CN106328966B - A kind of thermal battery electrolyte of containing metal particle and its preparation method and application - Google Patents

A kind of thermal battery electrolyte of containing metal particle and its preparation method and application Download PDF

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CN106328966B
CN106328966B CN201610729883.9A CN201610729883A CN106328966B CN 106328966 B CN106328966 B CN 106328966B CN 201610729883 A CN201610729883 A CN 201610729883A CN 106328966 B CN106328966 B CN 106328966B
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electrolyte
thermal battery
metal particle
licl
battery electrolyte
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CN106328966A (en
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刘志坚
曾鹏
黄海锋
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Central South University
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Central South University
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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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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to thermal battery electrolytes of a kind of containing metal particle and its preparation method and application；Belong to electrochemical energy technical field.The thermal battery electrolyte of containing metal particle designed by the present invention is nonconducting solid at normal temperature；It includes polybasic salt and metallic particles；The metallic particles is evenly distributed in polybasic salt.Preparation method are as follows: the metallic particles and polybasic salt taken will be distributed by setting group；It is uniformly mixed, obtains the electrolyte.When thermal battery electrolyte designed by the present invention is used for thermal cell, excellent chemical property is shown.Rationally, preparation process is simple for instant component design, convenient for large-scale application.

Description

A kind of thermal battery electrolyte of containing metal particle and its preparation method and application
Technical field
The present invention relates to thermal battery electrolytes of a kind of containing metal particle and its preparation method and application；Belong to electrochemical energy Source technology field.
Background technique
Thermal cell has specific energy big, and specific power is high, self discharge is small, and storage time is long, and activation is reliable rapidly, is suitable for each Kind of harsh conditions do not need the advantages that replacing and safeguarding using simple, conveniently.Therefore thermal cell becomes sophisticated weapon most manages One of mating power supply thought is widely used in the weaponrys such as guided missile, nuclear weapon, cannon, and application field constantly expands, and gradually expands Open up the fields such as aircraft emergency power supply, underground high temperature mine locating power supply, underwater ordnance electrical source of power, fire alarm power supply.
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 gradually develops to Li system thermal cell LiCl-LiBr-KBr and LiF-LiCl-LiBr ternary salt.
But either LiCl-KCl or LiCl-LiBr-KBr and LiF-LiCl-LiBr can have negative electrode material electric discharge The case where 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.
A kind of thermal battery electrolyte of containing metal particle of the present invention；The thermal battery electrolyte of the containing metal particle is in room temperature It is down solid insulator；It includes polybasic salt and metallic particles；The metallic particles is evenly distributed in polybasic salt.
Preferably, a kind of thermal battery electrolyte of containing metal particle of the present invention；The metallic particles be selected from magnesium powder, At least one of aluminium powder, iron powder, copper powder.Preferably at least one of magnesium powder, aluminium powder.
Preferably, a kind of thermal battery electrolyte of containing metal particle of the present invention；The granularity of the metallic particles is 5-100 microns, preferably 15-70 microns, further preferably 5-30 microns.
A kind of thermal battery electrolyte of containing metal particle of the present invention；The quality of metallic particles is in the thermal battery electrolyte The 0.5%-5% of polynary salt quality, preferably 2-5%, further preferably 3-5%.
A kind of thermal battery electrolyte of containing metal particle of the present invention；The polybasic salt is binary salt or ternary salt.
Preferably, the binary salt is LiCl-KCl.
Preferably, the ternary salt is in LiCl-LiBr-KBr ternary salt, LiF-LiCl-LiBr ternary salt One kind.
A kind of thermal battery electrolyte of containing metal particle of the present invention；The polybasic salt is conventional thermoelectric pond electrolyte.
Preferably, a kind of thermal battery electrolyte of containing metal particle of the present invention；The polybasic salt is LiCl- LiBr-KBr or LiF-LiCl-LiBr.
Preferably, a kind of thermal battery electrolyte of containing metal particle of the present invention；It include polybasic salt, magnesia and Metallic particles；The metallic particles is evenly distributed in the electrolyte being made of magnesia and polybasic salt.As further excellent Scheme is selected, the quality of the magnesia is the 35%-60% of polynary salt quality.The quality of the magnesia is preferably polybasic salt matter Measure 45%-55%, further preferably 50%.
A kind of preparation method of the thermal battery electrolyte of containing metal particle of the present invention, includes the following steps:
