技术领域Technical field
本发明属于材料技术领域，特别是涉及一种可控构筑硫化物包覆层的方法。The invention belongs to the field of material technology, and in particular relates to a method for controllably constructing a sulfide coating layer.
背景技术Background technique
近年来，在基底表面进行修饰，构筑均匀、完整的包覆层成为材料改性的重要手段之一。表面包覆改性是利用无机物或有机物在材料表面沉积，构筑一层化学组份不同的覆盖层，形成核-壳的复合结构。通过改变材料表界面的特性，实现其光、电、磁、催化等性能的提升，因而对包覆方法的探索在科学研究及实际应用方面均具有极大的价值。In recent years, modifying the surface of the substrate to build a uniform and complete coating has become one of the important means of material modification. Surface coating modification uses inorganic or organic substances to deposit on the surface of the material to build a covering layer with different chemical compositions to form a core-shell composite structure. By changing the characteristics of the material's surface interface, its optical, electrical, magnetic, catalytic and other properties can be improved. Therefore, the exploration of coating methods is of great value in both scientific research and practical applications.
硫化物优异的物理、化学性质使得其作为一种理想的包覆层，已被证明可以改善电极材料的低电导率的问题，同时作为包覆层可以抑制体积膨胀，缓解材料粉化。然而硫化物的均匀包覆通常难以实现，现有的技术主要通过简单的混合达到部分吸附的效果，不均匀的接触难以起到均匀包覆所期望的结果。尤其对于充放电过程中具有较大体积变化的电极材料，如：硅、锡、锑及其氧化物等，均匀、完整的包覆层能起到更好的抑制材料粉化的效果，从而可以实现更好的循环稳定性。现有的技术中，利用微米、亚微米级的硫化物颗粒与硅的混合，虽然一定程度上也提升了材料的循环稳定性，但大小不一的硫化物颗粒难以实现理想的完整包覆的效果，对材料稳定性的提升也有限。因此，发展一种能够实现均匀、完整可控的硫化物包覆方法对于电极材料的改性及性能的提升是非常有必要的。The excellent physical and chemical properties of sulfide make it an ideal coating layer, which has been proven to improve the problem of low conductivity of electrode materials. At the same time, as a coating layer, it can suppress volume expansion and alleviate material powdering. However, uniform coating of sulfide is usually difficult to achieve. The existing technology mainly achieves partial adsorption effect through simple mixing. Uneven contact is difficult to achieve the desired result of uniform coating. Especially for electrode materials that have large volume changes during the charge and discharge process, such as silicon, tin, antimony and their oxides, a uniform and complete coating layer can better inhibit the powdering of the material, thus enabling Achieve better cycle stability. In the existing technology, the mixing of micron and sub-micron sulfide particles and silicon is used to improve the cycle stability of the material to a certain extent, but it is difficult to achieve ideal complete coating of sulfide particles of different sizes. The effect and improvement in material stability are also limited. Therefore, it is very necessary to develop a sulfide coating method that can achieve uniform, complete and controllable sulfide coating for the modification of electrode materials and improvement of performance.
发明内容Contents of the invention
本发明的目的是提供一种利用硫化物对不同材料进行原位厚度可控的包覆的方法。The object of the present invention is to provide a method for coating different materials with controllable thickness in situ using sulfide.
本发明提供一种金属硫化物包覆层的方法，所述方法包括将核颗粒材料、配位剂、金属盐、沉淀控制剂于溶剂中混合均匀，反应，煅烧处理，得到含有金属硫化物包覆层的核-壳结构颗粒。The invention provides a method for coating a metal sulfide layer. The method includes uniformly mixing core particle materials, complexing agents, metal salts, and precipitation control agents in a solvent, reacting, and calcining to obtain a coating containing metal sulfide. Coated core-shell structured particles.
根据本发明的实施方案，所述方法包括如下步骤：According to an embodiment of the present invention, the method includes the following steps:
(1)在溶剂中加入配位剂、金属盐、沉淀控制剂配制得到溶液，后加入核颗粒材料，反应形成含有金属和硫包覆层的中间体；或，(1) Add a complexing agent, a metal salt, and a precipitation control agent to the solvent to prepare a solution, and then add the core particle material to react to form an intermediate containing a metal and sulfur coating layer; or,
将核颗粒材料、配位剂、金属盐、沉淀控制剂于溶剂中混合均匀，反应形成含有金属和硫包覆层的中间体；Mix the core particle material, coordination agent, metal salt, and precipitation control agent in the solvent evenly, and react to form an intermediate containing a metal and sulfur coating layer;
(2)将步骤(1)所制备的中间体经煅烧后，得到含有金属硫化物包覆层的核-壳结构颗粒。(2) After calcining the intermediate prepared in step (1), core-shell structure particles containing a metal sulfide coating layer are obtained.
