CN110459768A - A kind of iron phosphide/carbon composite material with octahedral structure and its preparation method and application - Google Patents

A kind of iron phosphide/carbon composite material with octahedral structure and its preparation method and application Download PDF

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CN110459768A
CN110459768A CN201910749728.7A CN201910749728A CN110459768A CN 110459768 A CN110459768 A CN 110459768A CN 201910749728 A CN201910749728 A CN 201910749728A CN 110459768 A CN110459768 A CN 110459768A
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iron phosphide
carbon composite
octahedral structure
composite material
preparation
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童汇
黄英德
毛高强
喻万景
丁治英
郑俊超
张宝
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
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Abstract

一种八面体结构磷化铁/碳复合材料及其制备方法与应用，该复合材料包括原位碳包覆的磷化铁，所述磷化铁颗粒尺寸为400~700nm，颗粒均匀，具有八面体结构；所述复合材料组装为锂离子电池后，其锂离子电池具有倍率性能好、循环稳定性好、电导率高等优点，本发明还包括所述八面体结构磷化铁/碳复合材料的制备方法，该操作方法简单、成本低、可控性强，适宜于工业化生产。

An iron phosphide/carbon composite material with an octahedral structure and its preparation method and application, the composite material includes iron phosphide coated with in-situ carbon, the particle size of the iron phosphide is 400-700nm, the particles are uniform, and have eight surface structure; after the composite material is assembled into a lithium-ion battery, the lithium-ion battery has the advantages of good rate performance, good cycle stability, and high electrical conductivity. The present invention also includes the octahedral iron phosphide/carbon composite material. The preparation method has the advantages of simple operation method, low cost and strong controllability, and is suitable for industrialized production.

Description

一种八面体结构磷化铁/碳复合材料及其制备方法与应用A kind of iron phosphide/carbon composite material with octahedral structure and its preparation method and application

技术领域technical field

本发明涉及一种锂离子电池负极材料及其制备方法与应用，具体涉及一种锂离子电池负极材料八面体磷化铁/碳复合材料及其制备方法与应用。The invention relates to a lithium ion battery negative electrode material and its preparation method and application, in particular to a lithium ion battery negative electrode material octahedral iron phosphide/carbon composite material and its preparation method and application.

背景技术Background technique

随着能源的日渐短缺和环境污染问题的日益严重，锂离子电池由于其能量密度高、循环寿命长、自放电小，环境友好等优点，被越来越广泛的应用于便携式电子设备、混合动力电动汽车和智能电网等领域。然而，随着对高比容量和高能量密度电池技术需求的不断增加，目前商用的石墨阳极材料由于其比较低的比容量(~ 350mAh.g-1)而不能满足要求。因此，开发出高能量密度、高循环稳定性，倍率性能优异的新型先进负极材料来替代传统的负极材料是重中之重。With the increasing shortage of energy and the increasingly serious problem of environmental pollution, lithium-ion batteries are more and more widely used in portable electronic devices and hybrid vehicles due to their advantages such as high energy density, long cycle life, small self-discharge, and environmental friendliness. fields such as electric vehicles and smart grids. However, with the increasing demand for high specific capacity and high energy density battery technology, the current commercial graphite anode materials cannot meet the requirements due to their relatively low specific capacity (~ 350mAh.g -1 ). Therefore, it is a top priority to develop new advanced anode materials with high energy density, high cycle stability, and excellent rate performance to replace traditional anode materials.

目前磷基化合物的研究中，磷化铁因为其价格低廉，储存量丰富且具有926mAh.g-1的高理论比容量而具有广阔的应用前景。然而磷化铁负极材料在充放电过程中剧烈的体积变化（~202%），团聚和电导率低，将导致磷化铁材料电极极化，粉碎，集流体接触使电极活性物质快速溶解，从而导致比容量的快速衰减，循环性能降低。In the current research on phosphorus-based compounds, iron phosphide has broad application prospects because of its low price, abundant storage capacity and high theoretical specific capacity of 926mAh.g -1 . However, the dramatic volume change (~202%), agglomeration and low conductivity of iron phosphide anode materials during charge and discharge will lead to electrode polarization of iron phosphide materials, crushing, and contact with current collectors to rapidly dissolve electrode active materials, thereby This leads to rapid decay of specific capacity and reduced cycle performance.

CN103094565A公开了一种磷酸铁锂/磷化铁/碳复合纳米纤维，包括如下质量百分比含量的组分：50~99%的磷酸铁锂、0.5~30%磷化铁和1~20%碳，所述磷酸铁锂/磷化铁/碳复合纳米纤维的平均直径在50~500nm之间，该纤维中存在磷化铁的球状颗粒。该发明提供的磷酸铁锂/磷化铁/碳复合纳米纤维具有良好的纤维形貌和导电性能，但该材料电化学性能调变的手段就是改变纺丝溶液的粘度， 而最有效的方式为改变聚合物的浓度，聚合物浓度高，则纤维粗；聚合物浓度低，则纤维细。该发明操作不方便且合成方法复杂。CN103094565A discloses a lithium iron phosphate/iron phosphide/carbon composite nanofiber, comprising the following components in mass percent: 50-99% lithium iron phosphate, 0.5-30% iron phosphide and 1-20% carbon, The average diameter of the lithium iron phosphate/iron phosphide/carbon composite nanofiber is between 50nm and 500nm, and there are spherical particles of iron phosphide in the fiber. The lithium iron phosphate/iron phosphide/carbon composite nanofibers provided by the invention have good fiber morphology and electrical conductivity, but the means of adjusting the electrochemical properties of the material is to change the viscosity of the spinning solution, and the most effective way is Change the concentration of the polymer, high polymer concentration, the fiber is thick; low polymer concentration, the fiber is thin. The invention is inconvenient to operate and the synthesis method is complicated.

