CN114551832A - Preparation method of nano composite material and lithium ion electrode negative electrode material thereof - Google Patents

Preparation method of nano composite material and lithium ion electrode negative electrode material thereof Download PDF

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CN114551832A
CN114551832A CN202210165549.0A CN202210165549A CN114551832A CN 114551832 A CN114551832 A CN 114551832A CN 202210165549 A CN202210165549 A CN 202210165549A CN 114551832 A CN114551832 A CN 114551832A
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李娟�
徐蓉
杨丽楠
杨慧贞
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Abstract

The invention relates to a preparation method of a nano composite material and a lithium ion electrode cathode material thereof, and aims to provide a preparation method of a nano composite materialα‑Fe2O3The cube is used as a template, phenolic resin is coated on the surface of the cube in situ, the carbon-coated ferroferric oxide cube is formed by annealing treatment, and then the carbon-coated ferroferric oxide cube is partially etched by hydrochloric acid to form a carbon box (Fe) taking ferroferric oxide as a core and a shell (Fe)3O4@ C); then, molybdenum selenide is coated in situ on the carbon shell through hydrothermal reaction, and the flaky molybdenum selenide coated nano composite material Fe taking ferroferric oxide as the core and carbon box as the shell is prepared after annealing3O4@C/MoSe2. The nano composite material of the invention prepares Fe by a step-by-step growth strategy3O4@C/MoSe2The nano composite material has the advantages of uniform dispersion, large inner cavity volume, good electrochemical performance, good cycle stability and rate capability when being used as a lithium ion electrode cathode material, and the like.

Description

一种纳米复合材料的制备方法及其锂离子电极负极材料A kind of preparation method of nanocomposite material and its lithium ion electrode negative electrode material

技术领域technical field

本发明涉及锂离子电极材料技术领域，特别涉及一种用于锂离子电池负极的纳米复合材料。The present invention relates to the technical field of lithium ion electrode materials, in particular to a nanocomposite material for a negative electrode of a lithium ion battery.

背景技术Background technique

为了满足人类日益增长的能源需求，开发具有优良性能的新一代锂离子电池(LIBs)至关重要。负极材料作为锂离子电池的重要组成部分，影响着整个电池的电化学性能。传统的以石墨材料制备负极的LIBs比容量低(372 mA h g-1)，难以满足人类在便携电子设备、电动汽车和大规模能量存储等应用领域中对LIBs的越来越高的应用要求。从而，寻找一种廉价、能量密度高、循环性能良好的负极材料已经成为研究锂离子电池研究领域的热点。To meet the growing energy demands of mankind, it is crucial to develop new-generation lithium-ion batteries (LIBs) with excellent performance. As an important part of lithium-ion batteries, anode materials affect the electrochemical performance of the entire battery. The low specific capacity (372 mA hg -1 ) of traditional graphite-based negative electrode LIBs makes it difficult to meet the increasingly high application requirements of LIBs in portable electronic devices, electric vehicles, and large-scale energy storage. Therefore, the search for a cheap, high energy density and good cycle performance negative electrode material has become a hot spot in the research field of Li-ion batteries.

四氧化三铁由于其储量丰富、成本低、环境友好、易于合成和理论容量高等特点，被公认为最有希望作为高性能锂离子电池(LIBs)的负极材料之一。然而，四氧化三铁固有的电导率低、体积膨胀效应大和初始库仑效率低等缺陷，严重阻碍了其作为LIBs负极材料的大规模应用。为应对这些缺陷，研究者在四氧化三铁改性方面做了大量的探索。例如，通过控制复合材料的尺寸在纳米级，减少充放电过程中的结构粉化和团聚；构建核壳纳米结构，其内部空间保证了足够的电极-电解液接触面积和大量的电化学活性位点，可以大大减少锂离子和电子的扩散距离并缓解电极材料在充放电过程中的体积变化；以碳材料作为功能性添加剂来改善电极材料的导电性。Ferric oxide is widely recognized as one of the most promising anode materials for high-performance lithium-ion batteries (LIBs) due to its abundant reserves, low cost, environmental friendliness, ease of synthesis, and high theoretical capacity. However, the inherent defects of low electrical conductivity, large volume expansion effect, and low initial Coulombic efficiency of ferric oxide severely hinder its large-scale application as an anode material for LIBs. In order to deal with these defects, researchers have done a lot of exploration in the modification of ferric tetroxide. For example, by controlling the size of the composite at the nanoscale, structure pulverization and agglomeration during charge and discharge are reduced; core-shell nanostructures are constructed, the internal space of which ensures sufficient electrode-electrolyte contact area and a large number of electrochemically active sites It can greatly reduce the diffusion distance of lithium ions and electrons and alleviate the volume change of electrode materials during charging and discharging; carbon materials are used as functional additives to improve the conductivity of electrode materials.

发明内容SUMMARY OF THE INVENTION

本发明针对四氧化三铁作为锂离子电池负极材料的电化学性能差的问题，提供一种分散较均匀，内腔体积大、电化学性能好的Fe3O4@C/MoSe2复合材料，以改善四氧化三铁作为锂离子电极材料的循环稳定性和倍率性能。Aiming at the problem of poor electrochemical performance of ferric oxide as a negative electrode material for lithium ion batteries, the invention provides a Fe 3 O 4 @C/MoSe 2 composite material with relatively uniform dispersion, large inner cavity volume and good electrochemical performance, In order to improve the cycle stability and rate performance of ferric oxide as a lithium ion electrode material.

