CN111129446A - Application of tungsten molybdenum sulfide in thermal battery - Google Patents
Application of tungsten molybdenum sulfide in thermal battery Download PDFInfo
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Abstract
The invention discloses an application of tungsten-molybdenum sulfide in a thermal battery, which adopts a thermal battery electrochemical system with tungsten-molybdenum sulfide as an anode and metal lithium and lithium alloy as a cathode, wherein the anode reacts to ensure that tungsten (molybdenum) metal ions accept electrons and are reduced into metal tungsten (molybdenum), and the cathode loses electrons by free-state lithium and is changed into lithium ions. The tungsten-molybdenum sulfide is used as the anode, and the decomposition temperature of the tungsten-molybdenum sulfide material is high, so that the self-discharge of the anode material is small in the long-time high-temperature discharge process, the material utilization rate is high and is higher than that of the iron-cobalt-nickel disulfide anode by more than 10%, the battery discharge is stable in the long-time discharge process, the voltage fluctuation is far smaller than that of the iron-cobalt-nickel-sulfur anode thermal battery system, and the tungsten-molybdenum sulfide anode thermal battery is very suitable for a component integration system with high voltage precision.
Description
Technical Field
The invention belongs to the technical field of chemical power thermal batteries, and particularly relates to application of tungsten-molybdenum sulfide in a thermal battery.
Background
The thermal battery is a high-temperature molten salt battery, is an electrochemical system established by heating a solid electrolyte to a molten ion type conductor by a self heating system, has the characteristics of large output power, long storage life, short activation time and the like, and is an ideal power supply of national defense equipment. As a military power source, in addition to the requirement for good electrochemical performance of batteries, extremely high requirements are placed on quality reliability. Because the thermal battery is a molten salt battery, the electrode material not only has sufficient capacity and good conductivity, but also has higher decomposition temperature to ensure good electrochemical performance and safe, stable and reliable output.
The research of the anode material of the thermal battery is mainly a disulfide system and a halide system, and FeS is common2，CoS2And FexCo1-xS2The composite anode material has halide system of NiCl2The anode material is reported by a plurality of domestic and foreign units. The research on the anode materials of domestic thermal batteries mainly focuses on the eighteenth research institute of the Chinese electronic science and technology group, the Shanghai space power research institute, the Meiling power limited Guizhou and other units, and FeS is respectively reported by publication numbers CN1043042A and CN101728510A2The positive electrode material, publication No. CN105406066, CN 107565105A reports CoS2Raw material modification preparation and purification process, wherein the North craftsman introduces the layered structure MoS2The modification of cobalt disulfide from the research direction of lithium ion intercalation, publication numbers CN102544482A, CN102856565B, respectively report CoS2Cathode materials and methods for treating the same, CN105140485A and CN106207085A report FeS2And CoS2Physical hybrid composites, CN107026256A reported FexCo1-xS2A chemical composite anode material preparation method, publication No. 108039468A reports NiS2And CoS2A physical hybrid composite cathode material. Publications CN102157722B and CN107644985A report NiCl2A preparation method of a thermal battery anode material. NiS of relevant units such as Hunan university2The preparation of materials is related to reports, and NiS is reported in U.S. Pat. No. 4, 8652674, 22And FeS2，COS2And (3) physically mixing the composite cathode material.
Investigation of the above Material, NiCl2The electrolyte is mutually soluble, and the working time is short. Therefore, the mainstream anode material of the thermal battery is mainly iron cobaltIn the transition metal disulfides such as nickel and the like, the anode materials have a pyrite structure, sulfur in the pyrite structure is-1 valence, the capacity of the electrode materials depends on the valence change of the sulfur, a first discharge platform of the anode materials is mainly utilized in the application of a thermal battery, and a subsequent discharge platform is cut off due to low potential, large internal resistance and fast voltage drop. The transition metals of the above materials only have an influence on the decomposition temperature and internal resistance of the electrode material. Therefore, when the transition metal disulfide such as iron, cobalt, nickel and the like is activated in the thermal battery, the high-temperature process of the battery can cause decomposition of the anode material, so that capacity loss is caused, and the generated sulfur vapor can cause serious thermal runaway when the sulfur vapor is out of control, so that short-circuit combustion and even explosion are caused.
Among the above positive electrode materials, FeS2The decomposition temperature is 550 ℃, the specific capacity is 1206As/g, CoS2The decomposition temperature is 650 ℃, the specific capacity is about 1044As/g, NiS2Between the two. Because the electrode material needs to bear high temperature when the thermal battery works, the actual output capacity is obviously lower than the theoretical capacity, FeS2The utilization rate is generally 50-65%, and CoS 260% -80% of positive electrode and NiS2The utilization rate of the anode is 55-70%, and the utilization rate can be improved by more than 10% by compounding two materials.
