CN116705973B - Sulfide positive electrode material - Google Patents

Sulfide positive electrode material Download PDF

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CN116705973B
CN116705973B CN202310897631.7A CN202310897631A CN116705973B CN 116705973 B CN116705973 B CN 116705973B CN 202310897631 A CN202310897631 A CN 202310897631A CN 116705973 B CN116705973 B CN 116705973B
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sulfide
positive electrode
temperature
electrode material
sulfur
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CN116705973A (en
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田千秋
宋仁宏
郭灏
胡文彬
韩晓鹏
王吉会
薛菲
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Tianjin University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/30—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a sulfide anode material; the cathode material is in a grape cluster shape formed by a sulfide carrier and a silicon dioxide embedding body, wherein the sulfide carrier is in a dot-shaped multi-particle aggregation shape, and the silicon dioxide is uniformly and discontinuously embedded in the surface interface of the sulfide particles in a dispersing manner. The decomposition temperature of the composite material is 400-1000 ℃, the grain size is not more than 100 mu m, and the mass content of silicon element is 0.01-10%. The positive electrode material has the characteristics of high thermal stability, good powder formability, large output capacity and high quality; the preparation method has the characteristics of simple process, safety, reliability, stable batch, capability of preparing in large quantity and the like.

Description

Sulfide positive electrode material
Technical Field
The invention belongs to the technical field of chemical power supply thermal batteries, and particularly relates to a sulfide positive electrode material.
Background
The current mature positive electrode material of the thermal battery is sulfide (Masset Patrick, guidotti Ronald A.thermal activated ("thermal") battery technology: part IIIb.Sulfur and oxide-based cathode materials [ J ]. Journal of Power Sources,2008,178 (1): 456-466), and the existence of sulfur impurities in the sulfide can cause positive electrode capacity loss or exothermic side reaction under high-temperature discharge, and serious thermal runaway of the battery. Therefore, sulfide with refined granularity is adopted to carry out high-temperature molten salt treatment so as to solve the problem of peak voltage and the problem of capacity output. However, small-scale sulfides have small inter-particle interaction force, high-purity sulfides, particularly cobalt-and nickel-containing sulfides, have the problems of difficult powder forming, low electrode forming rate and the like, and the heat shock is large when the battery is activated, the thinned sulfides have poor thermal stability and large capacity loss, and in addition, the interface action of the sulfides and molten salt is relatively slow, and the initial internal resistance is large. Therefore, research on a cathode raw material with high thermal stability, strong thermal shock resistance, good interface wetting effect and good powder formability is one of important development directions of thermal batteries.
In the current research, sulfide is mainly synthesized by adopting a high-temperature vulcanization method and a hydrothermal method, for example, CN202010236657.3 reports that a 3d track alloy sulfide material with a raspberry-shaped structure is synthesized by adopting the hydrothermal method. North worker uses MoS through hydrothermal method 2 The layered structure-based modified cobalt disulfide, cn20191041142. X and CN201910407429.5 proposed that tungsten molybdenum sulfide be applied to the thermal battery anode by high temperature heat treatment. Publication number CN102544482a reports CoS 2 Cathode material and treatment method thereof, CN201910941658.5 reports a method for preparing nickel cobalt sulfide cathode material by adopting ethanol hydrothermal method, and CN201610662968.X reports chemical precipitation and high temperature sulfide combined preparation of Fe x Co 1-x S 2 And a positive electrode material. In the above method, the raw material prepared in a liquid phase environment has a microscopic shapeThe method has the characteristics of good appearance, but has the problems of poor thermal stability, large peak voltage, short battery working time, low generation efficiency, difficult control, liquid phase waste liquid generation and the like. The material treated at high temperature needs to be added with a large amount of additives such as lithium oxide, molten salt and the like to improve the thermal environment of the anode, but the material also has the characteristics of poor powder molding and large thermal decomposition, and the synthetic method has the problems of long synthetic period, high safety control difficulty and the like.
Disclosure of Invention
Aiming at the characteristics of poor thermal stability, weak thermal shock resistance, poor powder forming property and poor interface wettability of sulfide serving as a raw material of the positive electrode of the thermal battery, the invention provides a sulfide positive electrode material; the silicon dioxide modified sulfide is used for optimizing the high-temperature environment where the thermal battery material is located, improving the interface wettability of the positive electrode and molten salt, improving the powder formability of the positive electrode material and improving the capacity output capacity and the quality reliability of the battery.