本发明的目的是这样实现的，一种用于锂离子电池负极的纳米复合材料，其特征在于，以α-Fe2O3立方体为模板，在其表面原位包覆酚醛树脂，经退火处理形成碳包覆四氧化三铁立方体，再用盐酸部分刻蚀形成以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料；接着通过水热反应在碳壳原位包覆硒化钼，退火后制得片状硒化钼包覆以四氧化三铁为核碳盒为壳纳米复合材料Fe3O4@C/MoSe2 The object of the present invention is achieved in this way, a nano-composite material for the negative electrode of lithium ion battery is characterized in that, using α- Fe 2 O 3 cube as a template, the surface of the phenolic resin is in-situ coated, and annealed Carbon-coated ferric oxide cubes are formed, and then partially etched with hydrochloric acid to form nanomaterials with ferric tetroxide as the core and carbon box as the shell (Fe 3 O 4 @C); Coated molybdenum selenide, annealed to obtain flake molybdenum selenide coated with Fe 3 O 4 @C/MoSe 2 with ferric oxide as the core and carbon box as the shell

在本发明中的纳米兰复合材料，通过逐步生长策略制备了Fe3O4@C/MoSe2纳米复合材料，此复合材料作为锂离子电池负极材料具有如下优点：首先，以四氧化三铁为核碳盒为壳的独特结构不仅缓解了电极材料在充放电过程中体积效应而且缩短了电子和离子传输路径，极大地加快了锂离子的迁移速率，增强电极反应动力学过程。其次，碳盒不仅增强了整体导电性，而且在充放电过程中作为结构粘合剂有助于结构完整性。最后，在碳盒外部高表面积包覆硒化钼纳米片为电化学反应提供更多的活性位点。因此，上述独特的组分及逐层包覆的协同效应和结构特征，使Fe3O4@C/MoSe2纳米复合材料作为锂离子电池负极表现出优异的循环稳定性和倍率性能。In the nano-blue composite material of the present invention, Fe 3 O 4 @C/MoSe 2 nano-composite material is prepared by a step-by-step growth strategy. This composite material has the following advantages as a negative electrode material for lithium ion batteries: First, using ferric tetroxide as a The unique structure of the core carbon box as the shell not only alleviates the volume effect of the electrode material during charging and discharging, but also shortens the electron and ion transport paths, greatly accelerates the migration rate of lithium ions, and enhances the kinetic process of the electrode reaction. Second, the carbon box not only enhances overall electrical conductivity, but also contributes to structural integrity as a structural adhesive during charge and discharge. Finally, coating molybdenum selenide nanosheets with high surface area on the outside of the carbon box provides more active sites for electrochemical reactions. Therefore, the above-mentioned unique composition and the synergistic effect and structural characteristics of layer-by-layer coating enable the Fe 3 O 4 @C/MoSe 2 nanocomposite to exhibit excellent cycling stability and rate capability as an anode for Li-ion batteries.

进一步地，第1步，制备核壳结构的Fe3O4@ C：以α-Fe2O3立方体为模板，将α-Fe2O3纳米立方体分散于体积比为（2～2.5）：1：（20～25）水、氨水和无水乙醇的混合液中，其中α-Fe2O3在混合液中的分散浓度为50 mg/100mL，将分散液于25～35℃水浴温度下机械搅拌，分散均匀，再加入间苯二酚与甲醛的混合溶液，继续恒温搅拌20～30 h，反应结束后，离心收集沉淀固相，将固相真空干燥后，于氩气保护下退火处理，再将退火后的固相用盐酸刻蚀25～35min，然后离心分离出刻蚀后的固相，用去离子水洗涤2或3次后真空干燥，得到以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料。Further, in the first step, Fe 3 O 4 @C with core-shell structure was prepared: using α- Fe 2 O 3 cubes as templates, the α- Fe 2 O 3 nanocubes were dispersed in a volume ratio of (2～2.5): 1: (20～25) In the mixed solution of water, ammonia water and absolute ethanol, the dispersion concentration of α- Fe 2 O 3 in the mixed solution is 50 mg/100 mL, and the dispersion solution is placed in a water bath temperature of 25～35 ℃ Stir mechanically to disperse evenly, then add the mixed solution of resorcinol and formaldehyde, and continue to stir at constant temperature for 20-30 h. After the reaction, the precipitated solid phase is collected by centrifugation. After the solid phase is vacuum-dried, it is annealed under argon protection. , and then the annealed solid phase was etched with hydrochloric acid for 25-35 min, and then the etched solid phase was separated by centrifugation, washed with deionized water for 2 or 3 times, and then vacuum-dried to obtain a carbon box with ferric oxide as the core Nanomaterials with shell (Fe 3 O 4 @C).

第2步，制备片状MoSe2包覆核壳Fe3O4@ C：将硒粉与水合肼混合，室温条件下搅拌3～5h，得到溶液A，将 Na2MoO4∙2H2O与去离子水中混合，制得溶液B，在搅拌条件下，将溶液A混入到溶液B中，搅拌0.5～1h后，向上述溶液中加入乙二胺，继续搅拌0.5～1h后，加入步骤1制备的核壳Fe3O4@C纳米材料，超声振动0.5～1h，最后将溶液转入聚四氟乙烯内衬的不锈钢高压反应釜中水热反应，待反应冷却至室温后，离心收集沉淀物，置于真空干燥箱内烘干处理，然后在管式炉里氩气保护下煅烧得到Fe3O4@C/MoSe2。The second step, preparation of sheet-like MoSe 2 -coated core-shell Fe 3 O 4 @ C: Mix selenium powder with hydrazine hydrate, and stir at room temperature for 3-5 h to obtain solution A, where Na 2 MoO 4∙ 2H 2 O is mixed with Mix with deionized water to prepare solution B, under stirring condition, mix solution A into solution B, stir for 0.5-1 h, add ethylenediamine to the above solution, continue stirring for 0.5-1 h, add step 1 to prepare The core-shell Fe 3 O 4 @C nanomaterials were subjected to ultrasonic vibration for 0.5-1 h, and finally the solution was transferred to a PTFE-lined stainless steel autoclave for hydrothermal reaction. After the reaction was cooled to room temperature, the precipitate was collected by centrifugation. , placed in a vacuum drying oven for drying, and then calcined in a tube furnace under argon protection to obtain Fe 3 O 4 @C/MoSe 2 .

进一步地，第1步中， α-Fe2O3、间苯二酚和甲醛的投料比例按物质的量为70～200：95：1。Further, in the first step, the feeding ratio of α- Fe 2 O 3 , resorcinol and formaldehyde is 70-200:95:1 according to the amount of substances.

进一步地，刻蚀用盐酸的浓度为4 mol/L。Further, the concentration of hydrochloric acid for etching was 4 mol/L.

进一步地，第1步中，退火温度为700~750 ℃，退火时间为3~5 h，真空干燥温度为60 ℃，真空干燥时间为12 h。Further, in the first step, the annealing temperature is 700-750 °C, the annealing time is 3-5 h, the vacuum drying temperature is 60 °C, and the vacuum drying time is 12 h.