In addition, in terms of battery research, patent publication No. CN102856565B emphasizes CoS2LiSi alloy thermal batteries, the weight of the heating powder exceeds 40%, and the batteries have potential safety hazards. Publication No. CN102569837B improves battery safety by designing the insulating assembly from the battery. A small thermal battery with stack temperature compensation is reported under publication No. CN 202534736U. Publication No. CN1043042A reports FeS2Eliminating peak treatment technique, which eliminates sulfur vapor in the initial stage of activation by introducing active material, and is always CoS after optimization treatment2，NiS2The representative polysulfide is used.
In the research of batteries, the batteries are mainly designed in the aspects of enhancing insulation, performing heat preservation compensation and processing sulfide materials in a heat control mode. In general, the materials have the same discharge principle, similar chemical structure and similar physical and chemical properties, and the iron-cobalt-nickel disulfide series thermal battery has the following defects:
(1) the decomposition temperature is relatively low, and the electrode utilization rate is low. The iron-cobalt-nickel disulfide positive electrode has decomposition phenomena at high temperature, the decomposition temperature is 550-650 ℃, the working temperature of a thermal battery is above 550 ℃, the local temperature impact can reach above 1000 ℃, the decomposition of the positive electrode material can cause the reduction of the capacity of the material, and the utilization rate is reduced.
(2) The voltage platform cannot be fully utilized, and the theoretical capacity is limited. The disulfide discharge of iron, cobalt and nickel is realized by accepting electrons through sulfur element, and sulfur and iron, cobalt and nickel exist in various compounds, so that a plurality of voltage platforms are represented in the discharge process of the battery, and the theoretical capacity of the first voltage platform in practical application is low.
(3) The heat influence is large, and the design difficulty of the battery is large. Because the disulfide of iron, cobalt and nickel is decomposed at high temperature, the generated sulfur can enter the diaphragm in the form of polysulfide and react with other substances such as free lithium dissolved in the negative electrode to generate a heat effect, thermal runaway is caused seriously, the burn-through short circuit of the battery is caused, and the safety and the reliability of the battery are reduced.
(4) High temperature processes reduce component insulation. Because the sulfur vapor decomposed in the high-temperature process has corrosiveness, lead-out of the battery and corrosion of partial metal components can be caused, so that the insulating strength and the structural strength are reduced, and the long-time short circuit or open circuit at the connection part at the later stage of the large-capacity thermal battery is caused.
Based on the points, the development of a novel thermal battery with higher decomposition temperature, larger output capacity and good environmental heat adaptability and a material suitable for the thermal battery have great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, solve the technical problems that the development of a thermal battery is restricted by the theoretical capacity of a positive electrode material, the decomposition temperature is low, the utilization rate of an electrode material is low, the safety performance is poor and the like in the existing iron-cobalt-nickel sulfide thermal battery system, and provide the application of tungsten-molybdenum sulfide in the thermal battery, wherein the tungsten-molybdenum sulfide is taken as a positive electrode, and metal lithium and lithium alloy are taken as a negative electrode of the thermal battery electrochemical system, the positive electrode reaction is that tungsten (molybdenum) metal ions accept electrons and are reduced into metal tungsten (molybdenum), and the negative electrode loses electrons by free lithium and is changed into lithium ions, and the electrochemical reaction is as follows:
and (3) positive pole reaction: w (Mo) S2+4e＝＝＝W(Mo)+2S2-
And (3) cathode reaction: li ═ Li++e
The technical purpose of the invention is realized by the following technical scheme.
The application of tungsten molybdenum sulfide in a thermal battery is characterized in that the tungsten molybdenum sulfide is used as a positive electrode material of the thermal battery, and at least one of tungsten metal or molybdenum metal is used as an electron acceptor in a discharging process.
The tungsten molybdenum sulfide is tungsten disulfide (WS)2) Molybdenum disulfide (MoS)2) Or a tungsten molybdenum sulfur composite. The tungsten disulfide is pure tungsten disulfide and contains S-coated WS2(for example, excessive sulfur reacts with tungsten to obtain tungsten disulfide containing S) or tungsten disulfide with W as a core-shell structure (for example, excessive tungsten reacts with sulfur to obtain tungsten disulfide on the surface, and W is in the interior); the tungsten molybdenum sulfur compound is a physical mixture (WS) of tungsten disulfide and molybdenum disulfide2/MoS2) For example, the mass ratio of tungsten disulfide to molybdenum disulfide is (5-9): (1-5); tungsten molybdenum sulfur chemical compound (W)xMo1-xSyX is more than 0 and less than 1, y is 2 or 3 or WMoS4) The preparation method is characterized by adopting a hydrothermal method, mixing substances containing a tungsten source, a molybdenum source and a sulfur source, carrying out hydrothermal reaction, and proportioning according to a stoichiometric ratio.
In the thermal battery of the invention, the anode material consists of 30-95 parts by mass of tungsten molybdenum sulfide, 0.1-5 parts by mass of additive, 0.01-10 parts by mass of electronic additive, 5-50 parts by mass of ionic conductive agent and 0-10 parts by mass of binder.
In addition, the tungsten-molybdenum sulfide is 50-80 parts by mass, the additive is 1-5 parts by mass, the electronic additive is 1-6 parts by mass, the ionic conductive agent is 10-40 parts by mass, and the binder is 2-6 parts by mass.