The method comprises the steps of preparing sulfide by a high-temperature vulcanization-high-temperature desulfurization method, vulcanizing the material at a high temperature, and ensuring the quality reliability of the product, wherein the sulfide has a good crystal structure and thermal stability; secondly, silicon dioxide with low heat conductivity coefficient is embedded on the surface of the granular material to form a thermal barrier so as to reduce heat conduction, so that the thermal shock environment generated at the moment of the combustion of the heating material of the initial-stage thermal battery is optimized and activated, the decomposition rate of sulfide under thermal shock is reduced, the utilization rate of active ingredients of the material is improved, and the output capacity of the battery is improved; meanwhile, the heat concentration and stress concentration in the high-temperature vulcanization reaction process can be reduced by introducing silicon dioxide, so that the safety of the synthesis process is ensured; then, the fine-grained silicon dioxide has good molten salt adsorption capacity, and can improve the interface state of sulfide and molten salt, so that the sulfide and molten salt can be quickly wetted to establish voltage, and the activation time is shortened. Finally, the doped silicon dioxide can enrich the surface structure morphology of particles, increase the friction force among the particles, optimize the particle size distribution of the powder material by introducing the silicon dioxide, improve the loose packing density of the material, reduce the stroke of a pressure head during powder pressing, prevent the phenomena of crack edge drop and the like of electrode plates, and improve the forming rate of the electrode.
Specifically, the invention aims at realizing the following technical scheme:
the invention relates to a sulfide positive electrode material of a thermal battery, which comprises a grape cluster structure formed by a sulfide carrier and a silicon dioxide embedding body, wherein the sulfide carrier is in a dot-shaped grape particle aggregation cluster shape, and the silicon dioxide is uniformly and discontinuously embedded in the surface interface of the sulfide particles. In the invention, sulfide is an active component of a thermal battery anode material and accepts electron transfer. The silicon dioxide is a modified component with optimized performance and is a chemical inert oxide, and the silicon dioxide has the effects of mainly adjusting the thermal environment, interface structure and performance and powder formability of the anode material, not participating in electrochemical reaction, but resisting the thermal shock decomposition of the anode material, accelerating activation, improving the forming rate of the electrode material, reducing the heat concentration and stress concentration in the high-temperature vulcanization reaction process and ensuring the safety of the vulcanization process.
As one embodiment, the sulfide includes iron disulfide (FeS 2 ) Cobalt disulfide (CoS) 2 ) Nickel disulfide (NiS) 2 ) Tungsten disulfide (WS) 2 ) Molybdenum disulfide (MoS) 2 ) And a sulfide composite containing at least one of two transition metal elements of iron cobalt nickel chromium manganese. For example, the sulfided composite may be iron disulfide (FeS) 2 ) Cobalt disulfide (CoS) 2 ) And nickel disulfide (NiS) 2 ) Mixtures, fe 0.33 Co 0.33 Ni 0.33 S 2 、Fe 0.2 Co 0.2 Ni 0.2 Cr 0.2 Mn 0.2 S 2 Or tungsten disulfide and Fe 0.33 Co 0.33 Ni 0.33 S 2 Mixtures, and the like.
As one embodiment, the molar ratio of sulfur to metal in the positive electrode material is 1.9 to 2.1:1, the mass ratio of the silicon dioxide is 0.01-10%, the decomposition temperature is 400-1000 ℃, and the particle size is not more than 100 mu m. The theoretical molar ratio of sulfur to metal in the positive electrode material is 2, and amorphous positive electrodes or inclusions can exist objectively or be artificially introduced in the process of synthesizing the material, so that the ratio is slightly deviated from the theoretical value. The content of silicon dioxide can be regulated by the mixing amount during the batching, the decomposition temperature is the inherent property of the material, but the metal element type and proportion of the positive electrode can be regulated, and the particle size can be controlled by crushing and classifying sieving.
The invention also relates to a preparation method of the sulfide anode material, which adopts a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: vacuum drying and sieving sulfur, metal powder and silicon dioxide respectively;
s2, preparing a vulcanizing agent: mixing sulfur and silicon dioxide according to a certain proportion, heating at 120-450 ℃ to obtain liquid molten sulfur, stirring for 1 s-1 h, quenching the formed suspension liquid molten sulfur, crushing, and sieving with a 60-300 mesh sieve to obtain a siliceous vulcanizing agent;
s3, high-temperature vulcanization reaction: mixing the silicon-containing vulcanizing agent obtained in the step S2 with metal powder, and carrying out high-temperature vulcanization reaction in a container to obtain a vulcanized product; wherein the metal powder is one or a combination of iron, cobalt, nickel, chromium, manganese, tungsten, molybdenum and alloys formed by the elements;
s4, high-temperature desulfurization: desulfurizing the vulcanized product obtained in the step S3 at a high temperature, wherein the desulfurizing temperature is 400-600 ℃, the desulfurizing time is 1-8 h, and crushing and sieving the desulfurized product (sieving through a 60-300 mesh sieve) after desulfurizing.
The method has the key steps that the primary dispersion is carried out by physical mixing of sulfur and silicon dioxide, and then the secondary dispersion is carried out by sulfur liquid phase transition at high temperature. The principle of secondary dispersion is that sulfur is utilized to generate phase change under high temperature environment to generate sulfur melt with high viscosity and the thick liquid phase characteristic of the sulfur melt can promote the further homogenization of silicon dioxide particles to form suspension, and the liquid phase characteristic of the sulfur melt can lead the sulfur and the silicon dioxide to form tight combination. In order to ensure that the silicon dioxide does not settle, the high Wen Xuan turbid liquid melt is rapidly quenched at a cooling speed of 100-500 ℃ per second, so that the uniform distribution of the silicon dioxide in the subsequent vulcanized product is ensured.
As one embodiment, the pretreatment process in the step S1 is characterized in that the sulfur drying flattening thickness is 1-20mm, the vacuum drying temperature is 40-100 ℃, the vacuum drying is carried out for 0.5-10 h, and after all materials are dried in vacuum, the materials are sieved by a sieve with more than 60 meshes (preferably a sieve with 60-300 meshes) for standby. In some embodiments, the sulfur is dried to a flattened thickness of 1-20mm and placed in a vacuum oven for vacuum drying at 40-100 ℃ for 0.5-10 hours. The pretreatment mainly solves the problem of water absorption of raw materials, the drying problem can still be solved by adopting modes such as forced air drying, freeze drying and the like, the flattening thickness of the materials is better in 1-20mm drying effect, the production efficiency is lower than 1mm, the drying time is longer than 20mm, if the water absorption is more, caking can occur, and the crushing difficulty is increased.
As one embodiment, the step S2 is to ball mill the silicon dioxide and sulfur for 0.5-24 h, and pass through a 60-300 mesh sieve, wherein the mass ratio of the silicon dioxide is 0.016-27.93%, preferably 0.02-15%. The ball milling is mainly used for realizing primary dispersion, the time is lower than 0.5h, the material is possibly uneven, and the production efficiency is low when the time exceeds 24h. The quality of the silicon dioxide is regulated according to the design state of the battery, the content is lower than 0.1%, the effect of the silicon dioxide is not shown, the proportion of active components is low when the silicon dioxide content is larger than 15%, and the capacity of the positive electrode is small.
As one implementation scheme, the step S2 quenching is to rapidly quench the high Wen Xuan turbid liquid melt at a cooling speed of 100-500 ℃/S, stir for 1S-10 min for solid-liquid separation and dry. Quenching may be performed by spraying the melt into cold air or rapidly into a low temperature liquid, for example, by spraying a 300℃high Wen Xuan turbid melt into cold water at-10 to 30℃or into a low temperature liquid phase gas (liquid nitrogen, liquid argon, liquid carbon dioxide, etc.).
In the process of mixing ingredients in the step S3, after weighing the silicon-containing vulcanizing agent and the metal powder according to the molar ratio of sulfur to metal (S/M) of 2-4:1, adding an interface regulator with the liquid-solid ratio of 0.5-5, placing the mixture into a powder mixer for ball milling for 10min-12h at the speed of 100-800 rpm, and drying to ensure uniform powder mixing. The key parameters for sulphide synthesis are the molar ratio of sulphur to metal (S/M) below 2, the possible presence of non-disulphide phases, the formation of heterogeneous transition metal states, for example with a S/Co ratio below 2, and the possible achievement of heterogeneous mixtures of cobalt disulphide and cobaltosic disulphide. The molar ratio of sulfur to metal (S/M) is more than 4, so that excessive sulfur participates after the vulcanization reaction, the subsequent desulfurization difficulty is increased, and the crystallinity of the product is reduced. Meanwhile, as the desulfurization process is adopted in the step S4, redundant sulfur can volatilize under the high temperature condition, so that the molar ratio of the sulfur to the metal element in the positive electrode material is basically 1.9-2.1: 1.
as an embodiment, another important key element of the invention is that an interface regulator is needed in the mixing process, the interface regulator has the characteristic of dissolving or slightly dissolving sulfur, and can promote the silicon-containing vulcanizing agent to be tightly combined with the metal powder, so as to increase the microcosmic contact area of the silicon-containing vulcanizing agent and the metal powder, thereby ensuring that the later vulcanization process can occur rapidly. The tight combination of the two can not only lead the vulcanization reaction to be rapidly and violently carried out and shape the grape particles of the sulfide in a high-temperature area, but also avoid the existence of the silicon dioxide in a particle mixing form and ensure the embedding characteristic of the silicon dioxide. The interface regulator comprises at least one of organic alcohols, carbon disulfide, water and acetone. Among them, the organic alcohols are preferably ethylene glycol, benzyl alcohol, isopropyl alcohol, propanol, ethanol, and methanol.
As an embodiment, in the high-temperature vulcanization reaction in the step S3, the high-temperature vulcanization temperature is 250-700 ℃ and the vulcanization time is 1-24 h. The high-temperature sulfide degree is lower than 250 ℃, the reaction rate is low, transition phases may exist in the sulfide product, the reaction temperature is too high, the safety design difficulty is high, and the produced sulfide can be decomposed to form multiphase products. The vulcanizing time is less than 1h, the vulcanizing reaction is incomplete, multiphase products can be formed, the vulcanizing time exceeds 24h, the generating efficiency is low, and the energy consumption is high. In addition, as the vulcanization reaction is a complex three-phase reaction, the reaction temperature, the reaction time and the reaction pressure have correlation, and the reasonable and safe reactor is arranged, so that the method has important significance.