The metallic particles and polybasic salt taken will be distributed by setting group；It is uniformly mixed, obtains the electrolyte.
When containing magnesia in a kind of thermal battery electrolyte of containing metal particle of the present invention, phase preparation method, including under State step:
Metallic particles, magnesia and the polybasic salt taken will be distributed by setting group；Under vacuum condition, melting mixing is uniform, obtains To the electrolyte.
A kind of application of the thermal battery electrolyte of containing metal particle of the present invention；Including being used for thermoelectricity as electrolyte for described Pond.
A kind of application of the thermal battery electrolyte of containing metal particle of the present invention；The cathode of the thermal cell is Li alloy.Make To be further preferred, the electrolyte of the thermal cell is by one of LiCl-LiBr-KBr, LiF-LiCl-LiBr and metal Particle composition.
A kind of application of the thermal battery electrolyte of containing metal particle of the present invention, the Li alloy are LiAl alloy, LiSi conjunction Gold, LiB alloy.
Using electrolyte designed by the present invention as electrolyte, using the LiB alloy of 61wt.% as negative electrode material, with CoS2For Positive electrode, the constant-current discharge under 520 DEG C of different current densities, the effective electric discharge for calculating battery by be discharged to peak pressure 75% are held Amount,
Using the mixture of conventional LiF-LiCl-LiBr and magnesia as electrolyte, (quality of magnesia accounts for polynary salt quality 50%), using the LiB alloy of 61wt.% as negative electrode material, with CoS2It is permanent under 520 DEG C of different current densities for positive electrode Electricity is banished, the effective discharge capacity for calculating battery by be discharged to peak pressure 75%,
Comparison discovery, in 200mA/cm2、500mA/cm2、1000mA/cm2Under current density, using designed by the present invention The thermal cell of electrolyte is respectively increased compared to by the effective discharge capacity of the thermal cell of electrolyte of conventional LiF-LiCl-LiBr 575C.g-1、1074C.g-1、767C.g-1。
When a kind of thermal battery electrolyte of containing metal particle of the present invention is as thermal cell；Can be widely applied to for guided missile, The fields such as Underwater Battery and nuclear weapon.
Advantage
The present invention breaks through conventional thought, by, with metallic particles is added in electrolyte, achieving expectation toward conventional thermal cell Less than effect.
The invention adopts the above technical scheme, which has the following advantages:
1, effective discharge capacity that a small amount of additive can greatly improve thermal cell especially Li system thermal cell improves Thermal cell mid-early stage pulsed discharge performance.
2, designed electrolyte performance is stablized, and preparation manipulation is simple.
3, designed electrolyte is from a wealth of sources, cheap, no pollution to the environment.
Detailed description of the invention
When Fig. 1 is that electrolyte prepared by embodiment 1 is used as Li system thermal cell with conventional electrolysis matter, in 520 DEG C of different electric currents Effective discharge capacity curve under density.
When Fig. 2 is that electrolyte prepared by embodiment 2 is used as Li system thermal cell with conventional electrolysis matter, in 520 DEG C of different electric currents Effective discharge capacity curve under density.
When Fig. 3 is that electrolyte prepared by embodiment 3 is used as Li system thermal cell with conventional electrolysis matter, in 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 1 gained thermal cell of comparative example, and 2# curve is that embodiment 1 is made Effective discharge capacity curve of standby electrolyte thermal battery；From figure 1 it appears that in 200mA/cm2、500mA/cm2、1000mA/ cm2Under current density, the difference of the ordinate and the ordinate of the corresponding points of 1# curve of the corresponding points of 2# curve is respectively 575C.g-1、1074C.g-1、767C.g-1, i.e., 575C.g has been respectively increased in effective discharge capacity-1、1074C.g-1、767C.g-1。
In Fig. 2,1# curve is effective discharge capacity curve of 1 gained thermal cell of comparative example, 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 in 50mA/cm2、100mA/cm2、200mA/ cm2、500mA/cm2Under current density, the difference point of the ordinate of the corresponding points of the ordinate and 1# curve of the corresponding points of 2# curve It Wei not 1274C.g-1、837C.g-1、316C.g-1、296C.g-1.1274C.g has been respectively increased in i.e. effective discharge capacity-1、 837C.g-1、316C.g-1、296C.g-1。
In Fig. 3,1# curve is 3 gained thermal cell of comparative example in 600mA/cm2It rations the power supply under electric discharge under pulse current density Pressure, 2# curve are electrolyte thermal battery prepared by example 3 in 600mA/cm2Electric discharge lower voltage limit, 3# under pulse current density Curve is 3 gained thermal cell of comparative example in 1200mA/cm2Electric discharge lower voltage limit, 4# curve under pulse current density are example 3 Prepared electrolyte thermal battery is in 1200mA/cm2Electric discharge lower voltage limit, 5# curve under pulse current density are 3 institute of comparative example Thermal cell is obtained in 2400mA/cm2Electric discharge lower voltage limit, 6# curve under pulse current density are electrolyte prepared by example 3 Thermal cell is in 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, Li system thermal cell is relative to common Li prepared by inventive embodiments 3 It is thermal cell, is significantly improved in mid-early stage pulsed discharge lower voltage limit.Therefore in Li system thermal cell LiF-LiCl-LiBr electricity Xie Zhizhong addition aluminium (Al) flour additive agent significantly improves battery mid-early stage pulsed discharge performance.
