CN115863583A - Sulfide positive electrode material of thermal battery and preparation method thereof - Google Patents
Sulfide positive electrode material of thermal battery and preparation method thereof Download PDFInfo
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Abstract
The scheme discloses a sulfide anode material of a thermal battery in the technical field of chemical power thermal batteries, the components of the anode material comprise a conductive agent and sulfide, the conductive agent is a nickel-containing composite conductive agent, the nickel-containing composite conductive agent comprises a first conductor and a second conductor of ternary perchloric acid, and at least metal elements contained in the nickel-containing composite conductive agent and the molar ratio of the metal elements to the sulfide are Ni: k: li = m:58.8:41.2, wherein m =1 to 5. The anode material is applied to a long-time tail-end large-current thermal battery, the no-load voltage is high, and the later-stage load capacity is strong.
Description
Technical Field
The invention belongs to the technical field of chemical power thermal batteries, and particularly relates to a sulfide anode material of a thermal battery and a preparation method thereof.
Background
Thermal batteries are a special chemical power source and widely used in the aerospace field due to their excellent power output performance and long storage life. The interfacial resistance of common thermal battery positive electrode materials (such as sulfide) is high at high temperature, so that an ionic conductive agent and an electronic conductive agent are required to be added for improving the interfacial resistance of the positive electrode. With the development of remote equipment, higher requirements are put forward on the performance of the thermal battery in the industry, such as small initial discharge current, higher voltage provided by the anode material at the initial stage, no load in the middle stage, higher ionic conductivity and electronic conductivity of the anode material at the later stage and the like, so that the anode material with high conductivity and high thermal shock resistance becomes one of important development directions of the thermal battery.
In the current research, the active substance in the anode material of the thermal battery is sulfide, and the anode material of the thermal battery is mainly constructed in a form of compounding the active substance and alkali metal halide molten salt, so that the anode material of the thermal battery is very suitable for a high-power thermal battery due to high ion mobility and high ion conductivity of alkali metal, for example, CN201910205114.2 reports a high-potential high-power heat-running thermal battery anode material consisting of fluoride, liF-NaF-LiCl and LiF-KF-LiCl eutectic salt. CN201910304122.2 reports a composite positive electrode material composed of sulfide and a potassium-containing electrolyte and capable of reducing self-discharge degree; CN201110067556.9 reports a cathode material composed of a nickel chloride cathode and an alkali metal halide eutectic salt; CN201910411142.X reports a positive electrode material composed of tungsten molybdenum sulfide and an alkali metal molten salt ion conductive agent.
Since the sulfide is decomposed at high temperature to generate sulfur vapor, which causes capacity loss of the positive electrode or exothermic side reaction, and seriously causes thermal runaway of the battery, the addition of a certain amount of alkali metal halide molten salt to the positive electrode material with the sulfide can reduce the interface resistance and prevent the electrolyte in the diaphragm from diffusing and migrating to the positive electrode. The alkali metal halide fused salt is subjected to thermal buffering, so that the decomposition of sulfides can be effectively reduced, the working time of the battery is prolonged, and meanwhile, the long-time tail-end heavy-current load thermal battery has the characteristics of small current in the initial discharge stage and large load current in the later stage.
In current thermal battery cathode material, also because adopted alkali metal fused salt as the ionic conduction agent, in long-time thermal battery, with the progress of depth of discharge and the thermal loss of thermal battery, the anodal accessory substance and the anodal process of discharging can increase the internal resistance of battery, the voltage is low, make the battery discharge later stage can not satisfy the heavy current load requirement, lead to long-time thermal battery's comprehensive properties to remain to improve, consequently, provide one kind and can promote voltage at the initial stage of discharging, can prolong battery operating time again, increase sulphide actual capacity output, can also reduce battery later stage internal resistance, satisfy the technique that the battery discharged later stage heavy current load required, be the technological problem that thermal battery technical field needs key attack.
Disclosure of Invention
The invention aims to provide a sulfide cathode material of a thermal battery aiming at the problems in the prior art.