CN105148958 A公开了一种基于硫化铁制备高活性硫掺杂磷化铁的方法，其特征在于包括如下步骤 ：硫化钠和硫酸亚铁分别溶于一定量的去离子水中，再将硫化钠逐滴加入到亚铁离子溶液中，得到的沉淀为硫化亚铁，离心、洗涤、干燥后备用；将一定量的硫化铁粉末和次磷酸钠混合，然后将上述混合物在惰性气体保护下升温到250~550℃后，热处理1~2h。反应完毕后将炉子温度降至室温，用含有 1％氧气的氮气钝化1小时，得到的催化剂备用；如果将硫化铁替换成负载型的硫化铁，可以得到负载型的硫掺杂磷化铁。虽然该合成方法简单，但是，合成的硫掺杂磷化铁材料性能不佳。CN105148958 A discloses a method for preparing highly active sulfur-doped iron phosphide based on iron sulfide, which is characterized in that it comprises the following steps: sodium sulfide and ferrous sulfate are respectively dissolved in a certain amount of deionized water, and then sodium sulfide is added dropwise Add it into the ferrous ion solution, and the precipitate obtained is ferrous sulfide, which is centrifuged, washed, and dried for later use; mix a certain amount of iron sulfide powder and sodium hypophosphite, and then raise the temperature of the above mixture to 250~ After 550℃, heat treatment for 1~2h. After the reaction is completed, the furnace temperature is lowered to room temperature, passivated with nitrogen containing 1% oxygen for 1 hour, and the obtained catalyst is ready for use; if the iron sulfide is replaced by a loaded iron sulfide, a loaded sulfur-doped iron phosphide can be obtained . Although the synthesis method is simple, the performance of the synthesized sulfur-doped iron phosphide material is poor.

CN106345501公开了一种基于磁性离子液体修饰碳纳米管复合材料制备磷化铁的方法及其产品和应用，所述制备方法包括如下步骤：（1）将磁性离子液体与碳纳米管以质量比0.1~0.2：0.1~0.4均匀混合，然后加入甲醇继续研磨15~45分钟，烘干得复合材料；（2）以质量比0.1~0.2:0.1~0.3，将步骤（1）制备的复合材料与次磷酸钠均匀混合，在氩气环境管式炉中250~400℃加热8~16小时得到磷化铁。将制备的磷化铁作为析氢催化剂负载到阴极并应用到电解水研究中，发现其具有良好的催化活性。但是该材料并不能应用于锂离子电池负极材料的使用。CN106345501 discloses a method for preparing iron phosphide based on a magnetic ionic liquid modified carbon nanotube composite material and its products and applications. The preparation method includes the following steps: (1) using a magnetic ionic liquid and carbon nanotubes at a mass ratio of 0.1 ~0.2:0.1~0.4 and mix evenly, then add methanol and continue to grind for 15~45 minutes, and dry to obtain the composite material; (2) The composite material prepared in step (1) and the second Sodium phosphate is evenly mixed, and heated in an argon ambient tube furnace at 250-400°C for 8-16 hours to obtain iron phosphide. The prepared iron phosphide was loaded on the cathode as a hydrogen evolution catalyst and applied to the research of electrolysis of water, and it was found that it had good catalytic activity. However, this material cannot be applied to the use of lithium-ion battery negative electrode materials.

CN102442652A公开了一种制备过渡金属磷化物Fe2P的新方法。采用磷酸铁作为前驱体，硼氢化钾作为还原剂，将铁的磷酸盐与还原剂按摩尔比1:1.5~1:2 在研钵中研磨，混合均匀，在 500~600 ℃氩气保护下反应 30min ；所得产物研细，用蒸馏水和无水乙醇分别洗涤三次，然后60℃真空干燥12h，得到产品 Fe2P。虽然该方法材料制备所需的主要原料来源丰富，价格低廉，成本较低。但是，所得材料性能不佳。CN102442652A discloses a new method for preparing transition metal phosphide Fe 2 P. Iron phosphate is used as the precursor, potassium borohydride is used as the reducing agent, the iron phosphate and the reducing agent are ground in a mortar with a molar ratio of 1:1.5~1:2, mixed evenly, under the protection of argon at 500~600 ℃ Reacted for 30 minutes; the obtained product was finely ground, washed three times with distilled water and absolute ethanol, and then vacuum-dried at 60° C. for 12 hours to obtain the product Fe 2 P. Although the main raw materials needed for material preparation in this method are rich in sources, low in price and relatively low in cost. However, the resulting material performed poorly.

发明内容Contents of the invention

本发明所要解决的技术问题是，克服现有技术存在的上述缺陷，提供一种体积膨胀小、电化学性能好，循环性能优异的八面体结构磷化铁/碳复合材料。The technical problem to be solved by the present invention is to overcome the above-mentioned defects in the prior art, and provide an octahedral iron phosphide/carbon composite material with small volume expansion, good electrochemical performance and excellent cycle performance.

本发明进一步要解决的技术问题是，提供一种操作简单，成本低的八面体结构磷化铁/碳复合材料的制备方法。The further technical problem to be solved by the present invention is to provide a method for preparing an octahedral iron phosphide/carbon composite material with simple operation and low cost.

