CN108832150B - Temperature-adjusting thermal battery heating material and preparation method thereof - Google Patents
Temperature-adjusting thermal battery heating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a temperature-adjusting thermal battery heating material and a preparation method thereof, wherein the heating material comprises the following components: ultra-fine Fe powder and LiClO4Powder, LiCl powder and NaCl powder, wherein the mass percentage of the superfine Fe powder is 62.9-82.0%, and the LiClO powder4Mass percent of powderThe content of the LiCl powder is 10.4-15.4 percent, the mass percent of the LiCl powder is 0.7-16.4 percent, and the mass percent of the NaCl powder is 3.1-9.4 percent. The invention has the greatest characteristic that the temperature balance in the thermal battery is maintained by eyes, a certain amount of NaCl is added by changing the design of the heating powder of the thermal battery, the LiCl after the exothermic reaction with the LiCl is ensured to form a NaCl-LiCl eutectic salt type thermal buffer material, and the working time of the thermal battery can be obviously prolonged.
Description
Technical Field
The invention belongs to the technical field of thermal batteries, and particularly relates to a temperature-adjusting thermal battery heating material and a preparation method thereof.
Background
The thermal battery is a primary storage battery which is in a working state after non-conductive solid-state salt electrolyte is heated and melted into a low-resistance ionic conductor by a heating system of the battery, and becomes the most important weapon matching power supply product due to the characteristics of high output power, short activation time, no need of maintenance during storage and the like.
Because the thermal battery is limited by the working principle and the physical and chemical properties of the electrode material, the thermal battery can normally work only when the internal temperature of the thermal battery is between the temperature of a working window, the lower limit of the temperature of the working window is the melting point temperature of the molten salt electrolyte, and the upper limit of the temperature of the working window is the thermal decomposition temperature of the electrode material. The most common LiB/LiF-LiCl-LiBr/CoS at present2Electrochemical system thermal batteries, for example, have operating window temperatures of from 450 ℃ (melting point of electrolyte) to 650 ℃ (CoS2Decomposition temperature) that may cause a shutdown or safety issue if the internal temperature of the thermal battery falls below or exceeds the operating window. In addition, due to the requirement of weaponry on environmental adaptability, thermal battery models generally require the ability of normal operation between-50 ℃ and +60 ℃, which means that the internal thermal equilibrium temperature needs to be maintained between 500 ℃ and 590 ℃, and the consistency of the performance of the thermal batteries at different temperatures is considered, which leads to the rapid increase of the design difficulty of the thermal batteries, especially the products with long working time.
Aiming at the problem, researchers at home and abroad mainly provideTwo solutions are provided, 1) a second group of heating sources is added into the thermal battery, so that the thermal battery has the capability of secondary heating. For example, a thermal battery set with improved performance (CN 1348227A) proposed by E-P company in the united states, however, this method requires a large number of additional components inside the thermal battery, which seriously affects the specific characteristics, and the secondary ignition source has a serious safety hazard when the thermal battery is in operation, so there is no formal thermal battery product adopting this technology. 2) A certain amount of phase-change thermal buffer material is added into the thermal battery, and the phase-change temperature of the material is between 500 and 600 ℃, so that the interior of the thermal battery has certain temperature regulation capacity. There are many reports on the technology of such thermal buffer materials, such as chinese patent: CN107528072A, a thermal battery with large length-diameter ratio used in high-temperature environment, CN 107732267A and the like, but the purpose and the emphasis of the patents are not completely to prolong the working time of the thermal battery and influence the specific characteristics of the thermal battery to a certain extent. In addition, the Chinese patent CN 102244206A also provides a heating powder with thermal buffering performance, which adds Li into the common heating powder2SO4NaCl eutectic salt, and the purpose of regulating the internal temperature of the thermal battery is realized by the melting phase change of the eutectic salt. However, in practice, Fe/KClO is used4The reaction product KCl of the heating powder is reacted with Li2SO4The NaCl binary system is mutually soluble to form a new ternary electrolyte system, the lowest eutectic point and the ion mobility both change, the melting point and the melting enthalpy both change obviously, the change degree is uncontrollable, and the possibility of practical application is not provided at the laboratory research stage.
