CN105789653A - Preparation method of thermal battery electrolyte containing hollow magnesia powder - Google Patents
Preparation method of thermal battery electrolyte containing hollow magnesia powder Download PDFInfo
- Publication number
- CN105789653A CN105789653A CN201610228180.8A CN201610228180A CN105789653A CN 105789653 A CN105789653 A CN 105789653A CN 201610228180 A CN201610228180 A CN 201610228180A CN 105789653 A CN105789653 A CN 105789653A
- Authority
- CN
- China
- Prior art keywords
- powder
- thermal battery
- mgo powder
- battery electrolyte
- hollow
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a thermal battery electrolyte containing hollow magnesia powder. The preparation method includes the specific steps that firstly, a precursor solution is prepared from a water-soluble carbon source and magnesium salt, and carbon sphere@MgO powder with a core-shell structure is synthesized with a hydrothermal method; then, the carbon sphere@MgO powder is heated to 500-800 DEG C at the heating rate of 1-5 DEG C/min for heat treatment so that carbon spheres in the composite powder can be removed; finally, the hollow MgO powder with the grain size ranging from 500 nm to 2 micrometers and the specific area being larger than 300 m<2>/g is obtained, wherein in preparation of the thermal battery electrolyte, the content of the hollow MgO powder in the whole electrolyte needs to be regulated to range from 25wt.% to 45wt.%; the hollow MgO powder and molten salt are subjected to co-melting for 4 h at a temperature higher than the melting point by 50 DEG C or above, electrolyte powder is obtained through ball milling and sieving, the powder is subjected to press molding, and the thermal battery electrolyte is obtained. The preparation method is easy and convenient to implement, raw materials are wide in source and moderate in price, and the service life of a prepared thermal battery can be prolonged to 1 h or above.
Description
Technical field
The present invention relates to thermal cell field, specifically the preparation method of a kind of thermal battery electrolyte containing hollow magnesia powder.
Technical background
In recent years, thermal cell achieved, in fields such as geological prospecting, deep space exploration, new-and high-tech weaponry and clean energy resource redundancy techniques, the development advanced by leaps and bounds, the performance showing excellence under the service state such as high power, quick activation.Thermal cell is a kind of congruent melting salt formation molten salt electrolyte being heated plurality of inorganic salt by external heat source, and enters reserve cell of one of duty.After battery activated, electrolyte melts rapidly and forms good ion conductor, and activated batteries also exports electric energy.Use molten salt electrolyte is the principal character of thermal cell so that it is be clearly distinguishable from other battery using aqueous electrolyte, organic bath and solid electrolyte.
Key one ring that insulating powder forms as thermal cell, the characteristic such as working life and security performance of directly affecting battery.Sieve then through ball milling after the insulating powder of usual thermal cell and molten salt electrolyte consolute, after obtaining the two mixed uniformly powder body, be pressed into electrolyte.Therefore the desirable electrolyte of thermal cell, both must possess good electronic isolation to isolate positive and negative pole material, be provided that stable ion transmission channel again.Consider the working condition of thermal cell high temperature (> 350 DEG C) and the corrosivity that negative material (Li alloy) is at high temperature extremely strong, for ensureing the operation of battery-efficient safety, isolated material in thermal battery electrolyte must use the material that good insulating, chemical stability and heat stability are strong.
MgO powder body wide material sources, cheap, can use through simple heat treatment.MgO powder can adsorb the electrolyte of a large amount of thawing by intergranular capillary force, effectively reduces the mobility of molten salt electrolyte, so the isolated material mainly used as current thermal battery electrolyte.Patent (CN103259033A) discloses a kind of semi-liquid metal electrode high-temperature battery, which uses MgO powder as battery isolated material.MgO powder is better to the stability of the battery cathode (Li and alloy thereof) of severe corrosive, will not decompose or dissolve under the condition that works long hours.But MgO is mixed with electrolyte with electrolyte in powder form exists many problems.For improving MgO powder to electrolytical adsorbance, it is necessary to improving the content of MgO powder in electrolyte, this will certainly cause that electrolytical internal resistance improves, and is unfavorable for thermal cell High-current output.Additionally, work long hours under condition, thermal battery electrolyte can be thinning gradually, and mechanical strength can constantly reduce.Molten salt electrolyte cannot continue to be adsorbed in MgO powder produce flowing, have a strong impact on the safety of battery.United States Patent (USP) (US7303593B1) discloses the technique that a kind of MgO of utilization powder prepares thermal battery electrolyte, this patent attempts to the multiple ball-milling medium such as liquid nitrogen or freon and MgO powder and thermal battery electrolyte is carried out mechanical ball milling, technique of sieving after ball milling effectively reduces the particle diameter of MgO powder, it is very low that this MgO powder and thermal battery electrolyte prepare electrolyte at high temperature electrolyte spill-out, but this complex operation, it is necessary to expensive ball-milling medium and longer Ball-milling Time.
