CN108539195B - Solid solution type FexCo1-xS2 positive electrode material for thermal battery and preparation method thereof - Google Patents

Solid solution type FexCo1-xS2 positive electrode material for thermal battery and preparation method thereof Download PDF

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CN108539195B
CN108539195B CN201810313847.3A CN201810313847A CN108539195B CN 108539195 B CN108539195 B CN 108539195B CN 201810313847 A CN201810313847 A CN 201810313847A CN 108539195 B CN108539195 B CN 108539195B
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韩婷婷
程锦
胡华荣
叶丹宏
罗重霄
姜义田
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Shanghai Institute of Space Power Sources
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

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Abstract

The invention aims to provide solid solution type Fe for a thermal batteryxCo1‑xS2The positive electrode material is prepared by accurately controlling the component content of a Fe-Co alloy framework by a Raney method and synthesizing Fe by a high-temperature solid-phase vulcanization methodxCo1‑xS2Solid solution. The preparation method provided by the invention can realize accurate regulation and control of the atomic ratio in a target product simply by changing the feeding ratio, and can provide the performance-oriented anode material in a customized manner according to the electrical performance requirement of the thermal battery. The solid solution type Fe obtained by adopting the preparation method provided by the inventionxCo1‑xS2The anode material has the characteristics of controllable active component content, high electrode potential, stable voltage platform, small polarization internal resistance and high thermal stability, the thermal decomposition temperature is not lower than 570 ℃, and the actual discharge specific capacity is not lower than 1300 As/g.

Description

Solid solution type FexCo1-xS2 positive electrode material for thermal battery and preparation method thereof
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to solid solution type Fe for a thermal batteryxCo1-xS2A positive electrode material and a preparation method thereof.
Background
MS2(M ═ Fe, Co) is currently the most widely used positive electrode material for lithium-based thermal batteries, among which FeS2The electrode potential to the Li negative electrode was 2.2V (specific CoS)2About 0.1V higher), the theoretical capacity is 1206As/g, which is slightly higher than CoS21045As/g, is very favorable for improving the output voltage of the thermal battery and the specific energy of the battery mass. However, since FeS2Has poor thermal stability, accelerates the decomposition in the later discharge period of the thermal battery, and improves the stability of the thermal batteryThe self-discharge rate increases, resulting in increased capacity loss and reduced operating time within the effective voltage platform. With FeS2In contrast, CoS2Has lower resistivity (0.002 omega cm) and higher decomposition temperature (650 ℃), has small solubility in electrolyte and high utilization degree, and has obvious advantages in reducing the internal resistance of the thermal battery and improving the output multiplying power of the thermal battery. In summary, FeS2And CoS2The performance of the composite material has complementary characteristics, and the composite material can be used as a multi-element positive electrode, so that the advantages can be made up, a high-capacity low-polarization electrochemical system can be constructed, and the performance of the thermal battery can be further improved.
In the traditional production application, the preparation of the composite anode mostly adopts a simple powder mixing mode (such as patent number: 201510527112.7, a composite anode material for a thermal battery and a preparation method thereof), although FeS (FeS)2-CoS2The composite anode material is superior to a single-component anode in electrochemical performance, but has the defect of FeS at high temperature2The decomposition is carried out first, and the safety and the reliability of the thermal battery are influenced. Patent numbers: 201610662968.X discloses a positive electrode material Fe for thermal batteryxCo1-xS2The powder and the preparation method thereof are a preparation method which combines chemical deposition and high-temperature solid-phase reaction; but Fe synthesized by chemical depositionxCo1-xS2The product still contains FeS from the micro2And CoS2Two components, not forming FexCo1-xS2Solid solution.
