阅读说明：本技术 一种热电池用复合加热片的制备方法及应用 (Preparation method and application of composite heating sheet for thermal battery ) 是由 孟剑 赵洪楷 盛德卫 段其智 潘志鹏 王京亮 李云伟 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种热电池用复合加热片的制备方法,所述复合加热片由加热物料和储热物料制成,其制备方法包括以下步骤：按比例称取Fe粉和KClO<Sub>4</Sub>粉,搅拌均匀后加入钠盐,混合均匀后过筛,获得加热物料；按比例称取LiOH、LiCl和KF粉,搅拌均匀后加入MgO粉末,混合均匀后过筛,制得储热物料；按顺序将加热物料和储热物料放入模具中,施加压力让粉料成型后脱膜,制得所述复合加热片。本申请热电池复合加热片中加热物料添加了钠盐,钠盐的存在可以有效分散加热物料中的活性物质,防止加热物料过燃,从而延长加热物料的热释放时间,保证热电池能够长时间工作。(The invention discloses a preparation method of a composite heating sheet for a thermal battery, wherein the composite heating sheet is prepared from a heating material and a heat storage material, and the preparation method comprises the following steps: weighing Fe powder and KClO according to proportion 4 Mixing the powder, adding sodium salt, mixing, and sieving to obtain a heated material; weighing LiOH, LiCl and KF powder in proportion, stirring uniformly, adding MgO powder, mixing uniformly, and sieving to obtain a heat storage material; and sequentially putting the heating material and the heat storage material into a mould, applying pressure to form the powder, and demoulding to obtain the composite heating sheet. The heating material has added the sodium salt in this application thermal battery composite heating piece, and the existence of sodium salt can effectively disperse the active material in the heating material, prevents that the heating material from burning excessively to the heat release time of extension heating material guarantees that the thermal battery can work for a long time.)

1. A preparation method of a composite heating sheet for a thermal battery is characterized in that the composite heating sheet is made of heating materials and heat storage materials, and the preparation method comprises the following steps:

(1) preparing a heating material: weighing Fe powder and KClO according to the proportion₄Mixing the powder, adding sodium salt, mixing, and sieving to obtain a heated material;

(2) preparing a heat storage material: weighing LiOH, LiCl and KF powder according to a proportion, stirring uniformly, adding MgO powder, mixing uniformly and sieving to obtain a heat storage material;

(3) preparing a composite heating sheet: and (3) sequentially putting the heating material in the step (1) and the heat storage material in the step (2) into a mold, applying pressure to mold the powder, and demoulding to obtain the composite heating sheet.

2. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: the outer surface of the composite heating sheet is a heating material, and the heat storage material or the heat storage material and the heating material are alternately arranged inside the composite heating sheet.

3. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in the step (1), the Fe powder and KClO₄The mass ratio of the powder is 80-90: 10-20.

4. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in step (1), the sodium salt is NaCl or Na₂SO₄And the mass of the sodium salt is 1-10% of that of the heating material.

5. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in the step (2), the mass ratio of LiOH, LiCl and KF is 2-12: 1-8: 1-5.

6. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in the step (2), the mass of the MgO powder is 10-50% of that of the heat storage material.

7. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in the step (3), the mass ratio of the heating material to the heat storage material is 2-8: 1-3; the diameter of the die is 10 mm-200 mm.

8. The method for manufacturing a composite heating sheet for a thermal battery according to claim 1, wherein: in step (3), the pressure is applied in the following manner: adding one powder into a die, applying a pressure of 200-3000 KN for press forming, adjusting the height of the die, adding the other powder into the die, and applying the same pressure for press forming.

9. A composite heating sheet for a thermal battery manufactured by the manufacturing method of any one of claims 1 to 8.

10. Use of the composite heat sheet for a thermal battery according to claim 9 as a battery positive electrode material.

Technical Field

The invention belongs to the technical field of thermal battery electrode materials, and particularly relates to a preparation method and application of a composite heating sheet for a thermal battery.

Background

The thermal battery is a thermal activation reserve battery, the electrolyte is non-conductive solid when stored at normal temperature, when in use, the heating agent in the thermal battery is ignited by an electric ignition head or a firing pin mechanism, so that the electrolyte is melted into an ion conductor to be activated, the storage time is theoretically unlimited, and the actual measurable value is more than 17 years. Because of its small internal resistance, wide range of use temperature, long storage time, quick and reliable activation and no need of maintenance, it has developed into an ideal power supply for modern weapons.