According to the scheme, the composition of the positive electrode material comprises a conductive agent and sulfide, the conductive agent is a nickel-containing composite conductive agent, the nickel-containing composite conductive agent comprises a first conductor and a second conductor of ternary perchloric acid, and at least metal elements contained in the nickel-containing composite conductive agent and the molar ratio of the metal elements to the sulfide are Ni: li: k = m:58.8:41.2, wherein m = 1-5.
The working principle and the beneficial technical effects of the scheme are as follows:
the invention discloses a sulfide anode material of a thermal battery, which is developed aiming at the characteristics of high heat, easy decomposition of an anode, low initial voltage and high later resistance of a long-time tail heavy-current load thermal battery.
The nickel-containing composite conductive agent at least contains metal elements and a molar ratio (Ni: li: K) of Ni: li: k = m:58.8:41.2, m =1 to 5. When the proportion m of the nickel element is less than 1, the electrolyte has small difference with the properties of the alkali metal halide electrolyte and has small influence on the heavy current load capacity of the battery at the later stage. When the proportion m of the nickel element is more than 5, the viscosity is increased, when the proportion of the nickel element is too large, a muddy melt is formed, and the added carbonaceous conductive agent can cause the metal nickel generated by rapid reduction to be layered and settled in the process of preparing the composite conductive agent, so that the composite conductive agent is uneven.
1. By introducing the heavy metal element nickel into a molten salt system with high ion migration speed, the melting point of molten salt is improved, the thermal shock influence of a heating material on an anode material at the initial activation stage is reduced, and the decomposition of an active material sulfide of the anode is reduced; and secondly, the viscosity of the material is changed by introducing a heavy metal element nickel, the high-temperature fluidity of the ion conductive agent is reduced, and the binding force with an active substance interface is improved.
2. Particularly, the second type of conductor of the ternary perchloric is utilized, the chloride ions have the high-temperature solvation effect on the heavy metal nickel ions, the uniform distribution of the metal nickel ions is realized, and a nickel-containing solvation combination body with the monomer voltage regulation function is constructed, so that the positive electrode material not only has high ion conductivity, but also can provide correction voltage in the initial low-current or no-load operation, and utilizes the weak electrochemical action or self-discharge effect to generate high-conductivity metal nickel, so that a high-activity electronic conductive agent is provided for the later electrochemical process of the battery, and the later-stage large battery load output is realized.
3. The nickel-containing composite conductive agent has a monomer voltage boosting function, and because the conductive agent contains metal nickel ions which can accept electrons more easily, the nickel-containing composite conductive agent has the voltage boosting function at the initial discharge stage of the battery, so that the voltage of a sulfide monomer is boosted to 2.1-2.6V from about 2V. Meanwhile, as the metal nickel ions generate electrochemical reaction at the positive electrode, the metal nickel with high electronic conductivity can be provided for the later period of the battery so as to bear higher current density.
Further, the sulfide is selected from FeS 2 ；CoS 2 ；NiS 2 ；Fe x Co y S 2 Wherein x + y =1; fe x Co y Ni z S 2 Wherein x + y + z =1; WS 2 ；MoS 2 Any one or a combination of more of them.
Further, the mass ratio of the sulfide is 50% to 95%. Preferably 70% to 90%. The rest components are composite conductive agents, and metal conductive agents and carbonaceous conductive agents can also be additionally added. Preferably, the mass ratio of the active substance is more than 95%, the material has poor formability, low ionic conductivity, high internal resistance of the battery and poor quality consistency. The mass ratio is lower than 50%, the capacity of the anode material is low, nickel ions can interfere with voltage for a long time, and the anode material is not suitable for a long-time tail end heavy-current load thermal battery.
Further, the first type conductor is an electronic conductor and comprises a metal conductive agent and a non-metal carbonaceous conductive agent.
Further, the content of the nonmetal carbon and the Ni is 0.01-5% of the total mass of the nickel-containing composite conductive agent. Wherein the content of the non-metallic carbon is preferably 1 to 3%. The specific content of metallic nickel can be determined by adding a carbonaceous conductive agent and the reduction time.
Further, the content of the non-metal carbon is 1-3% of the total mass of the nickel-containing composite conductive agent.