As one embodiment, in the high-temperature desulfurization of the step S4, the desulfurization temperature is 400-600 ℃ and the desulfurization time is 1-8 h. The desulfurization temperature is lower than 400 ℃, the desulfurization efficiency is low, the desulfurization time is long, the desulfurization temperature is higher than 600 ℃, and the generated product can be decomposed, so that multiphase sulfides coexist, and the quality of the material is reduced. The desulfurization time is flexibly adjusted according to the desulfurization temperature, and the desulfurization temperature is high, the desulfurization time is short, the effect is good, and the desulfurization time is flexibly determined according to the process at a reasonable temperature.
The invention also relates to application of the sulfide positive electrode material, wherein the sulfide positive electrode material can be used as a positive electrode active substance of a thermal battery, for example, in a conventional positive electrode material, sulfide, lithium oxide, molten salt electrolyte and carbon material are used for manufacturing a positive electrode through a high-temperature heat treatment process. The sulfide anode material can also be used as an auxiliary anode of a multi-anode system, for example, an iron disulfide anode is an anode, an auxiliary anode layer is added between the anode and the heating layer, and the auxiliary anode and a substrate or an anode current collecting plate can form an integrated structure through a coating process and the like. Can also be used as an additive for a positive electrode. In general, a material is a positive electrode as a positive electrode active material. If the number of the main active materials in the positive electrode is two or more than three, the positive electrode of the invention has relatively small using amount, namely the auxiliary positive electrode. If the positive electrode material is below 5% in the positive electrode, the positive electrode material is mainly used for regulating voltage or eliminating peak, or regulating activation process, and does not bear main capacity output, and is an additive.
Compared with the prior art, the invention has the following beneficial effects:
1) The material prepared by the invention is vulcanized at high temperature, has good crystal structure and thermal stability, and is beneficial to ensuring the quality reliability of products.
2) The silicon dioxide with low heat conductivity is embedded in the surface of the material to form a thermal barrier so as to reduce heat conduction, so that the thermal shock environment generated at the moment of the combustion of the heating material of the initial-stage thermal battery is optimized and the decomposition rate of sulfide under thermal shock is reduced. Therefore, the utilization rate of the active ingredient is high, and the output capacity of the battery is large.
3) The silicon dioxide in the material prepared by the invention has good molten salt adsorption capacity, and can improve the interface state of sulfide and molten salt, so that the material can quickly wet and establish voltage, and the activation time is shortened.
4) The material prepared by the invention has good surface morphology, can increase the friction force among particles, prevent the electrode plate from cracking, edge drop and other phenomena, and improve the forming rate of the electrode.
5) The method of the invention introduces silicon dioxide, which can reduce heat concentration and stress concentration in the high-temperature vulcanization process, ensure the safety of the synthesis process, has simple process, safety, reliability, stable batch and capability of macro preparation.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a SEM image of the sulfide of example 1;
FIG. 2 is a mapping graph of the material in example 1;
FIG. 3 is a TEM image of the material of example 1;
FIG. 4 is an XRD pattern for the material of example 1;
FIG. 5 is a thermal analysis of the material of example 1;
FIG. 6 is a graph of discharge in a battery;
fig. 7 is a diagram showing the activation process of the battery in example 1;
FIG. 8 is a comparative electrode diagram in example 1;
FIG. 9 is a graph showing the effect of sulfur/cobalt (S/M) molar ratio on product composition
FIG. 10 shows the effect of no secondary dispersion on silica distribution; wherein a is a product SEM image, and b is a product element distribution image;
FIG. 11 is a graph showing the effect of an interfacial modifier on silica distribution; wherein a is a product SEM image, and b is a product element distribution image;
FIG. 12 is a graph of peak temperature monitored after initiation of the sulfidation reaction;
FIG. 13 is a graph showing the peak pressure values monitored after initiation of the vulcanization reaction.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The positive electrode material of sulfide comprises sulfide carrier and silicon dioxide embedding body, wherein the sulfide carrier is in the form of dot-shaped grape particle aggregation string, and the silicon dioxide is uniformly and discontinuously dispersed (figure 2mapping graph) embedded in sulfide particle surface interface (figure 3 transmission). Wherein the sulfide is nickel disulfide (NiS 2 ) (XRD pattern of fig. 4) the decomposition temperature of the positive electrode material was 630 ℃ (thermal analysis pattern of fig. 5), the particle size was not more than 50 μm, and the mass content of silicon element was about 3.4%. The thermal battery sulfide positive electrode material is prepared by adopting a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: the sublimated sulfur powder, the metal nickel powder and the silicon dioxide powder are subjected to vacuum drying, wherein the thickness of the sublimated sulfur is flattened to 10mm during vacuum drying. Respectively placing sublimed sulfur, metal nickel powder and silicon dioxide into a vacuum drying oven, drying at 50 ℃ for 8 hours in vacuum, and sieving with a 200-mesh sieve for later use.
