CN108963291B - Thin thermal battery with independent electrode system and heating system - Google Patents
Thin thermal battery with independent electrode system and heating system Download PDFInfo
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Abstract
The invention discloses a thin thermal battery with an electrode system and a heating system independent, wherein the heating system is wrapped by a heat conduction insulating layer and is composed of a plurality of thin thermal batteriesThe periphery of the anode material supplies heat to an electrode system, the preparation method of the electrode system is a pressing method or a thermal spraying method, the active material of the anode material is an alloy compound and is a pure substance, and the heat conduction insulating layer adopts a material with the heat conductivity of 32-400W/(m.K) and the resistivity of more than 1015Omega cm, the material with melting point above 1200 deg.C, while guaranteeing the normal work of the battery, will not lengthen the activation time of the battery, have also solved the high-voltage safety problem brought by many single batteries to connect in series, the invention adopts the surrounding heating mode of all around to reduce the height of the thermal battery apparently, adopt the alloy compound with higher specific energy as the active material of the positive pole material, reduce the thickness of the positive pole piece in the same tabletting density, further reduce the height of the thermal battery.
Description
Technical Field
The invention relates to the field of thermal batteries, in particular to a thin thermal battery with an electrode system and a heating system which are independent.
Background
In the 60's of the 20 th century, united states company of Unidynamics and Sandia national laboratory together strived to develop a sheet-type thermal battery technology that achieved thermal battery sheets by powder cold pressing. Sheet technology has also been applied to heat sources for thermal batteries, and new sheet heat sources based on iron and potassium perchlorate have been developed. The material can maintain the same size after ignition, generates small amount of gas and is safer than zirconium/barium chromate hot paper. In addition, the heat output can be easily controlled by adjusting the ratio of iron to potassium perchlorate, and the heating plate also has the function of serving as an electronic conductor due to the excessive amount of iron powder in the heating plate. The development of full-sheet thermal batteries in the Sandia national laboratory was a great leap forward in the current time to improve thermal battery technology. Until now, the whole thermal battery is assembled by stacking a heating system → a current collector → a positive material → a diaphragm material → a negative material → a current collector → a heating system, stacking the heating system in series, stacking the heating system in parallel in reverse, and forming an electrode material by the current collector → the positive material → the diaphragm material → the negative material → the current collector, as shown in fig. 5. In order to reduce the height of the thermal battery, patent US8313853B2 describes a ceramic diaphragm prepared by using a tape casting technique, which can greatly reduce the thickness of the diaphragm in the thermal battery, and cannot significantly reduce the height of the thermal battery, and cannot adapt to the development trend of thinning the thermal battery.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the utility model provides a thin thermal battery of electrode system and independent heating system to solve prior art thermal battery height too high, can not adapt to the problem of the development trend of thermal battery slimming.
The technical scheme of the invention is as follows: a thin thermal battery with an electrode system and a heating system independent comprises the electrode system and the heating system, wherein the heating system is wrapped by a heat conduction insulating layer, and the heating system supplies heat to the electrode system from the periphery.
The preparation method of the electrode system is a pressing method or a thermal spraying method.
The pressing method comprises the steps of pressing the anode material, the diaphragm material, the cathode material and the current collector into tablets in a cold pressing mode, sequentially stacking the anode material, the diaphragm material, the cathode material and the current collector from top to bottom to form a single battery structure, and stacking the single battery structures to form an electrode system.
The thermal spraying process comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system.
The active material of the anode material is an alloy compound FexCo1-xS2、FexNi1-xS2、CoxNi1-xS2Or FexCoyNi1-x-yS2Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the product is pure.
The shape of the electrode system is solid column shape or hollow column shape.
The heat conducting insulating layer is made of a material with the heat conductivity of 32-400W/(m.K) and the resistivity of more than 1015Omega cm, the melting point is above 1200 deg.C, and the material is composite material composed of one or more of beryllium oxide, aluminum nitride, boron nitride or silicon nitride.
The current collector is made of graphite, stainless steel, metal nickel and alloy thereof or metal copper and alloy thereof.
The invention has the beneficial effects that: through separating the electrode system and the heating system of thermal battery with heat conduction insulating layer, change prior art's upper and lower heating methods into the heating methods that encircles all around, show the height that reduces the thermal battery, adopt the alloy compound who has higher specific energy simultaneously as the active material of positive electrode material, the active material of positive electrode material is than traditional thermal battery sulphide cathode material (FeS)2、CoS2、NiS2) The specific energy is higher, reduces the anodal powder quantity, reduces anodal piece thickness at same preforming density, further reduces the thermal battery height. In addition, due to the separation of the battery heating system and the electrode system, the thermal shock influence on the anode material caused by the instant activation of the heating sheet in the original thermal battery is greatly reduced, the utilization rate and the safety of the battery electrode material are improved, the application range of the using amount of the thermal battery heating material is widened, and meanwhile, the thermal conductivity of the thermal conductive insulating layer is 32-400W/(m.K), the resistivity is more than 1015Omega cm, good insulation of the material with the melting point of more than 1200 ℃, and solves the high voltage safety problem caused by the series connection of a plurality of single batteries.
Drawings
FIG. 1 is a schematic sectional view of the "embodiment 1" of the present invention;
FIG. 2 is a schematic top sectional view of "embodiment 1" of the present invention;
FIG. 3 is a schematic front view showing a sectional structure of "example 2" and "example 3" in the present invention;
FIG. 4 is a schematic top sectional view of "example 2" and "example 3" of the present invention;
fig. 5 is an assembly structural view of a prior art thermal battery.
Detailed Description
The invention will be further described with reference to the following drawings and specific embodiments:
example 1
Referring to fig. 1-2, the thin thermal battery of the present invention, in which an electrode system and a heating system are independent, is constructed such that the heating system is surrounded by a heat conductive insulating layer, the heating system supplies heat to the electrode system from the periphery, the heating system includes an ignition system composed of a mixture of zirconium and barium chromate and an electric igniter, and at the same time, a combustion system composed of a mixture of iron and potassium perchlorate is filled in the heat conductive insulating layer.
The preparation method of the electrode system is a pressing method or a thermal spraying method.
The pressing method comprises the steps of pressing the anode material, the diaphragm material, the cathode material and the current collector into tablets in a cold pressing mode, sequentially stacking the anode material, the diaphragm material, the cathode material and the current collector from top to bottom to form a single battery structure, and stacking the single battery structures to form an electrode system.
The thermal spraying process comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system.
The active material of the anode material is an alloy compound FexCo1-xS2、FexNi1-xS2、CoxNi1-xS2Or FexCoyNi1-x-yS2Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the active material of the positive electrode material is more than that of the sulfide positive electrode material (FeS) of the traditional thermal battery2、CoS2、NiS2) Higher specific energy, reduced powder consumption of the anode, and reduced anode capacity at the same tabletting densityThe sheet thickness, thereby further reducing the thermal cell height. Fe is selected for the present examplexCo1-xS2。
The method comprises the steps of preparing a diaphragm material from magnesium oxide and lithium chloride-potassium chloride-lithium bromide eutectic fused salt, preparing a negative electrode material from a lithium boron alloy sheet, preparing a current collector from a metal nickel sheet by using a thermal spraying method to form a single battery structure with the thickness of 0.6-0.7 mm, sequentially connecting two groups of 122 single batteries in series, stacking the two groups of 122 single batteries in parallel, preparing an electrode system with the total height of 161.2mm, wherein the electrode system is in a hollow cylindrical shape, has the thermal conductivity of 33W/(m.K), and has the resistivity of more than 1016Placing a heat conduction insulating pipe made of omega-cm boron nitride ceramics in the hollow of an electrode system, filling a heating material in the heat conduction insulating pipe, tightly wrapping a layer of aerogel with the thickness of 3mm on the outer layer of the electrode system to form an insulating layer, namely, after the thermal battery is completely assembled, placing the thermal battery into a titanium alloy cylinder with the height of 190mm, storing for 6h at the temperature of +60 ℃, activating and discharging, wherein the activation time is 0.35s, the peak voltage is 256.2V, and under the pulse current of 250A, the pulse voltage of 45s is 164.7V.
Example 2
Referring to fig. 3 to 4, the thin thermal battery of the present invention, in which the electrode system is independent from the heating system, the heating system is wrapped by a heat conductive insulating layer, the heating system supplies heat to the electrode system from the periphery, the heating system comprises a mixture of zirconium and barium chromate and an electric igniter as an ignition system, and simultaneously, a combustion system comprising a mixture of iron and potassium perchlorate is filled in the heat conductive insulating layer.
The preparation method of the electrode system is a pressing method or a thermal spraying method.
The pressing method comprises the steps of pressing the anode material, the diaphragm material, the cathode material and the current collector into tablets in a cold pressing mode, sequentially stacking the anode material, the diaphragm material, the cathode material and the current collector from top to bottom to form a single battery structure, and stacking the single battery structures to form an electrode system.
The thermal spraying process comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system.
The active material of the anode material is an alloy compound FexCo1-xS2、FexNi1-xS2、CoxNi1-xS2Or FexCoyNi1-x-yS2Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the active material of the positive electrode material is more than that of the sulfide positive electrode material (FeS) of the traditional thermal battery2、CoS2、NiS2) The specific energy is higher, reduces the anodal powder quantity, reduces positive plate thickness under the same preforming density to further reduce thermal battery height. Fe is selected for the present examplexNi1-xS2。
The diaphragm material is magnesium oxide and lithium chloride-potassium chloride-lithium bromide eutectic fused salt, the negative electrode material is a lithium boron alloy sheet, the current collector is a stainless steel sheet, the thickness of the stainless steel sheet is 1.0-1.1 mm by a pressing method, 146 single batteries are sequentially stacked in series to form an electrode system with the total height of 157.8mm, the electrode system is in a solid column shape, the electrode material is placed in a position with the thermal conductivity of 196.2W/(m.K), the resistivity is more than 1015And (2) sleeving another heat-conducting insulating circular tube of beryllium oxide ceramic with the diameter being 10mm larger than that of the heat-conducting insulating circular tube in the heat-conducting insulating circular tube of omega-cm ceramic, filling a heating material in the two heat-conducting insulating circular tubes, tightly wrapping a layer of aerogel with the thickness of 3mm on the outer layer of the heat-conducting insulating circular tube to form an insulating layer, namely, after the thermal battery is completely assembled, putting the thermal battery into a titanium alloy cylinder with the height of 190mm, storing the thermal battery for 6 hours at the temperature of +60 ℃, then activating and discharging, wherein the activation time is 0.95s, the peak voltage is 298.3V, and under the pulse current of 250A, the pulse voltage of 45s is 153.6V.
Example 3
Referring to fig. 3 to 4, the thin thermal battery of the present invention, in which the electrode system is independent from the heating system, the heating system is wrapped by a heat conductive insulating layer, the heating system supplies heat to the electrode system from the periphery, the heating system comprises a mixture of zirconium and barium chromate and an electric igniter as an ignition system, and simultaneously, a combustion system comprising a mixture of iron and potassium perchlorate is filled in the heat conductive insulating layer.
The preparation method of the electrode system is a pressing method or a thermal spraying method.
The pressing method comprises the steps of pressing the anode material, the diaphragm material, the cathode material and the current collector into tablets in a cold pressing mode, sequentially stacking the anode material, the diaphragm material, the cathode material and the current collector from top to bottom to form a single battery structure, and stacking the single battery structures to form an electrode system.
The thermal spraying process comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system.
