CN107528072B - Phase-change heat storage type explosion suppression material for thermal battery development and preparation method thereof - Google Patents
Phase-change heat storage type explosion suppression material for thermal battery development and preparation method thereof Download PDFInfo
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- CN107528072B CN107528072B CN201710545362.2A CN201710545362A CN107528072B CN 107528072 B CN107528072 B CN 107528072B CN 201710545362 A CN201710545362 A CN 201710545362A CN 107528072 B CN107528072 B CN 107528072B
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention discloses a phase-change heat storage type explosion suppression material for developing a thermal battery, which is prepared from MgO and MgCl2Adding BN fiber as main raw materialThe dimension is used as a structure enhancing component to ensure the structural strength of the explosion suppression material, and the phase-change heat storage type explosion suppression material with good chemical stability, high heat content, proper phase-change response temperature and excellent mechanical strength is obtained by carrying out solid-phase reaction preparation by a secondary pressing sintering method under the conditions of deoxidation and dehydration. The unit enthalpy of the obtained phase-change heat storage type explosion suppression material is about 160-250J/g, and chain thermal runaway of a fault thermal battery can be effectively cut off; the phase transition temperature is 715 ℃, and is basically positioned at a thermal runaway critical temperature point of the thermal battery; the mechanical impact resistance magnitude is more than 10000g, and the material basically covers all in-service and in-research product lines, thereby completely meeting the actual research and development requirements of the thermal battery model.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a phase-change heat storage type explosion suppression material for thermal battery development and a preparation method thereof.
Background
The thermal battery is a primary storage battery which uses a heating system of the battery to heat and melt non-conductive solid-state salt electrolyte into an ionic conductor to enter a working state, has the biggest characteristics of short activation time and no need of maintenance during storage, and is particularly suitable for serving as a matched power supply of various missile and weapon systems. However, due to the characteristics of the thermal battery, it is difficult to perform a charge and discharge test as with other chemical power sources, which means that it is difficult to make an accurate judgment on the safety and reliability of the thermal battery itself before activation. From the development experience of the unit and the public reports at home and abroad, the main safety problem of the thermal battery is chain thermal runaway caused by various design or process reasons, and the basic mechanism is as follows: local thermal runaway of the pile → decomposition of the sulfide positive pole → exothermic reaction of sulfur vapor and the lithium alloy negative pole → melting and overflowing of the lithium alloy negative pole → large-scale short circuit of the pile → further expansion of the thermal runaway → fusion penetration or explosion of the metal shell. Therefore, in the process of thermal battery development, weak links of design or process are accurately found, and thermal runaway is effectively avoided and is the most important safety consideration factor in the process of thermal battery development.
With the continuous development of weapon systems such as missiles and the like, the use requirements on high and low temperature and mechanical environment of the thermal battery are continuously improved, the design working temperature window of the thermal battery is usually 450-. On the other hand, after the thermal battery is subjected to metal shell fusion or explosion, it is very difficult to find the initial position and reason of thermal runaway occurrence, and design and process improvement can only be carried out by experience, but the improvement is difficult to solve the problem in a targeted manner, and the safety and reliability of the thermal battery model product must be ensured by a large amount of experiments and a method for greatly improving the redundancy, so that the development progress of the model product is seriously influenced, and great pressure is brought to the scientific research and production cost. Therefore, the method for effectively cutting off the chain thermal runaway to realize the accurate judgment of the fault reason is found, and the method becomes a work with military significance and economic value.
The invention provides a phase-change heat storage type explosion suppression material for thermal battery development for the first time, aiming at preventing chain thermal runaway of a fault thermal battery, ensuring the integrity of a fault galvanic pile and being beneficial to the analysis of problems in the development process and the improvement of technology.
At present, no public REPORTs of the technology appear, and only some research REPORTs about the fault thermal battery (such as J.Power Sources110(2002)357, which REPORTs a thermal model and a monomer thermal test device of the lithium-based thermal battery; SANDIA REPORT 2006-1902, which REPORTs a fault tree and corresponding solving measures of a typical thermal battery; J.Power Sources 54(1995)134, which REPORTs related safety characterization of the vehicle lithium-based thermal battery) only analyze the mechanism of chain thermal runaway theoretically, and lack of intuitive visual fault point judgment and analysis capability; the testing device can only carry out a static discharge test and is difficult to reflect the internal electrical condition of a real thermal battery product under a complex working condition, especially a high-magnitude mechanical environment.
Disclosure of Invention
The invention aims to provide a phase-change heat storage type explosion suppression material for thermal battery development and a preparation method thereof, wherein the phase-change heat storage type explosion suppression material can be used for adjusting enthalpy and geometric dimensions according to different thermal battery products and working conditions, cutting off chain thermal runaway of a fault thermal battery, ensuring the integrity of a galvanic pile structure, improving the diagnosis and analysis speed and accuracy of the fault thermal battery and realizing optimization and improvement in the subsequent development process of the product. By adopting the preparation method provided by the invention, the unit enthalpy of the obtained phase-change heat storage type explosion suppression material is about 160-250J/g, and chain thermal runaway of a fault thermal battery can be effectively cut off; the phase transition temperature is 715 ℃, and is basically positioned at a thermal runaway critical temperature point of the thermal battery; the mechanical impact resistance magnitude is more than 10000g, and the material basically covers all in-service and in-research product lines, thereby completely meeting the actual research and development requirements of the thermal battery model.
The invention is realized by the following technical scheme: a phase-change heat storage type explosion suppression material for thermal battery development comprises the following chemical components in percentage by mass: the mass content of MgO is 40-60%, and MgCl is adopted2The mass content of the BN fiber is 55-35%, and the mass content of the BN fiber is 5-10%.
The invention also provides a preparation method of the phase-change heat storage type explosion suppression material for developing the thermal battery, which comprises the following steps:
step one, calculating according to the amount of BN fiber accounting for 5-10% of the total mass of the phase-change heat storage type explosion suppression material, weighing the needed BN fiber, placing the BN fiber in an enamel tray, then placing the enamel tray into a vacuum drying box, wherein the vacuum degree of the vacuum drying box is not more than-0.08 MPa, and drying the BN fiber for 4-8 hours at the temperature of 170-200 ℃;
step two, weighing the required MgO according to the calculation that the MgO accounts for 40-60% of the total mass of the phase-change heat storage type explosion suppression material; placing MgO in a stainless steel tank, then placing the stainless steel tank in a muffle furnace, and calcining for 4-6h at 480-520 ℃;
step three, according to MgCl2Weighing required MgCl in 55-35% of the total mass of the phase-change heat storage type explosion suppression material2Mixing MgCl2Placing in an enamel tray, and then placing in a vacuum drying oven with vacuum degree of not more than-0.08 MPa at 170-200 deg.CDrying for 4-8h under the condition;
step four, calcining the MgO and drying the MgCl2Simultaneously adding the mixture into a ball mill, ball-milling and mixing uniformly, then placing the mixture into a quartz beaker, placing the quartz beaker into a vacuum sintering furnace, slowly heating to 750 plus 800 ℃ under the condition that the vacuum degree is not more than-0.08 MPa, calcining for 4-8h, naturally cooling to room temperature, and ball-milling and crushing the blocky product to obtain MgO and MgCl2The sintered mixture of (a);
step five, adding MgO and MgCl2The sintered mixture and the dried BN fiber are simultaneously added into a powder mixer to be uniformly mixed, the mixed powder is weighed according to the required weight and then is placed into a hard alloy die at the temperature of 1.5-3.5T/cm2Pressing into a required sheet precursor under the pressure of the pressure;
and step six, placing the precursor into a quartz vessel, placing the quartz vessel into a vacuum sintering furnace, slowly heating to 750-800 ℃ under the condition that the vacuum degree is not more than-0.08 MPa, calcining for 4-8h, and naturally cooling to room temperature to obtain the phase-change heat storage type explosion suppression material for developing the thermal battery.
Further, the specific surface area of the MgO is 20-70m2The fiber length of the BN fiber is preferably 50-100 mu m, and the MgCl is adopted2The purity is more than 97 percent, the total content of the rest metal halides is not more than 2 percent, and the powder mixer is preferably a three-dimensional, conical or biconical powder mixer without a propeller, a helical ribbon or a screw forced stirring and mixing function.
Compared with the prior art, the phase-change heat storage type explosion suppression material for thermal battery development and the preparation method thereof have the following technical advantages:
1) the invention firstly provides a phase-change heat storage type explosion suppression material for thermal battery development, and skillfully utilizes MgCl2The characteristic that the phase transition temperature (715 ℃) is between the normal thermal battery working window (450-The optimization and improvement in the subsequent development process of the existing product are purposeful.
2) The secondary pressing sintering method provided by the invention can flexibly and conveniently design and prepare the phase-change heat storage type explosion suppression materials with different geometric sizes and different heat content sizes according to the actual requirements of model products. At the same time, MgO and MgCl2After BN fiber is added into the sintering mixture, secondary sintering is carried out, a microstructure similar to 'steel bar-concrete' can be formed, and the mechanical strength of the material is greatly improved. The prepared phase-change heat storage type explosion suppression material has wide application range and basically covers all in-service and in-research product lines.
3) The phase-change heat storage type explosion suppression material for the development of the thermal battery has the advantages of low cost of raw materials, wide sources, simple process equipment and no discharge of any harmful waste in the whole preparation process, accords with low-carbon economy and sustainable development economic strategies, and has great military and economic values.
Detailed Description
Hereinafter, the present invention will be further illustrated by examples.
Example 1
The phase change heat storage type explosion suppression material for developing a target product thermal battery comprises the following components in parts by weight: MgO accounts for 60%, MgCl235 percent of BN fiber and 5 percent of BN fiber. Firstly, processing three raw materials at high temperature for later use, wherein the sintering temperature of MgO is 480 ℃, and the sintering time is 6 h; MgCl2The drying temperature is 170 ℃, and the drying time is 8 hours; the drying temperature of the BN fiber is 170 ℃, and the drying time is 8 h. Then mixing MgO with MgCl2After ball milling and mixing are carried out uniformly, the mixture is transferred into a quartz beaker, the quartz beaker is placed into a vacuum sintering furnace to be heated to 750 ℃ slowly, and after 8 hours of calcination, the quartz beaker is naturally cooled and ball milled and crushed. Uniformly mixing the obtained crushed product and BN fiber in a powder mixer, putting the mixture into a round hard alloy die at 1.5T/cm2Is pressed into a wafer-shaped precursor. And finally, slowly heating the precursor to 750 ℃ in a vacuum sintering furnace, calcining for 8 hours, and naturally cooling to obtain the required product.
Example 2
Phase-change heat storage type explosion suppression material for development of target product thermal batteryThe weight ratio of each component is as follows: MgO accounts for 40%, MgCl255 percent of BN fiber and 5 percent of BN fiber. Firstly, processing three raw materials at high temperature for later use, wherein the sintering temperature of MgO is 500 ℃, and the sintering time is 6 h; MgCl2The drying temperature is 180 ℃, and the drying time is 6 hours; the drying temperature of the BN fiber is 180 ℃, and the drying time is 6 h. Then mixing MgO with MgCl2After ball milling and mixing are carried out uniformly, the mixture is transferred into a quartz beaker, the quartz beaker is placed into a vacuum sintering furnace to be heated to 750 ℃ slowly, and after 8 hours of calcination, the quartz beaker is naturally cooled and ball milled and crushed. Uniformly mixing the obtained crushed product and BN fiber in a powder mixer, putting the mixture into a round hard alloy die at the temperature of 2.0T/cm2Is pressed into a wafer-shaped precursor. And finally, slowly heating the precursor to 750 ℃ in a vacuum sintering furnace, calcining for 8 hours, and naturally cooling to obtain the required product.
Example 3
The phase change heat storage type explosion suppression material for developing a target product thermal battery comprises the following components in parts by weight: MgO accounts for 60%, MgCl235 percent of BN fiber and 5 percent of BN fiber. Firstly, processing three raw materials at high temperature for later use, wherein the sintering temperature of MgO is 520 ℃, and the sintering time is 4 hours; MgCl2The drying temperature is 200 ℃, and the drying time is 4 hours; the drying temperature of the BN fiber is 200 ℃, and the drying time is 4 h. Then mixing MgO with MgCl2After ball milling and mixing are carried out uniformly, the mixture is transferred into a quartz beaker, the quartz beaker is placed into a vacuum sintering furnace to be heated to 800 ℃ slowly, and after calcining for 4 hours, the quartz beaker is cooled naturally and is ball milled and crushed. Uniformly mixing the obtained crushed product and BN fiber in a powder mixer, putting the mixture into a round hard alloy die at the temperature of 3.5T/cm2Is pressed into a wafer-shaped precursor. And finally, slowly heating the precursor to 800 ℃ in a vacuum sintering furnace, calcining for 4 hours, and naturally cooling to obtain the required product.