本发明解决其技术问题所采用的技术方案是，一种八面体结构磷化铁/碳负极材料复合材料，包括原位碳包覆的磷化铁，所述磷化铁颗粒尺寸为400~700nm。The technical solution adopted by the present invention to solve the technical problem is an octahedral structure iron phosphide/carbon negative electrode material composite material, including in-situ carbon-coated iron phosphide, and the particle size of the iron phosphide is 400~700nm .

本发明进一步解决其技术问题所采用的技术方案是，一种八面体结构磷化铁/碳复合材料的制备方法，包括以下步骤：The technical scheme that the present invention adopts to further solve its technical problem is, a kind of preparation method of iron phosphide/carbon composite material of octahedral structure, comprises the following steps:

（1）将FeCl3.6H2O粉末加入DMF溶液中，加热，搅拌，得混合溶液；(1) Add FeCl 3 .6H 2 O powder into DMF solution, heat and stir to obtain a mixed solution;

（2）向步骤（1）所得混合溶液中加入有机配体粉末，加热，搅拌，超声处理，得混合溶液；(2) Add organic ligand powder to the mixed solution obtained in step (1), heat, stir, and sonicate to obtain a mixed solution;

（3）将步骤（2）所得混合溶液置于至高压反应釜内，密封，加热，发生溶剂热反应，冷却，离心，洗涤，干燥，得黄色粉末；(3) Put the mixed solution obtained in step (2) into an autoclave, seal it, heat it, undergo a solvothermal reaction, cool it, centrifuge it, wash it, and dry it to obtain a yellow powder;

（4）将步骤（3）所得黄色粉末在氩气或氮气气氛中，焙烧，冷却，得黑色粉末；(4) Calcining and cooling the yellow powder obtained in step (3) in an argon or nitrogen atmosphere to obtain a black powder;

（5）将盛有步骤（4）所得黑色粉末的瓷舟置于石英管下游，盛有红磷的瓷舟置于石英管上游，在氩气或氮气气氛中，焙烧，冷却，得磷化铁/碳复合材料。(5) Place the porcelain boat containing the black powder obtained in step (4) downstream of the quartz tube, and place the porcelain boat containing red phosphorus upstream of the quartz tube. In an argon or nitrogen atmosphere, roast and cool to obtain phosphating. Iron/carbon composites.

优选地，步骤（1）中，所述混合溶液中FeCl3.6H2O的摩尔浓度为20mmol/L~40mmol/L，若所述混合溶液中FeCl3. 6H2O的摩尔浓度过高或者过低，均不易与步骤（2）中有机配体形成金属有机物骨架材料。Preferably, in step (1), the molar concentration of FeCl 3 .6H 2 O in the mixed solution is 20mmol/L~40mmol/L, if the molar concentration of FeCl 3 .6H 2 O in the mixed solution is too high or If it is too low, it is not easy to form a metal-organic framework material with the organic ligand in step (2).

优选地，步骤（1）中，所述加热温度为25~50℃，温度过低将无法保证FeCl3.6H2O粉末的溶解，温度过高则会导致所述混合溶液的溶剂蒸发。Preferably, in step (1), the heating temperature is 25-50° C. If the temperature is too low, the dissolution of the FeCl 3 .6H 2 O powder cannot be ensured, and if the temperature is too high, the solvent of the mixed solution will evaporate.

优选地，步骤（1）中，所述搅拌的速度为80~800 转/min（更优选400~700 转/min），所述搅拌的时间为0.5~2h。Preferably, in step (1), the stirring speed is 80-800 revolutions/min (more preferably 400-700 revolutions/min), and the stirring time is 0.5-2 hours.

优选地，步骤（2）中，所述有机配体为反丁烯二酸、对苯二甲酸、均苯三甲酸或3,5-二氨基苯甲酸等中的一种或几种，所述有机配体的作用是连接金属离子，形成有机物和金属离子相连的骨架材料。Preferably, in step (2), the organic ligand is one or more of fumaric acid, terephthalic acid, trimesic acid or 3,5-diaminobenzoic acid, etc., the The role of organic ligands is to connect metal ions to form a framework material in which organic matter and metal ions are connected.

优选地，步骤（2）中，所述有机配体与FeCl3.6H2O的摩尔比为0.25~2:1。若铁离子浓度过高，则所得金属有机物骨架材料易团聚，若铁离子浓度过低，则难以形成金属有机物骨架材料。Preferably, in step (2), the molar ratio of the organic ligand to FeCl 3 .6H 2 O is 0.25-2:1. If the concentration of iron ions is too high, the obtained metal-organic framework material is easy to agglomerate, and if the concentration of iron ions is too low, it is difficult to form the metal-organic framework material.

优选地，步骤（2）中，所述加热的温度为25~50℃；所述搅拌的速度为80～800 转/min，搅拌的时间为0.5~2 h。Preferably, in step (2), the heating temperature is 25-50° C.; the stirring speed is 80-800 rpm, and the stirring time is 0.5-2 h.

优选地，步骤（3）中，所述加热的温度为100~160℃，加热的时间为4~18h。若加热时间过短或者过长，会影响晶体的形成。Preferably, in step (3), the heating temperature is 100-160° C., and the heating time is 4-18 hours. If the heating time is too short or too long, the formation of crystals will be affected.

优选地，步骤（3）中，所述洗涤的方法为用乙醇和去离子水分别先后交叉离心洗涤。Preferably, in step (3), the washing method is sequentially cross-centrifugal washing with ethanol and deionized water.

优选地，步骤（3）中，所述离心的转速8000~10000 转/min，离心时间8~12 min，离心次数≥6次。Preferably, in step (3), the rotational speed of the centrifugation is 8000-10000 rpm, the centrifugation time is 8-12 min, and the number of centrifugation is ≥ 6 times.