The active material of the anode material is an alloy compound FexCo1-xS2、FexNi1-xS2、CoxNi1-xS2Or FexCoyNi1-x-yS2Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the active material of the positive electrode material is more than that of the sulfide positive electrode material (FeS) of the traditional thermal battery2、CoS2、NiS2) The specific energy is higher, reduces the anodal powder quantity, reduces positive plate thickness under the same preforming density to further reduce thermal battery height. Co is selected for the embodimentxNi1-xS2。
The diaphragm material is magnesium oxide and lithium chloride-potassium chloride-lithium bromide eutectic fused salt, the negative electrode material is a lithium boron alloy sheet, the current collector is a stainless steel sheet, the thickness of the stainless steel sheet is 1.0-1.1 mm by a pressing method, 146 single batteries are sequentially stacked in series to form an electrode system with the total height of 161.2mm, the electrode system is in a solid column shape, the electrode material is placed in a heat conduction rate of 98.3W/(m.K), and the resistivity of the electrode material is more than 1015The heat conducting insulating circular tube of silicon nitride ceramic with omega cm is sleeved with another heat conducting insulating circular tube of beryllium oxide ceramic with the diameter larger than that of the heat conducting insulating circular tube by 10mm, the two heat conducting insulating circular tubes are filled with heating materials, and then heat conduction is conductedAnd tightly wrapping a layer of aerogel with the thickness of 3mm on the outer layer of the edge pipe to form an insulating layer, namely after the thermal battery is assembled, putting the thermal battery into a titanium alloy cylinder with the height of 190mm, storing the thermal battery for 6 hours at the temperature of +60 ℃, and then activating and discharging, wherein the activation time is 0.71s, the peak voltage is 294.3V, and the 45 th pulse voltage is 160.1V under the pulse current of 250A.
Claims (2)
1. The utility model provides an independent slim thermal battery of electrode system and heating system, includes electrode system and heating system, its characterized in that: the heating system is wrapped by the heat conducting insulating layer and supplies heat to the electrode system from the periphery;
the heating system is an ignition system consisting of a mixture of zirconium and barium chromate and an electric ignition head, and meanwhile, a combustion system consisting of a mixture of iron and potassium perchlorate is filled in the heat-conducting insulating layer;
the preparation method of the electrode system is a pressing method or a thermal spraying method;
the pressing method comprises the steps that the positive electrode material, the diaphragm material, the negative electrode material and the current collector are respectively pressed into tablets in a cold pressing mode, and then the positive electrode material, the diaphragm material, the negative electrode material and the current collector are sequentially stacked up and down to form a single battery structure, and the single battery structures are stacked to form an electrode system;
the thermal spraying method comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system;
the active material of the anode material is an alloy compound FexCo1-xS2、FexNi1-xS2、CoxNi1-xS2Or FexCoyNi1-x- yS2Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the product is pure;
the shape of the electrode system is a solid column or a hollow column;
the heat conducting insulating layer is made of a material with the heat conductivity of 32-400W/(m.K) and electricityResistivity greater than 1015Omega cm, the melting point is above 1200 deg.C, and the composite material is composed of one or more of beryllium oxide, aluminum nitride, boron nitride or silicon nitride;
the thermally conductive insulating layer separates the battery heating system from the electrode system.
2. The thin thermal battery with independent electrode system and heating system as claimed in claim 1, wherein: the current collector is made of graphite, stainless steel, metal nickel and alloy thereof or metal copper and alloy thereof.
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| CN112234221A (en) * | 2020-10-15 | 2021-01-15 | 贵州梅岭电源有限公司 | Thermal battery based on enhanced heat transfer |
| CN114824664A (en) * | 2022-02-25 | 2022-07-29 | 中国电子科技集团公司第十八研究所 | Thermal buffer layer base material and application method thereof in thermal battery |
| CN114597433A (en) * | 2022-03-02 | 2022-06-07 | 贵州梅岭电源有限公司 | Composite sheet structure for reducing activation time of thermal battery and preparation method thereof |
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