CN110627031A - A kind of preparation method of molybdenum-doped cobalt phosphide carbon coral sheet composite material - Google Patents

A kind of preparation method of molybdenum-doped cobalt phosphide carbon coral sheet composite material Download PDF

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CN110627031A
CN110627031A CN201910910982.0A CN201910910982A CN110627031A CN 110627031 A CN110627031 A CN 110627031A CN 201910910982 A CN201910910982 A CN 201910910982A CN 110627031 A CN110627031 A CN 110627031A
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molybdenum
composite material
sheet composite
deionized water
carbon
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陶石
孙硕
谢天欢
钱斌
吴大军
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Changshu Institute of Technology
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Abstract

The invention discloses a preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material. The method has simple steps and mild conditions, is convenient for industrial large-scale production, and the prepared nano coral sheet has high structural stability and electronic conductivity, is applied to lithium ion battery electrodes, and has excellent rate capability and cycle performance.

Description

一种钼掺杂磷化钴碳珊瑚片复合材料的制备方法A kind of preparation method of molybdenum-doped cobalt phosphide carbon coral sheet composite material

技术领域technical field

本发明涉及一种锂离子电池材料领域的磷化钴碳复合材料的制备方法，特别是涉及一种钼掺杂磷化钴碳珊瑚片复合材料的制备方法。The invention relates to a preparation method of a cobalt phosphide carbon composite material in the field of lithium ion battery materials, in particular to a preparation method of a molybdenum-doped cobalt phosphide carbon coral sheet composite material.

背景技术Background technique

锂离子电池在当今世界收到了越来越多的关注，并且它已经成为了21世纪以来最具发展潜力的化学能源之一,锂离子电池由于能量密度高、循环寿命长、安全性高、无污染和高功率等特点，被广泛应用于混合动力汽车以及便携式电子设备。锂离子电池的负极材料是其重要的组成部分，影响着电化学性能的主要瓶颈之一。然而，目前商品化的锂离子电池的负极材料为石墨类材料，理论容量仅为372mAh g-1，且在大倍率充放电过程中存在严重的安全问题，已无法满足人们日益增长的需求，特别是在新能源汽车动力电池。因此研究和开发新型负极材料至关重要。Lithium-ion batteries have received more and more attention in today's world, and it has become one of the most potential chemical energy sources since the 21st century. Lithium-ion batteries have high energy density, long cycle life, high safety, and no Pollution and high power characteristics, are widely used in hybrid vehicles and portable electronic devices. The anode material of lithium-ion battery is an important part of it, which affects one of the main bottlenecks of electrochemical performance. However, the anode material of commercial lithium-ion batteries is graphite-based materials, the theoretical capacity is only 372mAh g -1 , and there are serious safety problems in the process of high-rate charge and discharge, which can no longer meet the growing needs of people, especially It is in the power battery of new energy vehicles. Therefore, it is very important to research and develop new anode materials.

过渡金属磷化物材料由于具有较高的理论可逆比容量、资源丰富和导电性良好等特点，已成为近年来能源化工领域的研究热点之一。其中，磷化钴具有较高的理论比容量，组成元素无毒以及成本较低，被广泛地作为锂离子电池负极材料而研究。然而，其在充放电过程中引起的较大的体积变化造成循环稳定性差和倍率性能低，限制其进一步的发展。通过掺杂金属是被认为是一种有效的改善途径，Wang等人(Electrochim Acta.,2019,301,319-324)利用制备出Mo-Li2ZnTi3O8纳米颗粒嵌入三维多孔石墨烯复合材料，在电流密度为2A g-1电流密度下循环300圈后还表现出210mAh g-1的可逆比容量。Xia等人(Front Mater,2019,6,00001)合成出Mo-TiO2纳米颗粒包覆在一维碳网络复合材料，在电流密度为850mAg-1电流密度下表现出449.2mAh g-1的可逆比容量。公开号为CN105161700A的中国专利公开了一种三氧化钼包覆钼掺杂二氧化钛纳米颗粒的制备方法，采用一步火焰喷雾燃烧技术，快速连续化制备三氧化钼包覆钼掺杂二氧化钛纳米复合颗粒材料，这种三氧化钼包覆钼掺杂二氧化钛纳米颗粒由于其纳米尺度小，导致其振实密度低，且比表面积小，作为锂离子电池负极材料容量比较低。公开号为CN109148843A的中国专利公开了一种具有良好高温性能的硼掺杂负极材料及其固相制备方法，以硼氧化合物为掺杂剂，直接通过固相反应一步使硼氧化合物在高温下分解产生氧化硼，控制氧化硼与负极材料表面进行反应，通过表面改性，一方面能够通过硼的催化作用，减少负极材料的表面缺陷，提高其石墨化度；另一方面能够通过氧化硼与负极材料表面的复合反应，减少负极材料的表面缺陷，但是，该制备方法利用非金属掺杂，由于其改性难度大，所以此材料作为锂离子电池负极材料不具有优势，循环稳定性和倍率性能会受到很大的限制。Transition metal phosphide materials have become one of the research hotspots in the field of energy and chemical industry in recent years due to their high theoretical reversible specific capacity, abundant resources and good electrical conductivity. Among them, cobalt phosphide has a high theoretical specific capacity, non-toxic constituent elements and low cost, and has been widely studied as an anode material for lithium-ion batteries. However, the large volume change caused by it during the charge-discharge process leads to poor cycle stability and low rate performance, which limits its further development. Doping metal is considered to be an effective way to improve. Wang et al. (Electrochim Acta., 2019, 301, 319-324) prepared Mo-Li 2 ZnTi 3 O 8 nanoparticles embedded in three-dimensional porous graphene composites, It also exhibited a reversible specific capacity of 210mAh g -1 after 300 cycles at a current density of 2A g -1 . Xia et al. (Front Mater, 2019, 6, 00001) synthesized a one-dimensional carbon network composite material coated with Mo-TiO 2 nanoparticles, which exhibited a reversible flow rate of 449.2mAh g -1 at a current density of 850mAg -1 Specific capacity. The Chinese patent with the publication number CN105161700A discloses a method for preparing molybdenum trioxide-coated molybdenum-doped titanium dioxide nanoparticles, using a one-step flame spray combustion technology to rapidly and continuously prepare molybdenum trioxide-coated molybdenum-doped titanium dioxide nanocomposite particle materials , the molybdenum trioxide-coated molybdenum-doped titanium dioxide nanoparticles have a small nanoscale, resulting in low tap density and small specific surface area, and their capacity as a negative electrode material for lithium-ion batteries is relatively low. The Chinese patent with the publication number CN109148843A discloses a boron-doped negative electrode material with good high-temperature performance and its solid-phase preparation method. The boron-oxygen compound is used as a dopant, and the boron-oxygen compound is directly made in one step by solid-state reaction at high temperature. Decompose to produce boron oxide, and control the reaction between boron oxide and the surface of the negative electrode material. Through surface modification, on the one hand, the catalytic effect of boron can reduce the surface defects of the negative electrode material and improve its graphitization degree; The recombination reaction on the surface of the negative electrode material reduces the surface defects of the negative electrode material. However, this preparation method uses non-metallic doping. Due to the difficulty in modification, this material does not have advantages as a negative electrode material for lithium-ion batteries. Cycle stability and rate Performance will be greatly limited.

发明内容Contents of the invention

本发明的目的针对上述问题，提出了一种钼掺杂磷化钴碳珊瑚片复合材料的制备方法，制备出磷化钴纳米片，具有较大的振实密度和比表面积。作为锂离子电池负极材料表现出优异的倍率性能和循环稳定性。In view of the above problems, the object of the present invention proposes a method for preparing a molybdenum-doped cobalt phosphide carbon coral sheet composite material, and prepares cobalt phosphide nanosheets with large tap density and specific surface area. As an anode material for lithium-ion batteries, it exhibits excellent rate capability and cycle stability.

