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CN106410150A - A core-shell structure MoO2-MoS2 sodium-ion battery negative electrode material and preparation method thereof - Google Patents

A core-shell structure MoO2-MoS2 sodium-ion battery negative electrode material and preparation method thereof Download PDF

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CN106410150A
CN106410150A CN201610963521.6A CN201610963521A CN106410150A CN 106410150 A CN106410150 A CN 106410150A CN 201610963521 A CN201610963521 A CN 201610963521A CN 106410150 A CN106410150 A CN 106410150A
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许占位
王天
姚恺
黄剑锋
杨军
沈学涛
曹丽云
徐鹏飞
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a MoO2-MoS2 negative electrode material of a sodium-ion battery with a core-shell structure and a preparation method of the MoO2-MoS2 negative electrode material, and belongs to the technical field of preparation of sodium-ion battery electrode materials. The preparation method comprises the following steps: adopting MoO3 as a precursor to carry out oxidation-reduction reaction with S powder and obtain MoO2, adopting an in-situ synthesis method to grow MoS2 nanosheets on an MoO2 template, and forming an MoO2-MoS2 composite material with the core-shell structure. An MoO2 skeleton plays a role in structure support, so that the superimposition of sheet-shaped MoS2 is avoided, the conductivity of the material is improved, and the cyclic stability of the material is also improved. The preparation process is simple and easy to control, the period is short, the energy consumption is low, the repeatability of products is high, the yield is large, and the benefit for large-scale production is achieved. The MoO2-MoS2 negative electrode material prepared by the method has a three-dimensional core-shell structure and also has the characteristics of high specific-discharge capacity, good cyclic stability and the like.

Description

一种核壳结构MoO2-MoS2钠离子电池负极材料及其制备方法A kind of core-shell structure MoO2-MoS2Na-ion battery negative electrode material and preparation method thereof

技术领域technical field

本发明属于钠离子电池电极材料制备技术领域,涉及一种核壳结构MoO2-MoS2钠离子电池负极材料及其制备方法,具体涉及一种采用原位合成法制备具有核壳结构的MoO2-MoS2高性能的钠离子电池负极材料的方法。The invention belongs to the technical field of preparation of electrode materials for sodium ion batteries, and relates to a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material and a preparation method thereof, in particular to an in-situ synthesis method for preparing MoO 2 with a core-shell structure - MoS 2 method for high-performance sodium-ion battery anode materials.

背景技术Background technique

随着人们对清洁能源和可再生资源的广泛关注,锂离子电池已被广泛用作各种电子产品的工作电源(手机、笔记本电脑、数码相机等)和移动式装备的动力电池(电动车、潜艇、导弹发射等)。然而锂资源的稀缺限制了锂离子电池技术的大规模应用。相对而言,钠储量较锂高,且分布广泛,占地球地壳质量的2.6%,因此钠离子电池成为研究者们关注的对象。With people's widespread attention to clean energy and renewable resources, lithium-ion batteries have been widely used as working power sources for various electronic products (mobile phones, laptops, digital cameras, etc.) and power batteries for mobile equipment (electric vehicles, submarines, missile launches, etc.). However, the scarcity of lithium resources limits the large-scale application of lithium-ion battery technology. Relatively speaking, sodium reserves are higher than lithium and widely distributed, accounting for 2.6% of the earth's crustal mass, so sodium-ion batteries have become the focus of researchers.

石墨结晶度高,具有层状的结构,用于二次电池负极材料,其在锂离子电池中理论容量为372mAh g-1,而用于钠离子电池,其理论容量约为20mAh g-1。[Qian J,Wu X,Cao Y,et al.High capacity and rate capability of amorphous phosphorus for sodiumion batteries[J].Angewandte Chemie,2013,125(17):4731-4734.],[Zhu Y,Han X,XuY,et al.Electrospun Sb/C fibers for a stable and fast sodium-ion batteryanode[J].ACS nano,2013,7(7):6378-6386.]为此研究者们不断探索钠离子电池负极可替代材料。其中,MoS2具有S-Mo-S夹心层状(类石墨烯)结构,层内原子通过强共价键结合,层与层之间存在弱范德华力作用以及较高的理论容量,因此受到人们的广泛关注。Graphite has a high crystallinity and a layered structure. It is used as a negative electrode material for secondary batteries. Its theoretical capacity in lithium-ion batteries is 372mAh g -1 , and in sodium-ion batteries, its theoretical capacity is about 20mAh g -1 . [Qian J, Wu X, Cao Y, et al.High capacity and rate capability of amorphous phosphorus for sodium ion batteries[J].Angewandte Chemie,2013,125(17):4731-4734.], [Zhu Y,Han X ,XuY,et al.Electrospun Sb/C fibers for a stable and fast sodium-ion battery node[J].ACS nano,2013,7(7):6378-6386.] For this reason, researchers continue to explore the anode of sodium-ion batteries Alternative materials. Among them, MoS 2 has an S-Mo-S sandwich layered (graphene-like) structure, atoms in the layer are bonded by strong covalent bonds, there are weak van der Waals forces between the layers and a high theoretical capacity, so it is attracted by people. widespread attention.

