CN105789653B - A kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder - Google Patents
A kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder Download PDFInfo
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- CN105789653B CN105789653B CN201610228180.8A CN201610228180A CN105789653B CN 105789653 B CN105789653 B CN 105789653B CN 201610228180 A CN201610228180 A CN 201610228180A CN 105789653 B CN105789653 B CN 105789653B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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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
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- H01M2300/0017—Non-aqueous electrolytes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention is a kind of preparation method of thermal battery electrolyte containing hollow magnesia powder, specifically: preparing precursor solution first with water-soluble carbon source and magnesium salts, has the carbon ball@MgO powder of core-shell structure through hydro-thermal method synthesis；Subsequent carbon ball@MgO powder rises to 500~800 DEG C under 1~5 DEG C/min of heating rate and is heat-treated, to remove the carbon ball in composite granule；Partial size is finally obtained between 500nm~2 μm, specific surface area is greater than 300m2The hollow MgO powder of/g；It is 25~45wt.% that preparation thermal battery electrolyte, which needs content of the hollow regulating MgO powder in entire electrolyte,.It by hollow MgO powder and fused salt at temperature congruent melting 4 hours higher than 50 DEG C of fusing point or more, is sieved to obtain electrolyte powder through ball milling, which forms by pressing mold, obtains the thermal battery electrolyte.Operation of the present invention is easy, and raw material sources are extensive, moderate, and 1h or more can be improved in the working life of the thermal cell of preparation.
Description
Technical field
The present invention relates to thermal cell field, the preparation side of specifically a kind of thermal battery electrolyte containing hollow magnesia powder
Method.
Technical background
In recent years, thermal cell was in geological prospecting, deep space exploration, new- and high-tech weaponry and clean energy resource redundancy technique etc.
Field achieves the development advanced by leaps and bounds, and shows excellent performance under the service states such as high power, quick activation.Thermoelectricity
Pond is a kind of congruent melting salt formation molten salt electrolyte that plurality of inorganic salt is heated by external heat source, and enters one kind of working condition
Reserve cell.After battery activated, electrolyte, which melts rapidly, forms good ion conductor, and activated batteries simultaneously export electricity
Energy.It is the main feature of thermal cell using molten salt electrolyte, it is made to be clearly distinguishable from other use aqueous electrolytes, Organic Electricity
Solve the battery of matter and solid electrolyte.
One ring of key that insulating powder is formed as thermal cell, it is special to directly affect working life and security performance of battery etc.
Property.It is sieved again through ball milling after the insulating powder and molten salt electrolyte consolute of usual thermal cell, obtains the mixed uniformly powder of the two
After be pressed into electrolyte.Therefore the ideal electrolyte of thermal cell, must both have preferable electronic isolation so that positive and negative anodes material is isolated
Material, can provide stable ion transmission channel again.In view of the operating condition and negative electrode material of thermal cell high temperature (350 DEG C of >)
(Li alloy) extremely strong corrosivity at high temperature, the isolation material for the operation for guaranteeing battery-efficient safety, in thermal battery electrolyte
Material must use good insulating, chemical stability and the strong material of thermal stability.
MgO powder is from a wealth of sources, cheap, can be used by being simply heat-treated.MgO powder passes through intergranular hair
Tubule power can adsorb the electrolyte largely melted, and the mobility of molten salt electrolyte is effectively reduced, so as current thermal cell
Electrolyte master isolated material to be used.Patent (CN103259033A) discloses a kind of semi-liquid metal electrode high-temperature battery,
Which use MgO powder as battery isolated material.Stability of the MgO powder to the battery cathode (Li and its alloy) of strong corrosive
Preferably, it will not decompose or dissolve under the conditions of working long hours.But MgO is mixed with electrolyte with electrolyte in powder form
There are many problems.To improve MgO powder to the adsorbance of electrolyte, it is necessary to improve the content of MgO powder in electrolyte, this will certainly
Cause the internal resistance of electrolyte to improve, is unfavorable for thermal cell High-current output.In addition, under the conditions of working long hours, thermal cell electrolysis
Matter can be gradually thinning, and mechanical strength can be reduced constantly.Molten salt electrolyte can not continue to be adsorbed in MgO powder and generate flowing, sternly
Ghost image rings the safety of battery.United States Patent (USP) (US7303593B1), which discloses, a kind of utilizes MgO powder preparation thermal battery electrolyte
Technique, the patent attempt to use a variety of ball-milling mediums such as liquid nitrogen or freon and carry out mechanical ball to MgO powder and thermal battery electrolyte
It grinds, sieving technique effectively reduces the partial size of MgO powder after ball milling, and the MgO powder and thermal battery electrolyte prepare electrolyte in high temperature
Lower electrolyte spill-out is very low, but the complex operation, needs expensive ball-milling medium and longer Ball-milling Time.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of system of thermal battery electrolyte containing hollow magnesia powder
Preparation Method, with the limitation for overcoming the above-mentioned powder of MgO in the prior art to apply in thermal battery electrolyte.
The present invention solves its technical problem, and the following technical solution is employed:
The preparation method of thermal battery electrolyte provided by the invention containing hollow magnesia powder, particular by following 3
What a step was realized:
(1) hollow MgO powder is prepared:
The solution containing water-soluble carbon source and anhydrous magnesium salts is prepared, which obtains presoma after water bath with thermostatic control is stirred
Solution, the precursor solution have the carbon ball MgO powder of core-shell structure through hydro-thermal method synthesis, which obtains through Overheating Treatment
Hollow MgO powder；
(2) thermal battery electrolyte powder is prepared:
Take content of the hollow MgO powder in entire electrolyte be 25wt.%~45wt.%, then by the hollow MgO powder with
Fused salt obtains thermal battery electrolyte powder after ball milling is sieved 150 mesh in >=temperature congruent melting 3.5-4.5 hours of 50 DEG C of fusing point；
(3) pressing mold forms:
Pressure by thermal battery electrolyte powder in 20MPa pushes mold forming, obtains the thermal cell electrolysis containing hollow MgO powder
Matter.
Precursor solution in the preparation method step (1) is made of following methods:
1) it weighs 1g~10g water-soluble carbon source and is dissolved in 100mL deionized water and uniformly mix, it is molten to obtain water-soluble carbon source
Liquid；
2) it weighs the anhydrous magnesium salts of 0.005mol~0.015mol to be dissolved in glucose solution, obtains anhydrous magnesium salt solution；
3) after water-soluble carbon source solution and anhydrous magnesium salt solution being mixed by 1:1 mass ratio, be placed in 60 DEG C of waters bath with thermostatic control
Middle stirring 1~4 hour, speed of agitator are 500~1000rpm, obtain the precursor solution.
Hollow MgO powder in the preparation method step (1) is made of following methods:
1) transfer precursor solution synthesizes carbon ball@MgO powder by hydro-thermal reaction method into reaction kettle, hydro-thermal reaction
Temperature is 140 DEG C~200 DEG C, and the reaction time is 2~6h；
2) carbon ball@MgO powder dry 1.5-2h in 70-85 DEG C of baking oven is taken out after reaction, by the carbon ball@after drying
MgO powder rises to 500 DEG C~800 DEG C under 1 DEG C~5 DEG C/min of heating rate and is heat-treated, and removes carbon ball@MgO powder
In nano carbon microsphere, obtain hollow MgO powder.
Hollow MgO powder in the preparation method step (1), average grain diameter be 500nm~2 μm, specific surface area be >=
300m2/g。
Water-soluble carbon source in the preparation method step (1) is one of glucose, sucrose, fructose.
Anhydrous magnesium salts in the preparation method step (1) is MgCl2、Mg(NO3)2、Mg(CH3COO)2In magnesium isopropoxide
One kind.
