CN115512977B - FeP hollow nanorod for super capacitor and preparation method thereof - Google Patents
FeP hollow nanorod for super capacitor and preparation method thereof Download PDFInfo
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Abstract
一种超级电容器用FeP空心纳米棒材料，所述FeP纳米棒为FeP纳米颗粒堆积形成空心结构纳米棒，是以MoO3纳米纤维作为模板，在其表面沉积FeOOH纳米颗粒，消除模板后磷化得到。本发明制备的FeP材料有着独特空心棒状形貌和发达的分级空隙结构，比表面积较大，故而有利于充放电过程中电解质离子的扩散和传输，进而增强电荷存储能力，其比电容可高达245.2F/g。本发明制备的FeP空心纳米棒材料的倍率表现和充放电过程中循环稳定性也极其出色，在较高电流密度下（5A/g）连续充放电10000次后依旧保持有86.2%的电容量，同样优于许多已报道的铁基超级电容器电极材料。
A FeP hollow nanorod material for a supercapacitor. The FeP nanorod is formed by stacking FeP nanoparticles to form a hollow structure nanorod. It uses MoO3 nanofibers as a template, deposits FeOOH nanoparticles on its surface, and phosphates it after eliminating the template. . The FeP material prepared by the present invention has a unique hollow rod shape and a developed hierarchical pore structure, and has a large specific surface area, so it is beneficial to the diffusion and transmission of electrolyte ions during the charging and discharging process, thereby enhancing the charge storage capacity, and its specific capacitance can be as high as 245.2 F/g. The rate performance and cycle stability of the FeP hollow nanorod material prepared in the present invention are also excellent, and it still maintains a capacitance of 86.2% after 10,000 continuous charge and discharge cycles at a relatively high current density (5A/g). It is also superior to many reported iron-based supercapacitor electrode materials.
Description
技术领域technical field
本发明涉及电化学技术领域，具体涉及一种超级电容器用的FeP空心纳米棒及其制备方法。The invention relates to the technical field of electrochemistry, in particular to a FeP hollow nanorod for a supercapacitor and a preparation method thereof.
背景技术Background technique
超级电容器因简单的构造、较快的充放电速度、长的使用寿命、大的工作温度范围和良好的稳定性，使之在储能领域展现出更为广阔的前景。影响超级电容器储能性质的因素有多个，比如电极材料、隔膜、电解液、集流体等，但其中影响最为显著的当属电极活性材料。当前市面上的商业超级电容器多采用基于双电层储能机理的多孔碳作为活性材料，虽然其充放电性质稳定，但比容量较低，电荷存储能力相对有限。为了克服这一缺点，近年来人们大力发展基于赝电容储能机理的电极活性材料，比如各种氧化物、硫化物、磷化物等。Due to its simple structure, fast charging and discharging speed, long service life, large operating temperature range and good stability, supercapacitors show a broader prospect in the field of energy storage. There are many factors that affect the energy storage properties of supercapacitors, such as electrode materials, separators, electrolytes, current collectors, etc., but the most significant impact is the electrode active material. Most of the commercial supercapacitors currently on the market use porous carbon based on the electric double layer energy storage mechanism as the active material. Although its charge and discharge properties are stable, its specific capacity is low and its charge storage capacity is relatively limited. In order to overcome this shortcoming, in recent years, people have vigorously developed electrode active materials based on the pseudocapacitive energy storage mechanism, such as various oxides, sulfides, and phosphides.
作为磷化物的典型代表，磷化铁在用作电极材料时拥有许多优点，如高的理论比容量，平坦的充放电曲线，成本低廉，储量丰富。但是磷化铁作为超级电容器电极材料时，也面临其他金属氧化物、硫化物存在的问题：导电性差，循环过程中容量衰减严重，具有较差的倍率性能，充放电过程产生较大的体积膨胀。由于存在上述技术问题，使得磷化铁的电化学性能较差，循环稳定性也不尽人意，故难以实现大规模的商业化应用。As a typical representative of phosphide, iron phosphide has many advantages when used as an electrode material, such as high theoretical specific capacity, flat charge-discharge curve, low cost, and abundant reserves. However, when iron phosphide is used as an electrode material for supercapacitors, it also faces the problems of other metal oxides and sulfides: poor conductivity, severe capacity decay during cycling, poor rate performance, and large volume expansion during charge and discharge. . Due to the above-mentioned technical problems, the electrochemical performance of iron phosphide is poor, and the cycle stability is not satisfactory, so it is difficult to realize large-scale commercial application.
现有技术中也常将其与其他材料比如碳进行复合，在一定程度上来降低上述问题带来的负面影响，但是效果并不明显，然而很少从FeP材料本身进行优化类解决上述问题，来改善FeP材料的性能。磷化铁的传统制备工艺是通过氧化铁和磷化氢(PH3)或者磷酸盐热分解产生的磷化氢在高温条件下反应合成。但制备出的磷化铁颗粒尺寸大，均匀性差，制备过程中难以调控产物的物相和形貌，孔隙结构不够发达，比表面积小，不利于充放电过程中电解质离子的扩散和传输，致使其电荷存储能力较差。因此，需要从工艺上进行优化，调控FeP的形貌尺寸及结构孔隙，从而提高其电化学储能性能。In the prior art, it is often combined with other materials such as carbon to reduce the negative impact of the above problems to a certain extent, but the effect is not obvious. However, it is rarely optimized to solve the above problems from the FeP material itself. Improve the performance of FeP materials. The traditional preparation process of iron phosphide is to synthesize iron oxide and phosphine (PH 3 ) or phosphine produced by thermal decomposition of phosphate under high temperature conditions. However, the prepared iron phosphide particles are large in size and poor in uniformity. It is difficult to control the phase and morphology of the product during the preparation process. Its charge storage ability is poor. Therefore, it is necessary to optimize the process to control the morphology, size and structural pores of FeP, so as to improve its electrochemical energy storage performance.