S2, preparing a vulcanizing agent: mixing 5% by mass (which means the mass ratio of the silicon dioxide to the sublimated sulfur) of silicon dioxide and sublimated sulfur according to a proportion, ball milling for 4 hours, sieving with a 200-mesh sieve, heating at 180 ℃ to obtain liquid molten sulfur, stirring for 5 minutes, rapidly pouring the formed suspension liquid molten sulfur into 5 ℃ cold water subjected to high-temperature rasterization and dispersion at a cooling speed of more than 200 ℃/s, stirring for 1 minute, performing solid-liquid separation, drying, crushing, sieving with the 200-mesh sieve, and obtaining the silicon-containing vulcanizing agent. The method has the key steps that the primary dispersion is carried out by physical mixing of sulfur and silicon dioxide, and then the secondary dispersion is carried out by sulfur liquid phase transition at high temperature. The principle of secondary dispersion is that sulfur is utilized to generate phase change under high temperature environment to generate sulfur melt with high viscosity and the thick liquid phase characteristic of the sulfur melt can promote the further homogenization of silicon dioxide particles to form suspension, and the liquid phase characteristic of the sulfur melt can lead the sulfur and the silicon dioxide to form tight combination. In order to ensure that the silicon dioxide does not settle, the high Wen Xuan turbid liquid melt is rapidly quenched at a cooling speed of 100-500 ℃ per second, so that the uniform distribution of the silicon dioxide in the subsequent vulcanized product is ensured. If no secondary dispersion possibly causes non-uniformity of silicon dioxide, particles are formed, and the scanning electron microscope image shown in fig. 10 corresponds to the image, wherein particles with non-uniformity of dispersion and even agglomeration appear, and the products are granular.
S3, high-temperature vulcanization reaction: weighing silicon-containing vulcanizing agent and metal nickel powder obtained in the step S2 according to a sulfur/metal (S/M) molar ratio of 2.5:1, namely 59g (1 mol) of nickel powder serving as a raw material, 84.2g (about 4.2g of 5% silicon dioxide) of 80g (2.5 mol) of sulfur-containing silicon vulcanizing agent, adding an interface regulator (143.2 g) with a liquid-solid ratio of 1:1, using a 5% glycol and 95% ethanol mixed solution as the interface regulator, placing the mixed solution into a powder mixer, ball-milling for 10min at a rotating speed of 400rpm/S, filtering, separating, and drying to ensure uniform powder mixing. And (3) carrying out high-temperature vulcanization reaction in a container, wherein the high-temperature vulcanization temperature is 550 ℃, and the vulcanization time is 4 hours, so as to obtain a vulcanized product. FIG. 12 is a graph showing the peak temperature monitored after initiation of the vulcanization reaction, and FIG. 13 is a graph showing the peak pressure value monitored after initiation of the vulcanization reaction; as can be seen from fig. 12 and 13, the temperature sensor and the pressure sensor are used to test, the temperature of the peak of the vulcanization reaction of the introduced silicon dioxide is 820 ℃ or higher, the pressure is only 3.4Mpa, the temperature of the peak of the vulcanization reaction of the non-introduced silicon dioxide is 989.7 ℃ and the pressure is 7.7Mpa or higher. It is illustrated that the introduction of silica can reduce the heat and stress concentrations of the high temperature vulcanization process.
S4, high-temperature desulfurization: and (3) desulfurizing the vulcanized product obtained in the step (S3) at a high temperature, wherein the desulfurizing temperature is 400 ℃, the desulfurizing time is 6 hours, then crushing the desulfurized product, and sieving the crushed product with a 200-mesh sieve to obtain the nickel disulfide anode in the cluster aggregation form.
The prepared material is used as a positive electrode active material of a thermal battery, and sulfide is used as the material: lithium oxide: the positive electrode is manufactured by a high-temperature heat treatment process according to the proportion of 80:2:18 through a molten salt electrolyte (binary electrolyte, chemical components by weight ratio of 45% LiCl and 55% KCl), the electrode with phi 52 is manufactured by a powder pressing method, compared with a commercial electrode, the electrode has no cracks, edge drop and the like (figure 6), and when a ternary full lithium electrolyte and a lithium boron alloy negative electrode (specifically, a ternary principle electrolyte (LiF-LiCl-LiBr with the weight ratio of about 9.6-22-68.4) with 50% of magnesium oxide and 50% of a diaphragm) are adopted, the negative electrode adopts a lithium boron alloy with the lithium content of 60% and the alloy main component is Li7B6 or Li5B 4), the electrode has high activation speed (figure 7) and stable voltage (figure 8).
Example 2
The positive pole material consists of sulfide carrier and silica embedded body, the sulfide carrier is in dot grape particle aggregation string form, and the silica is homogeneously and discontinuously embedded in the sulfide particle surface interface. Wherein the sulfide is cobalt disulfide (CoS) 2 ) The decomposition temperature of the positive electrode material is about 640 ℃, the particle size is not more than 74 mu m, and the mass content of silicon element is 7.2%. The thermal battery sulfide positive electrode material is prepared by adopting a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: the sublimated sulfur powder, the metal cobalt powder and the silicon dioxide powder are subjected to vacuum drying, wherein the thickness of the sublimated sulfur is flattened to be 5mm during vacuum drying. Respectively placing sublimed sulfur, metallic cobalt powder and silicon dioxide into a vacuum drying oven, vacuum drying at 60 ℃ for 6 hours, and sieving with a 200-mesh sieve for later use.