再进一步地，第二步中，硒粉和水合肼的投料比为1.6g～8.0g/100mL，Na2MoO4∙2H2O和去离子水的投料比例为：0.32 g～2.4g/100mL；溶液A和溶液B混合时，按硒粉和Na2MoO4∙2H2O摩尔比为2：1，硒粉和乙二胺的投料比为3.2g～24g/100mL；所述硒粉和核壳Fe3O4@C质量比为6～2:1。Further, in the second step, the feeding ratio of selenium powder and hydrazine hydrate is 1.6g～8.0g/100mL, and the feeding ratio of Na 2 MoO 4∙ 2H 2 O and deionized water is: 0.32 g～2.4g/100mL ; When solution A and solution B are mixed, the molar ratio of selenium powder and Na 2 MoO 4∙ 2H 2 O is 2:1, and the feeding ratio of selenium powder and ethylenediamine is 3.2g～24g/100mL; the selenium powder and The mass ratio of core-shell Fe 3 O 4 @C is 6-2:1.

再进一步地，第二步中水热温度为220~240℃，水热反应时间为22~24 h，真空干燥温度为60 ℃，真空干燥时间为12 h。退火温度为700~750 ℃，退火时间为2~3h。Further, in the second step, the hydrothermal temperature is 220-240 °C, the hydrothermal reaction time is 22-24 h, the vacuum drying temperature is 60 °C, and the vacuum drying time is 12 h. The annealing temperature is 700~750 ℃, and the annealing time is 2~3h.

本发明的另一个目的是提供一种以上述Fe3O4@C/MoSe2纳米复合材料制备锂离子电极负材料，具体为质量配比为7:2:1的Fe3O4@C/MoSe2、乙炔黑导电剂和PVDF粘结剂。Another object of the present invention is to provide a lithium ion electrode negative material prepared from the above-mentioned Fe 3 O 4 @C/MoSe 2 nanocomposite material, specifically Fe 3 O 4 @C/ MoSe 2 , acetylene black conductive agent and PVDF binder.

本发明的Fe3O4@C/MoSe2复合材料用作锂离子电池负极材料与现有技术相比，具有如下优点：Compared with the prior art, the Fe 3 O 4 @C/MoSe 2 composite material of the present invention has the following advantages when used as a negative electrode material for lithium ion batteries:

(1)选择Fe3O4基负极是由于Fe3O4具有924 mAh g-1的高理论容量，成本低、低毒性和铁的天然丰度；(1) Fe3O4 - based anode was chosen due to Fe3O4 's high theoretical capacity of 924 mAh g -1 , low cost, low toxicity and natural abundance of iron;

(2)采用独特的Fe3O4@C核壳结构不仅缓解了体积膨胀而且缩短了电子和离子传输路径，极大地加快了锂离子的迁移速率，增强电极反应动力学过程，从而大大增强其倍率性能；另外不仅增强了材料整体导电性而且在充放电过程中作为结构粘合剂有助于结构完整性。( 2 ) Adopting the unique Fe3O4 @C core-shell structure not only alleviates the volume expansion but also shortens the electron and ion transport paths, greatly accelerates the migration rate of lithium ions, and enhances the kinetic process of the electrode reaction, thereby greatly enhancing its Rate capability; additionally not only enhances the overall conductivity of the material but also contributes to structural integrity as a structural adhesive during charge and discharge.

(3) Fe3O4@C/MoSe2复合材料外部用高表面积硒化钼纳米片包覆，不仅有效的减少了Fe3O4@C聚集，而且为电化学反应提供更多的活性位点。(3) Fe 3 O 4 @C/MoSe 2 composites were coated with high surface area molybdenum selenide nanosheets, which not only effectively reduced Fe 3 O 4 @C aggregation, but also provided more active sites for electrochemical reactions point.

附图说明Description of drawings

图1为实施例1制备的α-Fe2O3纳米立方体（图1a）、Fe3O4@C (图1b)和Fe3O4@ C/MoSe2复合材料（图1c）的扫描电镜图。Fig. 1 is the scanning electron microscope of α- Fe 2 O 3 nanocubes (Fig. 1a), Fe 3 O 4 @C (Fig. 1b) and Fe 3 O 4 @C/MoSe 2 composites (Fig. 1c) prepared in Example 1 picture.

图2为实施例1制备的α-Fe2O3纳米立方体（图2a）、Fe3O4@C (图2b)和Fe3O4@C/MoSe2复合材料（图2c）的透射电镜图。Fig. 2 is the transmission electron microscope of α- Fe 2 O 3 nanocubes (Fig. 2a), Fe 3 O 4 @C (Fig. 2b) and Fe 3 O 4 @C/MoSe 2 composites (Fig. 2c) prepared in Example 1 picture.

图3为实施例1制备的Fe3O4@C/MoSe2和Fe3O4@C、C/MoSe2复合材料的XRD谱图。FIG. 3 is the XRD patterns of Fe 3 O 4 @C/MoSe 2 and Fe 3 O 4 @C, C/MoSe 2 composites prepared in Example 1. FIG.

图4为实施例1和对比例1制备的Fe3O4@C/MoSe2和Fe3O4@C、C/MoSe2复合材料作为电池负极在100 mA g-1电流密度下循环70圈的循环性能对比图。Fig. 4 shows that Fe 3 O 4 @C/MoSe 2 and Fe 3 O 4 @C, C/MoSe 2 composites prepared in Example 1 and Comparative Example 1 were used as battery anodes for 70 cycles at a current density of 100 mA g -1 The cycle performance comparison chart.

图5为实施例1和对比例1制备的Fe3O4@C/MoSe2和Fe3O4@C、C/MoSe2复合材料作为电池负极在不同电流密度的倍率性能对比图。FIG. 5 is a comparison diagram of the rate performance of Fe 3 O 4 @C/MoSe 2 and Fe 3 O 4 @C and C/MoSe 2 composite materials prepared in Example 1 and Comparative Example 1 as battery anodes at different current densities.