发明内容Contents of the invention
基于上述问题，本发明目的在于提供一种超级电容器用的FeP空心纳米棒材料。Based on the above problems, the object of the present invention is to provide a FeP hollow nanorod material for supercapacitors.
本发明目的在于提供上述FeP空心纳米棒材料的制备方法。通过制备出具有特定结构的FeP材料，从而提高其电化学性能。The purpose of the present invention is to provide a method for preparing the above-mentioned FeP hollow nanorod material. By preparing the FeP material with a specific structure, its electrochemical performance can be improved.
本发明目的通过如下技术方案实现：The object of the invention is achieved through the following technical solutions:
一种超级电容器用的FeP空心纳米棒材料，其特征在于：所述FeP纳米棒为FeP纳米颗粒堆积形成空心结构纳米棒，是以MoO3纳米纤维作为模板，在其表面沉积FeOOH纳米颗粒，消除模板后磷化得到。A kind of FeP hollow nanorod material that supercapacitor is used, it is characterized in that: described FeP nanorod is that FeP nanoparticle piles up and forms hollow structure nanorod, uses MoO3 nanofiber as template, deposits FeOOH nanoparticle on its surface, eliminates Post-template phosphorylation.
进一步，所述FeP空心纳米棒材料是通过先合成MoO3纳米纤维，将其分散于去离子水中，再加入Na2SO4和FeCl3∙6H2O组成的混合水溶液，加热处理，然后用氨水去除MoO3模板，最后采用NaH2PO2磷化处理制得。Further, the FeP hollow nanorod material is synthesized by first synthesizing MoO 3 nanofibers, dispersing them in deionized water, adding a mixed aqueous solution composed of Na 2 SO 4 and FeCl 3 ∙ 6H 2 O, heat treatment, and then using ammonia water Remove the MoO 3 template, and finally use NaH 2 PO 2 phosphating to make it.
进一步，上述MoO3纳米纤维和去离子水的质量体积比为1.2mg：1mL。Further, the mass volume ratio of the above-mentioned MoO 3 nanofibers and deionized water is 1.2mg: 1mL.
进一步，上述去离子水和混合水溶液的体积比为5:1。Further, the volume ratio of the deionized water and the mixed aqueous solution is 5:1.
进一步，上述混合水溶液中，Na2SO4、FeCl3∙6H2O和水的质量体积比为5.6mg：2.7-32.4mg：1mL。Further, in the above mixed aqueous solution, the mass volume ratio of Na 2 SO 4 , FeCl 3 ∙6H 2 O and water is 5.6mg:2.7-32.4mg:1mL.
进一步，上述磷化处理是将NaH2PO2和FeOOH纳米棒在N2氛围下，于350-360℃下保温1.5-2h。Further, the above phosphating treatment is to keep NaH 2 PO 2 and FeOOH nanorods at 350-360° C. for 1.5-2 hours under N 2 atmosphere.
进一步，上述NaH2PO2和FeOOH纳米棒的质量比为2-40：1。Further, the mass ratio of the aforementioned NaH 2 PO 2 to FeOOH nanorods is 2-40:1.
进一步，上述合成MoO3纳米纤维是将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维。Further, the above synthesis of MoO 3 nanofibers was carried out by dissolving (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then adding concentrated HNO 3 , stirring evenly, and reacting hydrothermally at 180 o C for 8 hours. The product was filtered, After washing with water and drying, MoO 3 nanofibers were obtained.
进一步，上述(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL。Further, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙4H 2 O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
进一步，上述加热处理的温度为90-100℃，处理时间为2h。Further, the temperature of the above heat treatment is 90-100° C., and the treatment time is 2 hours.
上述FeP空心纳米棒材料的制备方法，其特征在于：先合成MoO3纳米纤维，将其分散于去离子水中，再加入Na2SO4和FeCl3∙6H2O组成的混合水溶液，加热处理，然后去除MoO3模板，最后进行磷化处理。The method for preparing the above-mentioned FeP hollow nanorod material is characterized in that: first synthesize MoO 3 nanofibers, disperse them in deionized water, then add a mixed aqueous solution composed of Na 2 SO 4 and FeCl 3 ∙ 6H 2 O, heat treatment, The MoO3 template is then removed, and finally phosphating is performed.
在以MoO3为模板沉积制备FeP过程中，发现制备的FeP前驱体物质没有形成均匀沉积，在该过程中，生成的纳米颗粒少，且沉积不均匀，不能完全包覆MoO3模板，在刻蚀模板后，模板表面的纳米材料出现严重碎裂，不能形成完整的空心结构，此外前驱体物质沉积时出现了明显的聚集成团。将该前驱体物质磷化制备的成品中出现了Fe2O3、Fe2P等杂质。以上问题极大地影响了产物最终的电化学储能性质。In the process of preparing FeP by using MoO 3 as template deposition, it was found that the prepared FeP precursor material did not form a uniform deposition. After the template was etched, the nanomaterials on the surface of the template were severely fragmented, and a complete hollow structure could not be formed. In addition, the precursor substances were obviously aggregated into agglomerates during deposition. Fe 2 O 3 , Fe 2 P and other impurities appeared in the finished product prepared by phosphating the precursor material. The above problems greatly affect the final electrochemical energy storage properties of the product.