优选地，步骤（3）中，所述干燥的温度为60~100℃，干燥的时间为12~24 h。Preferably, in step (3), the drying temperature is 60-100° C., and the drying time is 12-24 h.

优选地，步骤（4）中，所述焙烧的温度为500~700℃，焙烧的时间为2~6h。所述焙烧温度下，有机物分解形成碳包覆在金属原子的表面，形成原位碳包覆的八面体结构。如果温度过高或者过低，则难以得到规则的八面体结构 。Preferably, in step (4), the temperature of the calcination is 500-700° C., and the calcination time is 2-6 hours. At the calcination temperature, the organic matter decomposes to form carbon coating on the surface of metal atoms, forming an octahedral structure coated with carbon in situ. If the temperature is too high or too low, it is difficult to obtain a regular octahedral structure.

优选地，步骤（4）中，所述氩气或氮气的纯度≥99.99%。Preferably, in step (4), the purity of the argon or nitrogen is ≥99.99%.

优选地，步骤（5）中，所述黑色粉末与红磷的质量比为1:5~10。Preferably, in step (5), the mass ratio of the black powder to red phosphorus is 1:5-10.

优选地，步骤（5）中，所述焙烧的温度为750~900℃，焙烧的时间为1~3h。在所述焙烧温度下，红磷升华为磷蒸汽，与上述步骤（4）所得黑色粉末反应，得到保留八面体结构的磷化铁/碳复合材料。Preferably, in step (5), the temperature of the calcination is 750-900° C., and the calcination time is 1-3 hours. At the calcination temperature, the red phosphorus is sublimated into phosphorus vapor, which reacts with the black powder obtained in the above step (4) to obtain an iron phosphide/carbon composite material retaining the octahedral structure.

优选地，步骤（5）中，所述冷却方式为自然冷却。Preferably, in step (5), the cooling method is natural cooling.

本发明的技术原理是：利用DMF作为合适的极性溶剂，使铁源与有机配体生成的金属有机物骨架材料能够在溶剂热过程中形成为八面体结构的材料；再通过焙烧使其中的有机物成分转化为碳，原位包覆在金属原子的表面，最后通过高温下的磷蒸汽对焙烧后的产物进行磷化，得到八面体结构的磷化铁/碳材料。由于保存了金属有机物骨架使得有利于保持结构的稳定，使得电极材料在充放电过程中非常稳定，同时原位碳包覆不仅可以缓解体积膨胀，还提高了材料的导电性，使其表现出优异的电化学性能。The technical principle of the present invention is: using DMF as a suitable polar solvent, the metal-organic framework material generated by the iron source and the organic ligand can be formed into a material with an octahedral structure in the solvothermal process; The composition is converted into carbon, which is coated on the surface of metal atoms in situ, and finally the roasted product is phosphated by phosphorus vapor at high temperature to obtain an octahedral iron phosphide/carbon material. Due to the preservation of the metal-organic framework, it is beneficial to maintain the stability of the structure, making the electrode material very stable during the charge and discharge process. At the same time, the in-situ carbon coating can not only relieve the volume expansion, but also improve the conductivity of the material, making it excellent electrochemical performance.

与现有技术相比，本发明具有以下的有益效果：Compared with the prior art, the present invention has the following beneficial effects:

（1）本发明八面体结构磷化铁/碳复合材料成分为FeP，属于微孔材料，使电解液可以有效的与材料接触，缩短了锂离子和电子的扩散路径，加速离子和电子的跃迁。同时原位碳包覆的八面体结构，不仅有效缓解了被限制在多孔碳骨架中的FeP纳米粒子循环过程的体积膨胀，同时保留的金属有机物骨架可以增加材料的导电性；（2）将所述磷化铁/碳复合材料制成锂离子电池负极，组装成电池，在0.1~3.0V电压范围内，1C（1C=1000mA.g-1）大倍率下，循环450圈后仍有737.7 mAh.g-1的放电比容量，容量保持率≥95%。在充放电过程中，由于稳定的结构而具有较好的循环性能；（3）本发明制备方法工艺过程简单，周期短，成本低。(1) The composition of the octahedral structure iron phosphide/carbon composite material of the present invention is FeP, which is a microporous material, so that the electrolyte can effectively contact the material, shorten the diffusion path of lithium ions and electrons, and accelerate the transition of ions and electrons . At the same time, the in-situ carbon-coated octahedral structure not only effectively alleviates the volume expansion of FeP nanoparticles confined in the porous carbon framework during the cycle process, but also the retained metal-organic framework can increase the conductivity of the material; (2) The lithium-ion battery negative electrode is made of the above-mentioned iron phosphide/carbon composite material, and assembled into a battery. In the voltage range of 0.1~3.0V, under the high rate of 1C (1C=1000mA.g -1 ), there is still 737.7 mAh after 450 cycles .g -1 specific discharge capacity, capacity retention ≥ 95%. In the process of charge and discharge, it has better cycle performance due to the stable structure; (3) The preparation method of the present invention has simple process, short cycle and low cost.

