CN106328966A - Thermal battery electrolyte containing metal particles and preparation method and application of thermal battery electrolyte - Google Patents
Thermal battery electrolyte containing metal particles and preparation method and application of thermal battery electrolyte Download PDFInfo
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- CN106328966A CN106328966A CN201610729883.9A CN201610729883A CN106328966A CN 106328966 A CN106328966 A CN 106328966A CN 201610729883 A CN201610729883 A CN 201610729883A CN 106328966 A CN106328966 A CN 106328966A
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- thermal battery
- battery electrolyte
- containing metal
- electrolyte
- metal particle
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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
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Abstract
The invention relates to a thermal battery electrolyte containing metal particles and a preparation method and application of the thermal battery electrolyte, and belongs to the technical field of electrochemical energy. The thermal battery electrolyte containing the metal particles is a non-conducting solid at a room temperature and comprises a multi-component salt and the metal particles; and the metal particles are uniformly distributed in the multi-component salt. The preparation method comprises the steps of preparing the metal particles and the multi-component salt according to set components; and mixing the metal particles and the multi-component salt evenly to obtain the electrolyte. When the thermal battery electrolyte is used for a thermal battery, the thermal battery electrolyte shows excellent electrochemical properties. The thermal battery electrolyte is reasonable in component design; the preparation technology is simple; and large-scale application is facilitated.
Description
Technical field
The present invention relates to thermal battery electrolyte of a kind of containing metal particle and its preparation method and application；Belong to electrochemical energy
Source technology field.
Background technology
It is big that thermal cell has specific energy, and specific power is high, self discharge is little, stores the time long, activates the most reliable, it is adaptable to each
Kind of harsh conditions, it is simple, convenient to use, it is not necessary to change and the advantage such as maintenance.Therefore thermal cell becomes sophisticated weapon manages most
One of supporting power supply thought, is widely used in the weaponrys such as guided missile, nuclear weapon, cannon, and its application constantly expands, and progressively expands
Exhibition is to fields such as aircraft emergency power supply, underground high temperature mine locating power supply, underwater ordnance electrical source of power, fire alarm power supplys.
Along with the development of thermal cell system, electrolyte is from early stage Ca system's thermal cell and Mg system thermal cell LiCl-KCl binary
Salt progressively develops into Li system thermal cell LiCl-LiBr-KBr and LiF-LiCl-LiBr ternary salt.
But either LiCl-KCl, or can there is negative material electric discharge in LiCl-LiBr-KBr and LiF-LiCl-LiBr
The situation of capacity loss.
Summary of the invention
Present invention finds a kind of effective discharge capacity height, the containing metal particle of battery mid-early stage pulsed discharge function admirable
Thermal battery electrolyte and its preparation method and application.
The thermal battery electrolyte of a kind of containing metal particle of the present invention；The thermal battery electrolyte of described containing metal particle is at room temperature
It it is down solid insulator；It includes polybasic salt and metallic particles；Described metallic particles is evenly distributed in polybasic salt.
Preferably, the thermal battery electrolyte of a kind of containing metal particle of the present invention；Described metallic particles selected from magnesium powder,
At least one in aluminium powder, iron powder, copper powder.It is preferably at least one in magnesium powder, aluminium powder.
Preferably, the thermal battery electrolyte of a kind of containing metal particle of the present invention；The granularity of described metallic particles is
5-100 micron, preferably 15-70 micron, more preferably 5-30 micron.
The thermal battery electrolyte of a kind of containing metal particle of the present invention；In described thermal battery electrolyte, the quality of metallic particles is
The 0.5%-5% of polybasic salt quality, preferably 2-5%, more preferably 3-5%.
The thermal battery electrolyte of a kind of containing metal particle of the present invention；Described polybasic salt is binary salt or ternary salt.
Preferably, described binary salt is LiCl-KCl.
Preferably, described ternary salt is in LiCl-LiBr-KBr ternary salt, LiF-LiCl-LiBr ternary salt
One.
The thermal battery electrolyte of a kind of containing metal particle of the present invention；Described polybasic salt is conventional thermoelectric pond electrolyte.
Preferably, the thermal battery electrolyte of a kind of containing metal particle of the present invention；Described polybasic salt is LiCl-
LiBr-KBr or LiF-LiCl-LiBr.
Preferably, the thermal battery electrolyte of a kind of containing metal particle of the present invention；It include polybasic salt, magnesium oxide and
Metallic particles；Described metallic particles is evenly distributed in the electrolyte being made up of magnesium oxide and polybasic salt.As the most excellent
Selecting scheme, the quality of described magnesium oxide is the 35%-60% of polybasic salt quality.The Functionality, quality and appealing design of described magnesium oxide elects polybasic salt matter as
Amount 45%-55%, more preferably 50%.
