, and roasting time is controlled at 1h～10h.Stir the electrolyte melt reach roasting time with quartz pushrod, mixing time is about 1 minute, in stove, takes out crucible then, and is poured on electrolyte melt rapidly on the corrosion resistant plate and in the glove box of argon gas or nitrogen protection, cools off.Grind to form 60 purpose powder to cooled melt piece and promptly obtain described four constituent element inorganic fused salt electrolyte.
Embodiment
The LiBr of weighing 22.5g, the KBr of 15.4g, the CsBr of 27.5g and the LiI of 34.6g; Put into the general chemistry porcelain crucible, put into the conventional, electric-resistance crucible furnace that operation temperature area can reach 1000 ℃ to the chemical porcelain crucible that fills the good medicine of weighing, in argon gas or nitrogen atmosphere, cure; Sintering temperature is 540 ℃; Roasting 2h stirs electrolyte melt with quartz pushrod then, and mixing time is about 1 minute; In stove, take out crucible then, and be poured on electrolyte melt rapidly on the corrosion resistant plate and in the glove box of argon gas or nitrogen protection, cool off.Grind to form 60 purpose powder to cooled melt piece and promptly obtain described four constituent element inorganic fused salt electrolyte LiBr-KBr-CsBr-LiI.
Adopt SETARAM SETSYS EVOLUTION 16/18 thermogravimetric synthesis analyzer that four constituent element inorganic fused salt electrolyte LiBr-KBr-CsBr-LiI are done the fusing point test, use the Al2O3 crucible, analyze atmosphere and adopt argon gas, 10 ℃/min of heating rate test.Test out the thermal cell that the present invention shown in Figure 1 has four constituent element inorganic fused salts and begin fusing with electrolyte at 236.4 ℃, melting heat is 32.3J/g.
Use the DDS-302B type electric conductivity appearance of measuring range, and to select the conductance electrode long number for use be that 10 platinum black electrode is done the conductivity test at 100 μ S/cm～2S/cm.Test out thermal cell that the present invention shown in Figure 2 has four constituent element inorganic fused salts with electrolytic conductivity-temperature relation curve chart.
Comparative Examples
From analytically pure medicine KCl of chemicals market purchasing and LiCl.55.2g KCl and the LiCl of 44.8g, put into the general chemistry porcelain crucible.Put into the conventional, electric-resistance crucible furnace that operation temperature area can reach 1000 ℃ to the chemical porcelain crucible that fills the good medicine of weighing, in air atmosphere, cure, sintering temperature is 540 ℃, and roasting time is 2h.Stir electrolyte melt with quartz pushrod behind the roasting 2h, mixing time is about 1 minute, in stove, takes out crucible then, and is poured on electrolyte melt rapidly on the corrosion resistant plate and in the normal atmospheric environment, cools off.Grind to form 60 purpose powder to cooled melt piece and promptly obtain two constituent element inorganic fused salt electrolyte KCl-LiCl.
Adopt SETARAM SETSYS EVOLUTION 16/18 thermogravimetric synthesis analyzer that three constituent element inorganic fused salt electrolyte KCl-LiCl are done the fusing point test, use the Al2O3 crucible, analyze atmosphere and adopt argon gas, 10 ℃/min of heating rate.Through test, the KCl-LiCl electrolyte just begins fusing at 351.4 ℃, and melting heat is up to 294.1J/g.
Use the DDS-302B type electric conductivity appearance of measuring range, and to select the conductance electrode long number for use be that 10 platinum black electrode is done the conductivity test at 100 μ S/cm～2S/cm.Accompanying drawing 4 is three constituent element inorganic fused salt electrolyte KCl-LiCl conductivity-temperature relation curve charts of Comparative Examples.
Can know from above result: because the present invention adopts four constituent element inorganic fused salt electrolyte LiBr-KBr-CsBr-LiI, fusing point only is 236.4 ℃, low 115.0 ℃ than two traditional constituent element inorganic fused salt electrolyte KCl-LiCl; Its melting heat has only 32.3J/g, has only 11% of traditional two constituent element inorganic fused salt electrolyte KCl-LiCl; Conductivity is greater than 0.1S/cm; Effective operation temperature area that can make thermal cell expands to 250 ℃～600 ℃ from 400 ℃-600 ℃, and effectively warm area has increased by 150 ℃.