And the electronic conductive agent provides a path for electron transmission conduction for the thermal battery, and a carbonaceous conductive agent or a metal conductive agent is selected, wherein the carbonaceous conductive agent is graphite, carbon black, acetylene black, a carbon nano tube, graphene or amorphous carbon, and the metal conductive agent is gold, silver, copper, nickel, platinum, tungsten, molybdenum or zinc.
Furthermore, the ionic conductor provides a path for ion transport for the thermal battery, and is selected from alkali metal halide fused salt, alkaline earth metal halide fused salt or alkali metal oxysalt fused salt, such as LiCl-KCl (44.8 wt% -55.2 wt%), LiF-LiCl-LiBr (9.6 wt% -22 wt% -68.4 wt%), LiF-LiBr-KBr (0.81 wt% -56 wt% -43.18 wt%), LiCl-LiBr-KBr (12.05 wt% -36.54 wt% -51.41 wt%), LiCl-KCl-RbCl-CsCl, LiNO3-KNO3，CaCl2-LiCl-KCl，LiSO4LiCl-LiBr (molten salts are commonly used in the thermal battery field as ion conductive agents).
Moreover, the binder is an organic binder or an inorganic binder, and is intended to be able to press-mold or slurry-coat the powder material, and commonly includes magnesium oxide, silicon dioxide, aluminum oxide, sodium silicate, PVC, PVDF, NMP, epoxy resin or polyethylene glycol.
In addition, in order to solve the voltage peak caused by the residual elemental sulfur or residual elemental sulfur in the thermal battery, the additive adopts active metal and alloy thereof, alkali metal oxide or peroxide and alkaline earth metal oxide; the active metal and the alloy thereof are lithium powder, calcium powder, lithium silicon alloy (lithium 44 wt%, the rest is silicon), lithium boron alloy (lithium 60 wt%, the rest is boron), lithium aluminum alloy (lithium 30 wt%, the rest is aluminum) and calcium silicon alloy (various alloys can be purchased from Beijing colored institute); the alkali metal oxide or peroxide is lithium oxide, sodium oxide, potassium oxide, lithium peroxide, sodium peroxide, potassium peroxide; the alkaline earth metal oxide is magnesium oxide and calcium oxide.
Further, the tungsten molybdenum sulfide is tungsten disulfide (WS)2) Molybdenum disulfide (MoS)2) Or a tungsten molybdenum sulfur composite. The tungsten molybdenum sulfur compound is a physical mixture (WS) of tungsten disulfide and molybdenum disulfide2/MoS2) Substances such as tungsten disulphide and molybdenum disulphideThe quantity ratio is (5-9): (1-5); the tungsten disulfide is pure tungsten disulfide and contains S-coated WS2(for example, excessive sulfur reacts with tungsten to obtain tungsten disulfide containing S) or tungsten disulfide with W as a core-shell structure (for example, excessive tungsten reacts with sulfur to obtain tungsten disulfide on the surface, and W is in the interior); tungsten molybdenum sulfur chemical compound (W)xMo1-xSyX is more than 0 and less than 1, y is 2 or 3 or WMoS4) The preparation method is characterized by adopting a hydrothermal method, mixing substances containing a tungsten source, a molybdenum source and a sulfur source, carrying out hydrothermal reaction, and proportioning according to a stoichiometric ratio.
And the positive electrode material has a particle size of 30nm to 200 μm, an angle of repose of 2 to 25 DEG, and a density of 2.5 to 7.6g/cm3。
The preparation method of the thermal battery anode material comprises the step of uniformly mixing the tungsten molybdenum sulfide, the additive, the electronic conductive agent, the ionic conductive agent and the binder.
The preparation method of the positive electrode material of the thermal battery is carried out according to the following steps:
step 1, pretreatment of the Material
(1) Pretreatment of tungsten molybdenum sulfide
Placing the tungsten molybdenum sulfide in inert protective gas, heating the tungsten molybdenum sulfide to 500-1200 ℃ at the heating rate of 5-30 ℃/min, carrying out heat preservation roasting for 0.5-6 h, cooling the tungsten molybdenum sulfide to 50-60 ℃ along with the furnace, and sieving the tungsten molybdenum sulfide with a sieve of 60-200 meshes; then heating the mixture to 300-600 ℃ at a heating rate of 5-10 ℃/min in a vacuum degree state of 0-0.1 MPa, performing heat preservation roasting for 0.5-1 h, slowly introducing balance transfer gas to 0.1MPa, performing heat preservation roasting for 0.1-1 h, vacuumizing, repeatedly performing atmosphere replacement for 2-10 times, and cooling to room temperature along with the furnace in a vacuum state
(2) Additive passivation treatment
Passivating the additive in an atmosphere environment, wherein the atmosphere environment is a mixed gas of water vapor and argon, the volume percentage of the water vapor is 5-20%, or the mixed gas of the water vapor and carbon dioxide, the volume percentage of the water vapor is 5-20%
In step 1, when the tungsten molybdenum sulfide is pretreated, the inert protective gas is nitrogen, helium or argon.