本发明中通过在FeCl3水溶液中加入Na2SO4，在其作用下，FeCl3水解生成大量的FOOH纳米颗粒，其形貌粒径均匀，此外，研究中发现，在以MoO3为模板的体系中，Na2SO4起到了促进FOOH纳米颗粒在MoO3表面沉积的作用，从而增强了FOOH在对MoO3的完整包覆，去除模板后，依然能保持其空心纳米棒结构，且由纳米颗粒沉积形成的纳米棒，颗粒之间形成了分级空隙结构，提高了材料的比表面积，从而促进充放电过程中电解质离子的扩散和传输，增强其电荷存储能力，此外纳米颗粒组成空心纳米棒中具有分级空隙结构，形成了多孔导电网格，提高了电极材料的导电性，同时缓解了充放电过程中的体积膨胀效应。In the present invention, by adding Na 2 SO 4 to the FeCl 3 aqueous solution, under its action, FeCl 3 is hydrolyzed to generate a large number of FOOH nanoparticles, which have uniform shape and particle size. In addition, it is found in the research that in the MoO 3 template In the system, Na 2 SO 4 plays a role in promoting the deposition of FOOH nanoparticles on the surface of MoO 3 , thereby enhancing the complete coating of FOOH on MoO 3 , and after removing the template, it can still maintain its hollow nanorod structure, and the nano The nanorods formed by particle deposition form a hierarchical void structure between the particles, which increases the specific surface area of the material, thereby promoting the diffusion and transport of electrolyte ions during charge and discharge, and enhancing its charge storage capacity. In addition, the nanoparticles are composed of hollow nanorods. With a hierarchical pore structure, a porous conductive grid is formed, which improves the conductivity of the electrode material and alleviates the volume expansion effect during charging and discharging.
进一步，上述MoO3纳米纤维和去离子水的质量体积比为1.2mg：1mL。Further, the mass volume ratio of the above-mentioned MoO 3 nanofibers and deionized water is 1.2mg: 1mL.
进一步，上述去离子水和混合水溶液的体积比为5:1。Further, the volume ratio of the deionized water and the mixed aqueous solution is 5:1.
进一步，上述混合水溶液中，Na2SO4、FeCl3∙6H2O和水的质量体积比为5.6mg：2.7-32.4mg：1mL。Further, in the above mixed aqueous solution, the mass volume ratio of Na 2 SO 4 , FeCl 3 ∙6H 2 O and water is 5.6mg:2.7-32.4mg:1mL.
进一步，上述磷化处理是将NaH2PO2和FeOOH纳米棒在N2氛围下，于350-360℃下保温1.5-2h。Further, the above phosphating treatment is to keep NaH 2 PO 2 and FeOOH nanorods at 350-360° C. for 1.5-2 hours under N 2 atmosphere.
进一步，上述NaH2PO2和FeOOH纳米棒的质量比为2-40：1。Further, the mass ratio of the aforementioned NaH 2 PO 2 to FeOOH nanorods is 2-40:1.
进一步，上述合成MoO3纳米纤维是将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维。Further, the above synthesis of MoO 3 nanofibers was carried out by dissolving (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then adding concentrated HNO 3 , stirring evenly, and reacting hydrothermally at 180 o C for 8 hours. The product was filtered, After washing with water and drying, MoO 3 nanofibers were obtained.
进一步，上述(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL。Further, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙4H 2 O, deionized water and concentrated sulfuric acid is 1.8g:300mL:60mL.
进一步，上述加热处理的温度为90-100℃，处理时间为2h。Further, the temperature of the above heat treatment is 90-100° C., and the treatment time is 2 hours.
最具体的，一种超级电容器用的FeP空心纳米棒的制备方法，其特征在于，按如下步骤进行：Most specifically, a method for preparing FeP hollow nanorods for supercapacitors is characterized in that, the steps are as follows:
步骤（一）制备MoO3纳米纤维Step (1) Preparation of MoO 3 nanofibers
将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入质量浓度为68%的浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维，(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL；Dissolve (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then add concentrated HNO 3 with a mass concentration of 68%, stir evenly, and conduct a hydrothermal reaction at 180 o C for 8 hours. The product is suction filtered, washed with water, and dried After obtaining MoO 3 nanofibers, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙ 4H 2 O, deionized water and concentrated sulfuric acid is 1.8g: 300mL: 60mL;
步骤（二）制备MoO3/FeOOH复合纳米纤维Step (2) Preparation of MoO 3 /FeOOH composite nanofibers
将120mg的MoO3纳米纤维加入100mL去离子水中并超声分散，再加入20mL预先溶解有112mg Na2SO4和54-648mg FeCl3∙6H2O的水溶液，将反应液搅拌下加热至90-100oC，保持2h，使FeOOH纳米颗粒均匀沉积至MoO3纳米纤维表面，合成出MoO3/FeOOH复合纳米纤维；Add 120 mg of MoO 3 nanofibers into 100 mL of deionized water and ultrasonically disperse, then add 20 mL of an aqueous solution in which 112 mg Na 2 SO 4 and 54-648 mg FeCl 3 ∙ 6H 2 O have been dissolved in advance, and heat the reaction solution to 90-100 °C while stirring o C, kept for 2 hours, so that FeOOH nanoparticles were evenly deposited on the surface of MoO 3 nanofibers, and MoO 3 /FeOOH composite nanofibers were synthesized;
步骤（三）制备FeOOH空心纳米棒Step (3) Preparation of FeOOH hollow nanorods
MoO3/FeOOH复合纳米纤维经抽滤、反复水洗后超声分散于50mL水中，快速搅拌下逐滴加入5mL质量分数为10%的氨水，反应过夜，使氨水充分溶解MoO3内核，从而获得FeOOH空心纳米棒；MoO 3 /FeOOH composite nanofibers were ultrasonically dispersed in 50 mL of water after suction filtration and repeated washing, and 5 mL of ammonia water with a mass fraction of 10% was added dropwise under rapid stirring, and reacted overnight to fully dissolve the MoO 3 core with ammonia water, thereby obtaining FeOOH hollow cores. Nano stave;
步骤（三）磷化处理Step (3) Phosphating treatment
取将干燥好的FeOOH空心纳米棒铺展于瓷舟一端，然后将NaH2PO2粉末置于磁舟另一端，将瓷舟放入气氛管式炉中，使NaH2PO2粉末处于上风端，然后在N2氛围中于350-360oC保持2h，NaH2PO2粉末和FeOOH空心纳米棒的质量比为2-40:1。Spread the dried FeOOH hollow nanorods on one end of the porcelain boat, then place the NaH 2 PO 2 powder on the other end of the magnetic boat, put the porcelain boat into the atmosphere tube furnace, and make the NaH 2 PO 2 powder at the windward end, Then keep at 350-360 o C for 2h in N 2 atmosphere, the mass ratio of NaH 2 PO 2 powder and FeOOH hollow nanorods is 2-40:1.
本发明具有如下技术效果：The present invention has following technical effect:
本发明制备的FeP材料可用作超级电容器电极活性成分，有着独特空心棒状形貌和发达的分级空隙结构，且比表面积较大，故而有利于充放电过程中电解质离子的扩散和传输，进而增强电荷存储能力，其比电容可高达245.2F/g，远超许多其他铁基材料和商业化多孔碳材料的比电容。本发明制备的FeP空心纳米棒材料的倍率表现和充放电过程中循环稳定性也极其出色，在较高电流密度下（5A/g）连续充放电10000次后依旧保持有86.2%的电容量，同样优于许多已报道的铁基超级电容器电极材料。The FeP material prepared by the present invention can be used as the active component of supercapacitor electrodes, has a unique hollow rod-like morphology and a developed hierarchical pore structure, and has a large specific surface area, so it is beneficial to the diffusion and transmission of electrolyte ions during charging and discharging, thereby enhancing The charge storage capacity, its specific capacitance can be as high as 245.2F/g, far exceeding the specific capacitance of many other iron-based materials and commercial porous carbon materials. The rate performance and cycle stability of the FeP hollow nanorod material prepared in the present invention are also excellent, and it still maintains a capacitance of 86.2% after 10,000 continuous charge and discharge cycles at a relatively high current density (5A/g). It is also superior to many reported iron-based supercapacitor electrode materials.
附图说明Description of drawings
图1：MoO3纳米纤维高、低倍下的扫描电镜图。Figure 1: SEM images of MoO 3 nanofibers at high and low magnifications.
图2：MoO3/FeOOH复合纳米纤维高、低倍下的扫描电镜图。Figure 2: SEM images of MoO 3 /FeOOH composite nanofibers at high and low magnifications.
图3：FeOOH空心纳米棒高、低倍下的扫描电镜图。Figure 3: SEM images of FeOOH hollow nanorods at high and low magnifications.
图4：是FeP空心纳米棒高、低倍下的扫描电镜图。Figure 4: SEM images of FeP hollow nanorods at high and low magnifications.
图5：FeP空心纳米棒高、低倍下的透射电镜图。Figure 5: TEM images of FeP hollow nanorods at high and low magnifications.
图6：FeOOH空心纳米棒和FeP空心纳米棒的XRD谱图。Figure 6: XRD patterns of FeOOH hollow nanorods and FeP hollow nanorods.
图7：FeP空心纳米棒的氮气吸附-脱附曲线。Figure 7: Nitrogen adsorption–desorption curves of FeP hollow nanorods.
图8：FeP空心纳米棒的孔径分布图。Figure 8: Pore size distribution map of FeP hollow nanorods.
图9：FeP空心纳米棒电极在不同扫速下的循环伏安曲线。Figure 9: Cyclic voltammetry curves of FeP hollow nanorod electrodes at different scan rates.
图10：FeP空心纳米棒电极在不同电流密度下的充放电曲线。Figure 10: Charge-discharge curves of FeP hollow nanorod electrodes at different current densities.
图11：FeP空心纳米棒电极在10000次连续充放电过程中的电容保持情况图。Figure 11: Capacitance retention of FeP hollow nanorod electrodes during 10,000 continuous charge-discharge cycles.
图12：FeP空心纳米棒电极连续充放电10000次过程中的最后10次充放电曲线图。Figure 12: The last 10 charge-discharge curves of the FeP hollow nanorod electrode during 10,000 continuous charge-discharge cycles.
图13：FeP空心纳米棒电极连续充放电10000次之前和之后的电化学阻抗谱图。Figure 13: Electrochemical impedance spectra of FeP hollow nanorod electrodes before and after 10,000 continuous charge-discharge cycles.
具体实施方式Detailed ways
下面通过实施例对本发明进行具体的描述，有必要在此指出的是，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。The present invention is specifically described by the following examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and cannot be interpreted as limiting the protection scope of the present invention. Those skilled in the art can according to the above-mentioned description SUMMARY OF THE INVENTION Some non-essential improvements and adjustments are made to the present invention.
实施例1Example 1
一种超级电容器用的FeP空心纳米棒的制备方法，按如下步骤进行：A kind of preparation method of the FeP hollow nanorod that supercapacitor is used, carries out as follows:
步骤（一）制备MoO3纳米纤维Step (1) Preparation of MoO 3 nanofibers
将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入质量浓度为68%的浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维，(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL；Dissolve (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then add concentrated HNO 3 with a mass concentration of 68%, stir evenly, and conduct a hydrothermal reaction at 180 o C for 8 hours. The product is suction filtered, washed with water, and dried After obtaining MoO 3 nanofibers, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙ 4H 2 O, deionized water and concentrated sulfuric acid is 1.8g: 300mL: 60mL;
步骤（二）制备MoO3/FeOOH复合纳米纤维Step (2) Preparation of MoO 3 /FeOOH composite nanofibers
将120mg的MoO3纳米纤维加入100mL去离子水中并超声分散，再加入20mL预先溶解有112mg Na2SO4和216mg FeCl3∙6H2O的水溶液，将反应液搅拌下加热至90oC，保持2h，使FeOOH纳米颗粒均匀沉积至MoO3纳米纤维表面，合成出MoO3/FeOOH复合纳米纤维；Add 120 mg of MoO 3 nanofibers into 100 mL of deionized water and ultrasonically disperse, then add 20 mL of an aqueous solution in which 112 mg Na 2 SO 4 and 216 mg FeCl 3 ∙ 6H 2 O have been dissolved in advance, and heat the reaction solution to 90 o C while stirring, keeping 2h, the FeOOH nanoparticles were uniformly deposited on the surface of MoO 3 nanofibers, and MoO 3 /FeOOH composite nanofibers were synthesized;
步骤（三）制备FeOOH空心纳米棒Step (3) Preparation of FeOOH hollow nanorods
将步骤（二）制备的MoO3/FeOOH复合纳米纤维经抽滤、反复水洗后超声分散于50mL水中，快速搅拌下逐滴加入5mL质量分数为10%的氨水，反应过夜，使氨水充分溶解MoO3内核，从而获得FeOOH空心纳米棒；The MoO 3 /FeOOH composite nanofibers prepared in step (2) were filtered, washed repeatedly, and ultrasonically dispersed in 50mL of water. Under rapid stirring, 5mL of ammonia water with a mass fraction of 10% was added dropwise and reacted overnight to fully dissolve MoO with ammonia water. 3 cores to obtain FeOOH hollow nanorods;
步骤（三）磷化处理Step (3) Phosphating treatment
取50mg 干燥的FeOOH空心纳米棒铺展于瓷舟一端，然后将500mg NaH2PO2粉末置于磁舟另一端，将瓷舟放入气氛管式炉中，使NaH2PO2粉末处于上风端，然后在N2氛围中于350oC保持2h。Take 50mg of dried FeOOH hollow nanorods and spread them on one end of the porcelain boat, then put 500mg of NaH 2 PO 2 powder on the other end of the magnetic boat, put the porcelain boat into the atmosphere tube furnace so that the NaH 2 PO 2 powder is at the upwind end, Then it was kept at 350 o C for 2 h in N 2 atmosphere.
通过上述水热过程合成得到的MoO3纳米纤维呈白色，图1是其扫描电镜图，不难发现表面较为光滑。以MoO3纳米纤维作为基底，通过液相反应，使FeCl3在Na2SO4作用下水解生成的FeOOH纳米颗粒，且成功且均匀地沉积于基底表面获得黄棕色的MoO3/FeOOH复合纳米纤维。图2为MoO3/FeOOH复合纳米纤维的扫描电镜图，很明显，其表面较为粗糙，由许多FeOOH纳米颗粒堆积而成，并形成了良好的孔隙结构。在使用稀氨水将MoO3模板刻蚀后，便得到黄棕色的FeOOH空心纳米棒（图3），但其长度明显小于MoO3/FeOOH复合纳米纤维。采用NaH2PO2作为磷源将FeOOH空心纳米棒在气氛管式炉中磷化后合成得到本发明中的FeP空心纳米棒。与FeOOH比较，FeP形貌并无明显改变（图3和图4），但其颜色呈现出灰黑色，而其透射电镜图则很好地证实了较为完好的空心棒状结构（图5）。图6是本实施例制备的FeOOH空心纳米棒和FeP空心纳米棒的XRD谱图，从图中可以看出，FeP空心纳米棒的XRD显示出8个特征峰，2θ角位于30.8°、32.7°、35.6°、37.1°、46.9°、48.2°、55.8°和59.4°，分别对应于FeP的（020）、（011）、（200）、（111）、（220）、（211）、（031）和（002）晶面；值得一提的是，该XRD谱图并未出现其他杂峰，再次表明了模板的彻底去除，且形成了较纯的最终产物FeP。图7是FeP空心纳米棒的N2吸附-脱附曲线，该谱图中在相对压力位于0.7-1.0范围内出现了明显的回滞环，表明了多孔特点，而图8则进一步确认了其介孔属性和孔径分布范围。此外，其通过相关计算，其比表面积高达280 m2/g，FeP空心纳米棒如此大的比表面积、空心结构以及多孔特征不但利于其充放电过程中电解质离子的传输和扩散同时也能增加活性位点，提升电荷存储能力。