Summary of the invention
The technical problem to be solved is: the preparation method providing a kind of thermal battery electrolyte containing hollow magnesia powder, to overcome the limitation that in above-mentioned prior art, MgO powder is applied in thermal battery electrolyte.
This invention address that its technical problem adopts following technical scheme:
The preparation method of the thermal battery electrolyte containing hollow magnesia powder provided by the invention, realizes particular by following 3 steps:
(1) hollow MgO powder is prepared:
The preparation solution containing water solublity carbon source and anhydrous magnesium salt, this solution obtains precursor solution after water bath with thermostatic control is stirred, and this precursor solution has the carbon ball MgO powder body of nucleocapsid structure through water heat transfer, and this powder body, through Overheating Treatment, obtains hollow MgO powder；
(2) thermal battery electrolyte powder body is prepared:
Taking hollow MgO powder content in whole electrolyte is 25wt.%～45wt.%, then by temperature congruent melting 3.5-4.5 hour at >=fusing point 50 DEG C of this hollow MgO powder and fused salt, obtains thermal battery electrolyte powder body after ball milling sieves 150 orders；
(3) pressing mold molding:
By the thermal battery electrolyte powder pressure mold forming at 20MPa, obtain the thermal battery electrolyte containing hollow MgO powder.
Precursor solution in described preparation method step (1) is made up of following methods:
1) weigh 1g～10g water solublity carbon source and be dissolved in Homogeneous phase mixing in 100mL deionized water, obtain water solublity carbon source solution；
2) weigh the anhydrous magnesium salt of 0.005mol～0.015mol and be dissolved in glucose solution, obtain anhydrous magnesium saline solution；
3) after water solublity carbon source solution and anhydrous magnesium saline solution being mixed by 1:1 mass ratio, being placed in 60 DEG C of waters bath with thermostatic control and stir 1～4 hour, speed of agitator is 500～1000rpm, obtains described precursor solution.
Hollow MgO powder in described preparation method step (1) is made up of following methods:
1) transfer precursor solution is to reactor, synthesizes carbon ball MgO powder body by hydro-thermal reaction method, and the temperature of hydro-thermal reaction is 140 DEG C～200 DEG C, and the response time is 2～6h；
2) carbon ball MgO powder body dry 1.5-2h in 70-85 DEG C of baking oven is taken out in reaction after terminating, carbon ball MgO powder body after drying is risen to 500 DEG C～800 DEG C under the heating rate of 1 DEG C～5 DEG C/min and carries out heat treatment, remove the nano carbon microsphere in carbon ball MgO powder body, obtain hollow MgO powder.
Hollow MgO powder in described preparation method step (1), its mean diameter is 500nm～2 μm, and specific surface area is >=300m2/g。
Water solublity carbon source in described preparation method step (1) is the one in glucose, sucrose, fructose.
Anhydrous magnesium salt in described preparation method step (1) is MgCl2、Mg(NO3)2、Mg(CH3COO)2With the one in magnesium isopropoxide.
Fused salt in described preparation method step (2) is inorganic congruent melting salt, this congruent melting salt is 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.%), the one in LiF-LiBr-KBr (0.8wt.%:56wt.%:43.2wt.%).
Thermal battery electrolyte prepared by the present invention relates to the electrolyte of lithium system thermal cell, and it is:
Li(Si)/LiCl-LiF-LiBr/FeS2, Li (B)/LiF-LiBr-KBr/FeS2, Li (B)/LiCl-LiF-LiBr/CoS2, Li (B)/LiF-LiBr-KBr/CoS2In one.