In the step 1, the tungsten molybdenum sulfide is placed in a quartz tube furnace or an atmosphere protection furnace, heated to 600-1000 ℃ at a heating rate of 10-20 ℃/min under inert protection gas, and is subjected to heat preservation roasting for 1-3 hours, and then is cooled to 50-60 ℃ along with the furnace.
In the step 1, the tungsten molybdenum sulfide after high-temperature roasting is placed into a vacuum roasting furnace, the pressure in the furnace is kept in a vacuum degree state of 0-0.1 MPa, the tungsten molybdenum sulfide is heated to 400-600 ℃ at a heating rate of 5-8 ℃/min and is roasted for 30-50 min in a heat preservation mode, then equilibrium transfer gas is slowly introduced to 0.1MPa and is roasted for 10-30 min in a heat preservation mode, then the furnace is vacuumized, atmosphere replacement is repeatedly carried out for 2-10 times, and the furnace is cooled in a vacuum state.
In the step 1, when the tungsten molybdenum sulfide is pretreated, the equilibrium transfer gas is a mixed gas of water vapor and argon, and the volume percentage of the water vapor is 1-20%; the mixed gas of water vapor and nitrogen, the volume percentage of the water vapor is 1-20%; the mixed gas of water vapor and carbon dioxide, the volume percentage of the water vapor is 1-20%.
In step 1, when the additive passivation treatment is performed, the passivation treatment time is 5s to 5min, preferably 5s to 1 min.
(1) Weighing the tungsten molybdenum sulfide pretreated by the material in the step 1, an additive, an electronic conductive agent, an ionic conductive agent and an inorganic binder in proportion, roasting the powder subjected to activation treatment for 0.5-5 h under the conditions of a vacuum degree of 0-0.1 MPa and a temperature of 250-500 ℃, cooling along with a furnace, crushing, and sieving by a sieve of 60-200 meshes to obtain the anode material for the thermal battery;
(2) preparing the tungsten molybdenum sulfide pretreated by the material in the step (1), an electronic conductive agent and an organic binder into slurry, and coating and drying the slurry to obtain the anode material of the thermal battery electrode.
In step 2, when coating and drying are performed, additives, ion conductive agents, and inorganic binders are added.
In the step 2, a planetary high-speed mixer is used for activation during activation treatment, a ball mill is used for activation, and a V-shaped powder mixer is used for activation (heat is generated during ball milling to play an activating role), wherein the treatment time is 5-30 min, and preferably 10-20 min.
In the invention, in each step of preparation process, the preparation is carried out in a drying room with the humidity not more than 5%, the temperature of 15-25 ℃ and the dew point of-40-30 ℃.
The thermal battery comprises a battery monomer consisting of a positive electrode material, an alkali metal halide diaphragm, an asbestos ring, a negative electrode material and a current collecting sheet, wherein the current collecting sheet is arranged on the other side (namely the side which is not in contact with the alkali metal halide diaphragm) of the negative electrode material; asbestos rings are arranged between the anode material and the current collecting sheet and positioned at two ends of the alkali metal halide diaphragm and two ends of the cathode material, so that high-temperature molten salt or metal lithium is prevented from flowing; arranging a heating sheet in each battery cell; the battery monomer consisting of the anode material, the alkali metal halide diaphragm, the asbestos ring, the cathode material and the current collecting sheet is connected in series or in parallel to form the thermal battery.
In the thermal battery of the present invention, the lithium content in the negative electrode material is more than 30 wt%, such as metallic lithium, passivated lithium powder or high lithium content lithium alloy material lithium aluminum alloy, lithium carbon alloy, lithium silicon alloy, lithium boron alloy.
In the thermal battery of the invention, the mass ratio of the anode material to the cathode material is (1-10): 1, preferably (4-8): 1.
in the thermal battery of the present invention, the alkali metal halide diaphragm is composed of an alkali metal molten salt and a porous material, and the mass ratio of the alkali metal molten salt to the porous material is (10-90): (90-10), preferably (30-60): (40-70), the thickness of the alkali metal halide diaphragm layer is 0.1-2.5 mm, preferably 0.5-2 mm; the porous material is MgAl2O4，Y2O3，ZrO2，BN，MgO，SiO2Or Al2O3The apparent specific volume is 6-20; the alkali metal molten salt takes one or more elements of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) as cations and takes halogen anions (X) of fluorine, chlorine, bromine and iodine-) Sulfate radical (SO)4 2-) Carbonate radical (CO)3 2-) Nitrate radical (NO)3 -) Hydroxyl radical (OH)-) One or more of the above anions are selected from LiCl-KCl (44.8-55.2 wt%), LiF-LiCl-LiBr (9.6-22-68.4 wt%), LiF-LiBr-KBr (0.81-56-43.18 wt%), LiCl-LiBr-KBr (12.05-36.54-51.41 wt%), LiCl-KCl-RbCl-CsCl, LiNO3-KNO3，CaCl2-LiCl-KCl，LiSO4-LiCl-LiBr，LiOH-NaOH-KOH。
In the thermal battery of the invention, the heating plate adopts Fe-KClO4Or Zr-BaCrO4The amount of the heating plate is 30-60%, preferably 40-50% of the mass of the battery cell. The battery controls the internal temperature of the battery by activating a system to ignite heating materials (heating sheets) in the battery (stack), the heating materials can be positioned between two series (parallel) single batteries, can be independently added into a positive electrode material, and can also perform centralized heat supply at two ends of the battery stack.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) good thermal stability of tungsten molybdenum sulfide, wide heat regulation range, FeS2，NiS2，CoS2Decomposition temperature is about 550 ℃, 600 ℃, 650 ℃, NiCl2Sublimed at 870 ℃ and tungsten molybdenum sulfide, especially WS2And MoS2Good thermal stability, WS2And MoS2The decomposition temperature is up to 1250 ℃ and 1370 ℃, is far higher than the decomposition temperature of the current iron-cobalt-nickel disulfide, and can bear the high temperature of more than 550 ℃ of the thermal battery, even the short-time local high temperature of more than 1000 ℃. Therefore, the safety is better under the conditions of high heat (more than 40 percent of the weight of the heating powder) and high-temperature no-load.