The MoO 3 nanofibers synthesized through the above hydrothermal process are white. Figure 1 is a scanning electron microscope image, and it is not difficult to find that the surface is relatively smooth. Using MoO 3 nanofibers as the substrate, through liquid phase reaction, FeCl 3 is hydrolyzed under the action of Na 2 SO 4 to form FeOOH nanoparticles, which are successfully and uniformly deposited on the surface of the substrate to obtain yellow-brown MoO 3 /FeOOH composite nanofibers . Figure 2 is a scanning electron microscope image of MoO 3 /FeOOH composite nanofibers. It is obvious that the surface is relatively rough, which is formed by the accumulation of many FeOOH nanoparticles and forms a good pore structure. After etching the MoO 3 template with dilute ammonia water, the yellow-brown FeOOH hollow nanorods (Fig. 3) were obtained, but their length was significantly smaller than that of MoO 3 /FeOOH composite nanofibers. Using NaH 2 PO 2 as phosphorus source, the FeOOH hollow nanorods were phosphated in an atmosphere tube furnace and then synthesized to obtain the FeP hollow nanorods of the present invention. Compared with FeOOH, the morphology of FeP has not changed significantly (Figure 3 and Figure 4), but its color is gray-black, and its transmission electron microscope image well confirms a relatively intact hollow rod structure (Figure 5). Figure 6 is the XRD spectrum of FeOOH hollow nanorods and FeP hollow nanorods prepared in this example. It can be seen from the figure that the XRD of FeP hollow nanorods shows 8 characteristic peaks, and the 2θ angles are located at 30.8° and 32.7° , 35.6°, 37.1°, 46.9°, 48.2°, 55.8° and 59.4°, corresponding to (020), (011), (200), (111), (220), (211), (031 ) and (002) crystal planes; it is worth mentioning that there are no other impurity peaks in the XRD spectrum, which again indicates the complete removal of the template and the formation of a relatively pure final product FeP. Figure 7 is the N adsorption-desorption curve of FeP hollow nanorods. In this spectrum, there is an obvious hysteresis loop in the relative pressure range of 0.7-1.0, indicating the porous characteristics, while Figure 8 further confirms its Mesopore properties and pore size distribution range. In addition, through relevant calculations, its specific surface area is as high as 280 m 2 /g. The large specific surface area, hollow structure and porous characteristics of FeP hollow nanorods are not only conducive to the transport and diffusion of electrolyte ions during the charge and discharge process, but also increase the activity. sites to enhance charge storage capacity.
实施例2Example 2
将实施例1中FeP空心纳米棒作为活性材料制备成超级电容器电极并用于电化学测试：FeP hollow nanorods are prepared as an active material into a supercapacitor electrode in Example 1 and used for electrochemical testing:
分别称取40mg实施例1中的FeP空心纳米棒、5mg乙炔黑和5mg聚偏氟乙烯，将它们转移至研钵中，加入少量甲基吡咯烷酮后充分研磨成糊状物，再以小毛刷将其均匀涂覆至尺寸为1cm×3cm的泡沫镍表面，涂覆面积为1cm×1cm，且只涂覆一面，接下来将该泡沫镍在压片机上压片，之后置于真空干燥箱中干燥后获得电极。以该泡沫镍电极为工作电极，Hg/HgO电极为参比电极，铂片为对电极，2M KOH为电解质，搭建出典型的三电极装置，进行电化学储能行为的测试。 Weigh 40mg of FeP hollow nanorods in Example 1, 5mg of acetylene black and 5mg of polyvinylidene fluoride, transfer them to a mortar, add a small amount of methylpyrrolidone and grind them fully into a paste, then use a small brush to It is evenly coated on the surface of nickel foam with a size of 1cm×3cm, the coating area is 1cm×1cm, and only one side is coated, and then the nickel foam is pressed on a tablet machine, and then placed in a vacuum drying oven to dry obtained electrodes. Using the nickel foam electrode as the working electrode, the Hg/HgO electrode as the reference electrode, the platinum sheet as the counter electrode, and 2M KOH as the electrolyte, a typical three-electrode device was built to test the electrochemical energy storage behavior.