The preparation method of the thermal battery electrolyte of a kind of containing metal particle of the present invention, comprises the steps:
The metallic particles and polybasic salt taken will be joined by setting component；Mix homogeneously, obtains described electrolyte.
When in the thermal battery electrolyte of a kind of containing metal particle of the present invention containing magnesium oxide time, phase preparation method, including under
State step:
Metallic particles, magnesium oxide and the polybasic salt taken will be joined by setting component；Under vacuum condition, melting mixing is uniform,
To described electrolyte.
The application of the thermal battery electrolyte of a kind of containing metal particle of the present invention；It is used for thermoelectricity as electrolyte including by described
Pond.
The application of the thermal battery electrolyte of a kind of containing metal particle of the present invention；The negative pole of described thermal cell is Li alloy.Make
For the most preferably, the electrolyte of described thermal cell is by the one in LiCl-LiBr-KBr, LiF-LiCl-LiBr and metal
Granule forms.
The application of the thermal battery electrolyte of a kind of containing metal particle of the present invention, described Li alloy is LiAl alloy, LiSi conjunction
Gold, LiB alloy.
With the electrolyte designed by the present invention as electrolyte, with the LiB alloy of 61wt.% as negative material, with CoS2For
Positive electrode, constant-current discharge under 520 DEG C of different electric current densities, by the appearance of effectively discharging of the 75% calculating battery being discharged to peak pressure
Amount,
With the mixture of conventional LiF-LiCl-LiBr and magnesium oxide, as electrolyte, (quality of magnesium oxide accounts for polybasic salt quality
50%), with the LiB alloy of 61wt.% as negative material, with CoS2For positive electrode, perseverance under 520 DEG C of different electric current densities
Banish electricity, by effective discharge capacity of the 75% calculating battery being discharged to peak pressure,
Contrast finds, at 200mA/cm2、500mA/cm2、1000mA/cm2Under electric current density, use designed by the present invention
The thermal cell of electrolyte is respectively increased compared to the conventional LiF-LiCl-LiBr effective discharge capacity of the thermal cell as electrolyte
575C.g-1、1074C.g-1、767C.g-1。
When the thermal battery electrolyte of a kind of containing metal particle of the present invention is as thermal cell；Can be widely applied to for guided missile,
The field such as Underwater Battery and nuclear weapon.
Advantage
The present invention breaks through conventional thought, by adding metallic particles in conventional thermal cell electrolyte, achieves expectation
Less than effect.
Due to the fact that and take above technical scheme, it has the advantage that
1, a small amount of additive just can be greatly improved effective discharge capacity of thermal cell especially Li system thermal cell and improves
Thermal cell mid-early stage pulsed discharge performance.
2, designed electrolyte stable performance, preparation manipulation is simple.
3, designed electrolyte wide material sources, low price, environmentally safe.
Accompanying drawing explanation
Fig. 1 is electrolyte prepared by embodiment 1 when being used as Li system thermal cell with conventional electrolysis matter, at 520 DEG C of different electric currents
Effective discharge capacity curve under density.
Fig. 2 is electrolyte prepared by embodiment 2 when being used as Li system thermal cell with conventional electrolysis matter, at 520 DEG C of different electric currents
Effective discharge capacity curve under density.
Fig. 3 is electrolyte prepared by embodiment 3 when being used as Li system thermal cell with conventional electrolysis matter, at 520 DEG C of different electric currents
Pulsed discharge lower voltage limit curve under density.
In Fig. 1,1# curve is effective discharge capacity curve of comparative example 1 gained thermal cell, and 2# curve is that embodiment 1 is made
Effective discharge capacity curve of standby electrolyte thermal battery；From figure 1 it appears that at 200mA/cm2、500mA/cm2、1000mA/
cm2Under electric current density, the vertical coordinate of the corresponding point of 2# curve is respectively with the difference of the vertical coordinate of the corresponding point of 1# curve
575C.g-1、1074C.g-1、767C.g-1, i.e. effectively discharge capacity has been respectively increased 575C.g-1、1074C.g-1、767C.g-1。
In Fig. 2,1# curve is effective discharge capacity curve of comparative example 1 gained thermal cell, and 2# curve is that embodiment 2 is made
Effective discharge capacity curve of standby electrolyte thermal battery；From figure 2 it can be seen that at 50mA/cm2、100mA/cm2、200mA/
cm2、500mA/cm2Under electric current density, the vertical coordinate of the corresponding point of 2# curve divides with the difference of the vertical coordinate of the corresponding point of 1# curve
Wei 1274C.g-1、837C.g-1、316C.g-1、296C.g-1.The most effective discharge capacity has been respectively increased 1274C.g-1、
837C.g-1、316C.g-1、296C.g-1。
In Fig. 3,1# curve is that comparative example 3 gained thermal cell is at 600mA/cm2Ration the power supply under electric discharge under pulse current density
Pressure, 2# curve are that electrolyte thermal battery prepared by example 3 is at 600mA/cm2Electric discharge lower voltage limit under pulse current density, 3#
Curve is that comparative example 3 gained thermal cell is at 1200mA/cm2Electric discharge lower voltage limit under pulse current density, 4# curve are example 3
Prepared electrolyte thermal battery is at 1200mA/cm2Electric discharge lower voltage limit under pulse current density, 5# curve are comparative example 3 institute
Obtain thermal cell at 2400mA/cm2Electric discharge lower voltage limit under pulse current density, 6# curve are electrolyte prepared by example 3
Thermal cell is at 2400mA/cm2Electric discharge lower voltage limit under pulse current density.As can be seen from Figure 3 600mA/cm2、
1200mA/cm2And 2400mA/cm2Under pulse current density, the Li system thermal cell prepared by inventive embodiments 3 is relative to common Li
It is thermal cell, all significantly improves at mid-early stage pulsed discharge lower voltage limit.Therefore at Li system thermal cell LiF-LiCl-LiBr electricity
Xie Zhizhong adds aluminum (Al) flour additive agent and significantly improves battery mid-early stage pulsed discharge performance.