Due to artificially synthesized CoS2FeS with pyrite type2The materials have similar crystal structures, and the difference of the atomic radiuses of Co atoms and Fe atoms is less than 15%, the Co atoms and the Fe atoms can form an infinite substitution solid solution, so that if Fe is prepared by a chemical synthesis methodxCo1-xS2Solid solution type materials, which make the crystal structure and physicochemical properties simple, may fundamentally solve the problem of poor thermal stability. Further, FexCo1-xS2The electrochemical activity and the structural stability of the material are in negative correlation and are related to the component proportion, so that the pair can be realized by adjusting the atomic ratio of Fe and CoThe performance of the anode material for the thermal battery is regulated. FexCo1-xS2Solid solutions can be used similar to CoS2Synthetic high temperature sintering method (such as Shenyang university of science 34(2015) 01), discloses a CoS for thermal batteries2High temperature solid phase synthesis and discharge performance test method), and although the solid solution prepared by the method has better consistency, Fe in the productxCo1-xS2Is low and the component ratio is not controlled.
Disclosure of Invention
The invention aims to provide solid solution type Fe for a thermal batteryxCo1-xS2The positive electrode material and the preparation method thereof aim at forming a series of positive electrode materials of the thermal battery, and the required positive electrode materials are selected according to the specific numerical values of the decomposition temperature and the capacitance of the positive electrode materials and the actual requirements of the thermal battery model products, so that the design difficulty of the thermal battery model products is reduced, the development process is shortened, and the development requirement of the weapon system component type spectrometry is met.
In order to achieve the above object, the present invention provides solid solution type Fe for a thermal batteryxCo1-xS2Positive electrode material, solid solution type Fe for target product thermal batteryxCo1-xS2The chemical component content of the anode material is as follows: fexCo1-xS2Of the positive electrode materials, FeS2The mass of the positive electrode material is 26-62% of the total mass of the positive electrode material; CoS2The mass of (b) is 28-64% of the total mass of the positive electrode material.
The invention also provides the solid solution type FexCo1-xS2The preparation method of the cathode material comprises the following steps:
firstly, weighing Al powder according to the weight percentage of 40 percent, weighing Fe powder according to the weight percentage of 18-42 percent and weighing Co powder according to the weight percentage of 42-18 percent in the Fe-Co-Al ternary alloy, and uniformly mixing and drying the three metal powders;
secondly, putting the dried powder into a quartz tube, introducing argon into the quartz tube for protection, heating the sample to 1000 ℃ to form alloy liquid, spraying the molten alloy liquid onto a copper roller which rotates at high speed and is introduced with cooling water by using argon, rapidly cooling the alloy to obtain a strip-shaped alloy product, crushing the strip-shaped alloy product, and screening 100-200 meshes of Fe-Co-Al alloy powder;
heating a NaOH aqueous solution with the mass concentration of 20% to 85-95 ℃, slowly adding Fe-Co-Al powder alloy into the NaOH aqueous solution, stirring for 2 hours (adding 95-105 g of alloy powder into each liter of NaOH aqueous solution), and obtaining a black precursor RQ Fe-Co after Al in the alloy is fully dissolved;
step four, respectively washing RQ Fe-Co with ethanol and water for 3-5 times until the pH value of the washing filtrate is neutral, immediately placing the wet precursor into a quartz bowl, and adding a proper amount of distilled water for preservation;
step five, weighing sulfur powder according to the amount of 80-100% of the total mass of the Fe-Co-Al alloy, pouring the sulfur powder into a quartz bowl filled with RQFe-Co and distilled water, uniformly stirring, then putting the quartz bowl into a vacuum reaction furnace, heating to 120 ℃, keeping the temperature for more than 24 hours after vacuumizing, vacuumizing once every half hour during the period, and ensuring that the vacuum degree in the reaction furnace is less than-0.09 MPa; closing the vacuum valve, heating to 250-300 ℃ under a closed condition, and keeping the temperature for 2-4 h; slowly introducing argon until the interior of the furnace body recovers to normal pressure, continuously introducing argon, opening an air escape valve, heating to 450-500 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature, and crushing the product to obtain solid solution type Fe for the thermal batteryxCo1-xS2And (3) a positive electrode material.