Further, the metal conductive agent is selected from one or a combination of at least two of gold, silver, platinum, manganese, iron, cobalt, nickel, copper, zinc, lead, tin, indium, antimony, bismuth, and the like. Preferably iron, cobalt, nickel, copper, zinc, gold, silver. The metal conductor mainly adopts high-conductivity metal, the metal can be physically added, and the carbonaceous conductive agent can be used for partially reducing nickel ions in the composite conductive agent. For example, in the preparation process, a certain amount of carbon material is added into molten salt, and at high temperature, the carbon reduces nickel ions to obtain metallic nickel.
Further, the non-metal carbon comprises any one or more of carbon nano tube, carbon nano fiber, graphene, carbon nano wire, ketjen black, conductive carbon black Super P, porous carbon, fullerene or conductive graphite.
The application further provides a preparation method of the sulfide anode material of the thermal battery for further improving the comprehensive performance of the anode material, which comprises the following steps:
s1, sulfide pretreatment
Carrying out segmented high-temperature heat treatment on the active substance sulfide under the protection of inert atmosphere, cooling, and screening by 80-200 meshes for later use;
s2, preparation of composite conductive agent
(1) Pretreatment: will contain Ni 2+ ，Li + ，K + Cation and Cl - Carrying out high-temperature vacuum drying on the anion raw materials, transferring the anion raw materials into a drying atmosphere, and weighing the corresponding raw materials according to the cation proportion for later use;
(2) Melting and roasting: uniformly mixing the raw materials without Ni, transferring the mixture into a crucible, adding the raw materials containing Ni on the crucible, transferring the mixture into a high-temperature furnace, and roasting the mixture at the temperature of 375-500 ℃ for 2-8 hours to form uniform and transparent melt;
(3) Composite carbon material: adding 0.01-5% of non-metallic carbonaceous conductive agent into the melt at high temperature, uniformly mixing to form suspension, and keeping the temperature for 1 min-1 h;
(4) And (3) rapidly cooling: pouring the obtained high-temperature melt suspension into a special condensation container for spreading, cooling, crushing and refining the cooled block materials, and sieving by 80-200 meshes to obtain the composite conductive agent;
s3, high-temperature roasting: preparing active substance sulfide and a composite conductive agent into powder according to a proportion, and mixing, wherein the mixing mode can be any one or combination of at least two of mechanical mixing, point, line, surface, body contact or coating after high-temperature melting;
s4, post-processing: and (4) crushing the mixed material in the step (S3), and screening by 80-200 meshes to obtain the sulfide cathode material.
Further, the step-by-step high-temperature heat treatment process in the step S1 comprises roasting at 80-200 ℃ for 4-8 h under the condition that the internal atmosphere is replaced by dry inert gas in a circulating manner, and then heating to 375-500 ℃ for high-temperature roasting for 2-8 h.
Further, the vacuum drying temperature in the pretreatment process is 60-300 ℃, and the drying time is 1-24 h.
Further, the special condensation container is a container with a heat exchange function at the bottom of the container, and the heat exchange medium comprises any one or a combination of water with the temperature not higher than 10 ℃, frozen brine, frozen glycol and low-temperature antifreeze solution containing glycol.
Further, the active substance sulfide in S3 and the composite conductive agent are mixed by ball milling at a speed of 200-1000 r/min by a powder mixer, and the mixture is uniformly mixed, then is sent into a high-temperature furnace protected by inert gas for high-temperature roasting, and is cooled along with the furnace.
Compared with the prior art, the invention has the following beneficial effects:
1) The thermal battery sulfide positive electrode material prepared by the invention realizes the uniform distribution of metal nickel ions by utilizing the high-temperature solvation effect of Cl ions on heavy metal Ni ions, and simultaneously realizes the rapid shaping of high-temperature molten salt by combining the adoption of liquefied gas for the rapid cooling to form a uniform nickel ion-containing conductive agent. The prepared nickel-ion-containing conductive agent has uniform components and high quality reliability.