Claims (2)
1. the thermal cell with four constituent element inorganic fused salts is used electrolyte, it is characterized in that: comprise LiBr, KBr; CsBr and LiI medicine, said mass percentage content: LiBr are 20%～25%, and KBr is 12%～18%; CsBr is 25%～30%, and LiI is 27%～43%.
2. the thermal cell with four constituent element inorganic fused salts according to claim 1 is used electrolyte, it is characterized in that: said electrolyte is 60 order powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106049297A CN102544536A (en) | 2010-12-24 | 2010-12-24 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106049297A CN102544536A (en) | 2010-12-24 | 2010-12-24 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102544536A true CN102544536A (en) | 2012-07-04 |
Family
ID=46350911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106049297A Pending CN102544536A (en) | 2010-12-24 | 2010-12-24 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102544536A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122510A (en) * | 2021-11-25 | 2022-03-01 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572909A (en) * | 2003-06-24 | 2005-02-02 | 住友电气工业株式会社 | Molten salt bath for electroforming and method of manufacturing metal product using the same |
-
2010
- 2010-12-24 CN CN2010106049297A patent/CN102544536A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572909A (en) * | 2003-06-24 | 2005-02-02 | 住友电气工业株式会社 | Molten salt bath for electroforming and method of manufacturing metal product using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122510A (en) * | 2021-11-25 | 2022-03-01 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
| CN114122510B (en) * | 2021-11-25 | 2024-03-19 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chung et al. | Mechanical and thermal failure induced by contact between a Li1. 5Al0. 5Ge1. 5 (PO4) 3 solid electrolyte and Li metal in an all solid-state Li cell | |
| Xu et al. | Enhanced performance of a lithium–sulfur battery using a carbonate‐based electrolyte | |
| Tanibata et al. | Preparation and characterization of highly sodium ion conducting Na 3 PS 4–Na 4 SiS 4 solid electrolytes | |
| JP5580457B2 (en) | Molten salt and thermal battery | |
| Fukunaga et al. | Intermediate-temperature ionic liquid NaFSA-KFSA and its application to sodium secondary batteries | |
| EP3201976B1 (en) | Electrolytes for calcium-based secondary cell and calcium-based secondary cell comprising the same | |
| Zhao et al. | High-performance antimony–bismuth–tin positive electrode for liquid metal battery | |
| US11342580B2 (en) | Solid electrolyte for all-solid sodium battery, and all-solid sodium battery | |
| JP5990703B2 (en) | ION CONDUCTIVE GLASS CERAMIC, PROCESS FOR PRODUCING THE SAME, AND ALL-SOLID BATTERY CONTAINING THE SAME | |
| CN107086300B (en) | It is a kind of for the negative electrode material of sodium-ion battery and its preparation and application | |
| Saffirio et al. | Li1. 4Al0. 4Ge0. 4Ti1. 4 (PO4) 3 promising NASICON-structured glass-ceramic electrolyte for all-solid-state Li-based batteries: Unravelling the effect of diboron trioxide | |
| CN104810545B (en) | Phosphate lithium fast-ionic conductor material and preparation method thereof | |
| CN105047889B (en) | A kind of method for preparing lithium sulfur battery anode material | |
| CN109786842A (en) | A kind of high safety high-energy-density lithium/fluorocarbons battery preparation method | |
| Yang et al. | Advanced intermediate temperature sodium copper chloride battery | |
| CN102544535A (en) | Electrolyte for thermal battery and provided with 5-component inorganic fused salt | |
| CN104868179A (en) | Rechargeable aluminum ion fused salt battery and preparation method thereof | |
| CN102569836A (en) | Preparation method of quadruple inorganic molten salt electrolyte | |
| WO2016050331A1 (en) | Calcium-based secondary cell and battery comprising the same | |
| CN106972162A (en) | A kind of sodium-ion battery double-doped hard carbon microballoon of negative material phosphorus sulphur and preparation method thereof | |
| Jhang et al. | Stable all-solid-state sodium-sulfur batteries for low-temperature operation enabled by sodium alloy anode and confined sulfur cathode | |
| CN102544482A (en) | Formula of thermal battery CoS2 cathode material and processing technology | |
| CN104064824A (en) | Water system rechargeable battery | |
| CN103825058A (en) | Novel paste electrolyte used for high-temperature molten salt battery and preparation method thereof | |
| CN110148779B (en) | Application of LiI-KI eutectic salt in low-temperature liquid molten salt lithium battery, low-temperature liquid molten salt lithium battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |