CN114628668B - FeP@NC with nitrogen-doped carbon as carrier and its preparation and application - Google Patents

FeP@NC with nitrogen-doped carbon as carrier and its preparation and application Download PDF

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CN114628668B
CN114628668B CN202011455750.XA CN202011455750A CN114628668B CN 114628668 B CN114628668 B CN 114628668B CN 202011455750 A CN202011455750 A CN 202011455750A CN 114628668 B CN114628668 B CN 114628668B
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李先锋
王灿沛
郑琼
张华民
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Dalian Institute of Chemical Physics of CAS
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Abstract

一种氮掺杂碳为载体的FeP@NC颗粒及其制备方法和应用，通过对聚合物纳米颗粒的原位磷化/碳化，合成了FeP纳米颗粒锚定分散于氮掺杂的三维碳框架上的珊瑚状的FeP复合物(FeP@NC)，首先以表面活性剂为模板和碳源，乙醇和水为溶剂，盐酸多巴胺(DA)作为前驱体的氮源和碳源，依次加入铁源和有机配体，自聚合形成珊瑚状的FeP@NC复合物的前驱体；然后将合成的前驱体和磷源分别置于两个瓷舟中，并将放有磷源的瓷舟放在管式炉的气流上游，放有聚合物颗粒的瓷舟放在管式炉的气流下游，使Ar气流经磷源的瓷舟后再流经聚合物颗粒的瓷舟，在Ar气氛中将管式炉从室温加热到600～1200℃并煅烧一段时间，即得FeP@NC，既可以缩短离子的传输路径，实现快速的电子和离子传输，也可以提高反应的速率，表现出较高的电化学活性，并且具有较好的倍率性能和大倍率循环稳定性。

A FeP@NC particle with nitrogen-doped carbon as a carrier and its preparation method and application. Through in-situ phosphating/carbonization of polymer nanoparticles, FeP nanoparticles are anchored and dispersed in a nitrogen-doped three-dimensional carbon framework. The coral-like FeP complex (FeP@NC) on the and organic ligands, self-polymerize to form the precursor of the coral-like FeP@NC composite; then place the synthesized precursor and phosphorus source in two porcelain boats, and place the porcelain boat with the phosphorus source in the tube. The air flow of the tube furnace is upstream of the furnace, and the porcelain boat containing polymer particles is placed downstream of the tube furnace, so that the Ar gas flows through the porcelain boat of the phosphorus source and then flows through the porcelain boat of the polymer particles. In the Ar atmosphere, the tubular furnace is The furnace is heated from room temperature to 600~1200℃ and calcined for a period of time to obtain FeP@NC, which can not only shorten the ion transmission path and achieve rapid electron and ion transmission, but also increase the reaction rate and show higher electrochemical performance. activity, and has good rate performance and high rate cycle stability.

Description

一种氮掺杂碳为载体的FeP@NC及其制备和应用FeP@NC with nitrogen-doped carbon as carrier and its preparation and application

技术领域Technical field

本发明属于碱金属电池技术领域，具体涉及钠离子电池、锂离子电池和钾离子电池。The invention belongs to the technical field of alkali metal batteries, and specifically relates to sodium-ion batteries, lithium-ion batteries and potassium-ion batteries.

背景技术Background technique

锂离子电池作为最重要的储能装置之一，已经广泛应用于便携式电子设备和汽车等领域。然而，由于地球上锂的高成本和资源短缺的因素，开发新的锂离子电池替代品迫在眉睫。而钠离子电池因钠源的丰富和低成本的优点引起了极大的关注。然而，由于钠离子的离子半径大于锂离子的离子半径，在重复的钠离子***/脱出过程中会产生较严重的体积变化，表现出可逆容量的持续降低和较差的循环稳定性。此外，钠离子半径较大(0.97nm)，比锂离子半径大55％，使得钠离子在主体材料中的快速***/脱出更加困难。开发具有稳定微观结构、高可逆容量和长循环寿命的新型电极材料是钠离子电池的当务之急。As one of the most important energy storage devices, lithium-ion batteries have been widely used in portable electronic devices and automobiles. However, due to the high cost and scarcity of lithium on Earth, the development of new lithium-ion battery alternatives is urgent. Sodium-ion batteries have attracted great attention due to their abundant sodium sources and low cost. However, since the ionic radius of sodium ions is larger than that of lithium ions, severe volume changes will occur during repeated sodium ion insertion/extraction processes, showing a continuous decrease in reversible capacity and poor cycle stability. In addition, the sodium ion radius is larger (0.97nm), which is 55% larger than the lithium ion radius, making the rapid insertion/extraction of sodium ions into the host material more difficult. Developing new electrode materials with stable microstructure, high reversible capacity, and long cycle life is a top priority for sodium-ion batteries.