S2, preparing a vulcanizing agent: mixing silicon dioxide and sublimed sulfur in a mass ratio of 10%, proportioning, ball milling for 5 hours, sieving with a 200-mesh sieve, heating at 160 ℃ to obtain liquid molten sulfur, stirring for 10 minutes, rapidly pouring the formed suspension liquid molten sulfur into 5 ℃ cold water subjected to high-temperature gridding dispersion at a cooling speed of more than 180 ℃/s, stirring for 5 minutes, carrying out solid-liquid separation, drying, crushing, sieving with the 200-mesh sieve, and obtaining the silicon-containing vulcanizing agent.
S3, high-temperature vulcanization reaction: and (2) weighing 59g (1 mol) of cobalt powder serving as a raw material after weighing the silicon-containing vulcanizing agent and the metal cobalt powder obtained in the step (S2) according to a sulfur/metal (S/Co) molar ratio of 2.5, 88.9g (about 8.9g of 10% silicon dioxide) of a silicon vulcanizing machine containing 80g (2.5 mol) of sulfur, adding an interface regulator (118.3 g) with a liquid-solid ratio of 0.8, and placing the interface regulator in a mixed solution of 10% carbon disulfide and 90% ethanol in a powder mixer for ball milling for 15min at a rotating speed of 500rpm/S to ensure uniform powder mixing. And (3) carrying out high-temperature vulcanization reaction in a container, wherein the high-temperature vulcanization temperature is 600 ℃, and the vulcanization time is 3 hours, so as to obtain a vulcanized product. The key parameter for sulphide synthesis is the sulphur/metal (S/M) molar ratio below 2, possibly with the presence of non-disulphide phases, forming a heterogeneous transition metal state, for example with an S/Co ratio below 2, possibly resulting in a heterogeneous mixture of cobalt disulphide and cobaltosic disulphide (figure 9). The molar ratio of sulfur to metal (S/M) is more than 4, so that excessive sulfur participates after the vulcanization reaction, the subsequent desulfurization difficulty is increased, and the crystallinity of the product is reduced. The other important key link of the invention is that an interface regulator is needed in the mixing process, the interface regulator has the characteristic of dissolving or slightly dissolving sulfur, the silicon-containing vulcanizing agent and the metal powder can be promoted to be tightly combined, and the microcosmic contact area of the silicon-containing vulcanizing agent and the metal powder is increased, so that the later vulcanizing process can be ensured to occur rapidly. The tight combination of the two can not only lead the vulcanization reaction to be rapidly and violently carried out and shape the grape particles of the sulfide in a high-temperature area, but also avoid the existence of the silicon dioxide in a particle mixing form and ensure the embedding characteristic of the silicon dioxide. Samples without interface modifier did not achieve intimate bonding of the silicon-containing sulfiding agent to the metal powder, and the product had a granular morphology, as distinguished from the punctiform multiparticulate aggregate morphology of the present invention, as shown in fig. 11. Samples without interface modifier were not subsequently tested for performance because of non-uniformity.
S4, high-temperature desulfurization: and (3) desulfurizing the vulcanized product obtained in the step (S3) at a high temperature of 440 ℃ for 3 hours, crushing the desulfurized product, and sieving the crushed product with a 200-mesh sieve to obtain the cobalt disulfide anode in the cluster aggregation form of the grape strings.
The prepared material is used as a positive electrode active material of a thermal battery, and sulfide is used as the material: lithium oxide: the molten salt electrolyte is used for manufacturing the positive electrode through a high-temperature heat treatment process in a ratio of 80:2:18, the material is prepared into an electrode with phi 52 through a powder pressing method, the electrode is compared with a commercial electrode, the conditions of no crack, edge drop and the like are achieved, under the condition that a ternary full-lithium electrolyte and a lithium-boron alloy negative electrode are adopted, the electrical property test is carried out, the battery can be normally discharged, the activation time is less than 0.8s, and the voltage curve is stable.
Example 3
The method comprises the following steps ofThe sulfide positive electrode material is characterized in that the positive electrode material is in a grape cluster structure formed by a sulfide carrier and a silicon dioxide embedding body, the sulfide carrier is in a punctiform grape particle aggregation cluster shape, and the silicon dioxide is uniformly and discontinuously embedded in the surface interface of the sulfide particles. Wherein the sulfide is iron disulfide (FeS) 2 ) The decomposition temperature of the positive electrode material is 530 ℃, the particle size is not more than 74 mu m, and the mass content of silicon element is 1.67%. The thermal battery sulfide positive electrode material is prepared by adopting a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: the sublimated sulfur powder, the metal iron powder and the silicon dioxide powder are subjected to vacuum drying, wherein the sublimated sulfur has a flattening thickness of 8mm during vacuum drying. Respectively placing sublimed sulfur, metal nickel powder and silicon dioxide into a vacuum drying oven, vacuum drying at 70 ℃ for 5 hours, and sieving with a 200-mesh sieve for later use.