本发明的技术方案是这样的：一种钼掺杂磷化钴碳珊瑚片复合材料的制备方法，包括：The technical scheme of the present invention is as follows: a method for preparing molybdenum-doped cobalt phosphide carbon coral sheet composite material, comprising:

步骤1、将含有2-甲基咪唑的水溶液快速倒入到硝酸钴水溶液中进行搅拌，静置反应后，取出沉淀物，用去离子水清洗后进行60～80℃真空干燥得到MOF-Co材料；Step 1. Quickly pour the aqueous solution containing 2-methylimidazole into the cobalt nitrate aqueous solution for stirring. After standing for the reaction, take out the precipitate, wash it with deionized water, and dry it under vacuum at 60-80°C to obtain the MOF-Co material ;

步骤2、将MOF-Co材料加入到含有钼酸铵的乙醇/去离子水混合溶液中，搅拌后将溶液放置在80～85℃的浴锅中反应，离心得沉淀再清洗后进行60～80℃真空干燥得前驱体，所述MOF-Co材料与钼酸铵质量比为2︰1～1︰2；Step 2. Add the MOF-Co material to the ethanol/deionized water mixed solution containing ammonium molybdate. After stirring, place the solution in a bath pot at 80-85°C to react, centrifuge to obtain a precipitate and then wash it for 60-80 The precursor is obtained by vacuum drying at ℃, and the mass ratio of the MOF-Co material to ammonium molybdate is 2:1～1:2;

步骤3、将步骤2制得前驱体放入刚玉舟的末端，次磷酸钠放入刚玉舟的前端，后放入管式炉中，在氮气气氛下以1.5～2℃/min速度升温到350～400℃保温2～2.5小时，得到钼掺杂磷化钴碳珊瑚片复合材料。Step 3. Put the precursor obtained in step 2 into the end of the corundum boat, put the sodium hypophosphite into the front end of the corundum boat, and then put it into the tube furnace, and raise the temperature to 350 °C at a rate of 1.5-2 °C/min under a nitrogen atmosphere. Heat preservation at ~400°C for 2 to 2.5 hours to obtain molybdenum-doped cobalt phosphide carbon coral flake composite material.

进一步地，所述步骤3中所述前驱体与次磷酸钠的质量比为1︰15～1︰25。Further, the mass ratio of the precursor to sodium hypophosphite in the step 3 is 1:15˜1:25.

进一步地，所述2-甲基咪唑的水溶液的浓度为0.3～0.4M，所述硝酸钴水溶液的浓度为0.04～0.05M。Further, the concentration of the 2-methylimidazole aqueous solution is 0.3-0.4M, and the concentration of the cobalt nitrate aqueous solution is 0.04-0.05M.

进一步地，所述步骤2中乙醇/去离子水的比例为1︰3～1︰4。Further, the ratio of ethanol/deionized water in step 2 is 1:3˜1:4.

进一步地，所述步骤1中静置反应的时间不少于4小时，所述步骤2中浴锅中反应时间不少于1小时。Further, the standing reaction time in the step 1 is not less than 4 hours, and the reaction time in the bath in the step 2 is not less than 1 hour.