过渡金属磷化物(TMPs)，如FeP、CoP、Ni2P和Sn4P3等，因其理论容量高、资源丰富和环境友好等特点受到了广泛的关注。其中FeP已被证明作为钠离子电池负极材料时具有良好的电化学性能，但由于其在放电/充电过程中体积变化大、扩散动力学差，导致较差的倍率性能和快速的循环容量衰减。而改善电荷转移动力学的一般方法主要包括根据τ＝L2/D(τ是扩散过程的时间)增加钠扩散系数(D)和减小扩散长度(L)。原则上，减小TMPs的特征尺寸可以有效地减小扩散长度，而通过适当的纳米结构工程构建离子/电子高速路径可以增强钠离子的扩散并提高电子电导率。制备具有独特微结构的多孔复合材料已被证明是进一步提高电极材料电化学性能的有效方法，不仅提供了额外的自由空间来缓冲体积变化，还为钠的***/提取提供了更多的活性位点。然而，由于缺乏合适的合成方法，珊瑚状结构(纳米FeP颗粒锚定分散于纳米级的碳基底上)的过渡金属磷化物的可控制备方法还未见报道。Transition metal phosphides (TMPs), such as FeP, CoP, Ni 2 P, and Sn 4 P 3 , have received widespread attention due to their high theoretical capacity, abundant resources, and environmental friendliness. Among them, FeP has been proven to have good electrochemical properties as an anode material for sodium-ion batteries. However, due to its large volume change and poor diffusion kinetics during the discharge/charge process, it results in poor rate performance and rapid cycle capacity fading. The general methods to improve charge transfer kinetics mainly include increasing the sodium diffusion coefficient (D) and reducing the diffusion length (L) according to τ=L 2 /D (τ is the time of the diffusion process). In principle, reducing the characteristic size of TMPs can effectively reduce the diffusion length, while constructing ion/electron high-speed pathways through appropriate nanostructure engineering can enhance the diffusion of sodium ions and increase electronic conductivity. Preparing porous composites with unique microstructure has been proven to be an effective method to further improve the electrochemical performance of electrode materials, not only providing additional free space to buffer volume changes, but also providing more active sites for sodium insertion/extraction point. However, due to the lack of suitable synthesis methods, the controllable preparation method of transition metal phosphides with coral-like structure (nano FeP particles anchored and dispersed on nanoscale carbon substrate) has not been reported.

发明内容Contents of the invention

本发明的目的在于提供一种氮掺杂碳为载体的FeP@NC及其制备和应用。The purpose of the present invention is to provide a FeP@NC with nitrogen-doped carbon as a carrier and its preparation and application.

本发明采用的技术方案：The technical solution adopted by the present invention:

通过对聚合物纳米颗粒的原位磷化/碳化，合成了FeP纳米颗粒锚定分散于氮掺杂的三维碳框架上的珊瑚状的FeP复合物(FeP@NC)。Through in-situ phosphating/carbonization of polymer nanoparticles, a coral-like FeP composite (FeP@NC) with FeP nanoparticles anchored and dispersed on a nitrogen-doped three-dimensional carbon framework was synthesized.

首先以表面活性剂为模板和碳源，乙醇和水为溶剂，盐酸多巴胺(DA)作为前驱体的氮源和碳源，依次加入铁源和有机配体，自聚合形成珊瑚状的FeP@NC复合物的前驱体；然后将合成的前驱体和磷源分别置于两个瓷舟中，并将放有磷源的瓷舟放在管式炉的气流上游，放有聚合物颗粒的瓷舟放在管式炉的气流下游，使Ar气流经磷源的瓷舟后再流经聚合物颗粒的瓷舟，在Ar气氛中将管式炉从室温加热到600～1200℃并煅烧一段时间，即得FeP@NC。First, surfactant is used as template and carbon source, ethanol and water are used as solvents, and dopamine hydrochloride (DA) is used as the nitrogen source and carbon source of the precursor. Iron source and organic ligands are added in sequence to self-polymerize to form coral-like FeP@NC. The precursor of the composite; then place the synthesized precursor and phosphorus source in two porcelain boats respectively, and place the porcelain boat with the phosphorus source upstream of the gas flow of the tube furnace, and place the porcelain boat with the polymer particles in it. Place it downstream of the gas flow of the tube furnace, let the Ar gas flow through the porcelain boat of the phosphorus source and then through the porcelain boat of the polymer particles. In the Ar atmosphere, heat the tube furnace from room temperature to 600~1200°C and calcine for a period of time. That is, FeP@NC is obtained.

优选的，步骤(1)中所述醇为乙醇，乙醇和水的体积比为1：(0.5～2)Preferably, the alcohol described in step (1) is ethanol, and the volume ratio of ethanol and water is 1: (0.5~2)

优选的，表面活性剂为聚丙二醇与环氧乙烷的加聚物(F127)，聚乙烯吡咯烷酮(PVP)，十六烷基磺酸钠等其他表面活性剂。Preferably, the surfactant is an addition polymer of polypropylene glycol and ethylene oxide (F127), polyvinylpyrrolidone (PVP), sodium cetyl sulfonate and other surfactants.

优选的，表面活性剂浓度为5～15(mg/ml)。Preferably, the surfactant concentration is 5 to 15 (mg/ml).

优选的，盐酸多巴胺的浓度为0～15(mg/ml)。Preferably, the concentration of dopamine hydrochloride is 0-15 (mg/ml).

优选的，铁源为Fe(NO3)3·9H2O，Fe(NO3)3，FeCl3，Fe2(SO4)3，FeSO4，Fe(NO3)2，FeCl2中的一种或几种。Preferably, the iron source is one of Fe(NO 3 ) 3 ·9H 2 O, Fe(NO 3 ) 3 , FeCl 3 , Fe 2 (SO 4 ) 3 , FeSO 4 , Fe(NO 3 ) 2 and FeCl 2 species or several species.

优选的，有机配体为1,3,5-苯三甲酸，对苯二甲酸、1,3,5-三甲苯和二甲基咪唑中的一种或二种以上。Preferably, the organic ligand is one or more of 1,3,5-benzenetricarboxylic acid, terephthalic acid, 1,3,5-trimethylbenzene and dimethylimidazole.

优选的，有机配体为1,3,5-苯三甲酸，与Fe(NO3)3·9H2O优选的摩尔量比为2：1～1:2。Preferably, the organic ligand is 1,3,5-benzenetricarboxylic acid, and the preferred molar ratio to Fe(NO 3 ) 3 ·9H 2 O is 2:1 to 1:2.

优选的，磷源为红磷、白磷、NaH2PO4或Na2HPO4。Preferably, the phosphorus source is red phosphorus, white phosphorus, NaH 2 PO 4 or Na 2 HPO 4 .

优选的，聚合物颗粒和磷源红磷质量比为1:(1～4)。Preferably, the mass ratio of polymer particles and phosphorus source red phosphorus is 1: (1-4).

优选的，加热速率为0.1～5℃ min-1。Preferably, the heating rate is 0.1 to 5°C min -1 .

优选的，煅烧温度为600～1200℃。Preferably, the calcination temperature is 600-1200°C.

优选的，煅烧时间为2～12h。Preferably, the calcination time is 2 to 12 hours.

本发明的另一目的在于提供上述方法制备的氮掺杂碳为载体的FeP@NC在碱金属离子电池中的应用。Another object of the present invention is to provide the application of the nitrogen-doped carbon-supported FeP@NC prepared by the above method in an alkali metal ion battery.

优选的，所述氮掺杂碳为载体的FeP@NC作为碱金属离子电池负极活性材料。Preferably, the FeP@NC with nitrogen-doped carbon as a carrier is used as an anode active material for an alkali metal ion battery.

优选的，碱金属离子电池为钠离子电池、锂离子电池和钾离子电池。Preferably, the alkali metal ion battery is a sodium ion battery, a lithium ion battery and a potassium ion battery.

本发明相对于现有技术具有的有益效果如下：The beneficial effects of the present invention compared with the prior art are as follows:

1.本发明的FeP@NC复合材料将FeP纳米颗粒锚定分散于纳米级的碳基底上，FeP的尺寸缩小到了10nm左右(平均直径)，并且其类珊瑚状的结构既可以缩短离子的传输路径，实现快速的电子和离子传输，也可以提高反应的速率，表现出较高的电化学活性。1. The FeP@NC composite material of the present invention anchors and disperses FeP nanoparticles on a nanoscale carbon substrate. The size of FeP is reduced to about 10nm (average diameter), and its coral-like structure can shorten the transmission of ions. path to achieve rapid electron and ion transport, which can also increase the rate of reaction and show higher electrochemical activity.

2.本发明的FeP@NC复合材料具有高度多孔结构的三维碳骨架可以促进钠离子扩散，缓冲体积变化，同时可以防止FeP纳米粒子在循环时聚集，具有较好的倍率性能和大倍率循环稳定性。2. The FeP@NC composite material of the present invention has a highly porous three-dimensional carbon skeleton that can promote the diffusion of sodium ions, buffer volume changes, and at the same time prevent the aggregation of FeP nanoparticles during cycling, and has good rate performance and high rate cycle stability. sex.

3.钠离子电池中应用最广的硬碳类材料价格较高，而Fe元素和P元素在地壳中含量较高，资源丰富，价格较低本发明的FeP@NC复合材料既可以提高理论比容量，也可以降低成本。3. The most widely used hard carbon materials in sodium-ion batteries are relatively expensive, while Fe and P elements are relatively high in the earth’s crust, are rich in resources, and are relatively low-priced. The FeP@NC composite material of the present invention can improve the theoretical ratio Capacity can also reduce costs.

附图说明Description of drawings

为了更清楚地说明本发明实施例，下面将对实施例涉及的附图进行简单地介绍。In order to explain the embodiments of the present invention more clearly, the drawings involved in the embodiments will be briefly introduced below.

图1：实施1合成的FeP@NC，实施例4合成的FeP@NC和实施例5合成的FeP@NC的XRD图。Figure 1: XRD patterns of FeP@NC synthesized in Example 1, FeP@NC synthesized in Example 4 and FeP@NC synthesized in Example 5.

图2：a:实施1合成的FeP@NC的SEM图；b和c：不同放大倍数的实施1合成的FeP@NC的TEM图；d：实施4合成的FeP@NC的SEM图；e和f：不同放大倍数的实施4合成的FeP@NC的TEM图；g：实施例5合成的FeP@NC的SEM图；e和f：不同放大倍数的实施例5合成的FeP@NC的TEM图。Figure 2: a: SEM image of FeP@NC synthesized in Implementation 1; b and c: TEM images of FeP@NC synthesized in Implementation 1 at different magnifications; d: SEM image of FeP@NC synthesized in Implementation 4; e and f: TEM images of FeP@NC synthesized in Example 4 at different magnifications; g: SEM images of FeP@NC synthesized in Example 5; e and f: TEM images of FeP@NC synthesized in Example 5 at different magnifications .

图3：实施1合成的FeP@NC，实施例4合成的FeP@NC和实施例5合成的FeP@NC的倍率表现图。Figure 3: Rate performance diagram of FeP@NC synthesized in Example 1, FeP@NC synthesized in Example 4 and FeP@NC synthesized in Example 5.

图4：实施1合成的FeP@NC在10A·g-1电流密度下的长循环图。Figure 4: Long cycle diagram of FeP@NC synthesized in Implementation 1 at a current density of 10A·g -1 .

具体实施方式Detailed ways

下面结合实施例对本发明进行详细的说明，但本发明的实施方式不限于此，显而易见地，下面描述中的实施例仅是本发明的部分实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，获得其他的类似的实施例均落入本发明的保护范围。The present invention will be described in detail below with reference to the examples, but the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some of the embodiments of the present invention. For those skilled in the art, without paying any attention to Under the premise of creative labor, other similar embodiments can be obtained and all fall within the protection scope of the present invention.