Thermal battery electrolyte prepared by the present invention, its thickness is 0.3mm～0.8mm, and density is 2.3g/cm3～2.7g/cm3。
Thermal battery electrolyte prepared by the present invention, its under 500 DEG C of conditions after 1h electrolyte conservation rate >=85wt.%.
The present invention compared with prior art has following major advantage:
1. comparing common MgO powder, the hollow MgO powder that the present invention adopts can adsorb and fix more molten salt electrolyte, and under high temperature, (500 DEG C) electrolyte conservation rate can reach more than 85wt.%.
2. the hollow MgO powder adopted is thermodynamically high with the battery material compatibility, electrolyte (350 DEG C～600 DEG C) overall dimensions in battery operated interval of preparation is stable, avoiding battery capacity reduction and battery failure problem that the conventional MgO electrolyte phase after discharge causes because structural strength reduces, the working life of thermal cell can bring up to more than 1h.
3. raw material sources are extensive, moderate, easy and simple to handle, are current high power, the desirable isolated material preparation method of long life thermal battery.
Accompanying drawing explanation
Fig. 1 is the electrolytical schematic diagram containing hollow MgO powder of embodiment 1.
Fig. 2 is the XRD figure sheet of the hollow MgO powder of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 product.
Fig. 3 is the low power SEM picture of the hollow MgO powder of embodiment 3 product.
Fig. 4 is the high power SEM picture of the hollow MgO powder of embodiment 3 product.
The electrolyte electrolyte conservation rate that Fig. 5 is embodiment 1～6 changes over trendgram.
Detailed description of the invention
The preparation method of the thermal battery electrolyte containing hollow MgO powder provided by the invention, specifically: prepare precursor solution first with water solublity carbon source and magnesium salt, there is through water heat transfer the carbon ball MgO powder body of nucleocapsid structure.Carbon ball MgO powder body rises to 500 DEG C～800 DEG C under the heating rate of 1 DEG C～5 DEG C/min and carries out heat treatment subsequently, to remove the carbon ball in composite granule.Finally giving particle diameter between 500nm～2 μm, specific surface area is more than 300m2The hollow MgO powder of/g.Preparation thermal battery electrolyte needs hollow regulating MgO powder content in whole electrolyte to be 25wt.%～45wt.%.By hollow MgO and fused salt in the temperature congruent melting 4 hours higher than fusing point more than 50 DEG C, sieve through ball milling and obtain electrolyte powder body.Electrolyte powder obtains the thermal battery electrolyte containing hollow MgO powder through pressing mold molding.Electrolyte thickness containing hollow MgO powder is 0.3mm～0.8mm, and density is 2.3g/cm3～2.7g/cm3.At 500 DEG C, electrolyte electrolyte conservation rate after 1h reaches more than 85wt.%.
Below in conjunction with embodiment and accompanying 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, as initial feed, synthesizes hollow MgO powder in accordance with the following methods.
(1) 6.5g glucose is dissolved in 100mL deionized water, to be mixed uniformly after weigh 0.95g (0.01mol) MgCl2It is dissolved in glucose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 2h, speed of agitator is 1000rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 160 DEG C, and the response time is 5h.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating, obtain carbon ball MgO powder body.
(3) carbon ball MgO powder body is risen to 600 DEG C by the heating rate of 2 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 160 DEG C, the response time is 5h, heat treatment heating rate and temperature respectively 2 DEG C/min and 600 DEG C time, hollow MgO powder mean diameter is 1.2 μm, and specific surface area is 450m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-KBr fused salt (2wt.%:37wt.%:57wt.%) and hollow MgO powder is used to prepare thermal battery electrolyte:
(1) weighing the hollow MgO powder of 0.456g and 0.744gLiCl-LiBr-KBr fused salt, the content in the electrolyte controlling hollow MgO powder is 38wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KBr fused salt in 400 DEG C of congruent meltings 4 hours, congruent melting powder is obtained；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder is through pressing mold molding, obtains the LiCl-LiBr-KBr electrolyte containing hollow MgO powder, and briquetting pressure is 20MPa.
LiCl-LiBr-KBr electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.56g/cm-3, the thickness after pressing mold molding is 0.5mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 94wt.%.
Embodiment 2:
1. the preparation of hollow MgO powder:
Use sucrose and Mg (NO3)2Powder synthesizes hollow MgO powder as initial feed.