MoS2是一个典型的层状结构材料,层与层之间的间距约为0.615nm,显著高于石墨(0.335nm)。这为钠离子的嵌入和脱出提供了条件。片状MoS2层间依靠范德华力相互连接,其在嵌/脱钠过程中易造成结构坍塌,从而发生活性物质聚集和大的体积变化,随着钠离子电池循环次数增加,容量也发生明显衰减。同时由于片状的MoS2经过充放电发生叠加及其导电性差等原因,当作为钠离子电池负极材料时,表现出较差的循环稳定性。[Zhang S,YuX,Yu H,et al.Growth of Ultrathin MoS2Nanosheets with Expanded Spacing of(002)Plane on Carbon Nanotubes for High-Performance Sodium-Ion Battery Anodes[J].ACS applied materials&interfaces,2014,6(24):21880-21885.],[Zhang S,Yu X,YuH,et al.Growth of Ultrathin MoS2Nanosheets with Expanded Spacing of(002)Planeon Carbon Nanotubes for High-Performance Sodium-Ion Battery Anodes[J].ACSapplied materials&interfaces,2014,6(24):21880-21885.],[Xu X,Fan Z,Yu X,etal.A Nanosheets‐on‐Channel Architecture Constructed from MoS2and CMK‐3forHigh‐Capacity and Long‐Cycle‐Life Lithium Storage[J].Advanced EnergyMaterials,2014,4(17).]MoS 2 is a typical layered structure material, and the spacing between layers is about 0.615nm, which is significantly higher than that of graphite (0.335nm). This provides conditions for the insertion and extraction of sodium ions. The flaky MoS 2 layers are connected to each other by van der Waals force, which can easily cause structural collapse during the intercalation/desodiumation process, resulting in active material aggregation and large volume changes. As the cycle number of sodium-ion batteries increases, the capacity also declines significantly. . At the same time, due to the stacking of flake MoS 2 after charging and discharging and its poor conductivity, it shows poor cycle stability when used as the anode material of sodium-ion batteries. [Zhang S, YuX, Yu H, et al.Growth of Ultrathin MoS 2 Nanosheets with Expanded Spacing of(002)Plane on Carbon Nanotubes for High-Performance Sodium-Ion Battery Anodes[J].ACS applied materials&interfaces,2014,6( 24):21880-21885.], [Zhang S, Yu X, YuH, et al. Growth of Ultrathin MoS 2 Nanosheets with Expanded Spacing of (002) Planeon Carbon Nanotubes for High-Performance Sodium-Ion Battery Anodes[J]. ACSapplied materials&interfaces,2014,6(24):21880-21885.], [Xu X, Fan Z, Yu X, et al. A Nanosheets‐on‐Channel Architecture Constructed from MoS 2 and CMK‐3 for High‐Capacity and Long‐Cycle‐ Life Lithium Storage[J].Advanced Energy Materials,2014,4(17).]

发明内容Contents of the invention

本发明的目的在于提供一种核壳结构MoO2-MoS2钠离子电池负极材料及其制备方法,该方法制备过程简单、易控,反应周期短,能耗低,重复性高,产率大,经该方法制得的MoO2-MoS2钠离子电池负极材料具有三维核壳结构,放电比容量高,循环稳定性好等特点。The object of the present invention is to provide a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material and its preparation method, the preparation process of which is simple, easy to control, short reaction cycle, low energy consumption, high repeatability, high yield , the negative electrode material of MoO 2 -MoS 2 sodium ion battery prepared by this method has the characteristics of three-dimensional core-shell structure, high discharge specific capacity, good cycle stability and the like.

本发明是通过以下技术方案来实现:The present invention is achieved through the following technical solutions:

本发明公开了一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:The invention discloses a preparation method of a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1)取钼酸铵,充分研磨均匀后,从室温升温至400~600℃下保温反应1~3h后,冷却至室温,将反应产物洗净、干燥,制得MoO3前驱体;1) Take ammonium molybdate, thoroughly grind it evenly, raise the temperature from room temperature to 400-600°C and keep it warm for 1-3 hours, then cool it to room temperature, wash and dry the reaction product to obtain the MoO 3 precursor;

2)将MoO3前驱体和S粉按照0.5:(1.0~5.0)的质量比,研磨均匀后,在惰性条件下,从室温升温至400~600℃,保温反应0.5~2h,然后继续升温至600~800℃,保温反应0.5~2h,冷却至室温,将反应产物洗净、干燥,制得具有核壳结构的MoO2-MoS2钠离子电池负极材料。2) Grind the MoO 3 precursor and S powder according to the mass ratio of 0.5: (1.0-5.0), after grinding evenly, under inert conditions, raise the temperature from room temperature to 400-600°C, keep the temperature for 0.5-2h, and then continue to heat up to 600-800°C, heat preservation reaction for 0.5-2h, cool to room temperature, wash and dry the reaction product, and prepare MoO 2 -MoS 2 sodium ion battery negative electrode material with core-shell structure.

步骤1)是将钼酸铵研磨均匀后置于瓷舟中,将瓷舟置于管式炉中,在空气气氛下,以5-10℃min-1的升温速率从室温升至400~600℃。Step 1 ) is to grind the ammonium molybdate evenly and place it in a porcelain boat, place the porcelain boat in a tube furnace, and raise the temperature from room temperature to 400~400℃ at a heating rate of 5-10°C min 600°C.

步骤1)中,将反应产物用去离子水清洗3~6次,然后真空干燥8~12h。In step 1), the reaction product is washed with deionized water for 3-6 times, and then vacuum-dried for 8-12 hours.

步骤2)是将研磨均匀后的反应物置于瓷舟中,将瓷舟置于管式炉中,在氩气气氛下发生反应。Step 2) is to place the uniformly ground reactants in a porcelain boat, place the porcelain boat in a tube furnace, and react under an argon atmosphere.

反应开始时,通入氩气的气体流速为100sccm,以5-10℃min-1的升温速率,从室温升温至100℃后,控制氩气的气体流速为0~100sccm,以5-10℃min-1的升温速率继续升温至400~600℃,保温反应0.5~2h,然后以5-10℃min-1的升温速率继续升温至600~800℃,保温反应0.5~2h,反应结束后调节氩气气体流速为10~100sccm。At the beginning of the reaction, the gas flow rate of the argon gas is 100 sccm, and the temperature rise rate is 5-10 ℃ min -1 . After the temperature is raised from room temperature to 100 Continue to heat up to 400-600°C at a heating rate of min -1 , keep warm for 0.5-2 hours, then continue to heat up to 600-800°C at a heating rate of 5-10°C min -1 , keep warm for 0.5-2 hours, adjust after the reaction The flow rate of argon gas is 10-100 sccm.

步骤2)中,将反应产物用去离子水清洗3~6次,然后真空干燥8~12h。In step 2), the reaction product is washed with deionized water for 3-6 times, and then vacuum-dried for 8-12 hours.

本发明还公开了采用上述的方法制得的核壳结构MoO2-MoS2钠离子电池负极材料。The invention also discloses the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material prepared by the above method.

与现有技术相比,本发明具有以下有益的技术效果:Compared with the prior art, the present invention has the following beneficial technical effects:

本发明公开的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,以合成的MoO3为前驱体,MoO3与S粉发生氧化还原反应得到MoO2,采用原位合成法使得MoS2纳米片包裹在少量MoO2纳米颗粒模板上,形成具有核壳结构的MoO2-MoS2复合材料,由于S粉在反应过程中升华是以气态的形式存在于反应环境中,所以让S粉与MoO3充分接触,能够实现MoO3被完全还原成MoO2,新合成的MoO2进一步部被S粉硫化,最终形成核壳结构MoO2-MoS2,S粉充当还原剂及硫化剂双重角色;MoO2骨架起到结构支撑的作用,避免了片状的MoS2叠加,提高了材料导电性的同时也提高了材料的循环稳定性。本发明制备过程简单易控,周期短,能耗低,产物的重复性高,产率大,有利于规模化生产。The preparation method of the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material disclosed by the present invention uses synthesized MoO 3 as a precursor, MoO 3 and S powder undergo redox reactions to obtain MoO 2 , and the in-situ synthesis method is used to make MoS 2 nanosheets are wrapped on a small amount of MoO 2 nanoparticle template to form a MoO 2 -MoS 2 composite material with a core-shell structure. Since the S powder sublimates in the reaction process and exists in the reaction environment in the form of a gas, so let the S powder Full contact with MoO 3 can realize the complete reduction of MoO 3 to MoO 2 , and the newly synthesized MoO 2 is further partially vulcanized by S powder, finally forming a core-shell structure MoO 2 -MoS 2 , and S powder acts as a reducing agent and a vulcanizing agent. ; The MoO 2 skeleton plays the role of structural support, avoiding the superposition of flaky MoS 2 , improving the conductivity of the material and improving the cycle stability of the material. The preparation process of the present invention is simple and easy to control, has short cycle, low energy consumption, high product repeatability and high yield, and is favorable for large-scale production.

进一步地,在反应过程中,当温度升至100℃后控制Ar气体流速为0-100sccm,其目的在于通过控制Ar气体流速使得MoO3与S粉升华后的S蒸汽充分接触。反应结束后调节氩气气体流速为10-100sccm,以排出反应环境中过剩的S。Further, during the reaction process, when the temperature rises to 100°C, the flow rate of Ar gas is controlled to be 0-100 sccm, the purpose of which is to fully contact MoO 3 with S vapor after sublimation of S powder by controlling the flow rate of Ar gas. After the reaction, adjust the flow rate of argon gas to 10-100 sccm to discharge excess S in the reaction environment.

进一步地,继续升温至600-800℃,再次保温0.5-2h,以确保S蒸汽与MoO3充分反应。Further, continue to raise the temperature to 600-800°C, and keep the temperature for 0.5-2h again to ensure the full reaction of S vapor and MoO 3 .