本发明所提供的技术方案的有益效果是，采用钼离子修饰钴基金属有机化合物为前驱体，再通过低温磷化法来实现钼掺杂磷化钴纳米珊瑚片的形成。其中2-甲基咪唑作为有机配体与钴离子结合形成金属有机化合物前驱体，磷化处理过程中，2-甲基咪唑会原位热解形成氮掺杂碳，能够极大的提高了复合材料的结构稳定性和电子导电性。采用本发明方法合成的纳米珊瑚片均匀分布，表现出优异的电化学性能。本发明制备方法，其步骤简单，条件温和，便于工业化大规模生产。The beneficial effect of the technical solution provided by the present invention is that molybdenum ions are used to modify the cobalt-based metal organic compound as a precursor, and then the formation of molybdenum-doped cobalt phosphide nano-coral flakes is realized by a low-temperature phosphating method. Among them, 2-methylimidazole is used as an organic ligand to combine with cobalt ions to form a metal-organic compound precursor. During the phosphating process, 2-methylimidazole will be pyrolyzed in situ to form nitrogen-doped carbon, which can greatly improve the recombination process. Structural stability and electronic conductivity of materials. The nano-coral flakes synthesized by the method of the invention are uniformly distributed and exhibit excellent electrochemical properties. The preparation method of the present invention has simple steps and mild conditions, and is convenient for large-scale industrial production.

附图说明Description of drawings

图1为实施例1钼掺杂磷化钴碳珊瑚片复合材料的SEM图。Fig. 1 is the SEM image of the molybdenum-doped cobalt phosphide carbon coral flake composite material in Example 1.

图2为实施例1钼掺杂磷化钴碳珊瑚片复合材料的XRD图。Fig. 2 is the XRD diagram of the molybdenum-doped cobalt phosphide carbon coral flake composite material in Example 1.

图3为实施例1钼掺杂磷化钴碳珊瑚片复合材料的TEM图。3 is a TEM image of the molybdenum-doped cobalt phosphide carbon coral sheet composite material in Example 1.

图4为实施例1钼掺杂磷化钴碳珊瑚片复合材料的倍率性能图。Fig. 4 is a graph of the rate performance of the molybdenum-doped cobalt phosphide carbon coral flake composite material in Example 1.

图5为实施例1钼掺杂磷化钴碳珊瑚片复合材料的循环性能图。Fig. 5 is the cycle performance diagram of the molybdenum-doped cobalt phosphide carbon coral sheet composite material in Example 1.

具体实施方式Detailed ways

下面结合实施例对本发明作进一步说明，但不作为对本发明的限定。The present invention will be further described below in conjunction with the examples, but not as a limitation of the present invention.

实施例1Example 1

取1.3136g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.582g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 1.3136g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.582g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.2g钼酸铵的乙醇/去离子水(1︰4，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在85℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:4, 100ml) containing 0.2g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 85°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰20放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以1.5℃/min升温至350℃保持2h，冷却后收集黑色粉末即为目标产物。其SEM、XRD和TEM见图1、2和3。Put the precursor and sodium hypophosphite obtained above into the two ends of the corundum boat at a mass ratio of 1:20, the sodium hypophosphite is located upstream, the precursor is located downstream, and the temperature is raised to 350 °C at 1.5 °C/min for 2 hours in a nitrogen atmosphere. The black powder collected after cooling is the target product. Its SEM, XRD and TEM are shown in Figures 1, 2 and 3.

实施例2Example 2

取1.3136g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.582g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 1.3136g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.582g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.4g钼酸铵的乙醇/去离子水(1︰3，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在80℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:3, 100ml) containing 0.4g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 80°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰20放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以2℃/min升温至350℃保持2.5h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into the two ends of the corundum boat at a mass ratio of 1:20, the sodium hypophosphite is located upstream, the precursor is located downstream, and the temperature is raised to 350 °C at 2 °C/min for 2.5 hours in a nitrogen atmosphere. , the black powder collected after cooling is the target product.

实施例3Example 3

取1.3136g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.582g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 1.3136g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.582g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.1g钼酸铵的乙醇/去离子水(1︰4，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在80℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:4, 100ml) containing 0.1g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 80°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰15放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以1.5℃/min升温至350℃保持2.5h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into both ends of the corundum boat at a mass ratio of 1:15, sodium hypophosphite is located upstream, and the precursor is located downstream. In a nitrogen atmosphere, heat up to 350 °C at 1.5 °C/min and keep for 2.5 hours. , the black powder collected after cooling is the target product.