2) Because the thermal battery works at high temperature, the positive electrode and the composite conductive agent can be tightly combined in the working process of the thermal battery through physical mixing or high-temperature melting treatment, and the dotted line surface body after the high-temperature melting treatment is contacted or coated, the activation of the battery can be accelerated, and the activation time is shortened.
3) The method for preparing the sulfide anode material of the thermal battery does not need to be matched with high-precision and sophisticated equipment, has simple and clear process flow, high efficiency and low cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a sulfide cathode material for a thermal battery according to the present invention;
FIG. 2 is a schematic diagram of a chalcogenide positive electrode material for a thermal battery of the present invention;
FIG. 3 is a discharge curve of a chalcogenide positive electrode material of a thermal battery in example 1.
Detailed Description
The following is a more detailed description of the preparation process, as illustrated in FIG. 1, by way of specific embodiments:
example 1
1. A preparation method of a sulfide positive electrode material of a thermal battery comprises the following steps:
s1, sulfide pretreatment
The active substance CoS 2 And carrying out segmented high-temperature heat treatment under the protection of argon atmosphere, wherein the segmented high-temperature treatment process comprises roasting at 180 ℃ for 4 hours under the condition of circularly replacing the internal atmosphere by dry argon, then heating to 450 ℃ for high-temperature roasting for 8 hours, and cooling and sieving by a 200-mesh sieve for later use.
S2, preparation of composite conductive agent
(1) Pretreatment: the chemical component is Li 2 NiCl 4 LiCl and KCl raw materials are subjected to high-temperature vacuum drying at 180 ℃ for 8 hours, transferred into a drying atmosphere, weighed according to the cation proportion and the metal cation molar proportion (Ni) 2+ ：Li + ：K + ) Is 2.5:58.8:41.2 (i.e. Li) 2 NiCl 4 LiCl, KCl feedstock molar ratio 2.5.
(2) Melting and roasting: mixing Ni-free raw materials (LiCl and KCl), transferring into crucible, and adding Ni-containing raw material (Li) 2 NiCl 4 ) And transferring the mixture into a high-temperature furnace, and roasting the mixture at the temperature of 450 ℃ for 8 hours to form a uniform and transparent melt.
(3) Composite carbon material: adding the carbon nano tube with the mass ratio of 0.1% of the raw material into the melt at high temperature, stirring and mixing uniformly for 30min, adding the carbon nano tube with the mass ratio of 1% of the raw material again, and stirring quickly to form suspension.
(4) And (3) rapidly cooling: and controlling the obtained high-temperature suspension in 30s, pouring the high-temperature suspension into a special stainless steel disc container, spreading the suspension, wherein the bottom of the stainless steel disc is provided with a water circulation cooling heat exchanger with the temperature of less than 10 ℃, the high-temperature suspension melt spread in the stainless steel disc can be cooled at an extremely high speed, and the cooled block-shaped material is crushed, refined and sieved by a 200-mesh sieve to obtain the composite conductive agent.
S3, high-temperature roasting: mixing active substance sulfide and composite conductive agent according to a ratio of 80 to 20, ball-milling and mixing by adopting a powder mixer at a speed of 300r/min, uniformly mixing, then sending into a high-temperature furnace protected by inert gas for high-temperature roasting at 400 ℃, roasting for 4h, and cooling along with the furnace.
And S4, post-processing. And crushing the roasted and cooled material, and sieving by a 200-mesh sieve to obtain the sulfide cathode material.
The positive electrode material is formed by high-temperature melting and combining 80% of cobalt disulfide serving as an active substance and 20% of a nickel-containing composite conductive agent, the nickel-containing composite conductive agent consists of a first conductor carbon nano tube, a reduced nickel powder electronic conductive agent and a second conductor ternary (Ni-K-Li) perchloride conductive agent (schematic diagram 2), and the molar ratio of metal elements in the composite conductive agent (Ni: K: li) is 2.5:58.8:41.2, the proportion of the carbon nano tube is about 1 percent, and the metallic nickel generated by reduction is about 1 percent. The anode material is applied to a long-time end high-current thermal battery, and the no-load voltage is 2.32V, as shown in FIG. 3.