Fused salt in the preparation method step (2) is inorganic congruent melting salt, the congruent melting salt be LiCl-KCl (45wt.%:
55wt.%), LiF-LiBr-LiCl (9.6wt.%:22wt.%:68.4wt.%), LiCl-LiBr-KCl (12wt.%:
36.5wt.%:51.5wt.%), LiCl-LiBr-KBr (12wt.%:37wt.%:57wt.%), LiF-LiBr-KBr
One of (0.8wt.%:56wt.%:43.2wt.%).
Thermal battery electrolyte prepared by the present invention is related to the electrolyte of lithium system thermal cell, are as follows:
Li(Si)/LiCl-LiF-LiBr/FeS2, Li (B)/LiF-LiBr-KBr/FeS2, Li (B)/LiCl-LiF-LiBr/
CoS2, Li (B)/LiF-LiBr-KBr/CoS2One of.
Thermal battery electrolyte prepared by the present invention, with a thickness of 0.3mm~0.8mm, density 2.3g/cm3~2.7g/
cm3。
Thermal battery electrolyte prepared by the present invention, under the conditions of 500 DEG C after 1h electrolyte conservation rate >=
85wt.%.
The present invention has major advantage below compared with prior art:
1. comparing common MgO powder, the hollow MgO powder that the present invention uses can adsorb and fix more molten salt electrolytes, high
(500 DEG C) electrolyte conservation rate can achieve 85wt.% or more under temperature.
2. hollow MgO powder used by is thermodynamically high with battery material compatibility, and the electrolyte of preparation is in battery work
Make in section (350 DEG C~600 DEG C) outer dimension stablize, avoid conventional MgO electrolyte after discharge the phase because structural strength drop
Battery capacity reduces caused by low and 1h or more can be improved in battery failure problem, the working life of thermal cell.
It is moderate 3. raw material sources are extensive, it is easy to operate, it is that current high power, long life thermal battery are preferably isolated
Material preparation method.
Detailed description of the invention
Fig. 1 is the schematic diagram of the electrolyte containing hollow MgO powder of embodiment 1.
Fig. 2 is the XRD diagram piece of embodiment 1, embodiment 2, embodiment 3 and the hollow MgO powder of 4 product of embodiment.
Fig. 3 is the low power SEM picture of the hollow MgO powder of 3 product of embodiment.
Fig. 4 is the high power SEM picture of the hollow MgO powder of 3 product of embodiment.
Fig. 5 is that the electrolyte electrolyte conservation rate of Examples 1 to 6 changes over time tendency chart.
Specific embodiment
The preparation method of thermal battery electrolyte provided by the invention containing hollow MgO powder, specifically: first with water-soluble
Property carbon source and magnesium salts prepare precursor solution, through hydro-thermal method synthesis have core-shell structure carbon ball@MgO powder.Subsequent carbon ball@
MgO powder rises to 500 DEG C~800 DEG C under 1 DEG C~5 DEG C/min of heating rate and is heat-treated, to remove in composite granule
Carbon ball.Partial size is finally obtained between 500nm~2 μm, specific surface area is greater than 300m2The hollow MgO powder of/g.Prepare thermal cell
It is 25wt.%~45wt.% that electrolyte, which needs content of the hollow regulating MgO powder in entire electrolyte,.By hollow MgO and fused salt
Temperature congruent melting 4 hours higher than 50 DEG C of fusing point or more, it is sieved to obtain electrolyte powder through ball milling.Electrolyte powder is by being compression molded into
Type obtains the thermal battery electrolyte containing hollow MgO powder.Electrolyte thickness containing hollow MgO powder is 0.3mm~0.8mm, close
Degree is 2.3g/cm3~2.7g/cm3.Electrolyte electrolyte conservation rate after 1h reaches 85wt.% or more at 500 DEG C.
Below with reference to embodiment and attached drawing, the invention will be further described, but does not limit the present invention.
Embodiment 1:
1. the preparation of hollow MgO powder:
Use glucose and MgCl2Powder synthesizes hollow MgO powder as initial feed in accordance with the following methods.
(1) 6.5g glucose is dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 0.95g (0.01mol)
MgCl2It is dissolved in glucose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 2h, speed of agitator 1000rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 160 DEG C, reaction time 5h.Reaction knot
The dry 2h in 80 DEG C of baking ovens is taken out after beam, obtains carbon ball@MgO powder.
(3) carbon ball@MgO powder is risen to 600 DEG C by 2 DEG C/min of heating rate to be heat-treated, obtains hollow MgO
Powder.
When hydrothermal temperature is 160 DEG C, reaction time 5h, heat treatment heating rate and temperature are respectively 2 DEG C/min
When with 600 DEG C, hollow MgO powder average grain diameter is 1.2 μm, specific surface area 450m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal cell electricity is prepared using LiCl-LiBr-KBr fused salt (2wt.%:37wt.%:57wt.%) and hollow MgO powder
Xie Zhi:
(1) the hollow MgO powder of 0.456g and 0.744g LiCl-LiBr-KBr fused salt are weighed, control hollow MgO powder in electricity
Solving the content in matter is 38wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KBr fused salt in 400 DEG C congruent melting 4 hours, obtain congruent melting powder；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder is formed by pressing mold, obtains the LiCl-LiBr-KBr electrolyte containing hollow MgO powder, briquetting pressure
For 20MPa.
The LiCl-LiBr-KBr electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.56g/cm-3, pressing mold is after molding with a thickness of 0.5mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
94wt.%.
Embodiment 2:
1. the preparation of hollow MgO powder:
Use sucrose and Mg (NO3)2Powder synthesizes hollow MgO powder as initial feed.
(1) 4.2g sucrose is weighed to be dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 0.74g (0.005mol) Mg
(NO3) 2 are dissolved in sucrose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 1h, speed of agitator 700rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 150 DEG C, and the reaction time is 4 hours.Instead
The dry 2h in 80 DEG C of baking ovens is taken out after answering.
(3) obtained carbon ball@MgO powder is risen to 700 DEG C by 3 DEG C/min of heating rate to be heat-treated, obtains sky
Heart MgO powder.
When hydrothermal temperature is 150 DEG C, the reaction time is 4 hours, heat treatment heating rate and temperature be respectively 3 DEG C/
When minute is with 700 DEG C, obtained MgO powder average grain diameter is 1.5 μm, specific surface area 350m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal cell is prepared using LiCl-LiBr-KBr (12wt.%:37wt.%:57wt.%) and the hollow MgO powder to be electrolysed
Matter.
(1) the hollow MgO powder of 0.54g and 0.96g LiCl-LiBr-KBr fused salt are weighed, being electrolysed for hollow MgO powder is controlled
Content in matter is 36wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KBr fused salt in 400 DEG C congruent melting 4 hours；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder forms to obtain the LiCl-LiBr-KBr electrolyte containing hollow MgO powder, briquetting pressure by pressing mold
For 20MPa.
The LiCl-LiBr-KBr electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.32g/cm-3, pressing mold is after molding with a thickness of 0.4mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
89wt.%.
Example example 3:
1. the preparation of hollow MgO powder:
Use glucose and MgCl2Powder synthesizes hollow MgO powder as initial feed.
(1) 6.5g glucose is weighed to be dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 0.95g (0.01mol)
MgCl2It is dissolved in glucose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 2h, speed of agitator 1000rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 200 DEG C, reaction time 6h.Reaction knot
The dry 2h in 80 DEG C of baking ovens is taken out after beam.
(3) obtained carbon ball@MgO powder is risen to 600 DEG C by 2 DEG C/min of heating rate to be heat-treated, obtains sky
Heart MgO powder.
When hydrothermal temperature is 200 DEG C, reaction time 6h, heat treatment heating rate and temperature are respectively 2 DEG C/min
When with 600 DEG C, obtained MgO powder average grain diameter is 1.8 μm, specific surface area 390m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal cell is prepared using LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) and the MgO powder to be electrolysed
Matter
(1) the hollow MgO powder of 0.32g and 0.68g LiCl-LiBr-LiF fused salt are weighed, being electrolysed for hollow MgO powder is controlled
Content in matter is 32wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C congruent melting 4 hours；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder forms to obtain the LiCl-LiBr-LiF electrolyte containing hollow MgO powder, briquetting pressure by pressing mold
For 20MPa.
The LiCl-LiBr-LiF electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.64g/cm-3, pressing mold is after molding with a thickness of 0.5mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
92wt.%.
Example example 4:
1. the preparation of hollow MgO powder:
Use sucrose and Mg (NO3)2Powder synthesizes hollow MgO powder as initial feed.
(1) 4.2g sucrose is weighed to be dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 0.74g (0.005mol) Mg
(NO3)2It is dissolved in sucrose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 1h, speed of agitator 700rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 180 DEG C, reaction time 3h.Reaction knot
The dry 2h in 80 DEG C of baking ovens is taken out after beam
(3) obtained carbon ball@MgO powder is risen to 500 DEG C by 2 DEG C/min of heating rate to be heat-treated, obtains sky
Heart MgO powder
When hydrothermal temperature is 180 DEG C, reaction time 3h, heat treatment heating rate and temperature are respectively 2 DEG C/min
When with 500 DEG C, obtained MgO powder average grain diameter is 2 μm, specific surface area 310m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal cell is prepared using LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) and the MgO powder to be electrolysed
Matter.
(1) the hollow MgO powder of 0.39g and 1g LiCl-LiBr-LiF fused salt are weighed, controls hollow MgO powder in the electrolyte
Content be 28wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C congruent melting 4 hours；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder forms to obtain the LiCl-LiBr-LiF electrolyte containing hollow MgO powder, briquetting pressure by pressing mold
For 20MPa.
The LiCl-LiBr-LiF electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.49g/cm-3, pressing mold is after molding with a thickness of 0.7mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
87wt.%.
Example example 5:
1. the preparation of hollow MgO powder:
Use glucose and Mg (CH3COO)2Powder synthesizes hollow MgO powder as initial feed.
(1) 3.0g glucose is weighed to be dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 1.14g (0.008mol)
Mg(CH3COO)2It is dissolved in glucose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 2h, speed of agitator is
1000rpm。
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 140 DEG C, and the reaction time is 4 hours.Instead
The dry 2h in 80 DEG C of baking ovens is taken out after answering.
(3) obtained carbon ball@MgO powder is risen to 650 DEG C by 2.5 DEG C/min of heating rate to be heat-treated, is obtained
Hollow MgO powder.
When hydrothermal temperature is 140 DEG C, the reaction time is 4 hours, and heat treatment heating rate and temperature are respectively 2.5
DEG C/min and at 650 DEG C, obtained MgO powder average grain diameter is 0.8 μm, specific surface area 540m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Using LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) and the MgO powder in 500 DEG C of preparation heat
Cell electrolyte
(1) the hollow MgO powder of 0.54g and 0.66g LiCl-LiBr-LiF fused salt are weighed, being electrolysed for hollow MgO powder is controlled
Content in matter is 45wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C congruent melting 4 hours；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder forms to obtain the LiCl-LiBr-LiF electrolyte containing hollow MgO powder, briquetting pressure by pressing mold
For 20MPa.
The LiCl-LiBr-LiF electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.68g/cm-3, pressing mold is after molding with a thickness of 0.6mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
98wt.%.
Example example 6:
1. the preparation of hollow MgO powder:
Use glucose and Mg (CH3COO)2Powder synthesizes hollow MgO powder as initial feed.
(1) 2.7g sucrose is weighed to be dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 1.14g (0.008mol) Mg
(CH3COO)2It is dissolved in sucrose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 1.5h, speed of agitator 800rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 140 DEG C, and the reaction time is 4 hours.Instead
The dry 2h in 80 DEG C of baking ovens is taken out after answering.
(3) obtained carbon ball@MgO powder is risen to 600 DEG C by 2.5 DEG C/min of heating rate to be heat-treated, is obtained
Hollow MgO powder.
When hydrothermal temperature is 140 DEG C, the reaction time is 4 hours, and heat treatment heating rate and temperature are respectively 2.5
DEG C/min and at 600 DEG C, obtained MgO powder average grain diameter is 1 μm, specific surface area 480m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal battery electrolyte is prepared using LiCl-LiBr-LiF (31wt.%:47wt.%:22wt.%) and the MgO powder.
(1) the hollow MgO powder of 0.46g and 0.69g LiCl-LiBr-LiF fused salt are weighed, being electrolysed for hollow MgO powder is controlled
Content in matter is 40wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C congruent melting 4 hours；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder forms to obtain the LiCl-LiBr-LiF electrolyte containing hollow MgO powder, briquetting pressure by pressing mold
For 20MPa.
The LiCl-LiBr-LiF electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.59g/cm-3, pressing mold is after molding with a thickness of 0.4mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
96wt.%.
Embodiment 7:
1. the preparation of hollow MgO powder:
Use glucose and MgCl2Powder synthesizes hollow MgO powder as initial feed in accordance with the following methods.
(1) 5.4g glucose is dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 0.95g (0.01mol)
MgCl2It is dissolved in glucose solution.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 2h, speed of agitator 1000rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 150 DEG C, reaction time 4h.Reaction knot
The dry 2h in 80 DEG C of baking ovens is taken out after beam, obtains carbon ball@MgO powder.
(3) carbon ball@MgO powder is risen to 550 DEG C by 2.5 DEG C/min of heating rate to be heat-treated, is obtained hollow
MgO powder.
When hydrothermal temperature is 150 DEG C, reaction time 4h, heat treatment heating rate and temperature are respectively 2.5 DEG C/minute
Clock and at 600 DEG C, hollow MgO powder average grain diameter is 1.5 μm, specific surface area 390m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermal battery electrolyte is prepared using LiCl-KCl fused salt (45wt.%:55wt.%) and hollow MgO powder:
(1) the hollow MgO powder of 0.4g and 0.8g LiCl-KCl fused salt are weighed, containing in the electrolyte of hollow MgO powder is controlled
Amount is 33wt.%；
(2) by hollow MgO powder and LiCl-KCl fused salt in 400 DEG C congruent melting 4 hours, obtain congruent melting powder；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder is formed by pressing mold, obtains the LiCl-KCl electrolyte containing hollow MgO powder, briquetting pressure is
20MPa。
The LiCl-KCl electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.31g/cm-3, pressing mold is after molding with a thickness of 0.3mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
95wt.%.
Embodiment 8:
1. the preparation of hollow MgO powder:
Use fructose and Mg (NO3)2Powder synthesizes hollow MgO powder as initial feed in accordance with the following methods.
(1) 1.8g fructose is dissolved in 100mL deionized water, it is to be mixed uniformly after weigh 1.48g (0.01mol) Mg
(NO3)2Powder is dissolved in fructose soln.Mixed solution is placed in 60 DEG C of waters bath with thermostatic control and stirs 2h, speed of agitator 1000rpm.
(2) precursor solution is transferred in hydrothermal reaction kettle, reaction temperature is 180 DEG C, reaction time 3h.Reaction knot
The dry 2h in 80 DEG C of baking ovens is taken out after beam, obtains carbon ball@MgO powder.
(3) carbon ball@MgO powder is risen to 650 DEG C by 4 DEG C/min of heating rate to be heat-treated, obtains hollow MgO
Powder.