附图说明Description of drawings

图1为本发明实施例1所得八面体结构磷化铁/碳复合材料的XRD图；Fig. 1 is the XRD pattern of octahedral structure iron phosphide/carbon composite material obtained in Example 1 of the present invention;

图2为本发明实施例1所得八面体结构磷化铁/碳复合材料的SEM图；Fig. 2 is the SEM picture of octahedral structure iron phosphide/carbon composite material obtained in Example 1 of the present invention;

图3为本发明实施例1所得八面体结构磷化铁/碳复合材料的前三次充放电曲线图；Fig. 3 is the first three charging and discharging curves of the octahedral iron phosphide/carbon composite material obtained in Example 1 of the present invention;

图4为本发明实施例1所得八面体结构磷化铁/碳复合材料的充电循环曲线图；Fig. 4 is the charging cycle graph of octahedral iron phosphide/carbon composite material obtained in Example 1 of the present invention;

图5为本发明实施例2所得八面体结构磷化铁/碳复合材料的SEM图；Fig. 5 is the SEM picture of octahedral structure iron phosphide/carbon composite material obtained in Example 2 of the present invention;

图6为本发明实施例2所得八面体结构磷化铁/碳复合材料的前三次充放电曲线图；Fig. 6 is the first three charge and discharge curves of the octahedral iron phosphide/carbon composite material obtained in Example 2 of the present invention;

具体实施方式Detailed ways

以下结合实施例对本发明作进一步详细说明，但本发明的保护范围并不限于以下实施例。以下所述各实施例所用化学试剂，如无特别说明，均通过常规商业途径购得。The present invention will be described in further detail below in conjunction with the examples, but the protection scope of the present invention is not limited to the following examples. The chemical reagents used in the various examples described below, unless otherwise specified, were purchased through conventional commercial channels.

实施例1Example 1

本发明八面体结构磷化铁/碳复合材料实施例包括原位碳包覆的磷化铁，所述磷化铁颗粒尺寸为400~700nm。An embodiment of the octahedral structure iron phosphide/carbon composite material of the present invention includes in-situ carbon-coated iron phosphide, and the particle size of the iron phosphide is 400-700 nm.

本实施例八面体结构磷化铁/碳负极材料复合材料的制备方法，包括以下步骤：The preparation method of the octahedral structure iron phosphide/carbon negative electrode material composite material of this embodiment comprises the following steps:

（1）称取1mmol的FeCl3.6H2O粉末加入到50ml的DMF溶液中，加热至30℃，搅拌1 h，搅拌的速度为800 转/min，得混合溶液；(1) Weigh 1 mmol of FeCl 3 .6H 2 O powder into 50 ml of DMF solution, heat to 30°C, stir for 1 h at a stirring speed of 800 rpm to obtain a mixed solution;

（2）向步骤（1）所得混合溶液中加入1mmol的对苯二甲酸粉末，加热至30℃，搅拌1 h，搅拌的速度为800 转/min，然后超声处理，得混合溶液；(2) Add 1 mmol of terephthalic acid powder to the mixed solution obtained in step (1), heat to 30°C, stir for 1 h at a stirring speed of 800 rpm, and then ultrasonically treat to obtain a mixed solution;

（3）将步骤（2）所得混合溶液置于聚四氟乙烯高压反应釜内，密封，置于高温干燥箱内，加热至120℃，反应8h，自然冷却，用乙醇和去离子水分别先后交叉离心洗涤6次，离心转速为8000转/min，每次离心时间为8min，然后将其置于烘箱中，60℃干燥24h，得黄色粉末；(3) Put the mixed solution obtained in step (2) in a polytetrafluoroethylene high-pressure reactor, seal it, put it in a high-temperature drying oven, heat it to 120°C, react for 8 hours, cool it naturally, and use ethanol and deionized water respectively Cross centrifugation and washing 6 times, the centrifugation speed is 8000 rpm, and the centrifugation time is 8 minutes each time, and then it is placed in an oven and dried at 60 ° C for 24 hours to obtain a yellow powder;

（4）将步骤（3）所得黄色粉末在高纯氩气气氛中，在700℃下，焙烧2h，自然冷却，得黑色粉末。(4) The yellow powder obtained in step (3) was calcined at 700°C for 2 hours in a high-purity argon atmosphere, and cooled naturally to obtain a black powder.

（5）将步骤（4）所得黑色粉末和红磷按照质量比1:5放到瓷舟里，将盛有黑色粉末的瓷舟置于石英管下游，盛有红磷的瓷舟置于石英管上游。在高纯氩气气氛中，在800℃下，焙烧2h，自然冷却，得棕色磷化铁/碳复合粉末。(5) Put the black powder and red phosphorus obtained in step (4) into a porcelain boat at a mass ratio of 1:5, place the porcelain boat containing the black powder downstream of the quartz tube, and place the porcelain boat containing red phosphorus in the quartz tube. pipe upstream. In a high-purity argon atmosphere, bake at 800°C for 2 hours and cool naturally to obtain brown iron phosphide/carbon composite powder.

经检测，本实施例所得八面体结构磷化铁/碳复合材料的成分为FeP，无杂质。After testing, the composition of the octahedral iron phosphide/carbon composite material obtained in this example is FeP without impurities.

如图2所示，本实施例所得八面体结构磷化铁/碳复合材料的磷化铁颗粒均匀。As shown in FIG. 2 , the iron phosphide particles of the octahedral structure iron phosphide/carbon composite material obtained in this embodiment are uniform.