The present invention also provides the following embodiments, achieving substantially the same effects as in example 1.
Example 2
A method of making a sulfide positive electrode material for a thermal battery, the method comprising the steps of:
s1, sulfide pretreatment
The active substance FeS 2 And carrying out sectional high-temperature heat treatment under the protection of argon atmosphere, wherein the sectional high-temperature treatment process comprises roasting for 4 hours at 180 ℃ under the condition of circularly replacing the internal atmosphere by adopting dry argon, and then heating to 450 ℃ for high-temperature roasting for 8 hours. Cooled and sieved by a 200-mesh sieve for standby.
S2, preparation of composite conductive agent
(1) Pretreatment: chemical composition is NiCl 2 LiCl and KCl raw materials are subjected to high-temperature vacuum drying at 180 ℃ for 8 hoursTransferring into dry atmosphere, weighing cation proportion, and metal cation molar ratio (Ni) 2+ ：Li + ：K + ) Is 2.5:58.8:41.2 (i.e., niCl) 2 LiCl, KCl feedstock molar ratio 2.5.
(2) Melting and roasting: mixing Ni-free raw materials (LiCl and KCl), transferring into crucible, and adding Ni-containing raw material (NiCl) 2 ) And transferring the mixture into a high-temperature furnace, and roasting the mixture for 8 hours at the temperature of 450 ℃ to form uniform and transparent melt.
(3) Composite carbon material: adding 1% of carbon nano tube into the melt at high temperature, uniformly mixing to form a suspension, and keeping the temperature for 5min.
(4) And (3) rapidly cooling: and immediately pouring the obtained high-temperature melt turbid liquid into a special stainless steel disc container, wherein a refrigerating fluid circulation cooling heat exchanger with water and ethylene glycol as main components is arranged at the bottom of the stainless steel disc, so that the high-temperature turbid liquid melt spread in the stainless steel disc can be cooled at a high speed, and the cooled block materials are crushed, refined and sieved by a 200-mesh sieve to obtain the composite conductive agent.
S3, high-temperature roasting: mixing active substance sulfide and composite conductive agent according to a ratio of 80 to 20, ball-milling and mixing at a speed of 300r/min by using a powder mixer, uniformly mixing, then sending into a high-temperature furnace protected by inert gas for high-temperature roasting, and cooling along with the furnace.
S4, post-processing: and crushing the roasted and cooled material, and sieving the crushed material with a 200-mesh sieve to obtain the sulfide cathode material.
Example 3
1. A method of making a sulfide positive electrode material for a thermal battery, the method comprising the steps of:
s1, sulfide pretreatment
The active substance FeS 2 And CoS 2 And respectively carrying out sectional high-temperature heat treatment under the protection of argon atmosphere, wherein the sectional high-temperature treatment process comprises roasting for 5 hours at 180 ℃ under the condition of circularly replacing the internal atmosphere by adopting dry argon, and then heating to 440 ℃ for high-temperature roasting for 12 hours. Cooled and sieved by a 200-mesh sieve for standby.
S2, preparation of composite conductive agent
(1) Pretreatment: chemical composition is NiCl 2 LiCl, KCl-LiCl eutectic raw material is subjected to high-temperature vacuum drying at 180 ℃ for 8h, transferred into a drying atmosphere, weighed according to the cation proportion and the molar ratio of metal cations (Ni) 2+ ：Li + ：K + ) Is 2.5:58.8:41.2 (i.e., niCl) 2 LiCl, liCl-KCl eutectic raw material molar ratio 2.5.
(2) Melting and roasting: the Ni-free raw material (LiCl and LiCl-KCl eutectic) is mixed uniformly, transferred into a crucible, and Ni-containing raw material (NiCl) is added on 2 ) And transferring the mixture into a high-temperature furnace, and roasting the mixture at 480 ℃ for 8 hours to form a uniform and transparent melt.
(3) Composite carbon material: adding 1% by mass of carbon nano tube into the melt at high temperature, uniformly mixing to form suspension, and keeping the temperature for 2min.