Further, the three metal powders are uniformly mixed by adopting a ball mill, a three-dimensional powder mixer, a V-shaped powder mixer or a powder sieving machine and the like, the copper roller which rotates at a high speed and is introduced with cooling water is added with proper amount of distilled water for preservation, and the amount of the added distilled water is preferably 5mm-10mm higher than that of RQ Fe-Co.
The invention relates to solid solution type Fe for a thermal batteryxCo1-xS2The technical advantages of the anode material and the preparation method thereof are mainly reflected in that:
1) the invention provides a solid for a thermal battery for the first timeSolution type FexCo1-xS2A method for synthesizing positive electrode material includes such steps as smelting Al to form alloy, extracting Al from alloy with alkali solution to obtain Fe-Co alloy, sulfurizing to synthesize Fe-Co alloyxCo1-xS2A solid solution material. Compared with the traditional high-temperature sintering method, the method has the greatest advantages that the synthesized product has single component and complete crystal structure, and meanwhile, the proportion of active components in the solid solution can be accurately controlled;
2) the invention creatively passes through the p-FexCo1-xS2The proportion of material atoms is accurately regulated, the chemical activity and the thermodynamic stability of the material are changed, a series of thermal battery anode materials can be formed, the required anode materials are selected according to the specific numerical values of the decomposition temperature and the capacitance of the anode materials and the actual requirements of thermal battery model products, and the design difficulty of thermal battery products is greatly reduced;
3) the invention provides solid solution type Fe for a thermal batteryxCo1-xS2The synthesis method of the anode material can obtain the required anode material by only changing the feed ratio and properly adjusting the process parameters on the premise of not changing the process flow and the production equipment, greatly improves the production flexibility, accords with the development trend of customized production in future industrial 4.0 planning, has military and economic significance, and provides certain reference significance for customized production of other materials.
Drawings
The invention relates to solid solution type Fe for a thermal batteryxCo1-xS2The positive electrode material and the method for producing the same are shown in the following examples and drawings.
FIG. 1 is Fe in examplexCo1-xS2TG spectra and decomposition of solid solutionsDescription of the temperature
FIG. 2 is Fe in examplexCo1-xS2Discharge capacity curve of solid solution (discharge test: with Fe)xCo1-xS2Solid solution is used as a positive electrode material, LiB is used as a negative electrode material, LiF-LiCl-LiBr is used as an electrolyte to construct a single battery, and 100mA/cm is used2Current density discharge (1.5V) cutoff voltage
Detailed Description
The following 5 examples are provided for solid solution type Fe for a thermal battery according to the present inventionxCo1-xS2The positive electrode material and the method for preparing the same are further described in detail.
Example 1
Solid solution type Fe for target product thermal batteryxCo1-xS2The weight ratio of the active components of the positive electrode material is as follows: fe accounts for 26%; co accounts for 64%. Firstly, weighing three powder materials according to the proportion of 60 wt% of Al powder, 18 wt% of Fe powder and 42 wt% of Co powder, mixing the powder materials, putting the mixture into a ball mill for ball milling for 12 hours, taking out the powder, and putting the powder into Ar2And (5) drying under protection. Putting the dried powder into a quartz tube, and putting the quartz tube in Ar2Heating to 1000 ℃ under protection for smelting; subjecting the molten alloy to Ar2Spraying the alloy onto a copper roller which rotates at a high speed (the rotating speed is 500rpm) and is filled with cooling water, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product; and crushing the fragile alloy strip, and screening 100-200 meshes of FeCoAl alloy. Heating a 20 wt% NaOH aqueous solution to 85 ℃, slowly adding FeCoAl alloy into the NaOH solution according to the proportion of 100g/L, and stirring for 2 hours to fully dissolve Al in the alloy to obtain a black solid product, which is marked as RQ FeCo; washing the product with ethanol and water for 3 times respectively until the pH value is 7, placing the product in a quartz bowl, and storing the product in distilled water for later use; weighing sulfur powder according to the amount of 90% of the total mass of the FeCoAl alloy, pouring the sulfur powder into a quartz bowl filled with RQ FeCo, uniformly stirring, then putting the quartz bowl into a tube furnace vacuum reaction furnace, vacuumizing, heating to 125 ℃, keeping the temperature for 24 hours, and vacuumizing once every two hours; closing the vacuum valve, heating to 250 ℃ under a sealed condition, and keeping the temperature for 4 hours; slowly introducing argon to the interior of the furnace body to recover to normal pressure, and continuously introducing argonOpening a gas release valve, heating to 500 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature and crushing to obtain the required product. The obtained solid solution type Fe for thermal battery0.3Co0.7S2The decomposition temperature of the positive electrode material was 604 ℃ and the capacity was 1350 As/g.