With the rapid development of the defense industry, the requirements of the application field on the thermal battery are higher and higher, especially for a long time. The main factors influencing the working time of the thermal battery are the thermal insulation performance of the thermal battery and the utilization rate of active substances of electrode materials. Along with insulating material aerogel ground is used, the thermal insulation performance of thermal battery obtains great promotion, and self heat can keep 3 ~ 24h after the battery activation, has satisfied the operating time requirement of thermal battery down. But in practice, the working time of the thermal battery is difficult to exceed 1h, which is mainly due to the FeS widely used at present₂、CoS₂Such as electrode materials, are subject to severe self-pyrolysis during operation. The pyrolysis reaction is mainly caused because for a long-time thermal battery, the internal temperature of the thermal battery is increased due to the excessive amount of the heating sheets, the internal temperature exceeds the pyrolysis temperature of the anode material, the anode material is pyrolyzed, and the working time of the thermal battery is shortened; and the reduction of the quantity of the heating sheets can lead to insufficient heat in the thermoelectric period, and the working time of the thermal battery can not meet the use requirement.

Therefore, a thermal battery material with a heating plate structure which has small thermal shock to the thermal battery monomer at the early stage and continuously supplies heat at the later stage is urgently needed in China.

Disclosure of Invention

The invention provides a preparation method and application of a composite heating sheet for a thermal battery, aiming at solving the technical problems.

In order to achieve the above purpose, the invention adopts the following technical scheme:

a preparation method of a composite heating sheet for a thermal battery is provided, wherein the composite heating sheet is made of a heating material and a heat storage material, and the preparation method comprises the following steps:

(1) preparing a heating material: weighing Fe powder and KClO according to the proportion₄Mixing the powder, adding sodium salt, mixing, and sieving to obtain a heated material;

(2) preparing a heat storage material: weighing LiOH, LiCl and KF powder according to a proportion, stirring uniformly, adding MgO powder, mixing uniformly and sieving to obtain a heat storage material;

(3) preparing a composite heating sheet: and (3) sequentially putting the heating material in the step (1) and the heat storage material in the step (2) into a mold, applying pressure to mold the powder, and demoulding to obtain the composite heating sheet.

Furthermore, the outer surface of the composite heating sheet is a heating material, and the heat storage material or the heat storage material and the heating material are alternately arranged inside the composite heating sheet.

Further, in the step (1), the Fe powder and KClO₄The mass ratio of the powder is 80-90: 10-20.

Further, in step (1), the sodium salt is NaCl or Na₂SO₄And the mass of the sodium salt is 1-10% of that of the heating material.

Further, in the step (2), the mass ratio of LiOH, LiCl and KF is 2-12: 1-8: 1-5.

Further, in the step (2), the mass of the MgO powder is 10% -50% of that of the heat storage material.

Further, in the step (3), the mass ratio of the heating material to the heat storage material is 2-8: 1-3; the diameter of the die is 10 mm-200 mm.

Further, in step (3), the pressure is applied by: adding one powder into a die, applying a pressure of 200-3000 KN for press forming, adjusting the height of the die, adding the other powder into the die, and applying the same pressure for press forming.

Further, a composite heating sheet for a thermal battery manufactured by the above-described manufacturing method.

Further, the composite heating sheet for the thermal battery is applied as a battery anode material.

The principle of the invention is as follows: the composite heating sheet is prepared by compounding and molding a heating material and a heat storage material, wherein the heating material can provide enough heat, the phase change heat absorption temperature of the heat storage material is 600 ℃, the working temperature of a thermal battery is about 550 ℃, and the pyrolysis temperature of a positive electrode material of the thermal battery is 650 ℃, so the heat storage material can absorb the redundant heat between the working temperature of the thermal battery and the pyrolysis temperature of the positive electrode material, the thermal shock to the positive electrode material caused by the overhigh temperature of the thermal battery is prevented, and when the heat provided by the heating material in the later period is insufficient, the heat storage material can release the heat, thereby ensuring that the thermal battery can work for a long time.

Due to the adoption of the technical scheme, the invention has the following beneficial effects:

(1) the heating material has added the sodium salt in this application thermal battery composite heating piece, and the existence of sodium salt can effectively disperse the active material in the heating material, prevents that the heating material from burning excessively to the heat release time of extension heating material guarantees that the thermal battery can work for a long time.

(2) This application thermal battery composite heating piece comprises heating material and heat-retaining material, and the heating material can provide sufficient heat for the thermal battery, and the heat-retaining material then can absorb unnecessary heat in earlier stage, avoids the big thermal shock to the thermal battery monomer, and when the heat that the heating material provided is not enough, this heat-retaining material later stage then can release the heat, guarantees the thermal supply in thermal battery later stage.

(3) The composite heating plate of the thermal battery is creatively designed, a specific preparation method is provided, the operation is simple, and the composite heating plate is suitable for large-scale industrial production.

Drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and for a person skilled in the art, without inventive step, other drawings can be obtained according to these drawings:

FIG. 1 is a flow chart of a process for manufacturing a composite heating plate for a thermal battery according to the present application;

fig. 2 is a discharge curve of a thermal battery prepared by applying the composite heating sheet prepared in example 1.

Detailed Description

The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.