Example 4
The phase change heat storage type explosion suppression material for developing a target product thermal battery comprises the following components in parts by weight: MgO 50% and MgCl240% of BN fiber and 10% of BN fiber. Firstly, processing three raw materials at high temperature for later use, wherein the sintering temperature of MgO is 500 ℃, and the sintering time is 6 h; MgCl2The drying temperature is 180 ℃, and the drying time is 6 hours; drying of BN fibresThe temperature is 180 ℃, and the drying time is 6 h. Then mixing MgO with MgCl2After ball milling and mixing are carried out uniformly, the mixture is transferred into a quartz beaker, the quartz beaker is placed into a vacuum sintering furnace to be heated to 750 ℃ slowly, and after calcination is carried out for 6 hours, the quartz beaker is cooled naturally and is ball milled and crushed. Uniformly mixing the obtained crushed product and BN fiber in a powder mixer, putting the mixture into a round hard alloy die at the temperature of 3.0T/cm2Is pressed into a wafer-shaped precursor. And finally, slowly heating the precursor to 750 ℃ in a vacuum sintering furnace, calcining for 6 hours, and naturally cooling to obtain the required product.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make variations and modifications of the present invention without departing from the spirit and scope of the present invention by using the methods and technical contents disclosed above.
Claims (4)
1. A phase-change heat storage type explosion suppression material for thermal battery development is characterized by comprising the following chemical components in percentage by mass: MgO accounts for 40-60% of the total mass of the phase-change heat storage type explosion suppression material; MgCl2Accounting for 55-35% of the total mass of the phase-change heat storage type explosion suppression material; BN fiber accounts for 5-10% of the total mass of the phase-change heat storage type explosion suppression material;
the preparation method of the phase-change heat storage type explosion suppression material for the development of the thermal battery comprises the following steps:
1) weighing the needed BN fiber according to the calculation that the BN fiber accounts for 5-10% of the total mass of the phase-change heat storage type explosion suppression material, placing the BN fiber in an enamel tray, then placing the enamel tray into a vacuum drying box, wherein the vacuum degree of the vacuum drying box is less than or equal to minus 0.08MPa, and drying the BN fiber for 4-8 hours at the temperature of 170-200 ℃;
2) weighing the required MgO according to the calculation that the MgO accounts for 40-60% of the total mass of the phase-change heat storage type explosion suppression material; placing MgO in a stainless steel tank, then placing the stainless steel tank in a muffle furnace, and calcining for 4-6h at 480-520 ℃;
3) according to MgCl2Weighing required MgCl in 55-35% of the total mass of the phase-change heat storage type explosion suppression material2Mixing MgCl2Placing the mixture in an enamel plate, then placing the mixture in a vacuum drying box, wherein the vacuum degree of the vacuum drying box is less than or equal to-0.08 MPa, and drying the mixture for 4 to 8 hours at the temperature of 170-200 ℃;
4) calcining MgO and drying MgCl2Simultaneously adding the mixture into a ball mill, ball-milling and mixing uniformly, then placing the mixture into a quartz beaker, placing the quartz beaker into a vacuum sintering furnace, slowly heating to 750 plus 800 ℃ under the condition that the vacuum degree is less than or equal to-0.08 MPa, calcining for 4-8h, naturally cooling to room temperature, and ball-milling and crushing the blocky product to obtain MgO and MgCl2The sintered mixture of (a);
5) mixing MgO and MgCl2The sintered mixture and the dried BN fiber are simultaneously added into a powder mixer to be uniformly mixed, the mixed powder is weighed according to the required weight and then is placed into a hard alloy die at the temperature of 1.5-3.5T/cm2Pressing into a required sheet precursor under the pressure of the pressure;
6) and placing the precursor into a quartz vessel, placing the quartz vessel into a vacuum sintering furnace, slowly heating to 800 ℃ at the vacuum degree of less than or equal to-0.08 MPa, calcining for 4-8h, and naturally cooling to room temperature to obtain the phase-change heat storage type explosion suppression material for developing the thermal battery.
2. The phase-change heat storage type explosion suppression material for thermal battery development as claimed in claim 1, wherein said MgO has a specific surface area of 20 to 70m2/g。
3. The phase change heat storage type explosion suppression material for thermal battery development as claimed in claim 1, wherein the BN fibers have a fiber length of 50 to 100 μm.
4. The phase-change heat storage type explosion suppression material for thermal battery development as claimed in claim 1, wherein said powder mixer employs a three-dimensional powder mixer with non-paddle, ribbon or screw forced stirring mixing function.
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| US4440837A (en) * | 1982-09-27 | 1984-04-03 | The United States Of America As Represented By The United States Department Of Energy | Positive electrode current collector for liquid metal cells |
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