(2) The specific capacity of the anode material is large, FeS2，CoS2，NiCl2The theoretical specific capacity of the anode material is 1206As/g, 1044As/g, 1484 As/g (no mutual solubility considered), while the tungsten molybdenum sulfide, such As WS2Can reach 1556As/g and MoS2Can reach 2412A s/g theory, and has capacity 10-50% higher than that of Fe-Co-Ni disulfide.
(3) The battery has long working time, and the self-discharge of the anode material is small and the material utilization rate is high in the long-time high-temperature discharge process due to the high decomposition temperature of the tungsten-molybdenum sulfide material, and is higher than that of the iron-cobalt-nickel disulfide anode by more than 10%.
(4) The battery has high voltage precision, and in the long-time discharging process, the battery discharges stably, the voltage fluctuation is far less than that of the thermal battery system of the iron-cobalt-nickel-sulfur anode, and the battery is very suitable for a component integration system with high voltage precision.
(5) The material prepared by the method has high process stability, and the process comprises the steps of firstly roasting with high-temperature argon gas for dehydration and sulfur removal, secondly deeply dehydrating and sulfur removal by vacuum-displacement roasting, and finally pretreating by mechanical activation sintering to enhance the interface property of the material and molten salt and ensure the process processability of the material and the stability of a battery. Because the content of water and free sulfur in the material is extremely low, the battery discharges stably, the process is operable and strong, and the method is suitable for mass production; the method can reduce the influence of thermal shock on the performance of the battery. On one hand, the material adopts tungsten molybdenum sulfide, so that the stability of the material is high; on the other hand, as the passivation treatment process of the additive with high activity is adopted in the process, sulfur generated by decomposition during thermal shock can quickly react with the additive to form sulfide with high stability, and peak voltage cannot be caused, so that the stability of the output performance of the battery is ensured.
Drawings
FIG. 1 is a schematic view of the structure of a thermal battery of the present invention.
Figure 2 is an SEM photograph of tungsten disulfide used in the present invention.
Figure 3 is a graph of TG testing for tungsten disulfide used in the present invention.
FIG. 4 shows Li (B)/LiCl-LiF-LiBr/WS in the present invention2Battery discharge profile.
FIG. 5 shows Li (B)/LiCl-LiF-LiBr/WS in the present invention2TEM images of the positive product tungsten after cell discharge.
FIG. 6 shows Li (B)/LiCl-LiF-LiBr/WS in the present invention2XRD photographs of the positive electrode product after cell discharge.
FIG. 7 shows Li (Si)/LiCl-KCl/MoS in the present invention2Battery discharge profile.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
As shown in fig. 1, the battery cell is composed of a positive electrode material, an alkali metal halide diaphragm, an asbestos ring, a negative electrode material and a current collecting plate, wherein the alkali metal halide diaphragm is arranged between the positive electrode material and the negative electrode material, and the current collecting plate is arranged on the other side of the negative electrode material; an asbestos ring is arranged between the anode material and the current collecting sheet and is positioned at two ends of the alkali metal halide diaphragm and the cathode material, so that the flowing of high-temperature molten salt or metal lithium is prevented; the method comprises the steps of arranging a heating sheet on the outer side of each monomer, connecting N battery monomers in series, arranging the heating sheet between every two adjacent battery monomers, inserting the single battery into the heating sheet to form a sandwich cake structure, finally connecting positive and negative electrodes at two ends to be led out to form a battery stack of a thermal battery with tungsten (molybdenum) metal ions as electron acceptors, and packaging the battery stack in a stainless steel cylinder.
Example 1-tungsten disulfide as tungsten molybdenum sulfide, as shown in figures 2 and 3, tungsten disulfide has lamellar morphology and high stability at high temperature.