(1) weigh 4.2g sucrose and be dissolved in 100mL deionized water, to be mixed uniformly after weigh 0.74g (0.005mol) Mg (NO3) 2 and be dissolved in sucrose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 1h, speed of agitator is 700rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 150 DEG C, and the response time is 4 hours.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating.
(3) the carbon ball MgO powder body obtained is risen to 700 DEG C by the heating rate of 3 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 150 DEG C, the response time is 4 hours, heat treatment heating rate and temperature respectively 3 DEG C/min and 700 DEG C time, the MgO powder mean diameter obtained is 1.5 μm, and specific surface area is 350m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-KBr (12wt.%:37wt.%:57wt.%) and this hollow MgO powder is used to prepare thermal battery electrolyte.
(1) weighing the hollow MgO powder of 0.54g and 0.96gLiCl-LiBr-KBr fused salt, the content in the electrolyte controlling hollow MgO powder is 36wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KBr fused salt in 400 DEG C of congruent meltings 4 hours；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder obtains the LiCl-LiBr-KBr electrolyte containing hollow MgO powder through pressing mold molding, and briquetting pressure is 20MPa.
LiCl-LiBr-KBr electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.32g/cm-3, the thickness after pressing mold molding is 0.4mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 89wt.%.
Example example 3:
1. the preparation of hollow MgO powder:
Use glucose and MgCl2Powder synthesizes hollow MgO powder as initial feed.
(1) weigh 6.5g glucose and be dissolved in 100mL deionized water, to be mixed uniformly after weigh 0.95g (0.01mol) MgCl2It is dissolved in glucose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 2h, speed of agitator is 1000rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 200 DEG C, and the response time is 6h.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating.
(3) the carbon ball MgO powder body obtained is risen to 600 DEG C by the heating rate of 2 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 200 DEG C, the response time is 6h, heat treatment heating rate and temperature respectively 2 DEG C/min and 600 DEG C time, the MgO powder mean diameter obtained is 1.8 μm, and specific surface area is 390m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) and this MgO powder is used to prepare thermal battery electrolyte
(1) weighing the hollow MgO powder of 0.32g and 0.68gLiCl-LiBr-LiF fused salt, the content in the electrolyte controlling hollow MgO powder is 32wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C of congruent meltings 4 hours；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder obtains the LiCl-LiBr-LiF electrolyte containing hollow MgO powder through pressing mold molding, and briquetting pressure is 20MPa.
LiCl-LiBr-LiF electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.64g/cm-3, the thickness after pressing mold molding is 0.5mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 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) weigh 4.2g sucrose and be dissolved in 100mL deionized water, to be mixed uniformly after weigh 0.74g (0.005mol) Mg (NO3)2It is dissolved in sucrose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 1h, speed of agitator is 700rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 180 DEG C, and the response time is 3h.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating
(3) the carbon ball MgO powder body obtained is risen to 500 DEG C by the heating rate of 2 DEG C/min and carry out heat treatment, obtain hollow MgO powder
When hydrothermal temperature is 180 DEG C, the response time is 3h, heat treatment heating rate and temperature respectively 2 DEG C/min and 500 DEG C time, the MgO powder mean diameter obtained is 2 μm, and specific surface area is 310m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) and this MgO powder is used to prepare thermal battery electrolyte.
(1) weighing the hollow MgO powder of 0.39g and 1gLiCl-LiBr-LiF fused salt, the content in the electrolyte controlling hollow MgO powder is 28wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C of congruent meltings 4 hours；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder obtains the LiCl-LiBr-LiF electrolyte containing hollow MgO powder through pressing mold molding, and briquetting pressure is 20MPa.
LiCl-LiBr-LiF electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.49g/cm-3, the thickness after pressing mold molding is 0.7mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 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) weigh 3.0g glucose and be dissolved in 100mL deionized water, to be mixed uniformly after weigh 1.14g (0.008mol) Mg (CH3COO)2It is dissolved in glucose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 2h, speed of agitator is 1000rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 140 DEG C, and the response time is 4 hours.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating.