附图说明Description of drawings

图1为本发明制得的MoO2-MoS2产物的XRD图;Fig. 1 is the XRD diagram of the MoO 2 -MoS 2 product prepared by the present invention;

图2为本发明制得的MoO2-MoS2产物的SEM照片;Fig. 2 is the SEM photo of the MoO 2 -MoS 2 product prepared by the present invention;

图3为本发明制得的MoO2-MoS2的循环性能测试图。Fig. 3 is a cycle performance test graph of MoO 2 -MoS 2 prepared in the present invention.

具体实施方式detailed description

下面结合具体的实施例对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。The present invention will be further described in detail below in conjunction with specific embodiments, which are explanations of the present invention rather than limitations.

本发明公开的一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:The preparation method of a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material disclosed by the present invention comprises the following steps:

步骤1、取钼酸铵,充分研磨均匀后,从室温升温至400~600℃下保温反应1~3h后,冷却至室温,将反应产物洗净、干燥,制得MoO3前驱体;Step 1. Take ammonium molybdate, thoroughly grind it evenly, raise the temperature from room temperature to 400-600°C and keep it warm for 1-3 hours, then cool it down to room temperature, wash and dry the reaction product to obtain the MoO 3 precursor;

步骤2、将MoO3前驱体和S粉按照0.5:(1.0~5.0)的质量比,研磨均匀后,在惰性条件下,从室温升温至400~600℃,保温反应0.5~2h,然后继续升温至600~800℃,保温反应0.5~2h,冷却至室温,将反应产物洗净、干燥,制得具有核壳结构的MoO2-MoS2钠离子电池负极材料。Step 2. Grind the MoO 3 precursor and S powder according to the mass ratio of 0.5: (1.0-5.0), and then, under inert conditions, raise the temperature from room temperature to 400-600°C, keep the temperature for 0.5-2 hours, and then continue to heat up to 600-800° C., heat-preserve for 0.5-2 hours, cool to room temperature, wash and dry the reaction product, and prepare MoO 2 -MoS 2 anode material for sodium ion battery with core-shell structure.

由于硫粉在反应过程中升华是以气态的形式存在与反映环境中,所以其目的在于让S粉与MoO3充分接触,以实现MoO3被完全还原成MoO2,然后新合成的MoO2进一步部被S粉硫化,最终形成核壳结构MoO2-MoS2,S粉充当还原剂及硫化剂双重角色。Since the sublimation of sulfur powder exists in the gaseous state and reflects the environment in the reaction process, the purpose is to make the S powder fully contact with MoO 3 to realize the complete reduction of MoO 3 to MoO 2 , and then the newly synthesized MoO 2 further Part of it is vulcanized by S powder, and finally forms a core-shell structure MoO 2 -MoS 2 , and S powder acts as a reducing agent and a vulcanizing agent.

MoO3+S→MoO2+SO2MoO 3 +S→MoO 2 +SO 2

MoO2+S→MoS2+SO2MoO 2 +S→MoS 2 +SO 2

具体实施例如下:Specific examples are as follows:

实施例1Example 1

一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1、前驱体MoO3的制备1. Preparation of precursor MoO 3

1)取钼酸铵,放入研钵中充分研磨。将研磨后的样品置于瓷舟中,在管式炉中以5℃min-1的升温速率升至400℃,保温1h后,在空气气氛条件下高温裂解得到MoO31) Take ammonium molybdate, put it into a mortar and grind it thoroughly. Put the ground sample in a porcelain boat, raise the temperature up to 400°C in a tube furnace at a rate of 5°C min -1 , keep it for 1 hour, and then pyrolyze it under air atmosphere to obtain MoO 3 ;

2)反应结束后冷却至室温,将产物用去离子水清洗3遍,真空干燥8h,即可得到纯相MoO3前驱体。2) Cool to room temperature after the reaction, wash the product three times with deionized water, and dry it in vacuum for 8 hours to obtain a pure-phase MoO 3 precursor.

2、MoO2-MoS2的制备2. Preparation of MoO 2 -MoS 2

1)取前驱体MoO3和S粉m(MoO3:S)=0.5:1.0的比例,通过研磨使其混合均匀,将研磨后的样品置于瓷舟中,在管式气氛炉氩气气氛条件下发生反应;1) Take the ratio of precursor MoO 3 and S powder m(MoO 3 :S)=0.5:1.0, mix them uniformly by grinding, put the ground sample in a porcelain boat, and place it in the argon atmosphere of the tube atmosphere furnace react under the conditions;

2)反应开始时通入Ar气体流速为100sccm,确保反应在惰性条件下进行。以5℃min-1的升温速率,当温度升至100℃后控制Ar气体流速为0sccm,继续升至400℃,保温0.5h以确保前驱体中钼酸铵完全裂解;2) At the beginning of the reaction, the Ar gas flow rate was 100 sccm to ensure that the reaction was carried out under inert conditions. With a heating rate of 5°C min -1 , when the temperature rises to 100°C, control the Ar gas flow rate to 0 sccm, continue to rise to 400°C, and keep warm for 0.5h to ensure that the ammonium molybdate in the precursor is completely cracked;