(1) High temperature roasting
Placing tungsten disulfide in a quartz tube furnace, introducing argon protective gas, heating the tungsten disulfide to 700 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation roasting for 2 hours, cooling the tungsten disulfide to 60 ℃ along with the furnace, and sieving the tungsten disulfide with a 60-200-mesh sieve.
(2) Vacuum-atmosphere replacement roasting
And (2) placing the tungsten disulfide roasted at the high temperature in the step (1) into a vacuum roasting furnace, keeping the pressure in the furnace in a vacuum degree state of 0.01MPa, heating the tungsten disulfide to 500 ℃ at a heating rate of 5 ℃/min, roasting for 1h, slowly introducing balance transfer gas to 0.1MPa, vacuumizing and repeatedly carrying out atmosphere replacement for 5 times after roasting for 1h, cooling along with the furnace in a vacuum state to obtain a tungsten disulfide sample, wherein the balance transfer gas is mixed gas of water vapor and argon, and the volume percentage of the water vapor is 5%.
(3) Additive passivation treatment
And passivating the additive lithium-silicon alloy for 5min in a special atmosphere environment, wherein the special atmosphere environment is a mixed gas of water vapor and carbon dioxide, and the volume percentage of the water vapor is 5%.
(4) Mechanically activated vacuum sintering
Weighing the tungsten disulfide, the additive, the electronic conductive agent, the ionic conductive agent and the inorganic binder which are processed in the steps (1), (2) and (3) in proportion, activating the weighed materials for 30min, roasting the processed powder for 4h under the conditions that the vacuum degree is 0.1MPa and the temperature is 450 ℃, and cooling along with the furnace; the mechanical activation comprises the steps of activating by adopting a planetary high-speed mixer and activating by adopting a ball mill; 45 parts by mass of tungsten disulfide, 5 parts by mass of additive lithium silicon alloy, 10 parts by mass of electronic additive graphite, 40 parts by mass of ionic conductive agent LiCl-KCl and 8 parts by mass of inorganic binder sodium silicate, wherein each part by mass is 1 g.
(5) Crushing and sieving
And (4) crushing the material obtained by cooling in the step (4), and sieving the crushed material with a 100-mesh sieve to obtain the anode material for the thermal battery.
The preparation process in each step is carried out in a drying room with the humidity not more than 3% and the temperature of 20 ℃.
The anode is the material of example 1, the cathode material is a lithium boron alloy containing 60 wt% of lithium, the mass ratio of the anode material to the lithium boron alloy is 1.2:1, the diaphragm is formed by compounding alkali metal halide LiCl-LiF-LiBr molten salt and a chemically inert porous material aluminum magnesium metal oxide, the mass ratio of the alkali metal halide to the porous material aluminum magnesium oxide is 20:80, the apparent specific volume of the aluminum magnesium oxide is 10-12, the thickness of the diaphragm layer in the single battery is 0.45-0.55 mm, and a battery heating system (heating plate) adopts Fe-KClO4In the system, the consumption of the heating material accounts for 45 wt% of the consumption of the whole battery, after the battery is activated, the highest surface temperature of the shell is 300 ℃, the highest internal temperature can reach more than 1000 ℃, and the voltage of a single battery is 1.2-1.45V. 31 monomers are packaged in a shell after being connected in series to serve As a battery unit, the positive electrode material is tungsten disulfide, constant current test is carried out, As shown in figure 4, the working time is 700s, the positive electrode utilization rate is over 90%, and the positive electrode specific capacity is up to 1440 As/g. After the experiment, the product after discharge was analyzed, as shown in fig. 5 and 6, the product was metal tungsten,according with the electrode reaction mechanism. The battery has no open circuit and short circuit after discharge test, the layered structure of the battery stack is clear, the interface of the composite electrode is clear, the electrode plate is not deformed, the mechanical strength is very high, and the working requirement of harsh environment mechanical conditions can be met.
Example 2 molybdenum disulfide as tungsten molybdenum sulfide
(1) High temperature roasting
Putting molybdenum disulfide in a quartz tube furnace, introducing argon protective gas, heating the molybdenum disulfide to 850 ℃ at the heating rate of 10 ℃/min, roasting for 4 hours, cooling to 60 ℃ along with the furnace, and sieving with a 100-mesh sieve.
(2) Vacuum-atmosphere replacement roasting
Putting the molybdenum disulfide roasted at the high temperature in the step (1) into a vacuum roasting furnace, keeping the pressure in the furnace in a vacuum degree state of 0.015MPa, heating the molybdenum disulfide to 600 ℃ at a heating rate of 10 ℃/min, roasting for 1h, slowly introducing balance transfer gas to 0.1MPa, vacuumizing and repeatedly carrying out atmosphere replacement for 5 times after roasting for 0.5h, cooling along with the furnace in a vacuum state to obtain a molybdenum disulfide sample, wherein the balance transfer gas is mixed gas of water vapor and argon, and the volume percentage of the water vapor is 10%.
(3) Additive passivation treatment
And passivating the additive lithium boron alloy for 5min in a special atmosphere environment, wherein the special atmosphere environment is a mixed gas of water vapor and carbon dioxide, and the volume percentage of the water vapor is 5%.