S2, preparing a vulcanizing agent: mixing 2% by mass of silicon dioxide and sublimed sulfur in proportion, ball milling for 5 hours, sieving with a 200-mesh sieve, heating at 160 ℃ to obtain liquid molten sulfur, stirring for 8 minutes, rapidly pouring the formed suspension liquid molten sulfur into 5 ℃ cold water subjected to high-temperature gridding dispersion at a cooling speed of more than 180 ℃/s, stirring for 2 minutes, performing solid-liquid separation, drying, crushing, sieving with a 200-mesh sieve, and obtaining the silicon-containing vulcanizing agent.
S3, high-temperature vulcanization reaction: and (2) weighing 56g (1 mol Fe) of iron powder serving as a raw material after weighing the silicon-containing vulcanizing agent obtained in the step (S2) and metal iron powder according to a sulfur/metal (S/Fe) molar ratio of 3, adding 98g (2 g of 2% mass silicon dioxide) of a silicon vulcanizing machine containing 96g (3 mol S) of sulfur, adding a mixed solution of 10% carbon disulfide and 90% acetone serving as an interface regulator (107.8 g) with a liquid-solid ratio of 0.7, and ball-milling for 15min at a rotating speed of 300rpm/S in a powder mixer to ensure uniform powder mixing. And (3) carrying out high-temperature vulcanization reaction in a container, wherein the high-temperature vulcanization temperature is 500 ℃, and the vulcanization time is 10 hours, so as to obtain a vulcanized product.
S4, high-temperature desulfurization: and (3) desulfurizing the vulcanized product obtained in the step (S3) at a high temperature, wherein the desulfurizing temperature is 450 ℃, the desulfurizing time is 8 hours, then crushing the desulfurized product, and sieving the crushed product with a 200-mesh sieve to obtain the iron disulfide anode in the cluster aggregation form.
The prepared material is used as a positive electrode active material of a thermal battery, and sulfide is used as the material: lithium oxide: the molten salt electrolyte is used for manufacturing the positive electrode through a high-temperature heat treatment process in a ratio of 75:5:20, the material is prepared into an electrode with phi 72 through a powder pressing method, and compared with a commercial electrode, the electrode has no crack, edge drop and other conditions, and under the condition that a ternary full-lithium electrolyte and a lithium-boron alloy negative electrode are adopted, the electric performance test is carried out, the voltage output curve of the battery is smooth, and the activation time is 0.7s.
Example 4
The positive pole material consists of sulfide carrier and silica embedded body, the sulfide carrier is in dot grape particle aggregation string form, and the silica is homogeneously and discontinuously embedded in the sulfide particle surface interface. Wherein the sulfide is iron cobalt disulfide (Fe 0.5 Co 0.5 S 2 ) The decomposition temperature of the positive electrode material is 585 ℃, the particle size is not more than 74 mu m, and the mass content of silicon element is 1.81%. The thermal battery sulfide positive electrode material is prepared by adopting a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: and carrying out vacuum drying on the sublimed sulfur powder, the metal cobalt powder, the metal iron powder and the silicon dioxide powder, wherein the thickness of the sublimed sulfur is 10mm when the sublimed sulfur is dried in vacuum. Respectively placing sublimed sulfur, metal nickel powder and silicon dioxide into a vacuum drying oven, vacuum drying at 60 ℃ for 7 hours, and sieving with a 200-mesh sieve for later use.
S2, preparing a vulcanizing agent: mixing 3% by mass of silicon dioxide and sublimed sulfur according to a proportion, carrying out ball milling for 5 hours, sieving with a 200-mesh sieve, heating at 150 ℃ to obtain liquid molten sulfur, stirring for 7 minutes, spraying the formed suspension liquid molten sulfur into liquid nitrogen at a cooling speed of more than 300 ℃/s, carrying out solid-liquid separation, crushing and sieving with a 200-mesh sieve to obtain the silicon-containing vulcanizing agent.
S3, high-temperature vulcanization reaction: and (2) weighing 28g (0.5 mol Fe) of iron powder, 29.5g (1 mol Co) of cobalt powder and 72.6g (about 2.2g of 3% silicon dioxide) of a silicon vulcanizing machine containing 70.4g (2.2 mol S) of sulfur according to the molar ratio of sulfur to metal (S/M) of 2.2, adding an interface regulator (130.1 g) with the liquid-solid ratio of 1, and then, using a mixed solution of 5% carbon disulfide, 5% ethylene glycol and 90% ethanol by volume as the interface regulator, and placing the mixed solution in a powder mixer for ball milling for 20min at the rotating speed of 400rpm/S to ensure uniform powder mixing. And (3) carrying out high-temperature vulcanization reaction in a container, wherein the high-temperature vulcanization temperature is 600 ℃, and the vulcanization time is 4 hours, so as to obtain a vulcanized product.