Detailed description of the invention
The additive of a kind of Li system thermal battery electrolyte is metal simple-substance powder, addition be electrolyte quality 0.5～
5.0wt.%.As added 4.0wt.% magnesium (Mg) flour additive agent in LiF-LiCl-LiBr, the effective discharge capacity of battery improves
575～1074C.g-1。
The additive of a kind of Li system thermal battery electrolyte is metal simple-substance powder, addition be electrolyte quality 0.5～
5.0wt.%.As added 5.0wt.% aluminum (Al) flour additive agent in LiF-LiCl-LiBr, the effective discharge capacity of battery improves
296～1274C.g-1。
Metal simple-substance powder is one or more in magnesium (Mg) powder, aluminum (Al) powder, ferrum (Fe) powder, copper (Cu) powder.
Using method: metal simple-substance powder is added directly in Li system thermal battery electrolyte, needs additive before using
Uniformly mix with electrolyte.
Additive is applicable to Li alloy anode thermal cell.
Example 1
Li system thermal cell with LiF-LiCl-LiBr electrolyte with by mass percentage:
LiF 9.56%；
LiCl 22%；
LiBr 68.44%.
4.0wt.% (accounting for LiF-LiCl-LiBr electrolyte quality) is added in Li system thermal cell LiF-LiCl-LiBr
Magnesium powder (granularity of magnesium powder is 75 microns), add and account for the magnesium oxide of LiF-LiCl-LiBr mass 50%, use Central South University Liu
Zhi Jian seminar produce negative material be Li content be the LiB alloy of 61wt.%, positive electrode is CoS2；Then at 520 DEG C
Constant-current discharge under different electric current densities, by effective discharge capacity of the 75% calculating battery being discharged to peak pressure, repetitive measurement, makes even
Average, then draw voltage-capacity curve, test result is as shown in 2# curve in Fig. 1.
Comparative example 1
The uniform embodiment of other conditions 1 is consistent, does not simply add magnesium powder；After its products obtained therefrom is assembled into thermal cell, survey
Trying its performance, its test result is as shown in 1# curve in Fig. 1.
From example 1 and comparative example 1 it can be seen that after adding magnesium powder LiF-LiCl-LiBr, Li system thermal cell effectively discharges
Capacity significantly improves, wherein 200mA/cm2、500mA/cm2、1000mA/cm2Effective discharge capacity powder under electric current density be you can well imagine
High 575C.g-1、1074C.g-1、767C.g-1.Therefore, at Li system thermal cell with LiF-LiCl-LiBr electrolyte adds magnesium
(Mg) powder can significantly improve effective discharge capacity.
Example 2
Li system thermal cell with LiF-LiCl-LiBr electrolyte with by mass percentage:
LiF 9.56%；
LiCl 22%；
LiBr 68.44%.
5.0wt.% (accounting for LiF-LiCl-LiBr electrolyte quality) is added in Li system thermal cell LiF-LiCl-LiBr
Aluminium powder (granularity of aluminium powder is 100 microns), add and account for the magnesium oxide of LiF-LiCl-LiBr mass 50%, use Central South University
The negative material that Liu Zhi heavily fortified point seminar produces be Li content be the LiB alloy of 61wt.%, positive electrode is CoS2；Then 520
Constant-current discharge under DEG C different electric current densities.By effective discharge capacity of the 75% calculating battery being discharged to peak pressure, repetitive measurement, take
Meansigma methods, then draw voltage-capacity curve, test result is as shown in 2# curve in Fig. 2.