(4) And (3) rapidly cooling: immediately pouring the obtained high-temperature melt suspension into a special stainless steel disc container, wherein the bottom of the stainless steel disc is provided with a heat exchanger for cooling by circulation of chilled brine at the temperature of-5 ℃, so that the high-temperature suspension melt spread in the stainless steel disc can be cooled at an extremely high speed, and the cooled block materials are crushed and refined and sieved by a 200-mesh sieve to obtain the composite conductive agent.
S3, high-temperature roasting: the active substance FeS 2 ，CoS 2 And the composite conductive agent is prepared into powder according to the proportion of 40.
S4, post-processing: and crushing the roasted and cooled material, and sieving by a 200-mesh sieve to obtain the sulfide cathode material.
The anode material is formed by combining 40% of cobalt disulfide, 40% of iron disulfide and 20% of nickel-containing composite conductive agent through high-temperature melting, wherein the nickel-containing composite conductive agent is composed of a first-class conductor carbon nano tube, a reduced nickel powder electronic conductive agent and a second-class conductor ternary (Ni-K-Li) perchloride ion conductive agent, and the molar ratio of metal elements in the composite conductive agent (Ni: K: li) is 3:58.8:41.2, the proportion of the carbon nano tube is about 1 percent, and the metallic nickel generated by reduction is about 1 percent. The anode material is applied to a long-time end large-current thermal battery, and the no-load voltage is 2.34V.
Example 4
The difference between the scheme and the embodiment 1 is that the cathode material in the scheme is formed by combining 75% of nickel disulfide, 18% of nickel-containing composite conductive agent, 2% of silver powder and 5% of graphite powder through high-temperature melting of active substances, the nickel-containing composite conductive agent is composed of a first conductor carbon nanotube, a reduced nickel powder electronic conductive agent and a second conductor ternary (Ni-K-Li) perchloride ion conductive agent, and the molar ratio of metal elements in the composite conductive agent (Ni: K: li) is 2.5:58.8:41.2, the proportion of the carbon nano tube is about 1 percent, and the metallic nickel generated by reduction is about 1 percent. The anode material is applied to a long-time end large-current thermal battery, and the no-load voltage is 2.30V.
Example 5
The difference between the scheme and the embodiment 1 is that the positive electrode material in the scheme is formed by combining 78% of iron disulfide serving as an active substance, 20% of nickel-containing composite conductive agent and 2% of silver powder through high-temperature melting, the nickel-containing composite conductive agent is composed of a first conductor carbon nano tube, a reduced nickel powder electronic conductive agent and a second conductor ternary (Ni-K-Li) perchloride ion conductive agent, and the molar ratio of metal elements in the composite conductive agent (Ni: K: li) is 4:58.8:41.2, the proportion of the carbon nano tube is about 1 percent, and the metallic nickel generated by reduction is about 2 percent. The anode material is applied to a long-time end large-current thermal battery, and the no-load voltage is 2.36V.
Claims (13)
1. A sulfide positive electrode material of a thermal battery, the components of the positive electrode material comprise a conductive agent and sulfide, and the sulfide positive electrode material is characterized in that: the conductive agent is a nickel-containing composite conductive agent, the nickel-containing composite conductive agent comprises a first conductor and a second conductor of ternary perchloric acid, and at least metal elements contained in the nickel-containing composite conductive agent and the molar ratio of the metal elements to the metal elements is Ni: li: k = m:58.8:41.2, wherein m =1 to 5.
2. A thermal battery positive sulfide cell according to claim 1A pole material characterized by: the sulfide is selected from FeS 2 ；CoS 2 ；NiS 2 ；Fe x Co y S 2 Wherein x + y =1; fe x Co y Ni z S 2 Wherein x + y + z =1; WS (WS) 2 ；MoS 2 Any one or a combination of more of them.
3. The sulfide positive electrode material for the thermal battery according to claim 1, wherein: the mass ratio of the sulfide is 50-95%.
4. The sulfide positive electrode material for the thermal battery according to claim 1, wherein: the first type of conductor is an electronic conductor and comprises a metal conductive agent and a non-metal carbonaceous conductive agent.