When hydrothermal temperature is 180 DEG C, reaction time 3h, heat treatment heating rate and temperature are respectively 4 DEG C/min
When with 650 DEG C, hollow MgO powder average grain diameter is 1.85 μm, specific surface area 325m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte forms (Fig. 1) by fused salt 1 and MgO hollow sphere 2.
Thermoelectricity is prepared using LiCl-LiBr-KCl fused salt (12wt.%:36.5wt.%:51.5wt.%) and hollow MgO powder
Pond electrolyte:
(1) the hollow MgO powder of 0.65g and 0.65g LiCl-LiBr-KCl fused salt are weighed, being electrolysed for hollow MgO powder is controlled
Content in matter is 50wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KCl fused salt in 400 DEG C congruent melting 4 hours, obtain congruent melting powder；
(3) it takes out ball milling after congruent melting powder cools down and crosses 150 meshes, obtain electrolyte powder；
(4) electrolyte powder is formed by pressing mold, obtains the LiCl-LiBr-KCl electrolyte containing hollow MgO powder, briquetting pressure
For 20MPa.
The LiCl-LiBr-KCl electrolyte containing hollow MgO powder of this embodiment preparation, detecting its density through densitometer is
2.69g/cm-3, pressing mold is after molding with a thickness of 0.8mm；At 500 DEG C after 1h, electrolyte conservation rate is the electrolyte sheet
88wt.%.
In above-described embodiment, ball milling can be carried out to congruent melting powder after cooling using planetary ball mill, milling atmosphere
Relative humidity is less than 3%.
Claims (10)
1. a kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder, it is characterized in that:
(1) it prepares hollow MgO powder: preparing the solution containing water-soluble carbon source and anhydrous magnesium salts, which is placed in 60 DEG C of thermostatted waters
It is stirred 1~4 hour in bath, speed of agitator is that 500~1000rpm obtains precursor solution, which closes through hydro-thermal method
At the carbon ball@MgO powder with core-shell structure, the temperature of the hydro-thermal reaction is 140 DEG C~200 DEG C, the reaction time is 2~
6h, the powder obtain hollow MgO powder through Overheating Treatment；
(2) prepare thermal battery electrolyte powder: take content of the hollow MgO powder in entire electrolyte be 25wt.%~
Then the hollow MgO powder and fused salt are sieved in >=temperature congruent melting 3.5-4.5 hours of 50 DEG C of fusing point through ball milling by 45wt.%
Thermal battery electrolyte powder is obtained after 150 mesh；
(3) pressing mold forms: the pressure by thermal battery electrolyte powder in 20MPa pushes mold forming, obtains the heat containing hollow MgO powder
Cell electrolyte.
2. the preparation method of the thermal battery electrolyte according to claim 1 containing hollow magnesia powder, it is characterised in that
The precursor solution, is made of following methods:
(1) it weighs 1g~10g water-soluble carbon source and is dissolved in 100mL deionized water and uniformly mix, obtain water-soluble carbon source solution；
(2) it weighs the anhydrous magnesium salts of 0.005mol~0.015mol to be dissolved in glucose solution, obtains anhydrous magnesium salt solution；
(3) it will obtain described containing water-soluble carbon after water-soluble carbon source solution and anhydrous magnesium salt solution mix by 1:1 mass ratio
The solution in source and anhydrous magnesium salts.
3. the preparation method of the thermal battery electrolyte according to claim 2 containing hollow magnesia powder, it is characterized in that will
Precursor solution is transferred in reaction kettle, is synthesized carbon ball@MgO powder by hydro-thermal reaction method, is taken out carbon ball@after reaction
MgO powder, the dry 1.5-2h in 70-85 DEG C of baking oven；Then by the carbon ball@MgO powder after drying at 1 DEG C~5 DEG C/min
500 DEG C~800 DEG C are risen under heating rate to be heat-treated, and are removed the nano carbon microsphere in carbon ball@MgO powder, are obtained hollow MgO
Powder.