实施例1Example 1

1.聚合物纳米颗粒的合成：1. Synthesis of polymer nanoparticles:

具体合成过程：将1.0g聚丙二醇与环氧乙烷的加聚物(F127)和1.0g盐酸多巴胺(DA)溶解在100mL水和乙醇(体积比为1：1)的混合溶液中，并在室温下剧烈搅拌以获得澄清溶液；然后将5.8083g的Fe(NO3)3·9H2O在500rpm的搅拌速率下加入到上述溶液中以形成澄清溶液；搅拌30分钟后，将3.0212g的1,3,5-苯三甲酸添加到上述混合溶液中，连续搅拌反应30分钟后，离心得到分离物后，用水和乙醇(体积比为1：1)混合液洗涤3次并干燥，即可得聚合物颗粒。Specific synthesis process: Dissolve 1.0g polypropylene glycol and ethylene oxide addition polymer (F127) and 1.0g dopamine hydrochloride (DA) in a mixed solution of 100mL water and ethanol (volume ratio 1:1), and add Stir vigorously at room temperature to obtain a clear solution; then add 5.8083g of Fe(NO 3 ) 3 ·9H 2 O to the above solution at a stirring rate of 500 rpm to form a clear solution; after stirring for 30 minutes, 3.0212g of 1 , 3,5-Benzenetricarboxylic acid is added to the above mixed solution, and after continuous stirring for 30 minutes, the separated product is obtained by centrifugation, washed 3 times with a mixture of water and ethanol (volume ratio 1:1) and dried to obtain polymer particles.

2.氮掺杂的珊瑚状的FeP@NC复合材料的合成：2. Synthesis of nitrogen-doped coral-like FeP@NC composites:

将步骤(1)合成的聚合物颗粒和红磷(质量比为1：2)分别置于两个瓷舟中，并将放有红磷的瓷舟放在管式炉的气流上游，放有聚合物颗粒的瓷舟放在管式炉的气流下游，通Ar气流经红磷的瓷舟后再流经聚合物颗粒的瓷舟，然后在Ar气氛中以1℃min-1的加热速率将管式炉从室温加热到600℃并煅烧6h，即可得到FeP@NC。Place the polymer particles synthesized in step (1) and red phosphorus (mass ratio 1:2) into two porcelain boats respectively, and place the porcelain boat containing red phosphorus upstream of the air flow of the tube furnace, and place The porcelain boat of polymer particles is placed downstream of the gas flow of the tube furnace. The Ar gas flows through the porcelain boat of red phosphorus and then flows through the porcelain boat of polymer particles. Then, the Ar gas is heated at a heating rate of 1°C min -1 in the Ar atmosphere. FeP@NC can be obtained by heating the tube furnace from room temperature to 600°C and calcining for 6 hours.

经检测，多孔载体NC中N的质量含量为0.97％，载体NC是由粒径100-500nm的颗粒聚集而成的粒径1-3μm的团簇，称之为珊瑚状团簇；After testing, the mass content of N in the porous carrier NC is 0.97%. The carrier NC is composed of particles with a particle size of 100-500 nm, and is formed into clusters with a particle size of 1-3 μm, which are called coral-like clusters;

活性成份FeP分布于多孔载体NC的内外表面，其为粒径4-20nm的颗粒。The active ingredient FeP is distributed on the inner and outer surfaces of the porous carrier NC, which is particles with a particle size of 4-20 nm.

3.氮掺杂的珊瑚状的FeP@NC复合材料的性能测试：3. Performance testing of nitrogen-doped coral-like FeP@NC composites:

利用上述方法制备的FeP@NC为电极活性物质，super P为导电剂，聚偏氟乙烯(PVDF)为粘结剂配制浆料，其组成比例为8:1:1；以铜箔为集流体，厚度为80微米刮涂电极，60℃烘干。此时电极担量约为1mg cm-2。以直径为1.6mm的钠片作为对电极，玻璃纤维膜为隔膜，以1M NaPF6为电解质，DGME作为电解液，组装成钠|FeP@NC半电池。在0.1A g-1(相对于FeP@NC)，0.2A g-1，0.5A g-1，1A g-1，2A g-1，5A g-1，10A g-1及20A g-1下进行倍率性能的充放电测试，在10A g-1的电流密度下进行大电流的长循环测试。The FeP@NC prepared by the above method is the electrode active material, super P is the conductive agent, and polyvinylidene fluoride (PVDF) is the binder to prepare the slurry. The composition ratio is 8:1:1; copper foil is used as the current collector. , with a thickness of 80 microns, scrape-coated electrodes and dried at 60°C. At this time, the electrode loading is approximately 1 mg cm -2 . A sodium|FeP@NC half cell was assembled using a sodium sheet with a diameter of 1.6 mm as the counter electrode, a glass fiber membrane as the separator, 1M NaPF 6 as the electrolyte, and DGME as the electrolyte. At 0.1A g -1 (relative to FeP@NC), 0.2A g -1 , 0.5A g -1 , 1A g -1 , 2A g -1 , 5A g -1 , 10A g -1 and 20A g -1 The charge and discharge test of the rate performance was carried out under the current density of 10A g -1 , and the long cycle test of high current was carried out at a current density of 10A g -1.