图9是FeP空心纳米棒电极在一系列扫速下的循环伏安图，每一条曲线的电位测试窗口都是-0.8V~0V，且都有一个宽的氧化还原峰，表明了其赝电容的储能特性。图10是其在一系列电流密度（0.2~5A/g）下的充放电曲线，经计算其0.2A/g电流密度下的最大比电容高达245.2F/g，远超许多其他铁基材料（如各种铁氧化物、铁硫化物等）和商业化多孔碳材料的比电容。本实施例中的FeP空心纳米棒电极倍率性质也是相当优异，比如将电流密度增大25倍后，即从0.2A/g提升到5A/g后，其比电容数值仍旧有145.1F/g，相当于其最大值的59.2%。值得注意的是，将该电极在5A/g的高电流电流密度下连续充放电10000次后，还能保有86.7%的电容量（图11），而在此测试过程中的最后10次充放电曲线保持着良好形状（图12），且反复充放电前后的电化学阻抗谱图也仅有着稍稍改变（图13），反映了其出众的循环稳定性和长的使用寿命，这些显著的电化学行为同样超出许多已报道的铁基超级电容器电极材料，展示出了优异的储能优势和光明的应用前景。Figure 9 is the cyclic voltammogram of the FeP hollow nanorod electrode at a series of scan rates. The potential test window of each curve is -0.8V~0V, and there is a broad redox peak, indicating its pseudocapacitance energy storage characteristics. Figure 10 shows its charge and discharge curves at a series of current densities (0.2~5A/g). It is calculated that its maximum specific capacitance at a current density of 0.2A/g is as high as 245.2F/g, far exceeding many other iron-based materials ( Such as various iron oxides, iron sulfides, etc.) and the specific capacitance of commercial porous carbon materials. The rate property of the FeP hollow nanorod electrode in this embodiment is also quite excellent. For example, after increasing the current density by 25 times, that is, after increasing from 0.2A/g to 5A/g, its specific capacitance value still has 145.1F/g, Equivalent to 59.2% of its maximum value. It is worth noting that the electrode can still retain 86.7% of the capacitance after 10,000 continuous charge-discharge cycles at a high current density of 5A/g (Figure 11), and the last 10 charge-discharge cycles during this test The curve maintains a good shape (Figure 12), and the electrochemical impedance spectrum before and after repeated charge and discharge changes only slightly (Figure 13), reflecting its outstanding cycle stability and long service life. The behavior also exceeds many reported iron-based supercapacitor electrode materials, showing excellent energy storage advantages and bright application prospects.
实施例3Example 3
一种超级电容器用的FeP空心纳米棒的制备方法，按如下步骤进行：A kind of preparation method of the FeP hollow nanorod that supercapacitor is used, carries out as follows:
步骤（一）制备MoO3纳米纤维Step (1) Preparation of MoO 3 nanofibers
将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入质量浓度为68%的浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维，(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL；Dissolve (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then add concentrated HNO 3 with a mass concentration of 68%, stir evenly, and conduct a hydrothermal reaction at 180 o C for 8 hours. The product is suction filtered, washed with water, and dried After obtaining MoO 3 nanofibers, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙ 4H 2 O, deionized water and concentrated sulfuric acid is 1.8g: 300mL: 60mL;
步骤（二）制备MoO3/FeOOH复合纳米纤维Step (2) Preparation of MoO 3 /FeOOH composite nanofibers
将120mg的MoO3纳米纤维加入100mL去离子水中并超声分散，再加入20mL预先溶解有112mg Na2SO4和54mg FeCl3∙6H2O的水溶液，将反应液搅拌下加热至100oC，保持2h，使FeOOH纳米颗粒均匀沉积至MoO3纳米纤维表面，合成出MoO3/FeOOH复合纳米纤维；Add 120 mg of MoO 3 nanofibers into 100 mL of deionized water and ultrasonically disperse them, then add 20 mL of an aqueous solution in which 112 mg of Na 2 SO 4 and 54 mg of FeCl 3 ∙ 6H 2 O have been dissolved in advance, and heat the reaction solution to 100 o C while stirring, keeping 2h, the FeOOH nanoparticles were uniformly deposited on the surface of MoO 3 nanofibers, and MoO 3 /FeOOH composite nanofibers were synthesized;
步骤（三）制备FeOOH空心纳米棒Step (3) Preparation of FeOOH hollow nanorods
将步骤（二）制备的MoO3/FeOOH复合纳米纤维经抽滤、反复水洗后超声分散于50mL水中，快速搅拌下逐滴加入5mL质量分数为10%的氨水，反应过夜，使氨水充分溶解MoO3内核，从而获得FeOOH空心纳米棒；The MoO 3 /FeOOH composite nanofibers prepared in step (2) were filtered, washed repeatedly, and ultrasonically dispersed in 50mL of water. Under rapid stirring, 5mL of ammonia water with a mass fraction of 10% was added dropwise and reacted overnight to fully dissolve MoO with ammonia water. 3 cores to obtain FeOOH hollow nanorods;
步骤（三）磷化处理Step (3) Phosphating treatment
取50mg 干燥的FeOOH空心纳米棒铺展于瓷舟一端，然后将100mg NaH2PO2粉末置于磁舟另一端，将瓷舟放入气氛管式炉中，使NaH2PO2粉末处于上风端，然后在N2氛围中于355oC保持2h。Take 50mg of dried FeOOH hollow nanorods and spread them on one end of the porcelain boat, then place 100mg of NaH 2 PO 2 powder on the other end of the magnetic boat, put the porcelain boat into the atmosphere tube furnace, make the NaH 2 PO 2 powder at the upwind end, Then it was kept at 355 o C for 2 h in N 2 atmosphere.
本实施例制备的FeP空心纳米棒表面较为粗糙，由许多纳米颗粒堆积而成，并形成了良好的孔隙结构，其比表面积达到277 m2/g。The surface of the FeP hollow nanorods prepared in this example is relatively rough, composed of many nanoparticles stacked, and a good pore structure is formed, and its specific surface area reaches 277 m 2 /g.
如实施例2的方法测试其性能，在0.2A/g电流密度下的最大比电容高达241.7F/g；在5A/g的高电流电流密度下连续充放电10000次后，还能保有83.9%的电容量。Its performance is tested by the method of Example 2, and the maximum specific capacitance at a current density of 0.2A/g is as high as 241.7F/g; after continuous charging and discharging for 10,000 times at a high current density of 5A/g, it can still retain 83.9% of capacitance.