电池的组装：称取0.40g本实施例所得八面体结构磷化铁/碳复合材料，加入0.05g乙炔黑作导电剂和0.05g N-甲基吡咯烷酮作粘结剂，混合均匀后，涂于铜箔上制成负极片，在真空手套箱中以金属锂片为正极，以锂电隔膜为隔膜，1mol/L LiPF6/EC:DMC（体积比1:1）为电解液，组装成CR2025的扣式电池。Battery assembly: Weigh 0.40g of the iron phosphide/carbon composite material with octahedral structure obtained in this example, add 0.05g of acetylene black as a conductive agent and 0.05g of N-methylpyrrolidone as a binder, mix well, and apply to The negative electrode sheet is made on copper foil, and the metal lithium sheet is used as the positive electrode in the vacuum glove box, the lithium battery diaphragm is used as the diaphragm, and 1mol/L LiPF 6 /EC:DMC (volume ratio 1:1) is used as the electrolyte, and assembled into CR2025 Button batteries.

由图3可知，在充放电电压为3~0.01V，电流密度为100mA.g-1下，所组装电池的首次充电比容量为1043.8mAh.g-1，二次充电比容量为956.9mAh.g-1，首次放电比容量为1827.4mAh.g-1，二次放电比容量为1037.6mAh.g-1，本实施例所得材料在充放电过程中能够保持结构的稳定，体积膨胀小，导电性好，使充放电反应高度可逆。It can be seen from Fig. 3 that when the charge and discharge voltage is 3~0.01V and the current density is 100mA.g -1 , the specific capacity of the assembled battery is 1043.8mAh.g -1 for the first charge and 956.9mAh for the second charge. g -1 , the specific capacity of the first discharge is 1827.4mAh.g -1 , and the specific capacity of the second discharge is 1037.6mAh.g -1 . The material obtained in this example can maintain a stable structure during the charging and discharging process, with small volume expansion and conductivity Good performance, making the charge-discharge reaction highly reversible.

由图4可知，在充放电电压为3~0.01V，电流密度为1A.g-1下，循环450圈后放电比容量为737.7mAh.g-1，比容量保持率为95%，充放电性能稳定，循环性能好。It can be seen from Figure 4 that at a charge-discharge voltage of 3-0.01V and a current density of 1A.g -1 , the discharge specific capacity after 450 cycles is 737.7mAh.g -1 , and the specific capacity retention rate is 95%. Stable performance and good cycle performance.

实施例2Example 2

（1）称取1.5mmol的FeCl3.6H2O粉末加入到80ml的DMF溶液中，加热至40℃，搅拌1 h，搅拌的速度为500 转/min，得混合溶液；(1) Weigh 1.5 mmol of FeCl 3 .6H 2 O powder into 80 ml of DMF solution, heat to 40°C, stir for 1 h at a stirring speed of 500 rpm to obtain a mixed solution;

（2）向步骤（1）所得混合溶液中加入1mmol的均苯三甲酸粉末，加热至40℃，搅拌0.5h，搅拌的速度为500 转/min，然后超声处理，得混合溶液；(2) Add 1 mmol of trimesic acid powder to the mixed solution obtained in step (1), heat to 40°C, stir for 0.5 h at a stirring speed of 500 rpm, and then ultrasonically treat to obtain a mixed solution;

（3）将步骤（2）所得混合溶液置于聚四氟乙烯高压反应釜内，密封，置于高温干燥箱内，加热至120℃，反应12h，自然冷却，然后用乙醇和去离子水分别先后交叉离心洗涤6次，离心转速为9000转/min，每次离心时间为8min，然后将其置于烘箱中，80℃干燥20h，得黄色粉末；(3) Put the mixed solution obtained in step (2) in a polytetrafluoroethylene high-pressure reactor, seal it, place it in a high-temperature drying oven, heat it to 120°C, react for 12 hours, cool naturally, and then use ethanol and deionized water to separate Cross centrifugation and washing 6 times successively, the centrifugation speed is 9000 rpm, and the centrifugation time is 8 minutes each time, and then it is placed in an oven and dried at 80°C for 20 hours to obtain a yellow powder;

（4）将步骤（3）所得黄色粉末在高纯氩气气氛中，在500℃下，焙烧3h，自然冷却，得黑色粉末。(4) The yellow powder obtained in step (3) was calcined in a high-purity argon atmosphere at 500°C for 3 hours, and cooled naturally to obtain a black powder.

（5）将步骤（4）所得黑色粉末和红磷按照质量比1:8放到瓷舟里，将盛有黑色粉末的瓷舟置于石英管下游，盛有红磷的瓷舟置于石英管上游。在高纯氩气气氛中，在750℃下，焙烧3h，自然冷却，得棕色磷化铁/碳复合粉末。(5) Put the black powder and red phosphorus obtained in step (4) into a porcelain boat at a mass ratio of 1:8, place the porcelain boat containing the black powder downstream of the quartz tube, and place the porcelain boat containing red phosphorus in the quartz tube. pipe upstream. In a high-purity argon atmosphere, roast at 750°C for 3 hours and cool naturally to obtain brown iron phosphide/carbon composite powder.

经检测，本实施例所得八面体结构磷化铁/碳复合材料的成分为FeP，无杂质。After testing, the composition of the octahedral iron phosphide/carbon composite material obtained in this example is FeP without impurities.

如图5所示，本实施例所得八面体结构磷化铁/碳复合材料结构形貌均一。电池的组装：称取0.40g本实施例所得八面体结构磷化铁/碳复合材料，加入0.05g乙炔黑作导电剂和0.05g N-甲基吡咯烷酮作粘结剂，混合均匀后，涂于铜箔上制成负极片，在真空手套箱中以金属锂片为正极，以锂电隔膜为隔膜，1mol/L LiPF6/EC:DMC（体积比1:1）为电解液，组装成CR2025的扣式电池。As shown in FIG. 5 , the octahedral iron phosphide/carbon composite material obtained in this embodiment has a uniform structure and morphology. Battery assembly: Weigh 0.40g of the iron phosphide/carbon composite material with octahedral structure obtained in this example, add 0.05g of acetylene black as a conductive agent and 0.05g of N-methylpyrrolidone as a binder, mix well, and apply on The negative electrode sheet is made on copper foil, and the metal lithium sheet is used as the positive electrode in the vacuum glove box, the lithium battery diaphragm is used as the diaphragm, and 1mol/L LiPF 6 /EC:DMC (volume ratio 1:1) is used as the electrolyte, and assembled into CR2025 Button batteries.