实施例4Example 4

取1.3136g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.582g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 1.3136g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.582g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.2g钼酸铵的乙醇/去离子水(1︰3，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在85℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:3, 100ml) containing 0.2g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 85°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰25放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以2℃/min升温至400℃保持2h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into the two ends of the corundum boat at a mass ratio of 1:25, the sodium hypophosphite is located upstream, the precursor is located downstream, and the temperature is raised to 400 °C at 2 °C/min for 2 hours in a nitrogen atmosphere. The black powder collected after cooling is the target product.

实施例5Example 5

取0.984g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.466g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 0.984g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.466g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.4g钼酸铵的乙醇/去离子水(1︰3，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在80℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:3, 100ml) containing 0.4g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 80°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰20放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以2℃/min升温至350℃保持2.5h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into the two ends of the corundum boat at a mass ratio of 1:20, the sodium hypophosphite is located upstream, the precursor is located downstream, and the temperature is raised to 350 °C at 2 °C/min for 2.5 hours in a nitrogen atmosphere. , the black powder collected after cooling is the target product.

实施例6Example 6

取1.23g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.524g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 1.23g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.524g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.1g钼酸铵的乙醇/去离子水(1︰4，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在80℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:4, 100ml) containing 0.1g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 80°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰15放入刚玉舟的两端，前驱***于上游，次磷酸钠位于下游，氮气气氛，以1.5℃/min升温至350℃保持2.5h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into both ends of the corundum boat at a mass ratio of 1:15, the precursor is located upstream, and the sodium hypophosphite is located downstream. In a nitrogen atmosphere, heat up to 350 °C at 1.5 °C/min and keep for 2.5 hours. , the black powder collected after cooling is the target product.

实施例7Example 7

取0.655g 2-甲基咪唑溶解到40ml的去离子水中得到溶液A，将0.29g六水合硝酸钴溶解到40ml的去离子水中得到溶液B，在搅拌的情况下将溶液A快速倒入溶液B中。室温搅拌10分钟后，静置反应4小时，取出沉淀物，用去离子水清洗三到四遍，后放入60～80℃真空干燥箱干燥得到MOF-Co材料。Dissolve 0.655g of 2-methylimidazole into 40ml of deionized water to obtain solution A, dissolve 0.29g of cobalt nitrate hexahydrate into 40ml of deionized water to obtain solution B, and quickly pour solution A into solution B while stirring middle. After stirring at room temperature for 10 minutes, let stand for reaction for 4 hours, take out the precipitate, wash it with deionized water three to four times, and put it into a vacuum oven at 60-80°C to dry to obtain the MOF-Co material.

将0.2g MOF-Co加入到含有0.4g钼酸铵的乙醇/去离子水(1︰3，100ml)混合溶液中，搅拌十分钟，然后将溶液放置在80℃的浴锅中反应1小时，离心得沉淀再清洗后60～80℃真空干燥得前驱体。Add 0.2g MOF-Co to the mixed solution of ethanol/deionized water (1:3, 100ml) containing 0.4g ammonium molybdate, stir for ten minutes, and then place the solution in a bath at 80°C for 1 hour, The precipitate was obtained by centrifugation, and then washed, and then vacuum-dried at 60-80° C. to obtain the precursor.

将上述得到的前驱体与次磷酸钠按质量比1︰20放入刚玉舟的两端，次磷酸钠位于上游，前驱***于下游，氮气气氛，以2℃/min升温至350℃保持2.5h，冷却后收集黑色粉末即为目标产物。Put the precursor and sodium hypophosphite obtained above into the two ends of the corundum boat at a mass ratio of 1:20, the sodium hypophosphite is located upstream, the precursor is located downstream, and the temperature is raised to 350 °C at 2 °C/min for 2.5 hours in a nitrogen atmosphere. , the black powder collected after cooling is the target product.