实施例4Example 4
一种超级电容器用的FeP空心纳米棒的制备方法，按如下步骤进行：A kind of preparation method of the FeP hollow nanorod that supercapacitor is used, carries out as follows:
步骤（一）制备MoO3纳米纤维Step (1) Preparation of MoO 3 nanofibers
将(NH4)2MoO4∙4H2O溶解于去离子水中，再加入质量浓度为68%的浓HNO3，搅拌均匀后在180oC下水热反应8h，产物经抽滤、水洗、干燥后得到MoO3纳米纤维，(NH4)2MoO4∙4H2O、去离子水和浓硫酸的质量体积比为1.8g：300mL：60mL；Dissolve (NH 4 ) 2 MoO 4 ∙4H 2 O in deionized water, then add concentrated HNO 3 with a mass concentration of 68%, stir evenly, and conduct a hydrothermal reaction at 180 o C for 8 hours. The product is suction filtered, washed with water, and dried After obtaining MoO 3 nanofibers, the mass volume ratio of (NH 4 ) 2 MoO 4 ∙ 4H 2 O, deionized water and concentrated sulfuric acid is 1.8g: 300mL: 60mL;
步骤（二）制备MoO3/FeOOH复合纳米纤维Step (2) Preparation of MoO 3 /FeOOH composite nanofibers
将120mg的MoO3纳米纤维加入100mL去离子水中并超声分散，再加入20mL预先溶解有112mg Na2SO4和648mg FeCl3∙6H2O的水溶液，将反应液搅拌下加热至90-100oC，保持2h，使FeOOH纳米颗粒均匀沉积至MoO3纳米纤维表面，合成出MoO3/FeOOH复合纳米纤维；Add 120 mg of MoO 3 nanofibers into 100 mL of deionized water and ultrasonically disperse, then add 20 mL of an aqueous solution in which 112 mg Na 2 SO 4 and 648 mg FeCl 3 ∙ 6H 2 O have been dissolved in advance, and heat the reaction solution to 90-100 o C while stirring , kept for 2h, so that FeOOH nanoparticles were uniformly deposited on the surface of MoO 3 nanofibers, and MoO 3 /FeOOH composite nanofibers were synthesized;
步骤（三）制备FeOOH空心纳米棒Step (3) Preparation of FeOOH hollow nanorods
将步骤（二）制备的MoO3/FeOOH复合纳米纤维经抽滤、反复水洗后超声分散于50mL水中，快速搅拌下逐滴加入5mL质量分数为10%的氨水，反应过夜，使氨水充分溶解MoO3内核，从而获得FeOOH空心纳米棒；The MoO 3 /FeOOH composite nanofibers prepared in step (2) were filtered, washed repeatedly, and ultrasonically dispersed in 50mL of water. Under rapid stirring, 5mL of ammonia water with a mass fraction of 10% was added dropwise and reacted overnight to fully dissolve MoO with ammonia water. 3 cores to obtain FeOOH hollow nanorods;
步骤（三）磷化处理Step (3) Phosphating treatment
取50mg干燥的 FeOOH空心纳米棒铺展于瓷舟一端，然后将2000mg NaH2PO2粉末置于磁舟另一端，将瓷舟放入气氛管式炉中，使NaH2PO2粉末处于上风端，然后在N2氛围中于360oC保持2h。Take 50mg of dried FeOOH hollow nanorods and spread them on one end of the porcelain boat, then put 2000mg of NaH 2 PO 2 powder on the other end of the magnetic boat, put the porcelain boat into the atmosphere tube furnace, so that the NaH 2 PO 2 powder is at the windward end, Then it was kept at 360 o C for 2 h in N 2 atmosphere.
本实施例制备的FeP空心纳米棒表面较为粗糙，由许多纳米颗粒堆积而成，并形成了良好的孔隙结构，其比表面积达到281 m2/g。The surface of the FeP hollow nanorods prepared in this example is relatively rough, composed of many nanoparticles stacked, and a good pore structure is formed, and its specific surface area reaches 281 m 2 /g.
如实施例2的方法测试其性能，在0.2A/g电流密度下的最大比电容高达244.3F/g；在5A/g的高电流电流密度下连续充放电10000次后，还能保有85.2%的电容量。Its performance is tested by the method of Example 2, and the maximum specific capacitance under the current density of 0.2A/g is as high as 244.3F/g; after continuous charging and discharging for 10,000 times under the high current density of 5A/g, it can still retain 85.2% of capacitance.
在大量试验过程中，我们尝试过使用NaCl等盐替换Na2SO4，发现其对于FeCl3水解生成FOOH纳米颗粒没有任何促进作用，水解产物（前驱体）主要为形貌不规则（尺寸不一的纳米片、纳米颗粒等）的Fe(OH)3和Fe2O3，且在MoO3模板表面沉积时并没有起到促进沉积的作用，依然存在沉积物团聚，前驱体不能完全包覆MoO3模板，使得去除模板后其结构坍塌，无法保持空心纳米管结构的问题。During a large number of experiments, we tried to replace Na 2 SO 4 with NaCl and other salts, and found that it did not promote the hydrolysis of FeCl 3 to form FOOH nanoparticles, and the hydrolyzed products (precursors) were mainly irregular in shape (different sizes) Nanosheets, nanoparticles, etc.) of Fe(OH) 3 and Fe 2 O 3 , and did not play a role in promoting deposition when deposited on the surface of the MoO 3 template, there is still sediment agglomeration, and the precursor cannot completely cover MoO 3 templates, so that the structure collapses after the template is removed, and the hollow nanotube structure cannot be maintained.
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