5. The sulfide positive electrode material for a thermal battery according to claim 4, wherein: the content of the nonmetal carbon and the Ni is 0.01 to 5 percent of the total mass of the nickel-containing composite conductive agent.
6. The sulfide positive electrode material for a thermal battery according to claim 5, wherein: the content of the non-metal carbon is 1-3% of the total mass of the nickel-containing composite conductive agent.
7. The sulfide positive electrode material for a thermal battery according to claim 4, wherein: the metal conductive agent is selected from one or a combination of at least two of gold, silver, platinum, manganese, iron, cobalt, nickel, copper, zinc, lead, tin, indium, antimony, bismuth and the like.
8. The sulfide positive electrode material for a thermal battery according to claim 4, wherein: the nonmetal carbon comprises any one or combination of more of carbon nano tubes, carbon nano fibers, graphene, carbon nano wires, ketjen black, conductive carbon black Super P, porous carbon, fullerene or conductive graphite.
9. The method for preparing the sulfide positive electrode material of the thermal battery according to claim 6, wherein the method comprises the following steps: the method comprises the following steps:
s1, sulfide pretreatment
Carrying out segmented high-temperature heat treatment on the active substance sulfide under the protection of inert atmosphere, cooling, and screening by 80-200 meshes for later use;
s2, preparation of composite conductive agent
(1) Pretreatment: will contain Ni 2+ ，Li + ，K + Cation and Cl - Carrying out high-temperature vacuum drying on the anion raw materials, transferring the anion raw materials into a drying atmosphere, and weighing the corresponding raw materials according to the cation proportion for later use;
(2) Melting and roasting: uniformly mixing the raw materials without Ni, transferring the mixture into a crucible, adding the raw materials containing Ni on the crucible, transferring the mixture into a high-temperature furnace, and roasting the mixture at the temperature of 375-500 ℃ for 2-8 hours to form uniform and transparent melt;
(3) Composite carbon material: adding 0.01-5% of non-metal carbonaceous conductive agent by mass into the melt at high temperature, uniformly mixing to form suspension, and preserving heat for 1 min-1 h;
(4) And (3) quick cooling: pouring the obtained high-temperature melt suspension into a special condensation container to spread, cooling, crushing and refining the cooled block materials, and sieving by 80-200 meshes to obtain the composite conductive agent;
s3, preparing powder and mixing: preparing active substance sulfide and composite conductive agent into powder according to a proportion, and mixing, wherein the mixing mode can be any one or the combination of at least two of mechanical mixing, point, line, surface, body contact or coating after high-temperature melting;
s4, post-processing: and (4) crushing the mixed material in the step (S3), and screening by 80-200 meshes to obtain the sulfide cathode material.
10. The method for preparing a sulfide positive electrode material of a thermal battery according to claim 9, wherein: the step of the step-by-step high-temperature heat treatment in the step S1 is to roast for 4 to 8 hours at the temperature of 80 to 200 ℃ under the condition of circularly replacing the internal atmosphere by dry inert gas, and then to roast for 2 to 8 hours at the temperature of 375 to 500 ℃.
11. The method for preparing a sulfide positive electrode material of a thermal battery according to claim 9, wherein: the vacuum drying temperature in the pretreatment process is 60-300 ℃, and the drying time is 1-24 h.
12. The method for preparing a sulfide positive electrode material of a thermal battery according to claim 9, wherein: the special condensation container is a container with a heat exchange function at the bottom of the container, and the heat exchange medium comprises any one or a combination of water with the temperature not higher than 10 ℃, frozen brine, frozen methanol, frozen ethanol, frozen glycol and low-temperature antifreeze solution containing glycol.
13. The method for preparing a sulfide positive electrode material of a thermal battery according to claim 9, wherein: and (4) mixing the active substance sulfide and the composite conductive agent in the step (S3) by adopting a powder mixer to perform ball milling and mixing at the speed of 200-1000 r/min, uniformly mixing, then sending into a high-temperature furnace protected by inert gas to perform high-temperature roasting, and cooling along with the furnace.
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| CN116705973B (en) * | 2023-07-20 | 2024-02-09 | 天津大学 | Sulfide positive electrode material |
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