具体实施方式Detailed ways

实施例1Example 1

第一步，制备核壳Fe3O4@ C ：将实验室制得的80mg α-Fe2O3纳米立方体、水与氨水超声下均匀分散于乙醇，其中，水、氨水、无水乙醇的体积比为2.5：1：20，α-Fe2O3的分散浓度为50 mg/100mL，将混合液于 250 mL的三口烧瓶中，在水浴温度为30 ℃条件下机械搅拌，再加入30mg间苯二酚与64μL甲醛溶液，搅拌24h，待反应结束后，将沉淀离心收集，置于真空干燥箱中60 ℃干燥12h。然后在管式炉氩气保护下700℃退火3h，将退火后的样品用40 mL盐酸(4 mol/L)刻蚀30min，然后水洗后离心分离出刻蚀后的固相，最后移至真空干燥箱60℃干燥12h，得到得到以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料。The first step, preparation of core-shell Fe 3 O 4 @ C: 80 mg of α- Fe 2 O 3 nanocubes, water and ammonia water prepared in the laboratory were uniformly dispersed in ethanol under ultrasonication, wherein the water, ammonia water and anhydrous ethanol The volume ratio was 2.5:1:20, and the dispersion concentration of α- Fe 2 O 3 was 50 mg/100 mL. The mixture was placed in a 250 mL three-necked flask, mechanically stirred at a water bath temperature of 30 °C, and then 30 mg of Hydroquinone and 64 μL of formaldehyde solution were stirred for 24 h. After the reaction was over, the precipitate was collected by centrifugation, and dried in a vacuum drying oven at 60 °C for 12 h. Then annealed at 700 °C for 3 h under the protection of argon in a tube furnace, the annealed sample was etched with 40 mL of hydrochloric acid (4 mol/L) for 30 min, then washed with water, centrifuged to separate the etched solid phase, and finally moved to vacuum Dry in a drying oven at 60 °C for 12 h to obtain nanomaterials with Fe 3 O 4 @C as the core and carbon box as the shell (Fe 3 O 4 @C).

(2) 制备片状MoSe2包覆核壳Fe3O4@ C：取0.16g的硒粉加入到10mL水合肼中，室温条件下搅拌5h，制得溶液A，取0.24g的Na2MoO4∙2H2O加入到50mL的去离子水中，制得溶液B，在搅拌条件下，将溶液A加入到溶液B中，搅拌0.5h后，向上述溶液中加入5mL乙二胺，继续搅拌0.5h后，向其中加入30mg核壳Fe3O4@C超声1h。最后将溶液转入聚四氟乙烯内衬的不锈钢高压反应釜中，在240℃水热条件下反应24h，待反应冷却至室温后，将沉淀离心收集，随后用去离子水和乙醇洗涤数次，最后置于真空干燥箱60℃烘干备用，然后在管式炉里氩气保护下700℃煅烧2h得到本实施例的片状硒化钼包覆以四氧化三铁为核碳盒为壳纳米复合材料Fe3O4@C/MoSe2。(2) Preparation of sheet-like MoSe 2 -coated core-shell Fe 3 O 4 @ C: add 0.16 g of selenium powder to 10 mL of hydrazine hydrate, stir at room temperature for 5 h to prepare solution A, and take 0.24 g of Na 2 MoO 4∙ 2H 2 O was added to 50 mL of deionized water to prepare solution B. Under stirring conditions, solution A was added to solution B. After stirring for 0.5 h, 5 mL of ethylenediamine was added to the above solution, and the stirring was continued for 0.5 h. After h, 30 mg of core-shell Fe 3 O 4 @C was added thereto and sonicated for 1 h. Finally, the solution was transferred into a stainless steel autoclave lined with PTFE, and reacted under hydrothermal conditions at 240 °C for 24 h. After the reaction was cooled to room temperature, the precipitate was collected by centrifugation, and then washed several times with deionized water and ethanol. , and finally placed in a vacuum drying oven at 60 °C for drying for later use, and then calcined at 700 °C for 2 hours in a tube furnace under the protection of argon gas to obtain the flake molybdenum selenide of the present example, with ferric tetroxide as the core and carbon box as the shell. Nanocomposite Fe 3 O 4 @C/MoSe 2 .

实施例2Example 2

(1) 制备核壳Fe3O4@ C：制备核壳Fe3O4@ C ：将实验室制得的80mg α-Fe2O3纳米立方体、水与氨水超声下均匀分散于乙醇，其中，水、氨水、无水乙醇的体积比为2：1：25，α-Fe2O3的分散浓度为50 mg/100mL，将混合液倒入250 mL的三口烧瓶中，在水浴温度为25 ℃条件下机械搅拌，再加入25mg间苯二酚与54μL甲醛溶液，搅拌30h，待反应结束后，将沉淀离心收集，置于真空干燥箱中60 ℃干燥12h；然后在管式炉氩气保护下750℃退火5h，将退火后的样品用40 mL盐酸(4 mol/L)刻蚀30min，用去离子水洗涤2次，最后移至真空干燥箱60℃干燥12h，得到本实用施的以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料。(1) Preparation of core-shell Fe 3 O 4 @ C: Preparation of core-shell Fe 3 O 4 @ C: 80 mg of α- Fe 2 O 3 nanocubes prepared in the laboratory, water and ammonia water were uniformly dispersed in ethanol under ultrasonication, wherein , the volume ratio of water, ammonia water and absolute ethanol is 2:1:25, the dispersion concentration of α- Fe 2 O 3 is 50 mg/100 mL, the mixture is poured into a 250 mL three-necked flask, and the temperature of the water bath is 25 Stir mechanically at ℃, then add 25 mg resorcinol and 54 μL formaldehyde solution, stir for 30 h, after the reaction is over, collect the precipitate by centrifugation, put it in a vacuum drying box at 60 ℃ for 12 h; then protect it in a tube furnace with argon gas Annealed at 750 °C for 5 h, the annealed sample was etched with 40 mL of hydrochloric acid (4 mol/L) for 30 min, washed twice with deionized water, and finally moved to a vacuum drying box at 60 °C for drying for 12 h, to obtain the sample of the present application. Ferric oxide is a nanomaterial with a core carbon box as a shell (Fe 3 O 4 @C).

(2) 制备片状MoSe2包覆核壳Fe3O4@ C：取0.80g的硒粉加入到10mL水合肼中，室温条件下搅拌5h，制得溶液A，取1.20 g的Na2MoO4∙2H2O加入到50mL的去离子水中，制得溶液B，在搅拌条件下，将溶液A加入到溶液B中，搅拌0.5h后，向上述溶液中加入5mL乙二胺，继续搅拌0.5h后，向其中加入150mg核壳Fe3O4@C超声1h。最后将溶液转入聚四氟乙烯内衬的不锈钢高压反应釜中，在220℃条件下反应22h，待反应冷却至室温后，将沉淀离心收集，随后用去离子水和乙醇洗涤数3次，最后置于真空干燥箱60℃烘干备用。然后在管式炉里氩气保护下750℃煅烧3h得到本实施例的片状硒化钼包覆以四氧化三铁为核碳盒为壳纳米复合材料Fe3O4@C/MoSe2。(2) Preparation of flake MoSe 2 -coated core-shell Fe 3 O 4 @ C: add 0.80 g of selenium powder to 10 mL of hydrazine hydrate, stir at room temperature for 5 h to prepare solution A, and take 1.20 g of Na 2 MoO 4∙ 2H 2 O was added to 50 mL of deionized water to prepare solution B. Under stirring conditions, solution A was added to solution B. After stirring for 0.5 h, 5 mL of ethylenediamine was added to the above solution, and the stirring was continued for 0.5 h. After h, 150 mg of core-shell Fe 3 O 4 @C was added thereto and sonicated for 1 h. Finally, the solution was transferred to a PTFE-lined stainless steel autoclave, and reacted at 220°C for 22 hours. After the reaction was cooled to room temperature, the precipitate was collected by centrifugation, and then washed with deionized water and ethanol for several times. Finally, it was placed in a vacuum drying oven for drying at 60°C for later use. Then, it was calcined at 750°C for 3 hours under argon protection in a tube furnace to obtain the flake molybdenum selenide-coated nanocomposite Fe 3 O 4 @C/MoSe 2 with Fe 3 O 4 @C/MoSe 2 as the core and carbon box as the shell of this example.

实施例3Example 3

(1) 制备核壳Fe3O4@ C：将实验室制得的80mg α-Fe2O3纳米立方体、水与氨水超声下均匀分散于乙醇，其中，水、氨水、无水乙醇的体积比为2：1：23，α-Fe2O3的分散浓度为50mg/100mL，将混合液倒入250 mL的三口烧瓶中，在水浴温度为35 ℃条件下机械搅拌，再加入75mg间苯二酚与160μL甲醛溶液，搅拌24h，待反应结束后，将水沉淀离心收集，置于真空干燥箱中60 ℃干燥12h。然后在管式炉氩气保护下720℃退火4h，将退火后的样品用40 mL盐酸(4 mol/L)刻蚀30min，用去离子水洗涤3次，最后移至真空干燥箱60 ℃干燥12h，得到本实用施的以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料。(1) Preparation of core-shell Fe 3 O 4 @ C: 80 mg of α- Fe 2 O 3 nanocubes, water and ammonia water obtained in the laboratory were uniformly dispersed in ethanol under ultrasonication. Among them, the volume of water, ammonia water and anhydrous ethanol The ratio is 2:1:23, and the dispersion concentration of α- Fe 2 O 3 is 50 mg/100 mL. Pour the mixture into a 250 mL three-necked flask, stir mechanically at a water bath temperature of 35 °C, and then add 75 mg of m-benzene. Diphenol and 160 μL formaldehyde solution were stirred for 24 h. After the reaction was over, the water precipitate was collected by centrifugation, and dried in a vacuum drying box at 60 °C for 12 h. Then annealed at 720 °C for 4 h under the protection of argon in a tube furnace, the annealed samples were etched with 40 mL of hydrochloric acid (4 mol/L) for 30 min, washed with deionized water for 3 times, and finally moved to a vacuum drying box to dry at 60 °C After 12 h, the nanomaterial with Fe 3 O 4 @C as the core and the carbon box as the shell (Fe 3 O 4 @C) used in the present application was obtained.

(2) 制备片状MoSe2包覆核壳Fe3O4@ C：取0.10g的硒粉加入到10mL水合肼中，室温条件下搅拌5h，制得溶液A，取0.16g的Na2MoO4∙2H2O加入到50mL的去离子水中，制得溶液B，在搅拌条件下，将溶液A加入到溶液B中，搅拌0.5h后，向上述溶液中加入5mL乙二胺，继续搅拌0.5h后，向其中加入60mg核壳Fe3O4@C超声1h。最后将溶液转入聚四氟乙烯内衬的不锈钢高压反应釜中，在230℃条件下反应24h，待反应冷却至室温后，将沉淀离心收集，随后用去离子水和乙醇洗涤3次，最后置于真空干燥箱60℃烘干备用。然后在管式炉里氩气保护下750℃煅烧3h得到本实施例的片状硒化钼包覆以四氧化三铁为核碳盒为壳纳米复合材料Fe3O4@C/MoSe2。(2) Preparation of sheet-like MoSe 2 -coated core-shell Fe 3 O 4 @ C: add 0.10 g of selenium powder to 10 mL of hydrazine hydrate, stir at room temperature for 5 h to prepare solution A, and take 0.16 g of Na 2 MoO 4∙ 2H 2 O was added to 50 mL of deionized water to prepare solution B. Under stirring conditions, solution A was added to solution B. After stirring for 0.5 h, 5 mL of ethylenediamine was added to the above solution, and the stirring was continued for 0.5 h. After h, 60 mg of core-shell Fe 3 O 4 @C was added thereto and sonicated for 1 h. Finally, the solution was transferred to a PTFE-lined stainless steel autoclave, and the reaction was carried out at 230 °C for 24 h. After the reaction was cooled to room temperature, the precipitate was collected by centrifugation, and then washed with deionized water and ethanol for 3 times. Dry in a vacuum drying oven at 60°C for later use. Then, it was calcined at 750°C for 3 hours under argon protection in a tube furnace to obtain the flake molybdenum selenide-coated nanocomposite Fe 3 O 4 @C/MoSe 2 with Fe 3 O 4 @C/MoSe 2 as the core and carbon box as the shell of this example.

对比例1：Comparative Example 1:

在实施例1基础上，省略步骤2）直接制备核壳Fe3O4@ C纳米材料。On the basis of Example 1, step 2) was omitted to directly prepare core-shell Fe 3 O 4 @C nanomaterials.

对比例2：Comparative Example 2:

在实施例1基础上，将步骤1）中的核壳Fe3O4@ C全部刻蚀形成空心C盒，步骤2）中核壳Fe3O4@ 换成空心C盒，制备C/MoSe2纳米材料。On the basis of Example 1, the core-shell Fe 3 O 4 @ C in step 1) was all etched to form a hollow C box, and the core-shell Fe 3 O 4 @ in step 2) was replaced with a hollow C box to prepare C/MoSe 2 nanomaterials.

二、制备电池：2. Prepare the battery:

本实施例中以实施例1和对比例1、2得到的复合材料作为锂离子电池负极进行锂离子电池组装。In this example, the composite materials obtained in Example 1 and Comparative Examples 1 and 2 were used as the negative electrode of the lithium ion battery to assemble the lithium ion battery.

以NMP（N-甲基吡咯烷酮）为溶剂，将制备好的Fe3O4@C/MoSe2复合材料作为活性物质，乙炔黑作为导电剂，PVDF（聚偏氟乙烯）作为粘结剂，三种物质的质量比为7:2:1，磁力搅拌8 h制得浆料，再将浆料均匀涂覆在铜箔表面，转至真空干燥箱内在120 ℃下干燥12 h，取出后用裁片机剪切成一定大小的圆形电极片。用分析天平对圆形电极片称重，计算活性物质的量，然后将其与电池壳等配件置于手套箱中，在氩气条件下组装电池。Using NMP (N-methylpyrrolidone) as the solvent, the prepared Fe 3 O 4 @C/MoSe 2 composite was used as the active material, acetylene black as the conductive agent, PVDF (polyvinylidene fluoride) as the binder, and three The mass ratio of these substances was 7:2:1, and the slurry was prepared by magnetic stirring for 8 h. Then, the slurry was evenly coated on the surface of the copper foil, and then transferred to a vacuum drying oven and dried at 120 °C for 12 h. The chip machine is cut into circular electrode sheets of a certain size. The circular electrode sheet was weighed with an analytical balance, the amount of active material was calculated, and then it was placed in a glove box with accessories such as the battery case, and the battery was assembled under argon atmosphere.

同时，以同样方法，分别以Fe3O4@C、C/MoSe2为负极材料进行电池的组装，并在同等测试条件下进行循环性能和倍率性能的测试。At the same time, in the same way, the batteries were assembled with Fe 3 O 4 @C and C/MoSe 2 as negative electrode materials, respectively, and the cycle performance and rate performance were tested under the same test conditions.

三、产物特性分析3. Analysis of product characteristics

图1所示为本实施例1制备的α-Fe2O3纳米立方体、核壳Fe3O4@C和Fe3O4@C/MoSe2复合材料的扫描电镜图。由图1(a)可以清晰地看出α-Fe2O3是立方体结构，直径约为400 nm。图1(b)为Fe3O4@C复合材料的SEM图，图中可以明显看出以四氧化三铁为核碳盒为壳的核壳结构（Fe3O4@C）。从图1(c)可看出硒化钼以纳米片的形态包覆在核壳结构外部且经过高温煅烧Fe3O4@C/MoSe2复合材料仍然继承了前驱体的核壳结构，但因为硒化钼纳米片包覆在Fe3O4@C表面将其核壳结构掩盖，所以Fe3O4@C/MoSe2呈现不规则结构。FIG. 1 shows the scanning electron microscope images of α -Fe 2 O 3 nanocubes, core-shell Fe 3 O 4 @C and Fe 3 O 4 @C/MoSe 2 composites prepared in Example 1. FIG. It can be clearly seen from Fig. 1(a) that α- Fe 2 O 3 is a cubic structure with a diameter of about 400 nm. Figure 1(b) is the SEM image of the Fe 3 O 4 @C composite material, and the core-shell structure (Fe 3 O 4 @C) with Fe 3 O 4 @C as the core and carbon box as the shell can be clearly seen. It can be seen from Fig. 1(c) that MoSe is coated on the outside of the core-shell structure in the form of nanosheets and the Fe 3 O 4 @C/MoSe 2 composite still inherits the core-shell structure of the precursor after high temperature calcination, but Fe 3 O 4 @C/MoSe 2 presents an irregular structure because MoSe nanosheets cover the surface of Fe 3 O 4 @C to cover its core-shell structure.

图2为本实施例1制备的α-Fe2O3纳米立方体、核壳Fe3O4@C和Fe3O4@C /MoSe2复合材料透射电镜图。由图2(a)可以清晰地看出制备的α-Fe2O3是实心立方体结构。图2(b)为Fe3O4@C复合材料的TEM图，可以明显看出以四氧化三铁为核碳盒为壳的核壳结构。从图2(c)中可清晰的看到硒化钼纳米片均匀包覆在Fe3O4@C表面。FIG. 2 is a transmission electron microscope image of the α- Fe 2 O 3 nanocube, core-shell Fe 3 O 4 @C and Fe 3 O 4 @C /MoSe 2 composites prepared in Example 1. FIG. It can be clearly seen from Fig. 2(a) that the prepared α- Fe 2 O 3 has a solid cubic structure. Figure 2(b) is the TEM image of the Fe 3 O 4 @C composite material, and it can be clearly seen that the core-shell structure with ferric tetroxide as the core and carbon box as the shell. It can be clearly seen from Fig. 2(c) that the MoSe nanosheets are uniformly coated on the surface of Fe 3 O 4 @C.

图3为实施例1和对比例1、2制备的Fe3O4@C/MoSe2 、Fe3O4@C和C/MoSe2复合材料的XRD谱图。在Fe3O4@C/MoSe2中，我们没有观察到Fe3O4的特征峰，这是由于Fe3O4被包在最里面。而Fe3O4@C/MoSe2复合材料中，2θ分别为31.07°、37.78°以及55.43°处有3个明显的特征衍射峰，它们分别对应于MoSe2的(100)、(103)和(110)晶面，与MoSe2的标准PDF卡片(JCPDScard no. 29-0914)完美匹配。3 is the XRD patterns of Fe 3 O 4 @C/MoSe 2 , Fe 3 O 4 @C and C/MoSe 2 composite materials prepared in Example 1 and Comparative Examples 1 and 2. FIG. In Fe 3 O 4 @C/MoSe 2 , we do not observe the characteristic peaks of Fe 3 O 4 , which is due to the fact that Fe 3 O 4 is encapsulated at the innermost. In the Fe 3 O 4 @C/MoSe 2 composite, there are three distinct characteristic diffraction peaks at 2θ of 31.07°, 37.78° and 55.43°, which correspond to (100), (103) and (103) of MoSe 2 , respectively. (110) crystal plane, which perfectly matches the standard PDF card of MoSe 2 (JCPDScard no. 29-0914).

图4为实施例1和对比例1、2制备的Fe3O4@C/MoSe2 、Fe3O4@C和C/MoSe2复合材料作为锂离子电池负极在100 mA g-1的电流密度下分别循环70圈，电压区间为0.01~3 V的循环性能测试图。由图5可以明显看出Fe3O4@C/MoSe2复合材料具有比Fe3O4@C、C/MoSe2更高的比容量，循环70圈后，容量依旧保持在878 mAhg-1，而Fe3O4@C、C/MoSe2电极的容量只有559mAhg-1和606mAhg-1。因而，Fe3O4@C/MoSe2复合材料具有良好的循环稳定性。Figure 4 shows the current at 100 mA g -1 of Fe 3 O 4 @C/MoSe 2 , Fe 3 O 4 @C and C/MoSe 2 composite materials prepared in Example 1 and Comparative Examples 1 and 2 as negative electrodes of lithium ion batteries Cycling performance test chart of 70 cycles under the density, and the voltage range is 0.01~3 V. It can be clearly seen from Figure 5 that the Fe3O4@C/MoSe2 composite has a higher specific capacity than Fe3O4@C and C/MoSe2. After 70 cycles, the capacity still remains at 878 mAhg-1, while Fe3O4@C, C/MoSe2 The capacities of MoSe2 electrodes are only 559mAhg-1 and 606mAhg-1. Therefore, the Fe3O4@C/MoSe2 composite has good cycling stability.

图5为实施例1和对比例1、2制备的Fe3O4@C/MoSe2 、Fe3O4@C和C/MoSe2复合材料作为锂离子电池负极在不同电流密度下的倍率性能测试图，电压区间为0.01~3.0 V。当充放电的电流密度为100 mA g-1、200 mA g-1、500 mA g-1、1000 mA g-1、2000 mA g-1、5000 mA g-1时，相比对比材料，它的放电容量分别基本平稳保持在1006 mAh g-1、886 mAh g-1、796mAh g-1、716 mAh g-1、665 mAh g-1、553 mAh g-1。当电流密度回到100 mA g-1时，它的放电容量能够平稳回到944 mAh g-1，说明采用本发明方法制备的Fe3O4@C/MoSe2复合材料具有优异的倍率性能以及良好的可逆性。Figure 5 shows the rate performance of Fe 3 O 4 @C/MoSe 2 , Fe 3 O 4 @C and C/MoSe 2 composites prepared in Example 1 and Comparative Examples 1 and 2 as negative electrodes for lithium ion batteries at different current densities Test chart, the voltage range is 0.01~3.0 V. When the charge-discharge current densities are 100 mA g -1 , 200 mA g -1 , 500 mA g -1 , 1000 mA g -1 , 2000 mA g -1 , 5000 mA g -1 , compared to the comparative material, it The discharge capacities of 1006 mAh g -1 , 886 mAh g -1 , 796 mAh g -1 , 716 mAh g -1 , 665 mAh g -1 , and 553 mAh g -1 , respectively, were basically stable. When the current density returns to 100 mA g -1 , its discharge capacity can smoothly return to 944 mAh g -1 , indicating that the Fe 3 O 4 @C/MoSe 2 composite prepared by the method of the present invention has excellent rate performance and Good reversibility.

Claims (8)