实施例2-18：Example 2-18:

与实施例1具有相同的氮掺杂的珊瑚状的FeP@NC复合材料的制备过程和将其组装成电池过程以及性能测试过程，所不同的是F127的浓度、盐酸多巴胺的浓度、金属盐的种类、金属盐和1,3,5-苯三甲酸的摩尔量比、磷源、升温速率、煅烧温度、煅烧时间和N的质量含量，相关数据如表1所示，所制备的钠离子电池的性能测试数据如表3所示。The preparation process of the nitrogen-doped coral-like FeP@NC composite material, the process of assembling it into a battery, and the performance testing process are the same as those in Example 1. The differences are the concentration of F127, the concentration of dopamine hydrochloride, and the concentration of the metal salt. Type, molar ratio of metal salt and 1,3,5-benzenetricarboxylic acid, phosphorus source, heating rate, calcination temperature, calcination time and mass content of N. The relevant data are shown in Table 1. The prepared sodium ion battery The performance test data is shown in Table 3.

对比例1-7：Comparative Examples 1-7:

与实施例1具有相同的氮掺杂的珊瑚状的FeP@NC复合材料的制备过程和将其组装成电池过程以及性能测试过程，所不同的是有机配体的种类、升温速率和物料的顺序，相关数据如表2所示，所制备的钠离子电池的性能测试数据如表3所示。The preparation process of the nitrogen-doped coral-like FeP@NC composite material, the process of assembling it into a battery and the performance testing process are the same as those in Example 1. The difference is the type of organic ligand, the heating rate and the order of the materials. , the relevant data are shown in Table 2, and the performance test data of the prepared sodium-ion battery are shown in Table 3.

表1实施例1-18的制备工艺参数Table 1 Preparation process parameters of Examples 1-18

表2对比例1-7的工艺参数Table 2 Process parameters of comparative examples 1-7

表3实施例1-18和对比例1-6的性能测试结果Table 3 Performance test results of Examples 1-18 and Comparative Examples 1-6

当对不同量的盐酸多巴胺(DA)合成出来的FeP@NC进行电化学测试时，实施例1合成出来的FeP@NC表现出了最好的电化学活性。所制备的复合材料在含有48.8％的碳含量下还显示出较高的倍率表现，在20A·g-1的电流密度下有176.5mAh·g-1的比容量，在10A·g-1的电流密度下循环10000圈后还有89mAh·g-1的比容量，具有较好的倍率表现和大电流长循环表现。When electrochemical tests were conducted on FeP@NC synthesized with different amounts of dopamine hydrochloride (DA), the FeP@NC synthesized in Example 1 showed the best electrochemical activity. The prepared composite material also showed higher rate performance when containing 48.8% carbon content, with a specific capacity of 176.5mAh·g -1 at a current density of 20A·g -1 and a specific capacity of 10A·g -1 After 10,000 cycles at current density, it still has a specific capacity of 89mAh·g -1 , which has good rate performance and high current and long cycle performance.