Specific embodiment
A kind of additive of Li system thermal battery electrolyte be metal simple-substance powder, additive amount be electrolyte quality 0.5~ 5.0wt.%.4.0wt.% magnesium (Mg) flour additive agent is added such as in LiF-LiCl-LiBr, the effective discharge capacity of battery improves 575~1074C.g-1。
A kind of additive of Li system thermal battery electrolyte be metal simple-substance powder, additive amount be electrolyte quality 0.5~ 5.0wt.%.5.0wt.% aluminium (Al) flour additive agent is added such as in LiF-LiCl-LiBr, the effective discharge capacity of battery improves 296~1274C.g-1。
Metal simple-substance powder is one of magnesium (Mg) powder, aluminium (Al) powder, iron (Fe) powder, copper (Cu) powder or a variety of.
Application method: metal simple-substance powder is added directly into Li system thermal battery electrolyte, is needed before use by additive It is uniformly mixed with electrolyte.
Additive is suitable for Li alloy anode thermal cell.
Example 1
Li system thermal cell is 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 LiF-LiCl-LiBr in Li system thermal cell Magnesium powder (granularity of magnesium powder be 75 microns), addition account for the magnesia of LiF-LiCl-LiBr mass 50%, using Central South University Liu The negative electrode material of Zhi Jian seminar production is the LiB alloy that Li content is 61wt.%, positive electrode CoS2；Then at 520 DEG C Constant-current discharge under different current densities, the effective discharge capacity for calculating battery by be discharged to peak pressure 75%, repeatedly measures, makes even Mean value, then voltage-capacity curve is drawn, test result is as shown in figure 1 shown in 2# curve.
Comparative example 1
The uniform embodiment 1 of other conditions is consistent, only that magnesium powder is not added；After its products obtained therefrom is assembled into thermal cell, survey Its performance is tried, test result is as shown in figure 1 shown in 1# curve.
After from example 1 and comparative example 1 as can be seen that magnesium powder is added in LiF-LiCl-LiBr, Li system thermal cell effectively discharges Capacity significantly improves, wherein 200mA/cm2、500mA/cm2、1000mA/cm2Effective discharge capacity powder under current density you can well imagine High 575C.g-1、1074C.g-1、767C.g-1.Therefore, magnesium is added in LiF-LiCl-LiBr electrolyte in Li system thermal cell (Mg) powder can significantly improve effective discharge capacity.
Example 2
Li system thermal cell is 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 LiF-LiCl-LiBr in Li system thermal cell Aluminium powder (granularity of aluminium powder be 100 microns), addition account for the magnesia of LiF-LiCl-LiBr mass 50%, using Central South University The negative electrode material of Liu Zhijian seminar production is the LiB alloy that Li content is 61wt.%, positive electrode CoS2；Then 520 Constant-current discharge under DEG C different current densities.The effective discharge capacity for calculating battery by be discharged to peak pressure 75%, repeatedly measures, takes Average value, then voltage-capacity curve is drawn, test result is as shown in 2# curve in Fig. 2.
Comparative example 2
The uniform embodiment 2 of other conditions is consistent, only that aluminium powder is not added；Its gained test result such as Fig. 2 in 1# curve It is shown.
After from example 2 and comparative example 2 as can be seen that aluminium powder is added in LiF-LiCl-LiBr electrolyte, Li system thermal cell has Effect discharge capacity significantly improves, wherein 50mA/cm2、100mA/cm2、200mA/cm2、500mA/cm2It is effective under current density Discharge capacity powder does not improve 1274C.g-1、837C.g-1、316C.g-1、296C.g-1.Therefore, in Li system thermal cell LiF- Aluminium (Al) powder is added in LiCl-LiBr can significantly improve effective discharge capacity.
Example 3
Li system thermal cell is 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 LiF-LiCl-LiBr in Li system thermal cell Aluminium powder (granularity of aluminium powder be 20 microns), addition account for the magnesia of LiF-LiCl-LiBr mass 50%, using Central South University Liu The negative electrode material of Zhi Jian seminar production is the LiB alloy that Li content is 61wt.%, positive electrode CoS2；Then at 520 DEG C Pulsed discharge is carried out under different current densities, recording impulse electric discharge lower voltage limit is repeatedly measured, is averaged, then draw voltage Curve.Test results are shown in figure 3.
Comparative example 3
The uniform embodiment 3 of other conditions is consistent, only that aluminium powder is not added；Test results are shown in figure 3 for its gained.
By comparative example 3 and example 3 it can be seen that after additive is added in LiF-LiCl-LiBr, 600mA/cm2、 1200mA/cm2And 2400mA/cm2Li system thermal cell mid-early stage pulsed discharge lower voltage limit under pulse current density obviously mentions It is high.Therefore battery mid-early stage can be significantly improved in Li system thermal cell addition aluminium (Al) powder in LiF-LiCl-LiBr electrolyte Pulsed discharge performance.