由图6可知，在充放电电压为3~0.01V，电流密度为100mA.g-1下，所组装电池的首次充电比容量为738.6 mAh.g-1，二次充电比容量为699.4mAh.g-1，首次放电比容量为1395.4mAh.g-1，二次放电比容量为747.8mAh.g-1，本实施例所得材料在充放电过程中能够保持结构的稳定，体积膨胀小，导电性好，使充放电反应高度可逆。It can be seen from Fig. 6 that when the charge and discharge voltage is 3~0.01V and the current density is 100mA.g -1 , the specific capacity of the assembled battery is 738.6 mAh.g -1 for the first charge and 699.4 mAh for the second charge. g -1 , the specific capacity of the first discharge is 1395.4mAh.g -1 , and the specific capacity of the second discharge is 747.8mAh.g -1 . The material obtained in this example can maintain a stable structure during the charging and discharging process, with small volume expansion and conductivity Good performance, making the charge-discharge reaction highly reversible.

经检测，在充放电电压为3~0.01V，电流密度为1A.g-1下，循环450圈后放电比容量为526.8mAh.g-1，比容量保持率为95%，充放电性能稳定，循环性能好。After testing, at a charge and discharge voltage of 3~0.01V and a current density of 1A.g -1 , the discharge specific capacity after 450 cycles is 526.8mAh.g -1 , the specific capacity retention rate is 95%, and the charge and discharge performance is stable. , good cycle performance.

实施例3Example 3

（1）称取2mmol的FeCl3.6H2O粉末加入到60ml的DMF溶液中，加热至50℃，搅拌1 h，搅拌的速度为400转/min，得混合溶液；(1) Weigh 2mmol of FeCl 3 .6H 2 O powder into 60ml of DMF solution, heat to 50°C, stir for 1 hour at a stirring speed of 400 rpm to obtain a mixed solution;

（2）向步骤（1）所得混合溶液中加入4mmol的氨基对苯二甲酸粉末，加热至50℃，搅拌2h，搅拌的速度为800转/min，超声处理，得混合溶液；(2) Add 4 mmol of aminoterephthalic acid powder to the mixed solution obtained in step (1), heat to 50° C., stir for 2 hours at a stirring speed of 800 rpm, and sonicate to obtain a mixed solution;

（3）将步骤（2）所得混合溶液置于聚四氟乙烯高压反应釜内，密封，置于高温干燥箱内，加热至150℃，反应16h，自然冷却，然后用乙醇和去离子水分别先后交叉离心洗涤6次，离心转速为10000转/min，每次离心时间为8min，然后将其置于烘箱中，100℃干燥16h，得黄色粉末；(3) Put the mixed solution obtained in step (2) in a polytetrafluoroethylene high-pressure reaction kettle, seal it, place it in a high-temperature drying oven, heat it to 150°C, react for 16 hours, cool it naturally, and then use ethanol and deionized water respectively Cross centrifugation and washing 6 times successively, the centrifugation speed is 10000 rpm, and the centrifugation time is 8 minutes each time, and then it is placed in an oven and dried at 100 ° C for 16 hours to obtain a yellow powder;

（4）将步骤（3）所得黄色粉末在高纯氩气气氛中，在600℃下，焙烧3h，自然冷却，得黑色粉末。(4) The yellow powder obtained in step (3) was calcined at 600°C for 3 hours in a high-purity argon atmosphere, and cooled naturally to obtain a black powder.

（5）将步骤（4）所得黑色粉末和红磷按照质量比1:10放到瓷舟里，将盛有黑色粉末的瓷舟置于石英管下游，盛有红磷的瓷舟置于石英管上游。在高纯氩气气氛中，在900℃下，焙烧2h，自然冷却，得棕色磷化铁/碳复合粉末。(5) Put the black powder and red phosphorus obtained in step (4) into a porcelain boat at a mass ratio of 1:10, place the porcelain boat containing the black powder downstream of the quartz tube, and place the porcelain boat containing red phosphorus in the quartz tube. pipe upstream. In a high-purity argon atmosphere, bake at 900°C for 2 hours and cool naturally to obtain brown iron phosphide/carbon composite powder.

经检测，本实施例所得八面体结构磷化铁/碳复合材料的成分为FeP，无杂质。After testing, the composition of the octahedral iron phosphide/carbon composite material obtained in this example is FeP without impurities.

经检测，本实施例所得八面体结构磷化铁/碳复合材料结构稳定，形貌均一，颗粒尺寸在400~700nm之间。After testing, the iron phosphide/carbon composite material with octahedral structure obtained in this example has a stable structure, uniform appearance, and a particle size between 400 and 700 nm.