3)再以5℃min-1的升温速率升至600℃,再次保温0.5h。反应结束后调节氩气气体流速为100sccm,以排出反应环境中过剩的S;3) Then raise the temperature to 600°C at a rate of 5°C min -1 , and keep the temperature for 0.5h again. After the reaction, adjust the flow rate of argon gas to 100 sccm to discharge excess S in the reaction environment;

4)待反应结束后自然冷却至室温,将产物用去离子水清洗3遍,真空干燥8h,即可得到核壳结构的MoO2-MoS2产物。4) Cool down to room temperature naturally after the reaction, wash the product three times with deionized water, and dry it in vacuum for 8 hours to obtain the MoO 2 -MoS 2 product with a core-shell structure.

参见图1,从图1可得,通过原位合成法可以进制备出MoO2-MoS2(红色曲线),其XRD的衍射图谱中每一个衍射峰均可以与MoO2和MoS2标准卡片的衍射峰相对应,表明了其较好的结晶性和较高的纯度。Referring to Fig. 1, it can be seen from Fig. 1 that MoO 2 -MoS 2 (red curve) can be prepared by in-situ synthesis method, and each diffraction peak in its XRD diffraction pattern can be compared with that of MoO 2 and MoS 2 standard cards The corresponding diffraction peaks indicate its better crystallinity and higher purity.

参见图2,从图中可以看出MoO2-MoS2的颗粒尺寸为纳米级,颗粒表面分布着尺寸均匀的MoS2纳米片。Referring to Figure 2, it can be seen from the figure that the particle size of MoO 2 -MoS 2 is nanoscale, and MoS 2 nanosheets of uniform size are distributed on the particle surface.

参见图3,图3表明了核壳结构的MoO2-MoS2(红色曲线)具有优异的循环稳定性和放电比容量。在50mA g-1的电流密度下,MoO2-MoS2负极材料用于钠离子电池,经过20圈循环,容量仍可以保持在200mAh g-1以上,并且库伦效率保持在96%以上。这表明核壳结构的MoO2-MoS2在放电比容量和循环稳定性方面较好。Referring to Fig. 3, Fig. 3 shows that MoO 2 -MoS 2 (red curve) with core-shell structure has excellent cycle stability and specific discharge capacity. At a current density of 50mA g -1 , the MoO 2 -MoS 2 anode material is used in Na-ion batteries, and after 20 cycles, the capacity can still be maintained above 200mAh g -1 , and the Coulombic efficiency remains above 96%. This indicates that the core-shell MoO 2 -MoS 2 is better in discharge specific capacity and cycle stability.

实施例2Example 2

一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1、前驱体MoO3的制备1. Preparation of precursor MoO 3

1)取钼酸铵,放入研钵中充分研磨。将研磨后的样品置于瓷舟中,在管式炉中以6℃min-1的升温速率升至400℃,保温1.5h后,在空气气氛条件下高温裂解得到MoO31) Take ammonium molybdate, put it into a mortar and grind it thoroughly. Place the ground sample in a porcelain boat, raise the temperature up to 400°C in a tube furnace at a rate of 6°C min -1 , keep it warm for 1.5h, and pyrolyze it under air atmosphere to obtain MoO 3 ;

2)反应结束后冷却至室温,将产物用去离子水清洗4遍,真空干燥9h,即可得到纯相MoO3前驱体。2) Cool to room temperature after the reaction, wash the product 4 times with deionized water, and dry it in vacuum for 9 hours to obtain a pure-phase MoO 3 precursor.

2、MoO2-MoS2的制备2. Preparation of MoO 2 -MoS 2

1)取前驱体MoO3和S粉m(MoO3:S)=0.5:2.0的比例,通过研磨使其混合均匀,将研磨后的样品置于瓷舟中,在管式气氛炉氩气气氛条件下发生反应;1) Take the ratio of precursor MoO 3 and S powder m(MoO 3 :S)=0.5:2.0, mix them evenly by grinding, put the ground sample in a porcelain boat, and put it in the argon atmosphere of the tube atmosphere furnace react under the conditions;

2)反应开始时通入Ar气体流速为100sccm,确保反应在惰性条件下进行。以6℃min-1的升温速率,当温度升至100℃后控制Ar气体流速为25sccm,继续升至450℃,保温0.8h以确保前驱体中钼酸铵完全裂解;2) At the beginning of the reaction, the Ar gas flow rate was 100 sccm to ensure that the reaction was carried out under inert conditions. With a heating rate of 6°C min -1 , when the temperature rises to 100°C, control the Ar gas flow rate to 25 sccm, continue to rise to 450°C, and keep warm for 0.8h to ensure that the ammonium molybdate in the precursor is completely cracked;

3)再以6℃min-1的升温速率升至650℃,再次保温0.8h。反应结束后调节氩气气体流速为100sccm,以排出反应环境中过剩的S;3) Then raise the temperature to 650°C at a rate of 6°C min -1 , and keep the temperature for 0.8h again. After the reaction, adjust the flow rate of argon gas to 100 sccm to discharge excess S in the reaction environment;

4)待反应结束后自然冷却至室温,将产物用去离子水清洗4遍,真空干燥9h,即可得到核壳结构的MoO2-MoS2产物。4) Cool down to room temperature naturally after the reaction, wash the product 4 times with deionized water, and dry it in vacuum for 9 hours to obtain the MoO 2 -MoS 2 product with a core-shell structure.