Example 2
Solid solution type Fe for target product thermal batteryxCo1-xS2The weight ratio of the active components of the positive electrode material is as follows: fe accounts for 34%; co accounts for 55%. Firstly, weighing three powder materials according to the proportion of 60 wt% of Al powder, 24 wt% of Fe powder and 36 wt% of Co powder, mixing the powder materials, putting the mixture into a ball mill for ball milling for 12 hours, taking out the powder, and putting the powder into an Ar powder mixer for ball milling2And (5) drying under protection. Putting the dried powder into a quartz tube, and putting the quartz tube in Ar2Heating to 1000 ℃ under protection for smelting; subjecting the molten alloy to Ar2Spraying the alloy onto a copper roller which rotates at a high speed (the rotating speed is 900rpm) and is filled with cooling water, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product; and crushing the fragile alloy strip, and screening 100-200 meshes of FeCoAl alloy. Heating a 20 wt% NaOH aqueous solution to 90 ℃, slowly adding FeCoAl alloy into the NaOH solution according to the proportion of 100g/L, and stirring for 2 hours to fully dissolve Al in the alloy to obtain a black solid product, which is marked as RQ FeCo; washing the product with ethanol and water for 4 times respectively until the pH value is 7, placing the product in a quartz bowl, and storing the product in distilled water for later use; weighing sulfur powder according to the amount of 90% of the total mass of the FeCoAl alloy, pouring the sulfur powder into a quartz bowl filled with RQ FeCo, uniformly stirring, then putting the quartz bowl into a tube furnace vacuum reaction furnace, vacuumizing, heating to 125 ℃, keeping the temperature for 24 hours, and vacuumizing once every two hours; closing the vacuum valve, heating to 300 ℃ under a sealed condition, and keeping the temperature for 2 hours; slowly introducing argon until the interior of the furnace body recovers to normal pressure, continuously introducing argon, opening an air escape valve, heating to 450 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature and crushing to obtain the required product. The obtained solid solution type Fe for thermal battery0.4Co0.6S2The decomposition temperature of the positive electrode material was 596 ℃ and the capacity was 1410 As/g.
Example 3
Solid solution type Fe for target product thermal batteryxCo1-xS2The weight ratio of the active components of the positive electrode material is as follows: fe accounts for 43 percent; co accounts for 46%. Firstly, weighing three powder materials according to the proportion of 60 wt% of Al powder, 30 wt% of Fe powder and 30 wt% of Co powder, mixing the powder materials, putting the mixture into a V-shaped powder mixer, mixing and drying. Putting the dried powder into a quartz tube, and putting the quartz tube in Ar2Heating to 1000 ℃ under protection for smelting; subjecting the molten alloy to Ar2Spraying the alloy onto a copper roller which rotates at a high speed (the rotating speed is 1500rpm) and is filled with cooling water, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product; and crushing the fragile alloy strip, and screening 100-200 meshes of FeCoAl alloy. Heating a 20 wt% NaOH aqueous solution to 85 ℃, slowly adding FeCoAl alloy into the NaOH solution according to the proportion of 95g/L, and stirring for 2 hours to fully dissolve Al in the alloy to obtain a black solid product, which is marked as RQ FeCo; washing the product with ethanol and water for 5 times respectively until the pH value is 7, placing the product in a quartz bowl, and storing the product in distilled water for later use; weighing sulfur powder according to 100% of the total mass of FeCoAl alloy, pouring the sulfur powder into a quartz bowl filled with RQ FeCo, uniformly stirring, then putting the quartz bowl into a tube furnace vacuum reaction furnace, vacuumizing, heating to 125 ℃, keeping the temperature for 24 hours, and vacuumizing once every two hours; closing the vacuum valve, heating to 270 ℃ under a closed condition, and keeping the temperature for 3 hours; slowly introducing argon until the interior of the furnace body recovers to normal pressure, continuously introducing argon, opening an air escape valve, heating to 470 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature and crushing to obtain the required product. The obtained solid solution type Fe for thermal battery0.5Co0.5S2The decomposition temperature of the positive electrode material was 589 ℃ and the capacity was 1380 As/g.