根据本发明的实施方案，所述溶剂选自水、有机溶剂，优选为有机溶剂。According to an embodiment of the present invention, the solvent is selected from water and organic solvents, preferably organic solvents.
优选地，所述有机溶剂为醇溶剂和/或酮溶剂。Preferably, the organic solvent is an alcohol solvent and/or a ketone solvent.
进一步地，所述醇溶剂选自甲醇、乙醇、乙二醇、丙醇、异丙醇、丙二醇、正丁醇中的至少一种，优选为乙醇。Further, the alcohol solvent is selected from at least one of methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, propylene glycol and n-butanol, preferably ethanol.
进一步地，所述酮溶剂选自丙酮。Further, the ketone solvent is selected from acetone.
根据本发明的实施方案，步骤(1)所述溶液中，所述配位剂的浓度为0.02～0.2mol/L，优选为0.02～0.1mol/L，例如为0.01mol/L、0.02mol/L、0.03mol/L、0.04mol/L、0.05mol/L、0.1mol/L、0.15mol/L、0.2mol/L。According to the embodiment of the present invention, in the solution of step (1), the concentration of the complexing agent is 0.02~0.2mol/L, preferably 0.02~0.1mol/L, for example, 0.01mol/L, 0.02mol/L L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L.
根据本发明的实施方案，所述配位剂选自乙二胺、丙二胺、丁二胺中的至少一种，优选为乙二胺。According to an embodiment of the present invention, the complexing agent is selected from at least one of ethylenediamine, propylenediamine and butanediamine, preferably ethylenediamine.
根据本发明的实施方案，步骤(1)所述溶液中，所述金属盐的浓度为0.004～0.04mol/L，优选为0.01～0.04mol/L，例如为0.005mol/L、0.01mol/L、0.02mol/L、0.03mol/L、0.04mol/L。According to the embodiment of the present invention, in the solution of step (1), the concentration of the metal salt is 0.004~0.04mol/L, preferably 0.01~0.04mol/L, for example, 0.005mol/L, 0.01mol/L , 0.02mol/L, 0.03mol/L, 0.04mol/L.
根据本发明的实施方案，所述金属盐为含有与所述沉淀剂发生配位沉淀的金属元素的金属盐。优选地，所述金属盐中含有铁、铜、铈或钽金属元素中的至少一种。According to an embodiment of the present invention, the metal salt is a metal salt containing a metal element that coordinates and precipitates with the precipitating agent. Preferably, the metal salt contains at least one of iron, copper, cerium or tantalum metal elements.
优选地，所述金属盐选自相应金属元素的氯化盐、硫酸盐、硝酸盐、醋酸盐和醇盐中的至少一种，例如为铁、铜、铈或钽金属元素的氯化盐、硫酸盐、硝酸盐、醋酸盐和醇盐中的至少一种。Preferably, the metal salt is selected from at least one of chloride, sulfate, nitrate, acetate and alkoxide of the corresponding metal element, such as a chloride salt of iron, copper, cerium or tantalum metal element. , at least one of sulfate, nitrate, acetate and alkoxide.
根据本发明的实施方案，步骤(1)所述溶液中，所述沉淀控制剂浓度为0.01～1.0mol/L，优选为0.01～0.1mol/L，例如为0.01mol/L、0.02mol/L、0.03mol/L、0.04mol/L、0.05mol/L、0.1mol/L、0.2mol/L、0.3mol/L、0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1.0mol/L。According to the embodiment of the present invention, in the solution of step (1), the concentration of the precipitation control agent is 0.01 to 1.0 mol/L, preferably 0.01 to 0.1 mol/L, for example, 0.01 mol/L, 0.02 mol/L , 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L , 0.8mol/L, 0.9mol/L, 1.0mol/L.
根据本发明的实施方案，所述沉淀控制剂选自硫代二乙酸、硫代二丙酸、二硫代乙酸、二硫代丙酸、二磺酸中的至少一种，优选为硫代二乙酸。According to an embodiment of the present invention, the precipitation control agent is selected from at least one of thiodiacetic acid, thiodipropionic acid, dithioacetic acid, dithiopropionic acid, and disulfonic acid, preferably thiodiacetic acid. Acetic acid.
根据本发明的实施方案，步骤(1)中，核颗粒材料的浓度为0.1g/L～150g/L，例如为1g/L、10g/L、20g/L、30g/L、40g/L、50g/L、60g/L、70g/L、80g/L、90g/L、100g/L、110g/L、120g/L、130g/L、140g/L、150g/L。According to the embodiment of the present invention, in step (1), the concentration of the core particle material is 0.1g/L to 150g/L, for example, 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L.
根据本发明的实施方案，所述核颗粒材料选自金属、非金属、碳化物、氮化物、氧化物、硫化物、磷化物、磷酸盐、锂盐、有机物颗粒中的至少一种。According to an embodiment of the present invention, the core particle material is selected from at least one of metals, non-metals, carbides, nitrides, oxides, sulfides, phosphides, phosphates, lithium salts, and organic particles.
优选地，所述核颗粒材料中，所述金属选自铝、钌、铑、钯、银、铂、金、锗、锡、锑及其合金中的至少一种。Preferably, in the core particle material, the metal is selected from at least one of aluminum, ruthenium, rhodium, palladium, silver, platinum, gold, germanium, tin, antimony and alloys thereof.
优选地，所述非金属选自碳、硅、磷、硫、硒中的至少一种。Preferably, the non-metal is selected from at least one of carbon, silicon, phosphorus, sulfur and selenium.
优选地，所述碳化物选自碳化钛、碳化钒、碳化铬、碳化钽、碳化钨、碳化硼、碳化硅中的至少一种。Preferably, the carbide is selected from at least one of titanium carbide, vanadium carbide, chromium carbide, tantalum carbide, tungsten carbide, boron carbide, and silicon carbide.
优选地，所述氮化物选自氮化钛、氮化钒、氮化铌、氮化钨、氮化硼、氮化硅、氮化磷中的至少一种。Preferably, the nitride is selected from at least one of titanium nitride, vanadium nitride, niobium nitride, tungsten nitride, boron nitride, silicon nitride, and phosphorus nitride.
优选地，所述氧化物选自二氧化硅、二氧化钛、五氧化二钒、二氧化锰、四氧化三锰、三氧化二铁、四氧化三铁、四氧化三钴、氧化镍、氧化锆、氧化钼、氧化铟锡、氧化锡、锂镧锆氧、中的至少一种。Preferably, the oxide is selected from the group consisting of silicon dioxide, titanium dioxide, vanadium pentoxide, manganese dioxide, manganese tetroxide, ferric oxide, ferric tetroxide, cobalt tetroxide, nickel oxide, zirconium oxide, molybdenum oxide, At least one of indium tin oxide, tin oxide, lithium lanthanum zirconium oxide.
优选地，所述硫化物选自二硫化钛、硫化铁、硫化钴、硫化镍、硫化钼、硫化锡、硫化锑中的至少一种。Preferably, the sulfide is selected from at least one selected from the group consisting of titanium disulfide, iron sulfide, cobalt sulfide, nickel sulfide, molybdenum sulfide, tin sulfide, and antimony sulfide.
优选地，所述磷化物选自磷化钛、磷化铁、磷化钴、磷化镍、磷化钼、磷化锡中的至少一种。Preferably, the phosphide is selected from at least one of titanium phosphide, iron phosphide, cobalt phosphide, nickel phosphide, molybdenum phosphide, and tin phosphide.
优选地，所述磷酸盐选自磷酸肽、焦磷酸钛、磷酸肽锂、磷酸钛铝锂、磷酸钒锂、磷酸钒钠、磷酸铁、磷酸铁锂、磷酸铁锰锂、磷酸钴锂中的至少一种。Preferably, the phosphate is selected from the group consisting of phosphopeptide, titanium pyrophosphate, lithium phosphate peptide, lithium titanium aluminum phosphate, lithium vanadium phosphate, sodium vanadium phosphate, iron phosphate, lithium iron phosphate, lithium iron manganese phosphate, and lithium cobalt phosphate. At least one.