(4) Mechanically activated vacuum sintering
Weighing the molybdenum disulfide, the additive, the electronic conductive agent, the ionic conductive agent and the inorganic binder which are processed in the steps (1), (2) and (3) in proportion, activating the weighed molybdenum disulfide, the electronic conductive agent, the ionic conductive agent and the inorganic binder for 30min, roasting the processed powder for 4h under the conditions that the vacuum degree is 0.1MPa and the temperature is 450 ℃, and cooling along with the furnace; the mechanical activation comprises the steps of activating by adopting a planetary high-speed mixer and activating by adopting a ball mill; 60 parts of molybdenum disulfide, 3 parts of additive lithium boron alloy, 1 part of electronic additive carbon nano tube, 50 parts of ion conductive agent LiF-LiCl-LiBr and 5 parts of inorganic binder sodium silicate, wherein each part is 1 g.
(5) Crushing and sieving
And (4) crushing the material obtained by cooling in the step (4), and sieving the crushed material with a 100-mesh sieve to obtain the anode material for the thermal battery.
The preparation process in each step is carried out in a drying room with the humidity not more than 3% and the temperature of 20 ℃.
The anode is the material of example 2, the cathode material is a lithium silicon alloy containing 44 wt% of lithium, the mass ratio of the anode material to the lithium silicon alloy is 3:1, the diaphragm is formed by compounding alkali metal halide LiCl-KCl molten salt and a chemically inert porous material aluminum magnesium metal oxide, the mass ratio of the alkali metal halide to the porous material aluminum magnesium oxide is 20:80, the apparent specific volume of the aluminum magnesium oxide is 10-12, the thickness of the diaphragm layer in the single battery is 0.45-0.55 mm, and a battery heating system (heating plate) adopts Fe-KClO4In the system, the consumption of the heating material accounts for 50 wt% of the consumption of the whole battery, after the battery is activated, the highest surface temperature of the shell is 300 ℃, the highest internal temperature can reach more than 1000 ℃, and the voltage of the monomer is 1.0-1.50V. The 14 monomers are packaged in the shell after being connected in series to serve as a battery unit, the positive electrode material is molybdenum disulfide, constant current testing is carried out, as shown in the attached drawing 7, normal electrical property output can be achieved, open circuit and short circuit do not occur, the layered structure of the battery stack is clear, the composite electrode interface is clear, electrode plates do not deform, high mechanical strength is achieved, and the working requirements of harsh environment mechanical conditions can be met.
Example 3 tungsten disulfide and molybdenum disulfide as tungsten molybdenum sulfide
(1) High temperature roasting
Putting molybdenum disulfide and tungsten disulfide in a quartz tube furnace, introducing argon protective gas, heating to 850 ℃ at the heating rate of 10 ℃/min, roasting for 4h, cooling to 60 ℃ along with the furnace, and sieving with a 100-mesh sieve.
(2) And (2) vacuum-atmosphere replacement roasting, namely putting the molybdenum disulfide and the tungsten disulfide which are roasted at the high temperature in the step (1) into a vacuum roasting furnace, keeping the pressure in the vacuum roasting furnace in a vacuum degree state of 0.015MPa, heating the molybdenum disulfide and the tungsten disulfide to 600 ℃ at a heating rate of 10 ℃/min, roasting for 1h, slowly introducing balance transfer gas to 0.1MPa, roasting for 0.5h, vacuumizing and repeatedly carrying out atmosphere replacement for 5 times, cooling along with the furnace in a vacuum state to obtain a molybdenum disulfide sample, wherein the balance transfer gas is a mixed gas of water vapor and argon, and the volume percentage of the water vapor is 10%.
(4) Mechanically activating and vacuum sintering, namely weighing the molybdenum disulfide, the tungsten disulfide, the additive, the electronic conductive agent, the ionic conductive agent and the inorganic binder which are processed in the steps (1), (2) and (3) in proportion, activating the weighed materials for 30min, roasting the processed powder for 4h under the conditions that the vacuum degree is 0.1MPa and the temperature is 450 ℃, and cooling along with a furnace; the mechanical activation comprises the steps of activating by adopting a planetary high-speed mixer and activating by adopting a ball mill; 15 parts of molybdenum disulfide, 45 parts of tungsten disulfide, 3 parts of additive lithium boron alloy, 1 part of electronic additive carbon nano tube, 30 parts of ionic conducting agent LiF-LiCl-LiBr and 5 parts of inorganic binder sodium silicate, wherein each part is 1 g.
(5) Crushing and sieving
And (4) crushing the material obtained by cooling in the step (4), and sieving the crushed material with a 100-mesh sieve to obtain the anode material for the thermal battery.
The preparation process in each step is carried out in a drying room with the humidity not more than 3% and the temperature of 20 ℃.