S4, high-temperature desulfurization: and (3) desulfurizing the vulcanized product obtained in the step (S3) at a high temperature of 500 ℃ for 6 hours, crushing the desulfurized product, and sieving the crushed product with a 200-mesh sieve to obtain the cobalt-nickel disulfide anode in the cluster aggregation form.
The prepared material is used as a positive electrode active material of a thermal battery, and sulfide is used as the material: lithium oxide: the molten salt electrolyte is used for manufacturing the positive electrode through a high-temperature heat treatment process in a ratio of 80:5:15, the material is prepared into an electrode with phi 52 through a powder pressing method, and compared with a commercial electrode, the electrode has no crack, edge drop and other conditions, under the condition that a ternary full-lithium electrolyte and a lithium-boron alloy negative electrode are adopted, the electric performance test is carried out, the output voltage of the battery is stable, the activation time is 0.85s, and the working time is 206s.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.

Claims (9)

1. The preparation method of the sulfide positive electrode material is characterized in that the positive electrode material comprises a grape cluster structure consisting of a sulfide carrier and a silicon dioxide embedding body, wherein the sulfide carrier is in a punctiform grape particle aggregation cluster form, and the silicon dioxide is uniformly and discontinuously embedded in a sulfide particle surface interface in a dispersing manner; the positive electrode material is prepared by adopting a high-temperature vulcanization-high-temperature desulfurization method under the protection of inert gas, and comprises the following specific steps:
s1, pretreatment: vacuum drying and sieving sulfur, metal powder and silicon dioxide respectively;
s2, preparing a vulcanizing agent: mixing sulfur and silicon dioxide according to a certain proportion, heating at 120-450 ℃ to obtain liquid molten sulfur, stirring for 1 s-1 h, quenching the formed suspension liquid molten sulfur, crushing and sieving with a 60-300 mesh sieve to obtain a siliceous vulcanizing agent;
s3, high-temperature vulcanization reaction: mixing the silicon-containing vulcanizing agent obtained in the step S2 with metal powder, and carrying out high-temperature vulcanization reaction to obtain a vulcanized product; wherein the metal powder is one or a combination of iron, cobalt, nickel, chromium, manganese, tungsten, molybdenum and alloys formed by the elements;
s4, high-temperature desulfurization: desulfurizing the vulcanized product obtained in the step S3 at a high temperature, wherein the desulfurizing temperature is 400-600 ℃, the desulfurizing time is 1-8 h, and crushing and sieving the desulfurized product after desulfurization.
2. The method of preparing a sulfide positive electrode material according to claim 1, wherein the sulfide includes iron disulfide FeS 2 Cobalt disulfide CoS 2 Nickel disulfide NiS 2 Tungsten disulfide WS 2 Molybdenum disulfide MoS 2 And a sulfide composite containing at least two transition metal elements of iron cobalt nickel chromium manganese.
3. The method for producing a sulfide positive electrode material according to claim 1, characterized in that a molar ratio of sulfur to a metal element in the positive electrode material is 1.9 to 2.1:1, the mass ratio of the silicon dioxide is 0.01-10%, the decomposition temperature is 400-1000 ℃, and the particle size is not more than 100 mu m.
4. The method for preparing a sulfide positive electrode material according to claim 1, wherein in the step S2, the mixed ingredients are prepared by ball milling silica and sulfur for 0.5 to 24 hours and sieving the mixture with a 60 to 300 mesh sieve; wherein the mass ratio of the silicon dioxide is 0.016 to 27.93 percent.
5. The method for producing a sulfide positive electrode material according to claim 1, wherein in the step S2, the quenching is performed by rapidly quenching the high-temperature suspended liquid molten sulfur at a cooling rate of 100 to 500 ℃/S, stirring for 1 to 30 minutes, performing solid-liquid separation, and drying.
6. The method for preparing a sulfide positive electrode material according to claim 1, wherein in the step S3, the mixture is prepared by weighing a silicon-containing vulcanizing agent and metal powder according to a sulfur/metal molar ratio of 2-4:1, adding an interface regulator with a liquid-solid ratio of 0.5-5:1, placing the mixture in a powder mixer, ball-milling the mixture at a speed of 100-800 rpm for 10min-12h, and drying the mixture.
7. The method for preparing a sulfide positive electrode material according to claim 6, wherein the interface regulator comprises at least one of organic alcohols, carbon disulfide, water, and acetone; wherein the organic alcohol comprises at least one of ethylene glycol, benzyl alcohol, isopropanol, propanol, ethanol, and methanol.
8. The method for producing a sulfide positive electrode material according to claim 1, wherein in step S3, the high-temperature vulcanization reaction is carried out at a vulcanization temperature of 250 to 700 ℃ for a vulcanization time of 1 to 24 hours.
9. Use of a sulfide positive electrode material produced according to the method of claim 1, characterized in that the positive electrode material is used as a battery positive electrode, an auxiliary positive electrode or an additive for a positive electrode.
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