利用F127两端分别具有亲水基团和疏水基团，中间为长链的特性，亲水基团显电负性，与三价铁结合，在搅拌条件下使三价铁离子形成胶束状颗粒；长链和另一端的疏水基的胶束状结构可以阻止与其它胶束的结合，避免团聚，分散度更高。而盐酸多巴胺主要作为氮源，由于其可以发生自聚合形成聚多巴胺并具有一定的黏性，因此可以掺杂进去一定的氮元素；同时，我们也发现当改变盐酸多巴胺的用量时，FeP的比例变化很小，因此其并不参与整个反应的聚合过程中，主要作为氮源。Fe(NO3)3·9H2O作为铁源，首先与F127通过静电作用形成胶束状颗粒，然后再与1,3,5-苯三甲酸进行配位聚合。而1,3,5-苯三甲酸，一方面可以通过范德华力与表面活性剂的疏水端作用，促进胶束的组装；另一方面，也可以进入到胶束内部与金属离子进行配位复合，从而有效的控制了颗粒的尺寸。Taking advantage of the fact that F127 has hydrophilic groups and hydrophobic groups at both ends and a long chain in the middle, the hydrophilic group is electronegative and combines with ferric iron to form micelles under stirring conditions. Particles; the long chain and the micelle-like structure of the hydrophobic group on the other end can prevent the combination with other micelles, avoid agglomeration, and achieve higher dispersion. Dopamine hydrochloride is mainly used as a nitrogen source. Since it can self-polymerize to form polydopamine and has a certain viscosity, it can be doped with a certain amount of nitrogen. At the same time, we also found that when the dosage of dopamine hydrochloride is changed, the proportion of FeP The change is very small, so it does not participate in the polymerization process of the entire reaction and mainly serves as a nitrogen source. As an iron source, Fe(NO 3 ) 3 ·9H 2 O first forms micellar particles with F127 through electrostatic interaction, and then coordinates polymerization with 1,3,5-benzenetricarboxylic acid. On the one hand, 1,3,5-benzenetricarboxylic acid can promote the assembly of micelles through the van der Waals force and the hydrophobic end of the surfactant; on the other hand, it can also enter the interior of the micelles to coordinate and complex with metal ions. , thereby effectively controlling the particle size.

从实验结果可以看出，盐酸多巴胺量的改变并不会大幅引起FeP在整个复合物中所占的比例，主要是作为氮源，优选的盐酸多巴胺的浓度为0～15(mg/ml)。It can be seen from the experimental results that changes in the amount of dopamine hydrochloride will not significantly affect the proportion of FeP in the entire complex. It is mainly used as a nitrogen source. The preferred concentration of dopamine hydrochloride is 0 to 15 (mg/ml).

从实验结果可以看出，最终复合物中FeP中的比例主要取决于三价铁离子的物质的量，加入过多的铁盐或者配体并不会大幅影响实验结果。本发明中优选的配体为1,3,5-苯三甲酸，与Fe(NO3)3·9H2O优选的摩尔量比为2：1～1:2。It can be seen from the experimental results that the proportion of FeP in the final composite mainly depends on the amount of ferric ions. Adding too much iron salt or ligand will not significantly affect the experimental results. The preferred ligand in the present invention is 1,3,5-benzenetricarboxylic acid, and the preferred molar ratio to Fe(NO 3 ) 3 ·9H 2 O is 2:1 to 1:2.

当将1,3,5-苯三甲酸替换为1,3,5-三甲苯时，也能够先形成胶束状的颗粒，1,3,5-三甲苯也能够以通过范德华力与表面活性剂的疏水端作用，促进胶束的组装，但由于胶束颗粒中的铁离子缺少有机配体，因此不能较好地控制聚合物颗粒的大小，导致聚合物颗粒较大，性能稍差。When 1,3,5-benzenetricarboxylic acid is replaced by 1,3,5-trimethylbenzene, micelle-like particles can also be formed first, and 1,3,5-trimethylbenzene can also interact with surface activity through van der Waals forces. The hydrophobic end of the agent promotes the assembly of micelles. However, because the iron ions in the micelle particles lack organic ligands, the size of the polymer particles cannot be well controlled, resulting in larger polymer particles and slightly poorer performance.

当先将1,3,5-三甲苯加入到溶液中或者先将Fe(NO3)3·9H2O与F127和盐酸多巴胺一块溶解时，致使无法先形成较均匀的胶束状的颗粒，颗粒的平均粒径较大，整体性能也较差。1,3,5-苯三甲酸换成对苯二甲酸时，由于对苯二甲酸的对称性结构会使其与铁离子形成的有机框架变大，进而使所形成的FeP颗粒变大，因此性能较差。When 1,3,5-trimethylbenzene is first added to the solution or Fe(NO 3 ) 3 ·9H 2 O is dissolved together with F127 and dopamine hydrochloride, more uniform micellar particles cannot be formed first. The average particle size is larger and the overall performance is poorer. When 1,3,5-benzenetricarboxylic acid is replaced with terephthalic acid, the symmetrical structure of terephthalic acid will make the organic framework formed by it and iron ions larger, thereby making the formed FeP particles larger. Poor performance.