对上述实施例进行测试，具体如下：The above-mentioned embodiment is tested, specifically as follows:

将合成的样品(活性物质)、乙炔黑(导电剂)和PVDF(粘结剂)按着质量比7:2:1，在NMP中混合均匀，然后涂在铜箔上，并置于真空干燥箱中100℃干燥10小时。取出之后切成直径为12mm的电极圆片。以此作为负极片，将金属锂片作为对电极，聚丙烯微孔膜Celgard2400为隔膜，泡沫镍为填充物，电解液为1M的LiPF6/EC+DMC(体积比1:1)，在充满氩气保护的手套箱中组装CR2016型纽扣电池。采用LAND CT2001A型(武汉蓝电)多通道电池测试***测试，电压范围为0.01-3.0V之间，温度为室温。由实施例1的产物制得的电极得到的倍率性能图如图4所示，循环性能图如图5所示。由实施例1至5的产物制得的电极得到的倍率性能及循环性能如下表所示。The synthesized sample (active material), acetylene black (conductive agent) and PVDF (binder) were mixed uniformly in NMP at a mass ratio of 7:2:1, then coated on copper foil, and placed in vacuum to dry Dry in an oven at 100°C for 10 hours. After taking it out, cut it into electrode discs with a diameter of 12mm. Use this as the negative electrode sheet, use the metal lithium sheet as the counter electrode, the polypropylene microporous membrane Celgard2400 as the diaphragm, the nickel foam as the filler, and the electrolyte as 1M LiPF 6 /EC+DMC (volume ratio 1:1). A CR2016 button cell was assembled in an argon-protected glove box. Tested with LAND CT2001A (Wuhan Landian) multi-channel battery test system, the voltage range is between 0.01-3.0V, and the temperature is room temperature. The rate performance diagram obtained from the electrode prepared from the product of Example 1 is shown in FIG. 4 , and the cycle performance diagram is shown in FIG. 5 . The rate performance and cycle performance of the electrodes prepared from the products of Examples 1 to 5 are shown in the table below.

Claims (5)

1. A preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material is characterized by comprising the following steps:
step 1, quickly pouring an aqueous solution containing 2-methylimidazole into an aqueous solution of cobalt nitrate, stirring, standing for reaction, taking out a precipitate, washing with deionized water, and performing vacuum drying at 60-80 ℃ to obtain an MOF-Co material;
step 2, adding an MOF-Co material into an ethanol/deionized water mixed solution containing ammonium molybdate, stirring, placing the solution in a bath kettle at 80-85 ℃ for reaction, centrifuging to obtain a precipitate, cleaning, and performing vacuum drying at 60-80 ℃ to obtain a precursor, wherein the mass ratio of the MOF-Co material to the ammonium molybdate is 2: 1-1: 2;
and 3, putting the precursor prepared in the step 2 into the tail end of a corundum boat, putting sodium hypophosphite into the front end of the corundum boat, then putting the corundum boat into a tubular furnace, heating to 350-400 ℃ at the speed of 1.5-2 ℃/min under the nitrogen atmosphere, and preserving the heat for 2-2.5 hours to obtain the molybdenum-doped cobalt phosphide-carbon coral sheet composite material.
2. The preparation method of the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the mass ratio of the precursor to the sodium hypophosphite in step 3 is 1: 15-1: 25.
3. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the concentration of the aqueous solution of 2-methylimidazole is 0.3-0.4M, and the concentration of the aqueous solution of cobalt nitrate is 0.04-0.05M.
4. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the ratio of ethanol to deionized water in the step 2 is 1: 3 to 1: 4.
5. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the standing reaction time in the step 1 is not less than 4 hours, and the reaction time in the water bath kettle in the step 2 is not less than 1 hour.
CN201910910982.0A 2019-09-25 2019-09-25 A kind of preparation method of molybdenum-doped cobalt phosphide carbon coral sheet composite material Pending CN110627031A (en)

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