Example 4
Solid solution type Fe for target product thermal batteryxCo1-xS2The weight ratio of the active components of the positive electrode material is as follows: fe accounts for 53%; co accounts for 37%. Firstly, weighing three powder materials according to the proportion of 60 wt% of Al powder, 36 wt% of Fe powder and 24 wt% of Co powder, mixing, sieving with a 40-mesh sieve for 5 times, uniformly mixing and drying. Putting the dried powder into a quartz tube, and putting the quartz tube in Ar2Under protection is heated toSmelting at 1000 ℃; then, the molten alloy is subjected to Ar quenching by a single-roll quenching method2Spraying the alloy onto a copper roller which rotates at a high speed (the rotating speed is 1200rpm) and is filled with cooling water, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product; and crushing the fragile alloy strip, and screening 100-200 meshes of FeCoAl alloy. Heating a 20 wt% NaOH aqueous solution to 95 ℃, slowly adding FeCoAl alloy into the NaOH solution according to the proportion of 105g/L, and stirring for 2 hours to fully dissolve Al in the alloy to obtain a black solid product, which is marked as RQ FeCo; washing the product with ethanol and water for 3 times respectively until the pH value is 7, placing the product in a quartz bowl, and storing the product in distilled water for later use; weighing sulfur powder according to 85% of the total mass of FeCoAl alloy, pouring the sulfur powder into a quartz bowl filled with RQ FeCo, uniformly stirring, then putting the quartz bowl into a tube furnace vacuum reaction furnace, vacuumizing, heating to 125 ℃, keeping the temperature for 24 hours, and vacuumizing once every two hours; closing the vacuum valve, heating to 270 ℃ under a closed condition, and keeping the temperature for 3 hours; slowly introducing argon until the interior of the furnace body recovers to normal pressure, continuously introducing argon, opening an air escape valve, heating to 450 ℃ again, keeping the temperature for 4 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature and crushing to obtain the required product. The obtained solid solution type Fe for thermal battery0.6Co0.4S2The decomposition temperature of the positive electrode material was 580 ℃ and the capacity was 1380 As/g.
Example 5
Solid solution type Fe for target product thermal batteryxCo1-xS2The weight ratio of the active components of the positive electrode material is as follows: fe accounts for 62%; co accounts for 28%. Firstly, weighing three powder materials according to the proportion of 60 wt% of Al powder, 42 wt% of Fe powder and 18 wt% of Co powder, mixing the powder materials, putting the mixture into a three-dimensional powder mixer, uniformly mixing the powder materials and drying the powder materials. Putting the dried powder into a quartz tube, and putting the quartz tube in Ar2Heating to 1000 ℃ under protection for smelting; then, the molten alloy is subjected to Ar quenching by a single-roll quenching method2Spraying the alloy onto a copper roller which rotates at a high speed (the rotating speed is 700rpm) and is filled with cooling water, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product; and crushing the fragile alloy strip, and screening 100-200 meshes of FeCoAl alloy. Heating 20 wt% NaOH aqueous solution to 90 deg.C, adding 100g/L NaOH solutionSlowly adding FeCoAl alloy and stirring for 2h to fully dissolve Al in the alloy to obtain a black solid product which is marked as RQ FeCo; washing the product with ethanol and water for 3 times respectively until the pH value is 7, placing the product in a quartz bowl, and storing the product in distilled water for later use; weighing sulfur powder according to 80% of the total mass of FeCoAl alloy, pouring the sulfur powder into a quartz bowl filled with RQ FeCo, uniformly stirring, then putting the quartz bowl into a tube furnace vacuum reaction furnace, vacuumizing, heating to 125 ℃, keeping the temperature for 24 hours, and vacuumizing once every two hours; closing the vacuum valve, heating to 300 ℃ under a sealed condition, and keeping the temperature for 2 hours; slowly introducing argon until the interior of the furnace body recovers to normal pressure, continuously introducing argon, opening an air escape valve, heating to 450 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder; naturally cooling to room temperature and crushing to obtain the required product. The obtained solid solution type Fe for thermal battery0.7Co0.3S2The decomposition temperature of the positive electrode material was 572 ℃ and the capacity was 1310 As/g.