1.一种纳米复合材料的制备方法，其特征在于，以α-Fe2O3立方体为模板，在其表面原位包覆酚醛树脂，经退火处理形成碳包覆四氧化三铁立方体，再用盐酸部分刻蚀形成以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料；接着通过水热反应在碳壳原位包覆硒化钼，退火后制得片状硒化钼包覆以四氧化三铁为核碳盒为壳纳米复合材料Fe3O4@C/MoSe2。1. a preparation method of nano-composite material, it is characterized in that, with α- Fe 2 O 3 cube is template, in-situ coating phenolic resin on its surface, through annealing treatment, form carbon-coated iron tetroxide cube, then Partially etched with hydrochloric acid to form nanomaterials with iron tetroxide as the core and carbon box as the shell (Fe 3 O 4 @C); then the carbon shell was in situ coated with molybdenum selenide by hydrothermal reaction, and the sheet was obtained after annealing Fe 3 O 4 @C/MoSe 2 nanocomposites with Fe 3 O 4 @C/MoSe 2 coated with ferric oxide as the core and carbon box as the shell. 2.权利要求1所述的纳米复合材料的制备方法，其特征在于，具体制备方法包含以下步骤：2. the preparation method of nanocomposite material according to claim 1, is characterized in that, concrete preparation method comprises the following steps: 第1步，制备核壳结构的Fe3O4@ C：以α-Fe2O3立方体为模板，将α-Fe2O3纳米立方体分散于体积比为（2～2.5）：1：（20～25）水、氨水和无水乙醇的混合液中，其中α-Fe2O3在混合液中的分散浓度为50 mg/100mL，将分散液于25～35℃水浴温度下机械搅拌，分散均匀，再加入间苯二酚与甲醛的混合溶液，继续恒温搅拌20～30 h，反应结束后，离心收集沉淀固相，将固相真空干燥后，于氩气保护下退火处理，再将退火后的固相用盐酸刻蚀25～35min，然后离心分离出刻蚀后的固相，用去离子水洗涤2或3次后真空干燥，得到以四氧化三铁为核碳盒为壳（Fe3O4@C）的纳米材料；Step 1, preparation of Fe 3 O 4 @C with core-shell structure: using α- Fe 2 O 3 cubes as templates, disperse α- Fe 2 O 3 nanocubes in a volume ratio of (2～2.5): 1:( 20～25) In the mixed solution of water, ammonia water and absolute ethanol, the dispersion concentration of α- Fe 2 O 3 in the mixed solution is 50 mg/100 mL, and the dispersion solution is mechanically stirred at 25～35 ℃ water bath temperature, Disperse uniformly, then add the mixed solution of resorcinol and formaldehyde, continue to stir at constant temperature for 20-30 h, after the reaction, collect the precipitated solid phase by centrifugation, vacuum dry the solid phase, anneal under argon protection, and then The annealed solid phase was etched with hydrochloric acid for 25 to 35 minutes, and then the etched solid phase was separated by centrifugation, washed with deionized water for 2 or 3 times, and then vacuum-dried to obtain a carbon box with ferric tetroxide as the core as the shell ( Fe 3 O 4 @C) nanomaterials; 第2步，制备片状MoSe2包覆核壳Fe3O4@ C：将硒粉与水合肼混合，室温条件下搅拌3～5h，得到溶液A，将 Na2MoO4∙2H2O与去离子水中混合，制得溶液B，在搅拌条件下，将溶液A混入到溶液B中，搅拌0.5～1h后，向上述溶液中加入乙二胺，继续搅拌0.5～1h后，加入步骤1制备的核壳Fe3O4@C纳米材料，超声振动0.5～1h，最后将溶液转入聚四氟乙烯内衬的不锈钢高压反应釜中水热反应，待反应冷却至室温后，离心收集沉淀物，依次用去离子水和乙醇洗涤后置于真空干燥箱内烘干处理，然后在管式炉里氩气保护下煅烧得到Fe3O4@C/MoSe2。The second step, preparation of sheet-like MoSe 2 -coated core-shell Fe 3 O 4 @ C: Mix selenium powder with hydrazine hydrate, and stir at room temperature for 3-5 h to obtain solution A, where Na 2 MoO 4∙ 2H 2 O is mixed with Mix with deionized water to prepare solution B, under stirring condition, mix solution A into solution B, stir for 0.5-1 h, add ethylenediamine to the above solution, continue stirring for 0.5-1 h, add step 1 to prepare The core-shell Fe3O4@C nanomaterials were ultrasonically vibrated for 0.5 to 1 h, and finally the solution was transferred to a PTFE-lined stainless steel autoclave for hydrothermal reaction. After the reaction was cooled to room temperature, the precipitates were collected by centrifugation. After washing with deionized water and ethanol, it was dried in a vacuum drying oven, and then calcined in a tube furnace under argon protection to obtain Fe 3 O 4 @C/MoSe 2 . 3.根据权利要求2所述的纳米复合材料的制备方法，其特征在于，第1步中， α-Fe2O3、间苯二酚和甲醛的投料比例按物质的量为：70～200：95：1 。3. The preparation method of nanocomposite material according to claim 2, is characterized in that, in the 1st step, the feeding ratio of α- Fe 2 O 3 , resorcinol and formaldehyde according to the amount of matter is: 70～200 :95:1. 4.根据权利要求2所述的纳米复合材料，其特征在于，第1步中，刻蚀用盐酸的浓度为4mol/L。4 . The nanocomposite material according to claim 2 , wherein in the first step, the concentration of hydrochloric acid for etching is 4 mol/L. 5 . 5.根据权利要求2所述的纳米复合材料的制备方法其特征在于，第1步中，退火温度为700~750 ℃，退火时间为3~5 h，真空干燥温度为60 ℃，真空干燥时间为12 h。5. The preparation method of nanocomposite material according to claim 2 is characterized in that, in the first step, the annealing temperature is 700～750 ℃, the annealing time is 3～5 h, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 60 ℃. for 12 hours. 6.根据权利要求1所述的纳米复合材料的制备方法，其特征在于，第2步中，硒粉和水合肼的投料比为1.6g～8.0g/100mL，Na2MoO4∙2H2O和去离子水的投料比例为：0.32 g～2.4g/100mL；溶液A和溶液B混合时，按硒粉和Na2MoO4∙2H2O摩尔比为2：1，硒粉和乙二胺的投料比为3.2g～24g/100mL；所述硒粉和核壳Fe3O4@C质量比为6～2:1。6. The preparation method of nanocomposite material according to claim 1, wherein in the second step, the feeding ratio of selenium powder and hydrazine hydrate is 1.6g～8.0g/100mL, Na 2 MoO 4∙ 2H 2 O The feeding ratio with deionized water is: 0.32 g ~ 2.4 g/100mL; when solution A and solution B are mixed, the molar ratio of selenium powder and Na 2 MoO 4∙ 2H 2 O is 2:1, selenium powder and ethylenediamine The feeding ratio of the selenium powder is 3.2g-24g/100mL; the mass ratio of the selenium powder and the core-shell Fe 3 O 4 @C is 6-2:1. 7.根据权利要求1所述的纳米复合材料的制备方法，其特征在于，第2步中，水热温度为220~240℃，水热反应时间为22~24 h，真空干燥温度为60 ℃，真空干燥时间为12 h，退火温度为700~750 ℃，退火时间为2~3h。7. The preparation method of nanocomposite material according to claim 1, is characterized in that, in the 2nd step, the hydrothermal temperature is 220～240 ℃, the hydrothermal reaction time is 22～24 h, and the vacuum drying temperature is 60 ℃ , the vacuum drying time is 12 h, the annealing temperature is 700~750 ℃, and the annealing time is 2~3 h. 8.一种采用权利要求1-7任项所述的纳米复合材料制备的锂离子电极负极材料，其特征在于，包括质量配比为7:2:1的Fe3O4@C/MoSe2、乙炔黑导电剂和PVDF粘结剂。8. a lithium ion electrode negative material prepared by adopting the nanocomposite material described in any one of claims 1-7, is characterized in that, comprising the Fe 3 O 4 @C/MoSe 2 that the mass ratio is 7:2:1 , acetylene black conductive agent and PVDF binder.
CN202210165549.0A 2022-02-23 2022-02-23 Preparation method of nano composite material and lithium ion electrode negative electrode material thereof Pending CN114551832A (en)

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CN114759164A (en) * 2022-06-13 2022-07-15 新乡市中天新能源科技股份有限公司 Preparation method and application of lithium battery negative plate
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CN115911286B (en) * 2022-10-27 2024-10-01 哈尔滨理工大学 Preparation method and application of iron selenide/molybdenum selenide heterostructure electrode material
CN115722666A (en) * 2022-12-02 2023-03-03 南京大学 Preparation method of carbon-coated nano zero-valent iron material with core-shell stable structure
CN117756186A (en) * 2023-12-25 2024-03-26 齐齐哈尔大学 Preparation method of a doped carbon-coated molybdate-based ferroferrite flower-like composite material with controllable morphology

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