电池的组装：称取0.40g本实施例所得八面体结构磷化铁/碳复合材料，加入0.05g乙炔黑作导电剂和0.05g N-甲基吡咯烷酮作粘结剂，混合均匀后，涂于铜箔上制成负极片，在真空手套箱中以金属锂片为正极，以锂电隔膜为隔膜，1mol/L LiPF6/EC:DMC（体积比1:1）为电解液，组装成CR2025的扣式电池。Battery assembly: Weigh 0.40g of the iron phosphide/carbon composite material with octahedral structure obtained in this example, add 0.05g of acetylene black as a conductive agent and 0.05g of N-methylpyrrolidone as a binder, mix well, and apply to The negative electrode sheet is made on copper foil, and the metal lithium sheet is used as the positive electrode in the vacuum glove box, the lithium battery diaphragm is used as the diaphragm, and 1mol/L LiPF 6 /EC:DMC (volume ratio 1:1) is used as the electrolyte, and assembled into CR2025 Button batteries.

经检测，在充放电电压为3~0.01V，电流密度为100mA.g-1下，所组装电池的首次充电比容量为637.3mAh.g-1，二次充电比容量为641mAh.g-1，首次放电电容量为1241mAh.g-1，二次放电电容量为672mAh.g-1，本实施例所得材料在充放电过程中能够保持结构的稳定，体积膨胀小，导电性好，使充放电反应高度可逆。After testing, when the charge and discharge voltage is 3~0.01V and the current density is 100mA.g -1 , the specific capacity of the assembled battery is 637.3mAh.g -1 for the first charge and 641mAh.g -1 for the second charge. , the first discharge capacity is 1241mAh.g -1 , and the second discharge capacity is 672mAh.g -1 . The material obtained in this example can maintain a stable structure, small volume expansion, and good conductivity during charging and discharging, making charging The discharge reaction is highly reversible.

经检测，在充放电电压为3～0.01V，电流密度为1A.g-1下，循环450圈后放电比容量为427.7mAh.g-1，比容量保持率为97%，充放电性能稳定，循环性能好。After testing, at a charge and discharge voltage of 3-0.01V and a current density of 1A.g -1 , the discharge specific capacity after 450 cycles is 427.7mAh.g -1 , the specific capacity retention rate is 97%, and the charge and discharge performance is stable. , good cycle performance.

Claims (10)

1. a kind of octahedral structure iron phosphide/carbon composite, which is characterized in that described including carbon-coated iron phosphide in situ Iron phosphide particle size is 400 ~ 700nm.
2. a kind of preparation method of octahedral structure iron phosphide/carbon composite, which comprises the following steps:
(1) by FeCl3.6H2O powder is added in DMF solution, heats, and stirring obtains mixed solution；
(2) organic ligand powder is added into mixed solution obtained by step (1), heats, stirs, ultrasonic treatment obtains mixed solution；
(3) mixed solution obtained by step (2) being placed in autoclave, is sealed, solvent thermal reaction occurs for heating, and it is cooling, Centrifugation is washed, dry, obtains yellow powder；
(4) it by yellow powder obtained by step (3) in argon gas or nitrogen atmosphere, roasts, it is cooling, obtain black powder；
(5) porcelain boat for filling black powder obtained by step (4) is placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule Upstream roasts in argon gas or nitrogen atmosphere, cooling, obtains iron phosphide/carbon composite.
3. octahedral structure iron phosphide/carbon composite preparation method according to claim 2, which is characterized in that step (1) in, FeCl in the mixed solution3.6H2The molar concentration of O is 20mmol/L ~ 40mmol/L, and the temperature of the heating is 25 ~ 50 DEG C, the speed of the stirring is 80 ~ 800 turns/min, more preferable 400 ~ 700 turns/min, time 0.5 of the stirring ~ 2h。
4. the iron phosphide of the octahedral structure according to Claims 2 or 3/carbon composite preparation method, which is characterized in that step Suddenly in (2), the organic ligand is fumaric acid, terephthalic acid (TPA), trimesic acid or 3, in 5- diaminobenzoic acid It is one or more of.
5. the iron phosphide of the octahedral structure according to one of claim 2 ~ 4/carbon composite preparation method, feature exist In, in step (2), the organic ligand and FeCl3.6H2The molar ratio of O is 0.25 ~ 2:1；The temperature of the heating is 25 ~ 50 ℃；The speed of the stirring is 80 ~ 800 turns/min, and the mixing time is 0.5 ~ 2 h.
6. the iron phosphide of the octahedral structure according to one of claim 2 ~ 5/carbon composite preparation method, feature exist In in step (3), the temperature of the heating is 100 ~ 160 DEG C, and the time of the heating is 4 ~ 18h.
7. the iron phosphide of the octahedral structure according to one of claim 2 ~ 6/carbon composite preparation method, feature exist In in step (3), the method for the washing is to be taken up in order of priority intersection centrifuge washing with ethyl alcohol and deionized water, the centrifugation 8000 ~ 10000 turns/min of revolving speed, 8 ~ 12 min of centrifugation time, are centrifuged number >=6 time, and the temperature of the drying is 60 ~ 100 DEG C, drying time is 12 ~ 24 h.
8. according to the iron phosphide of octahedral structure described in claim 2 ~ 7/carbon composite preparation method, which is characterized in that step Suddenly in (4), the temperature of the roasting is 500 ~ 700 DEG C, and the time of roasting is 2 ~ 6h, the purity of the argon gas or nitrogen >= 99.99%。
9. the iron phosphide of the octahedral structure according to one of claim 2 ~ 8/carbon composite preparation method, feature exist In in step (5), the mass ratio of the black powder and red phosphorus is 1:5 ~ 10, and the temperature of the roasting is 750 ~ 900 DEG C, roasting The time of burning is 1 ~ 3h.
10. a kind of octahedral structure iron phosphide as described in claim 1/application of the carbon composite in lithium ion battery.
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Application publication date: 20191115