Claims (6)

1. a kind of thermal battery electrolyte of containing metal particle；It is characterized by: the thermal battery electrolyte of the containing metal particle exists It is solid insulator under room temperature；It includes polybasic salt and metallic particles；The metallic particles is evenly distributed in polybasic salt；It is described Polybasic salt is binary salt or ternary salt；
The binary salt is LiCl-KCl；
The ternary salt is selected from one of LiCl-LiBr-KBr, LiF-LiCl-LiBr;
The quality of metallic particles is the 0.5%-5% of polynary salt quality in the thermal battery electrolyte of the containing metal particle；It is described Metallic particles is selected from least one of magnesium powder, aluminium powder, iron powder, copper powder.
2. a kind of thermal battery electrolyte of containing metal particle according to claim 1；It is characterized by: the grain of metallic particles Degree is 5-100 microns.
3. a kind of thermal battery electrolyte of containing metal particle according to claim 1；It is characterized by:
The polybasic salt is LiCl-LiBr-KBr or LiF-LiCl-LiBr.
4. a kind of method for preparing the thermal battery electrolyte as described in claim 1-3 any one, it is characterised in that including following Step:
The metallic particles and polybasic salt taken will be distributed by setting group；It is uniformly mixed, obtains the electrolyte.
5. a kind of application of the thermal battery electrolyte as described in claim 1-3 any one, it is characterised in that: including containing by described in The thermal battery electrolyte of metallic particles is used for thermal cell.
6. a kind of application of the thermal battery electrolyte of containing metal particle according to claim 5；It is characterized by: the heat The cathode of battery is Li alloy.
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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
CN202308167U (en) * 2011-11-14 2012-07-04 中国电子科技集团公司第十八研究所 Unit cell of nickel chlorite thermal battery
CN105789653A (en) * 2016-04-13 2016-07-20 武汉理工大学 Preparation method of thermal battery electrolyte containing hollow magnesia powder

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US8039138B2 (en) * 2007-08-14 2011-10-18 Millennium Engineering And Integration Company Chloride-free, sodium ion-free, and water-free thermal batteries using molten nitrate electrolytes
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Patent Citations (3)

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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
CN202308167U (en) * 2011-11-14 2012-07-04 中国电子科技集团公司第十八研究所 Unit cell of nickel chlorite thermal battery
CN105789653A (en) * 2016-04-13 2016-07-20 武汉理工大学 Preparation method of thermal battery electrolyte containing hollow magnesia powder

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