The anode is the material of embodiment 3, the cathode material is a lithium silicon alloy containing 44 wt% of lithium, the mass ratio of the anode material to the lithium silicon alloy is 3:1, the diaphragm is formed by compounding alkali metal halide LiCl-KCl molten salt and a chemically inert porous material aluminum magnesium metal oxide, the mass ratio of the alkali metal halide to the porous material aluminum magnesium oxide is 20:80, the apparent specific volume of the aluminum magnesium oxide is 10-12, the thickness of the diaphragm layer in the single battery is 0.45-0.55 mm, and a battery heating system (heating plate) adopts Fe-KClO4In the system, the consumption of the heating material accounts for 50 wt% of the consumption of the whole battery, after the battery is activated, the highest surface temperature of the shell is 300 ℃, the highest internal temperature can reach more than 1000 ℃, and the voltage of the monomer is 1.2-1.50V. 14 monomers are packaged in a shell after being connected in series to serve as a battery unit, the positive electrode material is molybdenum disulfide, constant current test is carried out, normal electrical property output can be realized, and normal electrical property output is not carried outThe open circuit and the short circuit occur, the layered structure of the battery stack is clear, the interface of the composite electrode is clear, the electrode plate is not deformed, the mechanical strength is very high, and the working requirement of the mechanical condition of a harsh environment can be met.
The thermal battery can be constructed by adjusting the process parameters according to the content of the invention, and the performance of the thermal battery is basically consistent with the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The application of the tungsten molybdenum sulfide in the thermal battery is characterized in that the tungsten molybdenum sulfide is used as the anode material of the thermal battery, and at least one of tungsten metal or molybdenum metal is used as an electron acceptor in the discharging process; the tungsten molybdenum sulfide is tungsten disulfide, molybdenum disulfide or a tungsten molybdenum sulfur compound.
2. Use of tungsten molybdenum sulphide in thermal batteries according to claim 1, characterized in that tungsten disulphide is pure tungsten disulphide, comprising S-coated WS2Or W is tungsten disulfide with a core-shell structure of a core.
3. Use of tungsten molybdenum sulphide in thermal batteries according to claim 1, characterized in that the tungsten molybdenum sulphide compound is a physical mixture (WS) of tungsten disulphide and molybdenum disulphide2/MoS2) For example, the mass ratio of tungsten disulfide to molybdenum disulfide is (5-9): (1-5); tungsten molybdenum sulfur chemical compound (W)xMo1-xSyX is more than 0 and less than 1, y is 2 or 3 or WMoS4)。
4. The use of the tungsten molybdenum sulfide as claimed in any one of claims 1 to 3 in a thermal battery, wherein the positive electrode material is composed of 30 to 95 parts by mass of the tungsten molybdenum sulfide, 0.1 to 5 parts by mass of the additive, 0.01 to 10 parts by mass of the electronic additive, 5 to 50 parts by mass of the ionic conductive agent, and 0 to 10 parts by mass of the binder, in parts by mass.
5. The use of the tungsten molybdenum sulfide in a thermal battery according to claim 4, wherein the tungsten molybdenum sulfide is 50 to 80 parts by mass, the additive is 1 to 5 parts by mass, the electronic additive is 1 to 6 parts by mass, the ionic conductive agent is 10 to 40 parts by mass, and the binder is 2 to 6 parts by mass.
6. The use of tungsten molybdenum sulfide in a thermal battery as claimed in claim 4, wherein the electronic conductive agent is selected from carbonaceous conductive agents or metal conductive agents, the carbonaceous conductive agent is graphite, carbon black, acetylene black, carbon nanotubes, graphene or amorphous carbon, and the metal conductive agent is gold, silver, copper, nickel, platinum, tungsten, molybdenum or zinc.
7. Use of tungsten molybdenum sulphide in thermal batteries according to claim 4, characterized in that the ionic conductor is selected from the group consisting of fused alkali metal halides, fused alkaline earth metal halides or fused alkali metal oxyacid salts, such as LiCl-KCl, LiF-LiCl-LiBr, LiF-LiBr-KBr, LiCl-LiBr-KBr, LiCl-KCl-RbCl-CsCl, LiNO3-KNO3，CaCl2-LiCl-KCl，LiSO4-LiCl-LiBr。
8. The use of tungsten molybdenum sulphide in thermal batteries according to claim 4, characterised in that the binder is an organic or inorganic binder comprising magnesium oxide, silica, alumina, sodium silicate, PVC, PVDF, NMP, epoxy resins or polyethylene glycols.
9. The use of tungsten molybdenum sulphide in thermal batteries according to claim 4 wherein the additive is selected from the group consisting of active metals and their alloys, alkali metal oxides or peroxides, alkaline earth metal oxides; the active metal and the alloy thereof are lithium powder, calcium powder, lithium-silicon alloy, lithium-boron alloy, lithium-aluminum alloy and calcium-silicon alloy; the alkali metal oxide or peroxide is lithium oxide, sodium oxide, potassium oxide, lithium peroxide, sodium peroxide, potassium peroxide; the alkaline earth metal oxide is magnesium oxide and calcium oxide.
10. The use of the tungsten molybdenum sulfide in a thermal battery according to claim 4, wherein the positive electrode material has a particle size of 30nm to 200 μm, an angle of repose of 2 to 25 °, and a density of 2.5 to 7.6g/cm3。
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