4. the preparation method of the thermal battery electrolyte according to claim 3 containing hollow magnesia powder, it is characterised in that
The hollow MgO powder, average grain diameter are 500nm~2 μm, and specific surface area is >=300m2/g。
5. the preparation method of the thermal battery electrolyte according to claim 2 containing hollow magnesia powder, it is characterised in that
The water-soluble carbon source is one of glucose, sucrose, fructose.
6. the preparation method of the thermal battery electrolyte according to claim 2 containing hollow magnesia powder, it is characterised in that
The anhydrous magnesium salts is MgCl2、Mg(NO3)2、Mg(CH3COO)2One of with magnesium isopropoxide.
7. the preparation method of the thermal battery electrolyte according to claim 1 containing hollow magnesia powder, it is characterised in that
The fused salt is congruent melting salt, which is:
The proportion of LiCl-KCl is 45wt.%:55wt.%, and the proportion of LiF-LiBr-LiCl is 9.6wt.%:22wt.%:
The proportion of 68.4wt.%, LiCl-LiBr-KCl are 12wt.%:36.5wt.%:51.5wt.%, and LiCl-LiBr-KBr's matches
Than being in 0.8wt.%:56wt.%:43.2wt.% for the proportion of 12wt.%:37wt.%:57wt.%, LiF-LiBr-KBr
One kind.
8. the preparation method of the thermal battery electrolyte according to claim 1 containing hollow magnesia powder, it is characterised in that
The thermal battery electrolyte of this method preparation is lithium system thermal cell, are as follows: Li/LiCl-LiF-LiBr/FeS2, Li/LiF-LiBr-
KBr/FeS2, Li/LiCl-LiF-LiBr/CoS2, Li/LiF-LiBr-KBr/CoS2One of.
9. the preparation method of the thermal battery electrolyte according to claim 1 containing hollow magnesia powder, it is characterised in that
The thermal battery electrolyte of this method preparation, with a thickness of 0.3mm~0.8mm, density 2.3g/cm3~2.7g/cm3。
10. the preparation method of the thermal battery electrolyte according to claim 1 containing hollow magnesia powder, it is characterised in that
This method preparation thermal battery electrolyte, under the conditions of 500 DEG C after 1h electrolyte conservation rate >=85wt.%.
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| CN106328966B (en) * | 2016-08-25 | 2019-04-09 | 中南大学 | A kind of thermal battery electrolyte of containing metal particle and its preparation method and application |
| CN107425208B (en) * | 2017-06-27 | 2019-12-03 | 北方特种能源集团有限公司西安庆华公司 | A kind of thermal cell electrolyte |
| CN107845820B (en) * | 2017-11-07 | 2019-05-10 | 西南科技大学 | Thermal battery electrolyte piece reforming apparatus and thermal battery electrolyte piece method of modifying |
| CN107732268B (en) * | 2017-11-23 | 2020-06-23 | 上海空间电源研究所 | Single battery of thermal battery for carrier rocket |
| CN107978766A (en) * | 2017-11-23 | 2018-05-01 | 上海空间电源研究所 | A kind of three-decker formula single cell of thermo battery |
| CN109167080B (en) * | 2018-09-12 | 2022-06-14 | 哈尔滨工业大学（威海） | High-voltage lithium thermal battery |
| CN109370531B (en) * | 2018-09-30 | 2021-01-22 | 贵州梅岭电源有限公司 | Preparation method of thermal buffer heat storage material for thermal battery |
| CN110212208A (en) * | 2019-04-30 | 2019-09-06 | 中国电子科技集团公司第十八研究所 | Electrolyte material for storage thermal battery |
| CN113130840B (en) * | 2021-04-19 | 2022-08-26 | 中国工程物理研究院电子工程研究所 | Thermal battery anode material with high performance and preparation method thereof |
| CN113851628B (en) * | 2021-08-19 | 2024-01-30 | 聊城大学 | Adhesive-free V 2 O 5 Molten salt electrode material, and preparation method and application thereof |
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