由于所形成的胶粒是通过弱键力结合得到的，当升温速率过快时会破坏其结构，最终导致颗粒变大，性能变差，本发明中优选的加热速率为0.1～5℃min-1。Since the formed colloidal particles are combined by weak bonds, their structure will be destroyed when the heating rate is too fast, eventually causing the particles to become larger and their performance to deteriorate. The preferred heating rate in the present invention is 0.1 to 5°C min - 1 .

由于受到胶粒中的表面活性剂，有机配体，盐酸多巴胺的碳化温度影响，碳化温度需要大于600℃，当提高煅烧的温度时，只是影响煅烧后的碳的石墨化程度及其表面含氧基团的含量，并不会明显影响FeP的含量，因此整体性能大体不变。本发明中优选的煅烧温度为600～1200℃。Due to the influence of the carbonization temperature of surfactants, organic ligands, and dopamine hydrochloride in the colloidal particles, the carbonization temperature needs to be greater than 600°C. When the calcining temperature is increased, it only affects the degree of graphitization of the calcined carbon and its surface oxygen content. The content of the group does not significantly affect the content of FeP, so the overall performance remains roughly unchanged. The preferred calcination temperature in the present invention is 600 to 1200°C.

当煅烧的时间过长时，可能导致FeP颗粒发生团聚，整体性能变差。本发明中优选的煅烧时间为2～12h。When the calcination time is too long, FeP particles may agglomerate and the overall performance will deteriorate. The preferred calcination time in the present invention is 2 to 12 hours.

最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention. scope.

Claims (9)

1. The preparation method of the FeP@NC taking nitrogen doped carbon as a carrier is characterized by comprising the following steps of:
(1) Taking a surfactant as a template and a carbon source, taking alcohol and water as solvents, taking dopamine hydrochloride as a nitrogen source and a carbon source of a precursor, sequentially adding an iron source and an organic ligand, and performing self-polymerization to form the precursor of the FeP@NC compound;
(2) Placing the precursor synthesized in the step (1) and a phosphorus source in two porcelain boats respectively, then placing the porcelain boat with the phosphorus source at the air flow upstream of a tube furnace, placing the porcelain boat with the precursor at the air flow downstream of the tube furnace, enabling inert gas to flow through the porcelain boat with the phosphorus source and then through the porcelain boat with the precursor, heating the tube furnace to 600-1200 ℃ from room temperature and calcining for a period of time to obtain FeP@NC;
the surfactant in the step (1) is addition polymer of polypropylene glycol and ethylene oxide, polyvinylpyrrolidone or sodium hexadecyl sulfonate; the concentration of the surfactant is 5-15 mg/ml; the concentration of the dopamine hydrochloride is 0-15 mg/ml.
2. The method according to claim 1, wherein in the step (1), the alcohol is ethanol, and the volume ratio of ethanol to water is 1: (0.5-2).
3. The method of claim 1, wherein the iron source in step (1) is Fe (NO 3 ) 3 ·9H 2 O、Fe(NO 3 ) 3 、FeCl 3 、Fe 2 (SO 4 ) 3 、FeSO 4 、Fe(NO 3 ) 2 And FeCl 2 One or more than two of them.
4. The method according to claim 3, wherein the organic ligand in the step (1) is one or more of 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 1,3, 5-trimethylbenzene and dimethylimidazole; the molar ratio of organic ligand to Fe in the iron source is 2: 1-1:2.
5. The process of claim 4, wherein the phosphorus source in step (2) is red phosphorus, white phosphorus, naH 2 PO 4 And Na (Na) 2 HPO 4 One or more than two of them; the mass ratio of the precursor to the phosphorus source is 1 (1-4).
6. The process according to claim 5, wherein the heating rate in step (2) is 0.1 to 5℃for a minute -1 The method comprises the steps of carrying out a first treatment on the surface of the The calcination time is 2-12 h; the inert gas is Ar.
7. A fep@nc particle with nitrogen-doped carbon as a carrier, characterized by being produced by the production method according to any one of claims 1 to 6.
8. Use of the fep@nc particles of claim 7 with nitrogen-doped carbon as a carrier in an alkali metal ion battery.
9. The use according to claim 8, characterized in that the fep@nc particles with nitrogen-doped carbon as carrier are used as an alkali metal ion battery negative electrode active material; the alkali metal ion battery is a sodium ion battery, a lithium ion battery or a potassium ion battery.
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