Comparative example 2
The uniform embodiment of other conditions 2 is consistent, does not simply add aluminium powder；1# curve in its gained test result such as Fig. 2
Shown in.
From example 2 and comparative example 2 it can be seen that after adding aluminium powder LiF-LiCl-LiBr electrolyte, Li system thermal cell has
Effect discharge capacity significantly improves, wherein 50mA/cm2、100mA/cm2、200mA/cm2、500mA/cm2Effective under electric current density
Discharge capacity powder does not improve 1274C.g-1、837C.g-1、316C.g-1、296C.g-1.Therefore, at Li system thermal cell LiF-
LiCl-LiBr adds aluminum (Al) powder and can significantly improve effective discharge capacity.
Example 3
Li system thermal cell with LiF-LiCl-LiBr electrolyte with by mass percentage:
LiF 9.56%；
LiCl 22%；
LiBr 68.44%.
5.0wt.% (accounting for LiF-LiCl-LiBr electrolyte quality) is added in Li system thermal cell LiF-LiCl-LiBr
Aluminium powder (granularity of aluminium powder is 20 microns), add and account for the magnesium oxide of LiF-LiCl-LiBr mass 50%, use Central South University Liu
Zhi Jian seminar produce negative material be Li content be the LiB alloy of 61wt.%, positive electrode is CoS2；Then at 520 DEG C
Carry out pulsed discharge, recording impulse electric discharge lower voltage limit, repetitive measurement under different electric current densities, average, then draw voltage
Curve.Test result is as shown in Figure 3.
Comparative example 3
The uniform embodiment of other conditions 3 is consistent, does not simply add aluminium powder；Its gained test result is as shown in Figure 3.
By comparative example 3 and example 3 it can be seen that LiF-LiCl-LiBr adds after additive, 600mA/cm2、
1200mA/cm2And 2400mA/cm2Li system thermal cell mid-early stage pulsed discharge lower voltage limit under pulse current density the most substantially carries
High.Therefore in Li system thermal cell LiF-LiCl-LiBr electrolyte, add aluminum (Al) powder can significantly improve battery mid-early stage
Pulsed discharge performance.
Claims (10)
1. the thermal battery electrolyte of a containing metal particle；It is characterized in that: the thermal battery electrolyte of described containing metal particle exists
It it is solid insulator under room temperature；It includes polybasic salt and metallic particles；Described metallic particles is evenly distributed in polybasic salt.
The thermal battery electrolyte of a kind of containing metal particle the most according to claim 1；It is characterized in that: described containing metal
The 0.5%-5% that quality is polybasic salt quality of metallic particles in the thermal battery electrolyte of grain.
The thermal battery electrolyte of a kind of containing metal particle the most according to claim 2；It is characterized in that: the grain of metallic particles
Degree is 5-100 micron.
The thermal battery electrolyte of a kind of containing metal particle the most according to claim 3；It is characterized in that: described metallic particles
At least one in magnesium powder, aluminium powder, iron powder, copper powder.
5. according to the thermal battery electrolyte of a kind of containing metal particle described in claim 1-4 any one；It is characterized in that: institute
Stating polybasic salt is binary salt or ternary salt.
The thermal battery electrolyte of a kind of containing metal particle the most according to claim 5；It is characterized in that:
Described binary salt is LiCl-KCl；
Described ternary salt one in LiCl-LiBr-KBr, LiF-LiCl-LiBr.
The thermal battery electrolyte of a kind of containing metal particle the most according to claim 5；It is characterized in that:
Described polybasic salt is LiCl-LiBr-KBr or LiF-LiCl-LiBr.
8. prepare the method for thermal battery electrolyte as described in claim 1,2,3,4,6,7 any one for one kind, it is characterised in that
Comprise the steps:
The metallic particles and polybasic salt taken will be joined by setting component；Mix homogeneously, obtains described electrolyte.
9. the application of thermal battery electrolyte as described in claim 1,2,3,4,6,7 any one, it is characterised in that: include
The thermal battery electrolyte of described containing metal particle is used for thermal cell.
The application of the thermal battery electrolyte of a kind of containing metal particle the most according to claim 9；It is characterized in that: described
The negative pole of thermal cell is Li alloy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110233258A (en) * | 2019-06-20 | 2019-09-13 | 湖南锐林新能源科技有限公司 | A kind of thermal cell modified lithium boron alloy composite negative pole material and preparation method thereof |
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| US20090047573A1 (en) * | 2007-08-14 | 2009-02-19 | Millennium Engineering And Integration Company | Chloride-free thermal batteries using molten nitrate electrolytes |
| US20100092851A1 (en) * | 2007-08-14 | 2010-04-15 | Millennium Engineering And Integration Company | Chloride-free, sodium ion-free, and water-free thermal batteries using molten nitrate electrolytes |
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