Disclosure of Invention
The invention aims to reconcile the contradiction between the weight ratio characteristic and the working time of the battery in the prior thermal battery technical field, and enable the combustion product of the heating material of the thermal battery to have a certain degree of phase change heat storage capacity on the premise of reducing extra weight to the greatest extent so as to achieve the purpose of prolonging the working time of the thermal battery. In addition, the temperature regulation type thermal battery heating material provided by the invention can adjust the proportion according to actual needs, meets the actual requirements of thermal battery models and products in different working times on phase change heat storage capacity, and has wide application range and great application prospect.
Specifically, to achieve the above object, the present invention provides a temperature regulation type thermal battery heating material comprising: ultra-fine Fe powder and LiClO4Powder, LiCl powder and NaCl powder, wherein the mass percentage of the superfine Fe powder is 62.9-82.0%, and the LiClO powder4The mass percentage of the powder is 10.4-15.4%, the mass percentage of the LiCl powder is 0.7-16.4%, and the mass percentage of the NaCl powder is 3.1-9.4%.
Preferably, ultra-fine Fe powder and LiClO4The mass ratio of the powder is 84: 16-86: 14.
Preferably, LiClO4The ratio of the sum of the amounts of the substances of the powder and the LiCl powder to the amount of the substance of the NaCl powder was always 3: 1.
Preferably, after the heating material is burnt, the formed NaCl-LiCl binary eutectic salt thermal buffer material accounts for 10-30% of the total mass of the heating material after burning. LiClO4The product after combustion includes LiCl, so the NaCl-LiCl binary eutectic salt here includes not only LiCl and NaCl originally added to the heating material, but also LiClO4LiCl generated after combustion; this "proportion" refers to the proportion of the binary eutectic salt to the weight of all the heating materials after the heating materials are burned.
The invention also provides a preparation method of the temperature regulation type thermal battery heating material, which comprises the following steps:
step 1, respectively weighing the required superfine Fe powder and LiClO4Drying the powder, LiCl powder and NaCl powder for later use;
step 2, ultrafine Fe powder and LiClO4Adding the powder and a certain amount of stainless steel grinding rods into a ceramic ball milling tank, and performing ball milling and mixing uniformly;
and 3, adding the required LiCl powder and NaCl powder into the ball milling tank, performing ball milling uniformly again, and sieving by using a 100-mesh sieve to obtain the required product.
Preferably, in the step 2, the rotation speed of the ball milling tank is 30-40 r/min during ball milling and mixing.
Preferably, the ball milling mixing time is 4-6 h.
Preferably, in step 2, the addition amount of the stainless steel grinding rods in the ball milling tank is 70-100 g/L.
The invention has the biggest characteristic that the design of the heating powder of the thermal battery can be changed through theoretical calculation, and a certain amount of LiCl and NaCl are added to ensure that the LiCl after the exothermic reaction with the LiCl forms a NaCl-LiCl eutectic salt type thermal buffer material. In addition, the temperature regulation type thermal battery heating material provided by the invention can be calculated according to actual needs, and heating materials with different thermal buffering properties can be obtained by changing the addition proportion of raw materials. The preliminary calculation method is as follows:
1) the equivalent heat release of the heating material can be known from the formula (1), and LiClO is determined according to the total heat required by the thermal battery4The amount of (c);
4Fe+LiClO4→LiCl+4FeO ΔH=-3020 J/g （1）
where Δ H is the enthalpy change of the chemical reaction and is understood to be the amount of heat released per unit mass of reactants to complete the reaction.
2) Determining Fe powder and LiClO according to the geometric dimension of the thermal battery4The proportion of the powder is basically in inverse proportion of the size to the mass proportion of the Fe powder;
3) determining the usage amount of the NaCl-LiCl eutectic salt according to the working time of the thermal battery and the external heat dissipation condition;
4) according to the formula (2) and the usage amount of NaCl-LiCl, determining the additionally required heat amount and combining the calculated value in the step 1 for calculation;
ΔHfusion(NaCl-LiCl)=455 J/g （2）
ΔHfusionby (NaCl-LiCl) is meant the heat absorbed per mass of NaCl-LiCl eutectic salt at its melting point by the transformation from a solid to a liquid state.
5) Finally determining the superfine Fe powder and LiClO4Powder, LiCl powder and NaCl powder.
By using the temperature regulation type thermal battery heating material, the exothermic reaction product of the heating material is used as a part of thermal buffer material, so that the composition of the thermal buffer material is ensured to be constant all the time, and the thermal buffer material has stable melting enthalpy and the lowest eutectic point.