优选地，所述锂盐选自锰酸锂、钴酸锂、镍酸锂、镍锰酸锂、镍钴锰酸锂、富锂镍钴锰酸锂中的至少一种，例如为NCM622。Preferably, the lithium salt is selected from at least one of lithium manganate, lithium cobalt oxide, lithium nickelate, lithium nickel manganate, lithium nickel cobalt manganate, and lithium-rich lithium nickel cobalt manganate, for example, NCM622.
优选地，所述有机物选自酚醛树脂、脲醛树脂、三聚氰胺数值、聚苯乙烯中的至少一种。Preferably, the organic substance is selected from at least one of phenolic resin, urea-formaldehyde resin, melamine resin, and polystyrene.
根据本发明示例性的方案，所述核颗粒材料选自硅、氧化硅、锡、氧化锡、锑、氧化锑中的最少一种，优选硅或者硅的衍生物。According to an exemplary solution of the present invention, the core particle material is selected from at least one of silicon, silicon oxide, tin, tin oxide, antimony, and antimony oxide, preferably silicon or a derivative of silicon.
根据本发明的实施方案，步骤(1)中，所述反应在搅拌条件下进行。According to an embodiment of the present invention, in step (1), the reaction is carried out under stirring conditions.
根据本发明的实施方案，步骤(1)中，所述反应的温度为10～40℃，例如为10℃、20℃、30℃、40℃；所述反应的时间为1～24h，例如为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、15h、20h。According to the embodiment of the present invention, in step (1), the reaction temperature is 10-40°C, such as 10°C, 20°C, 30°C, 40°C; the reaction time is 1-24h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 15h, 20h.
根据本发明的实施方案，步骤(2)中，所述煅烧的温度为400～1000℃，例如为400℃、500℃、600℃、700℃、800℃、900℃、1000℃；所述煅烧的时间为1～24h，例如为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、15h、20h。According to the embodiment of the present invention, in step (2), the calcination temperature is 400-1000°C, for example, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C; the calcination temperature The time is 1 to 24h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 15h, 20h.
根据本发明的实施方案，步骤(2)中，所述煅烧的气氛选自空气、氧气、氮气、氩气、氢气、氢氩混合气、氢氮混合气中的至少一种。According to an embodiment of the present invention, in step (2), the calcining atmosphere is selected from at least one of air, oxygen, nitrogen, argon, hydrogen, hydrogen-argon mixed gas, and hydrogen-nitrogen mixed gas.
本发明还提供一种含有金属硫化物包覆层的核-壳结构颗粒，所述核-壳结构颗粒由上述方法制备得到，其中，所述金属硫化物包覆层在核颗粒表面原位生长，所述金属硫化物包覆层均匀、连续、完整。The present invention also provides a core-shell structure particle containing a metal sulfide coating layer. The core-shell structure particle is prepared by the above method, wherein the metal sulfide coating layer grows in situ on the surface of the core particle. , the metal sulfide coating layer is uniform, continuous and complete.
根据本发明的实施方案，所述金属硫化物选自硫化锰、硫化铁、硫化铜、硫化锌、硫化锡、硫化铈、硫化钽中的至少一种。According to an embodiment of the present invention, the metal sulfide is selected from at least one selected from the group consisting of manganese sulfide, iron sulfide, copper sulfide, zinc sulfide, tin sulfide, cerium sulfide, and tantalum sulfide.
示例性地，所述核-壳结构颗粒可以为硫化铁包覆聚苯乙烯纳米颗粒、硫化铈包覆铝纳米颗粒、硫化铁包覆硅纳米颗粒、硫化钽包覆NCM622颗粒。Exemplarily, the core-shell structure particles may be iron sulfide-coated polystyrene nanoparticles, cerium sulfide-coated aluminum nanoparticles, iron sulfide-coated silicon nanoparticles, or tantalum sulfide-coated NCM622 particles.
根据本发明的实施方案，所述金属硫化物包覆层的厚度为1～200nm。优选地，所述包覆层的厚度为1～50nm，例如为10nm、20nm、30nm、40nm、50nm。According to an embodiment of the present invention, the thickness of the metal sulfide coating layer is 1 to 200 nm. Preferably, the thickness of the coating layer is 1 to 50 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, or 50 nm.
根据本发明的实施方案，所述核结构的平均粒径为50nm～10μm，例如50nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1μm、10μm或上述任意两个数值间的范围值。According to an embodiment of the present invention, the average particle size of the core structure is 50 nm to 10 μm, such as 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 μm, 10 μm or any two of the above values range of values.
根据本发明的实施方案，以所述核壳材料的总重量为基准，所述金属硫化物的含量为0.01％～10％，例如为0.01％、0.05％、0.1％、0.5％、1％、5％、10％。优选地，所述金属与硫元素的摩尔比为1:1～1:3，例如为1:1、1:1.5、1:2、1:2.5、1:3。According to an embodiment of the present invention, based on the total weight of the core-shell material, the content of the metal sulfide is 0.01% to 10%, such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%. Preferably, the molar ratio of the metal to sulfur is 1:1 to 1:3, for example, 1:1, 1:1.5, 1:2, 1:2.5, 1:3.
本发明还提供上述核-壳结构颗粒在储能领域的应用，优选用于碱金属离子电池。The present invention also provides the application of the above-mentioned core-shell structure particles in the field of energy storage, preferably in alkali metal ion batteries.
根据本发明的实施方案，所述碱金属离子电池选自锂离子电池、钠离子电池或钾离子电池中的任一种。According to an embodiment of the present invention, the alkali metal ion battery is selected from any one of a lithium ion battery, a sodium ion battery or a potassium ion battery.
本发明还提供一种高能量型储能器件，所述高能量型储能器件包含上述核-壳结构颗粒。优选地，所述高能量型储能器件为锂离子电池。The present invention also provides a high-energy energy storage device, which contains the above-mentioned core-shell structure particles. Preferably, the high-energy energy storage device is a lithium-ion battery.
本发明的有益效果：Beneficial effects of the present invention:
本发明的方法可用作对核颗粒材料进行原位厚度可控包覆的改性手段。The method of the present invention can be used as a modification method for in-situ thickness-controllable coating of core particle materials.
本发明制备得到的含有金属硫化物包覆层核-壳结构颗粒，通过在核颗粒材料表面原位包覆厚度可控的包覆层，能够用作碱金属离子电池。The core-shell structure particles containing a metal sulfide coating layer prepared by the present invention can be used as an alkali metal ion battery by in-situ coating a coating layer with controllable thickness on the surface of the core particle material.
本发明的包覆方法得到的金属硫化物包覆层厚度可控，是对金属硫化物自身的沉淀动力学过程进行控制，即金属离子自由度的控制、溶液离子强度的控制、核颗粒材料表面电性及吸附能力的调控，降低自身成核均相生长的趋势，促进金属硫化物在上述核表面原位生长，从而得到一层均匀、连续、完整的金属硫化物包覆层，并且金属硫化物包覆层的厚度可以通过改变初始金属盐或上述作为核的颗粒材料的量进行调节。本发明采用的液相法，其所提供的包覆方法简单，反应条件温和，普适性强，并且在碱金属离子电池领域有着很高的实用性和应用前景。The thickness of the metal sulfide coating layer obtained by the coating method of the present invention is controllable, which controls the precipitation kinetic process of the metal sulfide itself, that is, the control of the degree of freedom of metal ions, the control of the ionic strength of the solution, and the control of the surface of the core particle material. The regulation of electrical properties and adsorption capacity reduces the tendency of self-nucleation and homogeneous growth, and promotes the in-situ growth of metal sulfide on the surface of the above-mentioned core, thereby obtaining a uniform, continuous, and complete metal sulfide coating layer, and metal sulfide The thickness of the material coating layer can be adjusted by changing the amount of the initial metal salt or the above-mentioned particulate material as the core. The liquid phase method adopted in the present invention provides a simple coating method, mild reaction conditions, strong universality, and has high practicability and application prospects in the field of alkali metal ion batteries.
本发明利用金属硫化物原位生长的方法在核颗粒材料的表面实现一层均匀的金属硫化物包覆层，可以阻止核颗粒材料与电解质溶液之间的副反应，而且可以降低核颗粒材料的表面膜阻抗和电荷转移阻抗，加快了锂离子的扩散速度，使得核颗粒材料的循环性能和倍率性能显著改善。并且通过对金属硫化物包覆层的厚度进行调控，能够对材料的电化学性能进行优化，确定最佳的金属硫化物包覆层厚度以及最佳的电化学性能。The present invention uses the method of in-situ growth of metal sulfide to achieve a uniform metal sulfide coating layer on the surface of the core particle material, which can prevent side reactions between the core particle material and the electrolyte solution, and can reduce the damage of the core particle material. The surface film resistance and charge transfer resistance speed up the diffusion rate of lithium ions, significantly improving the cycle performance and rate performance of core particle materials. And by regulating the thickness of the metal sulfide coating layer, the electrochemical properties of the material can be optimized to determine the optimal metal sulfide coating layer thickness and the best electrochemical performance.
本发明提供了一种简便易行、条件温和、普适性强、均匀可控的方法。该方法是基于室温的液相法，通过在溶液中配位剂稳定金属盐，以及沉淀控制剂对配位后金属盐的沉淀动力学的调控，实现了金属离子的缓慢沉淀，达到均匀、连续、完整、厚度可控的包覆效果。此外，该方法在不同的基底表面均可实现可控的包覆。The invention provides a method that is simple, easy to implement, has mild conditions, has strong universal applicability, is uniform and controllable. This method is based on a liquid phase method at room temperature. By stabilizing the metal salt in the solution with a complexing agent and regulating the precipitation kinetics of the metal salt after coordination by a precipitation control agent, the slow precipitation of metal ions is achieved to achieve uniform and continuous , complete and controllable thickness coating effect. In addition, this method can achieve controllable coating on different substrate surfaces.
附图说明Description of the drawings
图1为实施例1的硫化铁包覆聚苯乙烯纳米颗粒的透射电子显微镜照片。Figure 1 is a transmission electron microscope photograph of the iron sulfide-coated polystyrene nanoparticles of Example 1.
图2为实施例2的硫化铈包覆铝纳米颗粒的透射电子显微镜照片。Figure 2 is a transmission electron microscope photograph of the cerium sulfide-coated aluminum nanoparticles of Example 2.
图3为实施例3的硫化铁包覆硅纳米颗粒的透射电子显微镜照片。Figure 3 is a transmission electron microscope photograph of the iron sulfide-coated silicon nanoparticles of Example 3.
图4为实施例3的硫化铁包覆硅纳米颗粒在840mA/g充放电电流下的循环性能。Figure 4 shows the cycle performance of the iron sulfide-coated silicon nanoparticles in Example 3 under a charge and discharge current of 840 mA/g.
图5为实施例4的硫化钽包覆NCM 622颗粒的透射电子显微镜照片。Figure 5 is a transmission electron microscope photograph of the tantalum sulfide-coated NCM 622 particles of Example 4.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following examples are only illustrative and explain the present invention and should not be construed as limiting the scope of the present invention. All technologies implemented based on the above contents of the present invention are covered by the scope of protection intended by the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1Example 1
制备具有核-壳结构的硫化铁包覆的聚苯乙烯纳米颗粒Preparation of iron sulfide-coated polystyrene nanoparticles with core-shell structure
将作为核的平均粒径为700nm的聚苯乙烯纳米颗粒0.1g、作为配位剂的乙二胺100μL、作为铁盐的氯化铁0.1g和作为沉淀控制剂的硫代二乙酸0.15g在35ml乙醇中混合，在室温搅拌下反应5小时，经离心、洗涤、干燥，将得到含硫和铁的硫化物包覆的聚苯乙烯纳米颗粒，将得到的颗粒于700℃氩气气氛下煅烧3小时，得到硫化铁包覆的聚苯乙烯颗粒。0.1 g of polystyrene nanoparticles with an average particle diameter of 700 nm as the core, 100 μL of ethylenediamine as the complexing agent, 0.1 g of ferric chloride as the iron salt, and 0.15 g of thiodiacetic acid as the precipitation control agent were placed in Mix in 35 ml of ethanol and react for 5 hours under stirring at room temperature. After centrifugation, washing and drying, polystyrene nanoparticles coated with sulfide containing sulfur and iron will be obtained. The obtained particles will be calcined in an argon atmosphere at 700°C. After 3 hours, iron sulfide-coated polystyrene particles were obtained.
该硫化铁包覆的聚苯乙烯纳米颗粒为核-壳结构，其透射电镜照片如图1所示。构成核的材料为平均粒径在700nm的聚苯乙烯纳米颗粒，构成壳的材料为硫化物，壳的厚度为50nm，且硫化铁均匀覆盖在聚苯乙烯纳米颗粒的表面。The iron sulfide-coated polystyrene nanoparticles have a core-shell structure, and their transmission electron microscope pictures are shown in Figure 1. The material constituting the core is polystyrene nanoparticles with an average particle size of 700nm. The material constituting the shell is sulfide. The thickness of the shell is 50nm, and iron sulfide evenly covers the surface of the polystyrene nanoparticles.
实施例2Example 2
制备具有核-壳结构的硫化铈包覆的铝纳米颗粒Preparation of cerium sulfide-coated aluminum nanoparticles with core-shell structure
将平均粒径80nm的铝颗粒80mg、硫代二乙酸0.15g、硝酸铈0.2g和乙二胺100μL在35ml乙醇中混合，在搅拌下于室温条件反应5小时，经离心、洗涤、干燥，将得到的颗粒于700℃氩气气氛下煅烧3小时，得到硫化铈包覆的铝颗粒。Mix 80 mg of aluminum particles with an average particle size of 80 nm, 0.15 g of thiodiacetic acid, 0.2 g of cerium nitrate, and 100 μL of ethylenediamine in 35 ml of ethanol, and react at room temperature for 5 hours under stirring. After centrifugation, washing, and drying, The obtained particles were calcined at 700°C in an argon atmosphere for 3 hours to obtain cerium sulfide-coated aluminum particles.
该硫化铈包覆的铝颗粒为核-壳结构，其透射电镜照片如图2所示。构成核的材料为平均粒径在80nm的铝颗粒，构成壳的材料为硫化铈，壳的厚度为15nm，且硫化铈均匀覆盖在铝颗粒的表面。The cerium sulfide-coated aluminum particles have a core-shell structure, and their transmission electron microscope pictures are shown in Figure 2. The material constituting the core is aluminum particles with an average particle size of 80 nm, and the material constituting the shell is cerium sulfide. The thickness of the shell is 15 nm, and the cerium sulfide evenly covers the surface of the aluminum particles.
实施例3Example 3
一、制备具有核-壳结构的硫化铁包覆的硅颗粒1. Preparation of iron sulfide-coated silicon particles with core-shell structure
将平均粒径50nm的硅颗粒60mg、硫代二乙酸0.15g、氯化铁0.1g和乙二胺100μL在35ml乙醇中混合，在搅拌下于室温反应5小时，经离心、洗涤、干燥，将得到的颗粒于700℃氩气气氛下煅烧3小时，得到硫化铁包覆的硅颗粒。Mix 60 mg of silicon particles with an average particle size of 50 nm, 0.15 g of thiodiacetic acid, 0.1 g of ferric chloride, and 100 μL of ethylenediamine in 35 ml of ethanol, and react at room temperature for 5 hours under stirring. After centrifugation, washing, and drying, The obtained particles were calcined at 700°C in an argon atmosphere for 3 hours to obtain iron sulfide-coated silicon particles.
该硫化铁包覆的硅颗粒为核-壳结构，其透射电镜照片如图3所示。构成核的材料为平均粒径在50nm的硅颗粒，构成壳的材料为硫化铁，壳的厚度为10nm，且硫化铁均匀覆盖在硅颗粒的表面。The iron sulfide-coated silicon particles have a core-shell structure, and their transmission electron micrographs are shown in Figure 3. The material constituting the core is silicon particles with an average particle size of 50 nm, and the material constituting the shell is iron sulfide. The thickness of the shell is 10 nm, and the iron sulfide evenly covers the surface of the silicon particles.
二、制备硫化铁包覆的硅电极2. Preparation of iron sulfide-coated silicon electrodes
将上述制备的硫化铁包覆的硅颗粒0.16g与导电添加剂乙炔黑0.02g、粘结剂5％质量浓度的海藻酸钠0.4g和少许溶剂水混合，经制浆、涂片(铜片作为集流体)、干燥，得到硫化铁包覆的硅电极。0.16g of the iron sulfide-coated silicon particles prepared above were mixed with 0.02g of conductive additive acetylene black, 0.4g of sodium alginate with a 5% mass concentration of binder and a little solvent water, and then slurried and smeared (copper sheet was used as current collector) and dried to obtain an iron sulfide-coated silicon electrode.
三、组装电池3. Assemble the battery
以上述制备的硫化铁包覆的硅电极作为工作电极，与金属锂作为负极组装成电池3，电解液选择浓度为1M的碳酸脂电解液，其中溶剂为DMC：DEC：EC＝1：1：1(W/W/W)，溶质为LiPF6。The iron sulfide-coated silicon electrode prepared above is used as the working electrode, and the metallic lithium is used as the negative electrode to assemble a battery 3. The electrolyte is a carbonate electrolyte with a concentration of 1M, and the solvent is DMC:DEC:EC=1:1: 1(W/W/W), the solute is LiPF6 .
四、电池测试4. Battery test
使用充放电仪对上述电池进行恒电流充放电测试，测试电压区间为0.005～1.5V，测试温度为25℃。电池比容量和充放电电流均以硅的质量计算。Use a charge and discharge instrument to conduct a constant current charge and discharge test on the above-mentioned batteries. The test voltage range is 0.005~1.5V, and the test temperature is 25°C. Battery specific capacity and charge and discharge current are calculated based on the mass of silicon.
对比例1Comparative example 1
组装对比电池1，其不同之处在于，负极材料为未进行包覆的硅颗粒材料，其余参照实施例3。Comparative battery 1 was assembled. The difference was that the negative electrode material was uncoated silicon particle material. The rest were as described in Example 3.
图4为实施例3和对比例1的电池在840mA/g的充放电电流下的循环性能，由图可知，实施例3的电池3在经过100圈循环后，容量为768mAh/g，而对比电池1几乎无容量。这是由于对比例1的负极材料未经过包覆，硅负极材料极易膨胀变形导致的。由此可知，采用本发明的方法在硅负极材料表面可以形成均匀、完整的包覆层，有利于发挥材料高容量特性，避免材料粉化造成循环稳定性下降。Figure 4 shows the cycle performance of the batteries of Example 3 and Comparative Example 1 under a charge and discharge current of 840mA/g. It can be seen from the figure that the battery 3 of Example 3 has a capacity of 768mAh/g after 100 cycles, while the capacity of the battery 3 of Example 3 is 768mAh/g. Battery 1 has almost no capacity. This is because the negative electrode material in Comparative Example 1 is not coated and the silicon negative electrode material is easily expanded and deformed. It can be seen from this that the method of the present invention can form a uniform and complete coating layer on the surface of the silicon negative electrode material, which is conducive to exerting the high capacity characteristics of the material and avoiding the reduction of cycle stability caused by pulverization of the material.
实施例4Example 4
制备具有核-壳结构的硫化钽包覆的NCM622颗粒Preparation of tantalum sulfide-coated NCM622 particles with core-shell structure
将NCM622颗粒600mg(平均粒径为500nm)、硫代二乙酸0.15g、氯化钽0.13g和乙二胺100μL在35ml乙醇中混合，在搅拌下于室温条件下反应5小时，经离心、洗涤、干燥，将得到的颗粒于700℃氩气气氛下煅烧3小时，得到硫化钽包覆的NCM622颗粒。该硫化钽包覆的NCM622颗粒为核-壳结构，其透射电镜照片如图5所示。构成核的材料为粒径在100～500nm的NCM622颗粒，构成壳的材料为硫化钽，壳的厚度为20nm，且硫化钽均匀覆盖在NCM622颗粒的表面。Mix 600 mg of NCM622 particles (average particle size 500 nm), 0.15 g of thiodiacetic acid, 0.13 g of tantalum chloride and 100 μL of ethylenediamine in 35 ml of ethanol, react at room temperature for 5 hours under stirring, and then centrifuge and wash. , dried, and the obtained particles were calcined in an argon atmosphere at 700°C for 3 hours to obtain tantalum sulfide-coated NCM622 particles. The tantalum sulfide-coated NCM622 particles have a core-shell structure, and their transmission electron microscope pictures are shown in Figure 5. The material constituting the core is NCM622 particles with a particle size of 100 to 500 nm. The material constituting the shell is tantalum sulfide. The thickness of the shell is 20nm, and the tantalum sulfide evenly covers the surface of the NCM622 particles.
以上，对本发明的示例性实施方式进行了说明。但是，本发明不拘囿于上述实施方式。本领域技术人员在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。As above, the exemplary embodiments of the present invention have been described. However, the present invention is not limited to the above-described embodiment. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
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| CN202210648057.7ACN114976007B (en) | 2022-06-08 | 2022-06-08 | Method for controllably constructing sulfide coating layer |
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