实施例3Example 3

一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1、前驱体MoO3的制备1. Preparation of precursor MoO 3

1)取钼酸铵,放入研钵中充分研磨。将研磨后的样品置于瓷舟中,在管式炉中以7℃min-1的升温速率升至500℃,保温2h后,在空气气氛条件下高温裂解得到MoO31) Take ammonium molybdate, put it into a mortar and grind it thoroughly. Put the ground sample in a porcelain boat, raise the temperature up to 500°C in a tube furnace at a rate of 7°C min -1 , keep it warm for 2 hours, and pyrolyze it under air atmosphere to obtain MoO 3 ;

2)反应结束后冷却至室温,将产物用去离子水清洗5遍,真空干燥10h,即可得到纯相MoO3前驱体。2) Cool to room temperature after the reaction, wash the product 5 times with deionized water, and dry it in vacuum for 10 hours to obtain a pure-phase MoO 3 precursor.

2、MoO2-MoS2的制备2. Preparation of MoO 2 -MoS 2

1)取前驱体MoO3和S粉m(MoO3:S)=0.5:3.0的比例,通过研磨使其混合均匀,将研磨后的样品置于瓷舟中,在管式气氛炉氩气气氛条件下发生反应;1) Take the ratio of precursor MoO 3 and S powder m(MoO 3 :S)=0.5:3.0, mix them evenly by grinding, put the ground sample in a porcelain boat, and put it in the argon atmosphere of the tube atmosphere furnace react under the conditions;

2)反应开始时通入Ar气体流速为100sccm,确保反应在惰性条件下进行。以7℃min-1的升温速率,当温度升至100℃后控制Ar气体流速为50sccm,继续升至500℃,保温1.2h以确保前驱体中钼酸铵完全裂解;2) At the beginning of the reaction, the Ar gas flow rate was 100 sccm to ensure that the reaction was carried out under inert conditions. With a heating rate of 7°C min -1 , when the temperature rises to 100°C, control the Ar gas flow rate to 50 sccm, continue to rise to 500°C, and keep warm for 1.2 hours to ensure that the ammonium molybdate in the precursor is completely cracked;

3)再以7℃min-1的升温速率升至700℃,再次保温1.2h。反应结束后调节氩气气体流速为100sccm,以排出反应环境中过剩的S;3) Then raise the temperature to 700°C at a rate of 7°C min -1 , and keep the temperature for 1.2h again. After the reaction, adjust the flow rate of argon gas to 100 sccm to discharge excess S in the reaction environment;

4)待反应结束后自然冷却至室温,将产物用去离子水清洗5遍,真空干燥10h,即可得到核壳结构的MoO2-MoS2产物。4) After the reaction is finished, cool down to room temperature naturally, wash the product with deionized water for 5 times, and dry it in vacuum for 10 hours to obtain the MoO 2 -MoS 2 product with a core-shell structure.

实施例4Example 4

实施例3Example 3

一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1、前驱体MoO3的制备1. Preparation of precursor MoO 3

1)取钼酸铵,放入研钵中充分研磨。将研磨后的样品置于瓷舟中,在管式炉中以8℃min-1的升温速率升至550℃,保温2.5h后,在空气气氛条件下高温裂解得到MoO31) Take ammonium molybdate, put it into a mortar and grind it thoroughly. Put the ground sample in a porcelain boat, raise the temperature up to 550°C in a tube furnace at a rate of 8°C min -1 , keep it warm for 2.5 hours, and then pyrolyze it in an air atmosphere to obtain MoO 3 ;

2)反应结束后冷却至室温,将产物用去离子水清洗6遍,真空干燥11h,即可得到纯相MoO3前驱体。2) Cool to room temperature after the reaction, wash the product 6 times with deionized water, and dry it in vacuum for 11 hours to obtain a pure-phase MoO 3 precursor.

2、MoO2-MoS2的制备2. Preparation of MoO 2 -MoS 2

1)取前驱体MoO3和S粉m(MoO3:S)=0.5:4.0的比例,通过研磨使其混合均匀,将研磨后的样品置于瓷舟中,在管式气氛炉氩气气氛条件下发生反应;1) Take the ratio of precursor MoO 3 and S powder m(MoO 3 :S)=0.5:4.0, mix them uniformly by grinding, put the ground sample in a porcelain boat, and put it in the argon atmosphere of the tube atmosphere furnace react under the conditions;

2)反应开始时通入Ar气体流速为100sccm,确保反应在惰性条件下进行。以8℃min-1的升温速率,当温度升至100℃后控制Ar气体流速为75sccm,继续升至550℃,保温1.5h以确保前驱体中钼酸铵完全裂解;2) At the beginning of the reaction, the Ar gas flow rate was 100 sccm to ensure that the reaction was carried out under inert conditions. With a heating rate of 8°C min -1 , when the temperature rises to 100°C, control the Ar gas flow rate to 75 sccm, continue to rise to 550°C, and keep warm for 1.5h to ensure that the ammonium molybdate in the precursor is completely cracked;

3)再以8℃min-1的升温速率升至750℃,再次保温1.5h。反应结束后调节氩气气体流速为100sccm,以排出反应环境中过剩的S;3) Then raise the temperature to 750°C at a rate of 8°C min -1 and keep the temperature for 1.5h again. After the reaction, adjust the flow rate of argon gas to 100 sccm to discharge excess S in the reaction environment;

4)待反应结束后自然冷却至室温,将产物用去离子水清洗6遍,真空干燥11h,即可得到核壳结构的MoO2-MoS2产物。4) After the reaction is finished, cool down to room temperature naturally, wash the product with deionized water for 6 times, and dry it in vacuum for 11 hours to obtain the MoO 2 -MoS 2 product with a core-shell structure.

实施例5Example 5

实施例3Example 3

一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,包括以下步骤:A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, comprising the following steps:

1、前驱体MoO3的制备1. Preparation of precursor MoO 3

1)取钼酸铵,放入研钵中充分研磨。将研磨后的样品置于瓷舟中,在管式炉中以10℃min-1的升温速率升至600℃,保温3h后,在空气气氛条件下高温裂解得到MoO31) Take ammonium molybdate, put it into a mortar and grind it thoroughly. Put the ground sample in a porcelain boat, raise the temperature up to 600°C in a tube furnace at a rate of 10°C min -1 , keep it warm for 3 hours, and then pyrolyze it in an air atmosphere to obtain MoO 3 ;

2)反应结束后冷却至室温,将产物用去离子水清洗5遍,真空干燥12h,即可得到纯相MoO3前驱体。2) Cool to room temperature after the reaction, wash the product 5 times with deionized water, and dry it in vacuum for 12 hours to obtain a pure-phase MoO 3 precursor.

2、MoO2-MoS2的制备2. Preparation of MoO 2 -MoS 2

1)取前驱体MoO3和S粉m(MoO3:S)=0.5:5.0的比例,通过研磨使其混合均匀,将研磨后的样品置于瓷舟中,在管式气氛炉氩气气氛条件下发生反应;1) Take the ratio of precursor MoO 3 and S powder m(MoO 3 :S)=0.5:5.0, mix them evenly by grinding, put the ground sample in a porcelain boat, and put it in the argon atmosphere of the tube atmosphere furnace react under the conditions;

2)反应开始时通入Ar气体流速为100sccm,确保反应在惰性条件下进行。以10℃min-1的升温速率,当温度升至100℃后控制Ar气体流速为50sccm,继续升至600℃,保温2h以确保前驱体中钼酸铵完全裂解;2) At the beginning of the reaction, the Ar gas flow rate was 100 sccm to ensure that the reaction was carried out under inert conditions. With a heating rate of 10°C min -1 , when the temperature rises to 100°C, control the Ar gas flow rate to 50 sccm, continue to rise to 600°C, and keep warm for 2 hours to ensure that the ammonium molybdate in the precursor is completely cracked;

3)再以10℃min-1的升温速率升至800℃,再次保温2h。反应结束后调节氩气气体流速为100sccm,以排出反应环境中过剩的S;3) Then raise the temperature to 800°C at a rate of 10°C min -1 , and keep the temperature for another 2 hours. After the reaction, adjust the flow rate of argon gas to 100 sccm to discharge excess S in the reaction environment;

4)待反应结束后自然冷却至室温,将产物用去离子水清洗5遍,真空干燥12h,即可得到核壳结构的MoO2-MoS2产物。4) After the reaction is finished, cool down to room temperature naturally, wash the product with deionized water for 5 times, and dry it in vacuum for 12 hours to obtain the MoO 2 -MoS 2 product with a core-shell structure.

本发明以MoO3为前驱体,其与S粉发生氧化还原反应得到MoO2,采用原位合成法使得MoS2纳米片长在MoO2模板上,形成具有三维核壳结构的MoO2-MoS2复合材料。三维核壳结构具有贯通,比表面积大等特点。三维核壳结构电极材料会使得二次电池在充/放电过程中结构稳定,能有效避免二维电极材料结构的塌陷,将二维的MoS2结构进行优化,以构建三维核壳结构MoO2-MoS2用于钠离子电池负极材料,从而提高钠离子电池的电化学性能。In the present invention, MoO 3 is used as a precursor, and MoO 2 is obtained through oxidation-reduction reaction with S powder, and the in-situ synthesis method is used to make MoS 2 nanosheets grow on the MoO 2 template to form MoO 2 -MoS 2 with a three-dimensional core-shell structure. composite material. The three-dimensional core-shell structure has the characteristics of penetration and large specific surface area. The three-dimensional core-shell structure electrode material will stabilize the structure of the secondary battery during charging/discharging, and can effectively avoid the collapse of the two-dimensional electrode material structure. The two-dimensional MoS 2 structure is optimized to build a three-dimensional core-shell structure MoO 2 - MoS2 is used as an anode material for Na - ion batteries, thereby improving the electrochemical performance of Na-ion batteries.