The invention provides a temperature regulation type thermal battery heating material and a preparation method thereof, and the technical advantages are mainly reflected in that:
1) the temperature regulation type thermal battery heating material provided by the invention aims at improving the working time of a thermal battery, maintains the internal temperature within a working window as much as possible, selects LiCl-NaCl binary molten salt with the lowest eutectic point of 550 ℃ as a phase-change type thermal buffer material, and ensures that a reaction product LiCl of the heating material is used as a partial component of the buffer material and the chemical composition is stable by adding raw material amount ratio control;
2) in order to expand the application range of the heating material to the maximum extent, the provided preparation method and the raw material component range can ensure that the heating materials with different heat buffering properties (namely the LiCl-NaCl binary molten salt has different contents) can realize the burning rate performance of more than 9cm/s on the premise of not influencing the ignition sensitivity of the heating material, and a preliminary design calculation method is provided;
3) the temperature-regulating thermal battery heating material provided by the invention has the advantages that the process equipment required by the preparation is consistent with the traditional thermal battery heating material, the production process has high universality and good economy, the engineering application prospect is good, the three wastes are not discharged, and the development trend of green chemical engineering is met.
Detailed Description
The technical solution of the present invention is further described below with reference to examples.
Example 1
Weighing the required raw materials according to the content of each component in the temperature regulation type thermal battery heating material, wherein the total weight of the raw materials is 1000g, wherein the weight of the raw materials is 629 g of ultrafine Fe powder, and the weight of the raw materials is LiClO4120 g of powder, 93 g of NaCl powder and 158 g of LiCl powder. Drying, and mixing with superfine Fe powder and LiClO4Adding the powder and 500 g of stainless steel grinding rod into a 5L ceramic ball-milling tank, and carrying out ball-milling mixing for 4 h; adding required LiCl powder and NaCl powder into a ball milling tank,ball milling and mixing for 4 h again, and sieving with a 100-mesh sieve to obtain the required product; the LiCl-NaCl binary fused salt is generated after the heating powder is combusted, the phase change heat storage capacity is about 136.5 kJ (under the normal condition, the longer the working time of a thermal battery model product is, the higher the requirement on the heat storage capacity of the phase change heat storage material is), and the combustion speed of the heating powder is 9.43 cm/s. The heating material used by the thermal battery has higher requirement on the burning rate performance, 9cm/s is an index for evaluating the burning rate performance in the industry, and the heating material can be used as the heating material for the thermal battery only when the value is reached or exceeded.
Example 2
Weighing the required raw materials according to the content of each component in the temperature regulation type thermal battery heating material, wherein the total weight of the raw materials is 1000g, 808 g of superfine Fe powder and LiClO4154 g of powder, 31 g of NaCl powder and 7 g of LiCl powder. Drying, and mixing with superfine Fe powder and LiClO4Adding the powder and 350 g of stainless steel grinding rod into a 5L ceramic ball-milling tank, and carrying out ball-milling mixing for 4 h; adding the required LiCl powder and NaCl powder into a ball milling tank, carrying out ball milling and mixing for 4 hours again, and sieving by using a 100-mesh sieve to obtain a required product; after the heating powder is combusted, 100g of LiCl-NaCl binary fused salt is generated, the phase change heat storage capacity is about 45.5 kJ, and the combustion speed of the heating powder is 9.96 cm/s.
Example 3
Weighing the required raw materials according to the content of each component in the temperature regulation type thermal battery heating material, wherein the total weight of the raw materials is 1000g, 820 g of superfine Fe powder and LiClO4134 g of powder, 31 g of NaCl powder and 15 g of LiCl powder. Drying, and mixing with superfine Fe powder and LiClO4Adding the powder and 500 g of stainless steel grinding rod into a 5L ceramic ball-milling tank, and carrying out ball-milling mixing for 6 h; adding the required LiCl powder and NaCl powder into a ball milling tank, carrying out ball milling and mixing for 6h again, and sieving by using a 100-mesh sieve to obtain a required product; after the heating powder is combusted, 100g of LiCl-NaCl binary fused salt is generated, the phase change heat storage capacity is about 45.5 kJ, and the combustion speed of the heating powder is 9.78 cm/s.
Example 4
Weighing the required raw materials according to the content of each component in the temperature-adjusting thermal battery heating materialThe total weight of the raw materials is 1000g, wherein, the superfine Fe powder is 639 g, LiClO4104 g of powder, 93 g of NaCl powder and 164 g of LiCl powder. Drying, and mixing with superfine Fe powder and LiClO4Adding the powder and 500 g of stainless steel grinding rod into a 5L ceramic ball-milling tank, and carrying out ball-milling mixing for 6 h; adding the required LiCl powder and NaCl powder into a ball milling tank, carrying out ball milling and mixing for 6h again, and sieving by using a 100-mesh sieve to obtain a required product; after the heating powder is combusted, 300 g of LiCl-NaCl binary molten salt is generated, the phase change heat storage capacity is about 136.5 kJ, and the combustion speed of the heating powder is 9.02 cm/s.
Example 5
Weighing the required raw materials according to the content of each component in the temperature regulation type thermal battery heating material, wherein the total weight of the raw materials is 1000g, and the weight of the raw materials is 723 g of superfine Fe powder and LiClO4123 g of powder, 64 g of NaCl powder and 90 g of LiCl powder. Drying, and mixing with superfine Fe powder and LiClO4Adding the powder and 500 g of stainless steel grinding rod into a 5L ceramic ball-milling tank, and carrying out ball-milling mixing for 6 h; adding the required LiCl powder and NaCl powder into a ball milling tank, carrying out ball milling and mixing for 6h again, and sieving by using a 100-mesh sieve to obtain a required product; 206 g of LiCl-NaCl binary fused salt is generated after the heating powder is burnt, the phase change heat storage capacity is about 93.7 kJ, and the burning speed of the heating powder is 9.25 cm/s.
In conclusion, the formula is adjusted, so that the combustion product of the heating powder has the heat storage capacity, the function is realized by directly adding the eutectic salt instead of the eutectic salt, and the side reaction is avoided; moreover, the heat storage capacity of the heating powder can be adjusted by the proportion to meet the requirements of thermal batteries with different service lives. On the premise of not influencing the ignition sensitivity of the heating material, the preparation method and the raw material component range provided by the invention can ensure that the heating materials with different thermal buffering properties (adjusting the mixture ratio) can realize the burning rate property of more than 9 cm/s; the process equipment required by the preparation of the temperature-regulating type thermal battery heating material provided by the invention is consistent with that of the traditional thermal battery heating material, the production process has high universality and good economy, has good engineering application prospect, does not discharge three wastes, and accords with the development trend of green chemical engineering.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (6)
1. A temperature regulated thermal battery heating material, the heating material comprising: ultra-fine Fe powder and LiClO4Powder, LiCl powder and NaCl powder, wherein the mass percentage of the superfine Fe powder is 62.9-82.0%, and the LiClO powder4The mass percentage of the powder is 10.4-15.4%, the mass percentage of the LiCl powder is 0.7-16.4%, and the mass percentage of the NaCl powder is 3.1-9.4%; LiClO4The ratio of the sum of the amounts of the substances of the powder and the LiCl powder to the amount of the substance of the NaCl powder was always 3: 1; after the heating material is burnt, the formed NaCl-LiCl binary eutectic salt thermal buffer material accounts for 10-30% of the total mass of the heating material after burning.
2. The temperature-regulated thermal battery heating material as claimed in claim 1, wherein the ultra-fine Fe powder and LiClO4The mass ratio of the powder is 84: 16-86: 14.
3. The method for preparing a temperature-regulated thermal battery heating material according to claim 1 or 2, comprising:
step 1, respectively weighing the required superfine Fe powder and LiClO4Drying the powder, LiCl powder and NaCl powder for later use;
step 2, ultrafine Fe powder and LiClO4Adding the powder and a certain amount of stainless steel grinding rods into a ceramic ball milling tank, and performing ball milling and mixing uniformly;
and 3, adding the required LiCl powder and NaCl powder into the ball milling tank, performing ball milling uniformly again, and sieving by using a 100-mesh sieve to obtain the required product.
4. The method for preparing a temperature-regulating thermal battery heating material as claimed in claim 3, wherein in the step 2, the rotation speed of the ball-milling pot is 30-40 rpm during ball-milling and mixing.
5. The method of claim 4, wherein the ball milling and mixing time is 4-6 hours.
6. The method for preparing a temperature-regulated thermal battery heating material according to claim 3, wherein in step 2, the amount of the stainless steel grinding rod added to the ball-milling pot is 70 to 100 g/L.
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