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 (2)

1. Solid solution type Fe for thermal batteryxCo1-xS2The preparation method of the cathode material is characterized by comprising the following steps:
step 1, weighing Al powder according to the weight percentage of 40 percent, weighing Fe powder according to the weight percentage of 18-42 percent and weighing Co powder according to the weight percentage of 42-18 percent in the Fe-Co-Al ternary alloy, and uniformly mixing and drying the three metal powders;
step 2, heating the mixed metal powder to alloy liquid under the protective atmosphere, cooling, crushing and screening Fe-Co-Al alloy powder of 100-200 meshes;
step 3, heating a NaOH aqueous solution with the mass concentration of 20% to 85-95 ℃, slowly adding Fe-Co-Al alloy powder into the NaOH solution, and stirring until Al is fully dissolved to obtain a black precursor RQFe-Co;
step 4, washing the precursor RQFe-Co until the pH value of the filtrate is neutral, placing the wet precursor RQFe-Co in a container, and adding distilled water for storage;
and 5, adding sulfur powder into the precursor RQ Fe-Co stored in the distilled water, carrying out vacuum heating reaction, cooling, and crushing the obtained product to obtain solid solution type Fe for the thermal batteryxCo1-xS2A positive electrode material;
in the step 1, three kinds of metal powder are mixed by adopting a ball mill, a three-dimensional powder mixer, a V-shaped powder mixer or a powder sieving machine;
in the step 2, the protective gas is any one or a combination of at least two of helium, argon, neon or nitrogen;
in the step 2, the molten alloy liquid is sprayed to a copper roller which rotates at a high speed and is filled with cooling water by using protective gas, so that the alloy is rapidly cooled to obtain a strip-shaped alloy product;
the copper roller rotates at a high speed and is filled with cooling water, and the rotating speed of the copper roller is 500-1500 rpm;
in the step 3, the stirring time is 2 hours;
in the step 3, 95g-105g of Fe-Co-Al alloy powder is added into each liter of NaOH aqueous solution;
in the step 4, the amount of the distilled water is that the liquid level is higher than the precursor RQ Fe-Co5mm-10 mm.
2. A solid solution type Fe for a thermal battery according to claim 1xCo1-xS2The preparation method of the cathode material is characterized in that in the step 5, the vacuum heating reaction is carried out, namely, the container filled with RQ Fe-Co and sulfur powder is placed into a vacuum reaction furnace, the vacuum reaction furnace is vacuumized and then heated to 120 ℃ and is kept at the constant temperature for more than 24 hours, and the vacuum degree in the reaction furnace is ensured to be less than-0.09M in the periodPa; closing the vacuum valve, heating to 250-300 ℃ under a closed condition, and keeping the temperature for 2-4 h; and (3) slowly introducing protective gas until the interior of the furnace body recovers to normal pressure, continuously introducing argon gas, opening a gas release valve, heating to 450-500 ℃ again, keeping the temperature for 2 hours, and removing residual elemental sulfur powder.
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