Claims (7)

1.一种核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,包括以下步骤:1. A method for preparing a core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material, characterized in that, comprising the following steps: 1)取钼酸铵,充分研磨均匀后,从室温升温至400~600℃下保温反应1~3h后,冷却至室温,将反应产物洗净、干燥,制得MoO3前驱体;1) Take ammonium molybdate, thoroughly grind it evenly, raise the temperature from room temperature to 400-600°C and keep it warm for 1-3 hours, then cool it to room temperature, wash and dry the reaction product to obtain the MoO 3 precursor; 2)将MoO3前驱体和S粉按照0.5:(1.0~5.0)的质量比,研磨均匀后,在惰性条件下,从室温升温至400~600℃,保温反应0.5~2h,然后继续升温至600~800℃,保温反应0.5~2h,冷却至室温,将反应产物洗净、干燥,制得具有核壳结构的MoO2-MoS2钠离子电池负极材料。2) Grind the MoO 3 precursor and S powder according to the mass ratio of 0.5: (1.0-5.0), after grinding evenly, under inert conditions, raise the temperature from room temperature to 400-600°C, keep the temperature for 0.5-2h, and then continue to heat up to 600-800°C, heat preservation reaction for 0.5-2h, cool to room temperature, wash and dry the reaction product, and prepare MoO 2 -MoS 2 sodium ion battery negative electrode material with core-shell structure. 2.根据权利要求1所述的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,步骤1)是将钼酸铵研磨均匀后置于瓷舟中,将瓷舟置于管式炉中,在空气气氛下,以5-10℃min-1的升温速率从室温升至400~600℃。2. the core-shell structure MoO according to claim 1 2 -MoS 2 The preparation method of sodium ion battery negative electrode material, it is characterized in that, step 1) is to place in the porcelain boat after the ammonium molybdate is ground evenly, and the porcelain boat Placed in a tube furnace, in an air atmosphere, the temperature rises from room temperature to 400-600°C at a rate of 5-10°C min -1 . 3.根据权利要求1所述的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,步骤1)中,将反应产物用去离子水清洗3~6次,然后真空干燥8~12h。3. The preparation method of the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material according to claim 1, characterized in that, in step 1), the reaction product is washed with deionized water for 3 to 6 times, and then vacuum Dry for 8-12 hours. 4.根据权利要求1所述的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,步骤2)是将研磨均匀后的反应物置于瓷舟中,将瓷舟置于管式炉中,在氩气气氛下发生反应。4. The preparation method of the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material according to claim 1, characterized in that step 2) is to place the uniformly ground reactant in a porcelain boat, and place the porcelain boat The reaction took place under an argon atmosphere in a tube furnace. 5.根据权利要求4所述的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,反应开始时,通入氩气的气体流速为100sccm,以5-10℃min-1的升温速率,从室温升温至100℃后,控制氩气的气体流速为0~100sccm,以5-10℃min-1的升温速率继续升温至400~600℃,保温反应0.5~2h,然后以5-10℃min-1的升温速率继续升温至600~800℃,保温反应0.5~2h,反应结束后调节氩气气体流速为10~100sccm。5. The preparation method of the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material according to claim 4, characterized in that, when the reaction starts, the gas flow rate of argon gas is 100 sccm, and at 5-10 ℃ min -1 heating rate, after the temperature is raised from room temperature to 100°C, control the gas flow rate of argon to 0-100sccm, continue to heat up to 400-600°C at a heating rate of 5-10°C min -1 , and keep the temperature for 0.5-2h. Then continue to heat up to 600-800°C at a heating rate of 5-10°C min -1 , keep the temperature for 0.5-2 hours, and adjust the flow rate of argon gas to 10-100 sccm after the reaction. 6.根据权利要求1所述的核壳结构MoO2-MoS2钠离子电池负极材料的制备方法,其特征在于,步骤2)中,将反应产物用去离子水清洗3~6次,然后真空干燥8~12h。6. The preparation method of the core-shell structure MoO 2 -MoS 2 sodium ion battery negative electrode material according to claim 1, characterized in that, in step 2), the reaction product is washed with deionized water for 3 to 6 times, and then vacuum Dry for 8-12 hours. 7.采用权利要求1~6中任意一项所述的方法制得的核壳结构MoO2-MoS2钠离子电池负极材料。7. The anode material of core-shell structure MoO 2 -MoS 2 sodium ion battery prepared by the method according to any one of claims 1-6.
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