(3) the carbon ball MgO powder body obtained is risen to 650 DEG C by the heating rate of 2.5 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 140 DEG C, the response time is 4 hours, heat treatment heating rate and temperature respectively 2.5 DEG C/min and 650 DEG C time, the MgO powder mean diameter obtained is 0.8 μm, and specific surface area is 540m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-LiF fused salt (31wt.%:47wt.%:22wt.%) is used to prepare thermal battery electrolyte with this MgO powder in 500 DEG C
(1) weighing the hollow MgO powder of 0.54g and 0.66gLiCl-LiBr-LiF fused salt, the content in the electrolyte controlling hollow MgO powder is 45wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C of congruent meltings 4 hours；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder obtains the LiCl-LiBr-LiF electrolyte containing hollow MgO powder through pressing mold molding, and briquetting pressure is 20MPa.
LiCl-LiBr-LiF electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.68g/cm-3, the thickness after pressing mold molding is 0.6mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 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) weigh 2.7g sucrose and be dissolved in 100mL deionized water, to be mixed uniformly after weigh 1.14g (0.008mol) Mg (CH3COO)2It is dissolved in sucrose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 1.5h, speed of agitator is 800rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 140 DEG C, and the response time is 4 hours.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating.
(3) the carbon ball MgO powder body obtained is risen to 600 DEG C by the heating rate of 2.5 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 140 DEG C, the response time is 4 hours, heat treatment heating rate and temperature respectively 2.5 DEG C/min and 600 DEG C time, the MgO powder mean diameter obtained is 1 μm, and specific surface area is 480m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-LiF (31wt.%:47wt.%:22wt.%) and this MgO powder is used to prepare thermal battery electrolyte.
(1) weighing the hollow MgO powder of 0.46g and 0.69gLiCl-LiBr-LiF fused salt, the content in the electrolyte controlling hollow MgO powder is 40wt.%；
(2) by hollow MgO powder and LiCl-LiBr-LiF fused salt in 500 DEG C of congruent meltings 4 hours；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder obtains the LiCl-LiBr-LiF electrolyte containing hollow MgO powder through pressing mold molding, and briquetting pressure is 20MPa.
LiCl-LiBr-LiF electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.59g/cm-3, the thickness after pressing mold molding is 0.4mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 96wt.%.
Embodiment 7:
1. the preparation of hollow MgO powder:
Use glucose and MgCl2Powder, as initial feed, synthesizes hollow MgO powder in accordance with the following methods.
(1) 5.4g glucose is dissolved in 100mL deionized water, to be mixed uniformly after weigh 0.95g (0.01mol) MgCl2It is dissolved in glucose solution.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 2h, speed of agitator is 1000rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 150 DEG C, and the response time is 4h.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating, obtain carbon ball MgO powder body.
(3) carbon ball MgO powder body is risen to 550 DEG C by the heating rate of 2.5 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 150 DEG C, the response time is 4h, heat treatment heating rate and temperature respectively 2.5 DEG C/min and 600 DEG C time, hollow MgO powder mean diameter is 1.5 μm, and specific surface area is 390m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-KCl fused salt (45wt.%:55wt.%) and hollow MgO powder is used to prepare thermal battery electrolyte:
(1) weighing the hollow MgO powder of 0.4g and 0.8gLiCl-KCl fused salt, the content in the electrolyte controlling hollow MgO powder is 33wt.%；
(2) by hollow MgO powder and LiCl-KCl fused salt in 400 DEG C of congruent meltings 4 hours, congruent melting powder is obtained；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder is through pressing mold molding, obtains the LiCl-KCl electrolyte containing hollow MgO powder, and briquetting pressure is 20MPa.
LiCl-KCl electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.31g/cm-3, the thickness after pressing mold molding is 0.3mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 95wt.%.
Embodiment 8:
1. the preparation of hollow MgO powder:
Use fructose and Mg (NO3)2Powder, as initial feed, synthesizes hollow MgO powder in accordance with the following methods.
(1) 1.8g fructose is dissolved in 100mL deionized water, to be mixed uniformly after weigh 1.48g (0.01mol) Mg (NO3)2Powder is dissolved in fructose soln.Being placed in by mixed solution in 60 DEG C of waters bath with thermostatic control and stir 2h, speed of agitator is 1000rpm.
(2) being transferred in hydrothermal reaction kettle by precursor solution, reaction temperature is 180 DEG C, and the response time is 3h.Dry 2h in 80 DEG C of baking ovens is taken out in reaction after terminating, obtain carbon ball MgO powder body.
(3) carbon ball MgO powder body is risen to 650 DEG C by the heating rate of 4 DEG C/min and carry out heat treatment, obtain hollow MgO powder.
When hydrothermal temperature is 180 DEG C, the response time is 3h, heat treatment heating rate and temperature respectively 4 DEG C/min and 650 DEG C time, hollow MgO powder mean diameter is 1.85 μm, and specific surface area is 325m2/g。
2. prepared by thermal battery electrolyte:
Thermal battery electrolyte is formed (Fig. 1) by fused salt 1 and MgO hollow ball 2.
LiCl-LiBr-KCl fused salt (12wt.%:36.5wt.%:51.5wt.%) and hollow MgO powder is used to prepare thermal battery electrolyte:
(1) weighing the hollow MgO powder of 0.65g and 0.65gLiCl-LiBr-KCl fused salt, the content in the electrolyte controlling hollow MgO powder is 50wt.%；
(2) by hollow MgO powder and LiCl-LiBr-KCl fused salt in 400 DEG C of congruent meltings 4 hours, congruent melting powder is obtained；
(3) take out ball milling mistake 150 mesh sieves after congruent melting powder cools down, obtain electrolyte powder；
(4) electrolyte powder is through pressing mold molding, obtains the LiCl-LiBr-KCl electrolyte containing hollow MgO powder, and briquetting pressure is 20MPa.
LiCl-LiBr-KCl electrolyte containing hollow MgO powder prepared by this embodiment, detecting its density through densimeter is 2.69g/cm-3, the thickness after pressing mold molding is 0.8mm；This electrolyte sheet is at 500 DEG C after 1h, and electrolyte conservation rate is 88wt.%.
In above-described embodiment, it is possible to adopting planetary ball mill that the congruent melting powder after cooling is carried out ball milling, the relative humidity of milling atmosphere is less than 3%.
Claims (10)
1. a preparation method for the thermal battery electrolyte containing hollow magnesia powder, is characterized in that:
(1) hollow MgO powder is prepared:
The preparation solution containing water solublity carbon source and anhydrous magnesium salt, this solution obtains precursor solution after water bath with thermostatic control is stirred, and this precursor solution has the carbon ball MgO powder body of nucleocapsid structure through water heat transfer, and this powder body, through Overheating Treatment, obtains hollow MgO powder；
(2) thermal battery electrolyte powder body is prepared:
Taking hollow MgO powder content in whole electrolyte is 25wt.%～45wt.%, then by temperature congruent melting 3.5-4.5 hour at >=fusing point 50 DEG C of this hollow MgO powder and fused salt, obtains thermal battery electrolyte powder body after ball milling sieves 150 orders；
(3) pressing mold molding:
By the thermal battery electrolyte powder pressure mold forming at 20MPa, obtain the thermal battery electrolyte containing hollow MgO powder.
2. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 1, it is characterised in that described precursor solution, is made up of following methods:
(1) weigh 1g～10g water solublity carbon source and be dissolved in Homogeneous phase mixing in 100mL deionized water, obtain water solublity carbon source solution；
(2) weigh the anhydrous magnesium salt of 0.005mol～0.015mol and be dissolved in glucose solution, obtain anhydrous magnesium saline solution；
(3) after water solublity carbon source solution and anhydrous magnesium saline solution being mixed by 1:1 mass ratio, being placed in 60 DEG C of waters bath with thermostatic control and stir 1～4 hour, speed of agitator is 500～1000rpm, obtains described precursor solution.
3. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 2, it is characterized in that being transferred in reactor by precursor solution, carbon ball MgO powder body is synthesized by hydro-thermal reaction method, the temperature of hydro-thermal reaction is 140 DEG C～200 DEG C, response time is 2～6h, reaction takes out carbon ball MgO powder body after terminating, dry 1.5-2h in 70-85 DEG C of baking oven；Then the carbon ball MgO powder body after drying is risen to 500 DEG C～800 DEG C under the heating rate of 1 DEG C～5 DEG C/min and carry out heat treatment, remove the nano carbon microsphere in carbon ball MgO powder body, obtain hollow MgO powder.
4. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 3, it is characterised in that described hollow MgO powder, its mean diameter is 500nm～2 μm, and specific surface area is >=300m2/g。
5. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 2, it is characterised in that described water solublity carbon source is the one in glucose, sucrose, fructose.
6. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 2, it is characterised in that described anhydrous magnesium salt is MgCl2、Mg(NO3)2、Mg(CH3COO)2With the one in magnesium isopropoxide.
7. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 1, it is characterized in that described fused salt is congruent melting salt, this congruent melting salt is 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.%), the one in LiF-LiBr-KBr (0.8wt.%:56wt.%:43.2wt.%).
8. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 1, it is characterised in that thermal battery electrolyte prepared by the method is lithium system thermal cell, it is:
Li(Si)/LiCl-LiF-LiBr/FeS2, Li (B)/LiF-LiBr-KBr/FeS2, Li (B)/LiCl-LiF-LiBr/CoS2, Li (B)/LiF-LiBr-KBr/CoS2In one.
9. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 1, it is characterised in that thermal battery electrolyte prepared by the method, its thickness is 0.3mm～0.8mm, and density is 2.3g/cm3～2.7g/cm3。
10. the preparation method of the thermal battery electrolyte containing hollow magnesia powder according to claim 1, it is characterised in that thermal battery electrolyte prepared by the method, its under 500 DEG C of conditions after 1h electrolyte conservation rate >=85wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610228180.8A CN105789653B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610228180.8A CN105789653B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105789653A true CN105789653A (en) | 2016-07-20 |
| CN105789653B CN105789653B (en) | 2019-01-29 |
Family
ID=56396449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610228180.8A Active CN105789653B (en) | 2016-04-13 | 2016-04-13 | A kind of preparation method of the thermal battery electrolyte containing hollow magnesia powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105789653B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328966A (en) * | 2016-08-25 | 2017-01-11 | 中南大学 | Thermal battery electrolyte containing metal particles and preparation method and application of thermal battery electrolyte |
| CN107425208A (en) * | 2017-06-27 | 2017-12-01 | 北方特种能源集团有限公司西安庆华公司 | A kind of thermal cell electrolyte |
| CN107732268A (en) * | 2017-11-23 | 2018-02-23 | 上海空间电源研究所 | A kind of cell of carrier rocket thermal cell |
| CN107845820A (en) * | 2017-11-07 | 2018-03-27 | 西南科技大学 | Thermal battery electrolyte piece reforming apparatus and thermal battery electrolyte piece method of modifying |
| 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 |
| CN109167080A (en) * | 2018-09-12 | 2019-01-08 | 哈尔滨工业大学（威海） | A kind of high voltage lithium thermal cell |
| CN109370531A (en) * | 2018-09-30 | 2019-02-22 | 贵州梅岭电源有限公司 | A kind of preparation method of thermal cell heat buffering heat accumulating |
| 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 |
| CN113130840A (en) * | 2021-04-19 | 2021-07-16 | 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 |
| CN113851628A (en) * | 2021-08-19 | 2021-12-28 | 聊城大学 | No adhesive type V2O5Molten salt electrode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228520A1 (en) * | 2002-06-06 | 2003-12-11 | Kaun Thomas D. | Process for manufacturing thermal battery with thin fiber separator |
| JP2005129277A (en) * | 2003-10-22 | 2005-05-19 | Matsushita Electric Ind Co Ltd | Thermal battery |
| CN102849760A (en) * | 2012-08-22 | 2013-01-02 | 中国科学院过程工程研究所 | Hollow nanometer magnesia microsphere and preparation method thereof |
| CN103825058A (en) * | 2014-02-28 | 2014-05-28 | 华中科技大学 | Novel paste electrolyte used for high-temperature molten salt battery and preparation method thereof |
-
2016
- 2016-04-13 CN CN201610228180.8A patent/CN105789653B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030228520A1 (en) * | 2002-06-06 | 2003-12-11 | Kaun Thomas D. | Process for manufacturing thermal battery with thin fiber separator |
| JP2005129277A (en) * | 2003-10-22 | 2005-05-19 | Matsushita Electric Ind Co Ltd | Thermal battery |
| CN102849760A (en) * | 2012-08-22 | 2013-01-02 | 中国科学院过程工程研究所 | Hollow nanometer magnesia microsphere and preparation method thereof |
| CN103825058A (en) * | 2014-02-28 | 2014-05-28 | 华中科技大学 | Novel paste electrolyte used for high-temperature molten salt battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARIA-MAGDALENA TITRICI ET AL.: ""A Generalized Synthesis of Metal Oxide Hollow Sphere Using a Hydrothermal Approach"", 《CHEMISTRY OF MATERIALS》 * |
| 宋学兵等: ""热电池用电解质流动抑制剂的控制"", 《电池工业》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106328966A (en) * | 2016-08-25 | 2017-01-11 | 中南大学 | Thermal battery electrolyte containing metal particles and preparation method and application of thermal battery electrolyte |
| CN107425208A (en) * | 2017-06-27 | 2017-12-01 | 北方特种能源集团有限公司西安庆华公司 | A kind of thermal cell electrolyte |
| 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 |
| CN107845820A (en) * | 2017-11-07 | 2018-03-27 | 西南科技大学 | Thermal battery electrolyte piece reforming apparatus and thermal battery electrolyte piece method of modifying |
| 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 |
| CN107732268A (en) * | 2017-11-23 | 2018-02-23 | 上海空间电源研究所 | A kind of cell of carrier rocket thermal cell |
| CN109167080A (en) * | 2018-09-12 | 2019-01-08 | 哈尔滨工业大学（威海） | A kind of high voltage lithium thermal cell |
| CN109370531A (en) * | 2018-09-30 | 2019-02-22 | 贵州梅岭电源有限公司 | A kind of preparation method of thermal cell heat buffering heat accumulating |
| 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 |
| CN113130840A (en) * | 2021-04-19 | 2021-07-16 | 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 |
| 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 |
| CN113851628A (en) * | 2021-08-19 | 2021-12-28 | 聊城大学 | No adhesive type V2O5Molten salt electrode material and preparation method and application 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105789653B (en) | 2019-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105789653A (en) | Preparation method of thermal battery electrolyte containing hollow magnesia powder | |
| CN101764207B (en) | Lithium titanate for lithium ion battery negative electrode material and preparation method thereof | |
| CN105118967B (en) | A kind of doping tertiary cathode material of metal oxide coating modification and preparation method thereof | |
| CN101964415B (en) | Method for preparing lithium-ion battery anode material | |
| CN105428648B (en) | A kind of preparation method of battery anode material of lithium iron phosphate | |
| WO2014013837A1 (en) | Active material particles for lithium ion secondary batteries, and lithium ion secondary battery using same | |
| JP2009298687A (en) | Crystallized glass and method for producing the same | |
| CN107275634B (en) | Method for synthesizing high-tap-density and high-capacity spherical lithium-rich manganese-based positive electrode material without complexing agent | |
| CN112490403B (en) | Pole piece with uniform thickness of lug ceramic coating and preparation method thereof | |
| CN105958037B (en) | Sodium-ion battery cathode copper sulfide/graphene composite material and preparation method | |
| CN108899480A (en) | A kind of long circulation life height ratio capacity nickel cobalt aluminium positive electrode and preparation method thereof | |
| CN105576206B (en) | A kind of Cu for negative electrode of lithium ion battery2V2O7The preparation method of graphene composite material | |
| CN104900865A (en) | High practicality lithium nickel manganese oxide and preparation method thereof | |
| CN102820459A (en) | Preparation method for lithium titanate material with high specific energy from mesoporous titanium dioxide | |
| CN104828878B (en) | A kind of preparation method of the nickel ion doped material of graphene coated | |
| CN104733714B (en) | Modification method of lithium ion battery cathode material | |
| CN109052490B (en) | A kind of ternary cathode material of lithium ion battery and preparation method thereof | |
| CN115571867B (en) | Hard carbon anode material and preparation method and application thereof | |
| CN101771146A (en) | Lithium ion battery anode material and preparation method thereof | |
| CN106082286B (en) | A kind of thermal battery electrolyte inhibitor MgO and preparation method thereof | |
| WO2012147555A1 (en) | Lithium carbonate production method and lithium carbonate production device | |
| CN111313026B (en) | Porous nitrogen-doped carbon/amorphous antimony compound, preparation method and application | |
| CN109037645B (en) | Method for preparing metal oxide @ chlorine-doped graphene lithium ion battery anode material in one step | |
| CN103715408B (en) | The sol-gel process for preparing of lithium ion battery negative material zinc titanate lithium | |
| CN110040736A (en) | A kind of preparation method of silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |