CN114057241A - 一种镶嵌有钼酸镍纳米颗粒的自支撑低晶相氢氧化镍纳米片电极的制备方法及应用 - Google Patents
一种镶嵌有钼酸镍纳米颗粒的自支撑低晶相氢氧化镍纳米片电极的制备方法及应用 Download PDFInfo
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims description 5
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- 229910005809 NiMoO4 Inorganic materials 0.000 claims abstract description 20
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- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 12
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 12
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Abstract
本发明提供了一种自支撑低晶相Ni(OH)2·0.75H2O@NiMoO4纳米片电极的制备方法及应用，一步合成的产物为多层片状阵列，在结构中均匀细小NiMoO4颗粒镶嵌于Ni(OH)纳米片中，Ni(OH)2·0.75H2O和NiMoO4界面紧密接触不但有利于电解液的渗透、暴露尽可能的活性点外，还减小了电荷的传递阻抗、循环稳定性得到较好提升。
Description
技术领域
本发明提供了一种自支撑低晶相Ni(OH)2·0.75H2O@NiMoO4纳米片电极材料及制备方法，可应用于能量存储和能量转换领域。
背景技术
氢氧化镍（Ni(OH)2）纳米材料具有环境友好、理论容量高的优点，在超电容领域广泛研究和报道。但因Ni(OH)2本质低的电导，作为超电容的正极循环特性较差。最近报道的基于Ni(OH)2的核壳结构电极材料电化学特性有极大提高，但该材料大都采用多步的合成工艺制备，不但制备工序繁琐，且在使用中这种核壳材料极易剥落。
基于此，本发明提出了一种低成本、简单的一步水热法来合成成分可调的自支撑Ni(OH)/NiMoO4纳米片阵列电极。该电极材料的结构优势在于：一步合成的产物为多层片状阵列，在结构中均匀细小NiMoO4颗粒镶嵌于Ni(OH)纳米片中，Ni(OH)2·0.75H2O和NiMoO4界面紧密接触不但有利于电解液的渗透、暴露尽可能的活性点外，还减小了电荷的传递阻抗、循环稳定性得到较好提升。
发明内容
本发明的目的在于提供一种自支撑低晶相Ni(OH)2·0.75H2O@NiMoO4纳米片电极的制备方法及应用，一步合成自支撑高比容量的Ni(OH)2基核壳纳米片阵列，降低材料的阻抗、提升电极循环的寿命。
为实现上述目的，本发明采用如下技术方案：
自支撑低晶相Ni(OH)2·0.75H2O@NiMoO4纳米片电极的制备过程如下：
（1）以泡沫镍为衬底，将泡沫镍在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇中分别超声15分钟，最后在60℃烘箱中干燥10h；
（2）为了合成具有成分可调的氧化钼纳米颗粒镶嵌的层状Ni(OH)2 .0.75H2O 纳米片，将4.36~8.72g Ni(NO3)2·6H2O、3.63~7.26g Na2MoO4·2H2O和2.7~30.03g尿素溶于100ml去离子水中，混合液搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时。 待冷却至室温后样品取出，随后样品在去离子水中超声3分钟，60℃干燥6 h。
（3）采用三电极体系以Ni(OH)2·0.75H2O@NiMoO4 纳米片为工作电极、铂片为对电极、Hg/HgO为参比电极在 2M KOH电解液CV充放电激活500~1000圈，使Ni(OH)2·0.75H2O@NiMoO4纳米片电极形成分层多孔的结构。在泡沫镍衬底上所形成的自由站立的Ni(OH)2·0.75H2O@NiMoO4 纳米片电极比表面约为114m2/g，孔径为3.5 nm。
产物的结构特征如下：
1、产物结构为两相组成即：由Ni(OH)2·0.75H2O和NiMoO4组成，且NiMoO4纳米颗粒均匀镶嵌于低晶相Ni(OH)2·0.75H2O纳米片中；
2、Ni(OH)2·0.75H2O纳米片和NiMoO4颗粒成分比例可调。
本发明的优点在于：
（1）采用一步水热法在泡米镍衬底上合成了自支撑分层多孔的低晶相Ni(OH)2·0.75H2O@ NiMoO4纳米片阵列；
（2）本发明合成的产物为分层超薄的导电纳米片阵列。其中产物结构为NiMoO4纳米颗粒均匀镶嵌于低晶相Ni(OH)2·0.75H2O纳米片中；
（3）Ni(OH)2·0.75H2O纳米片和NiMoO4颗粒成分比例可调；
（4）Ni(OH)2·0.75H2O和NiMoO4界面紧密接触不但有利于电解液的渗透、暴露尽可能的活性点外，还减小了电荷的传递阻抗。
标准三电极体系下即：在1.8 A g-1条件下该电极的容量为2000 F g-1；两电极体系下即：以合成的产物为正极、活性碳为负极，在功率密度为318.84 W kg-1的条件下可获得了较高的能量密度（70.76 Wh kg-1），5000圈的充放电显示该材料具有较高的循环稳定性。
基于本发明所合成的产物具有独特特征结合其优良的电化学特性以及简便的制作工艺，该电极材料有望在能量存储领域获得应用。
附图说明
图1为不同合成条件下产物的形貌，（a）实施例1形貌，（b）实施例2形貌，（c）实施例3形貌，（d）实施例4形貌；
图2中（a-c）是实施例2产物的透射电镜照片，（d）选区衍射(SAED)照片；
图3中(a)实施例2产物的XRD图谱，(b-d)产物的XPS谱；
图4为产物的循环伏安（CV）曲线；
图5为产物的恒流充放电（GCD）曲线；
图6为实施例2产物在不同电流密度条件下的电容特性；
图7为实施例2产物和活性炭的CV曲线；
图8为ASC器件在不同电流密度下的GCD曲线；
图9为ASC器件循环稳定性。
具体实施方式
为让本发明的上述特征和优点能更明显易懂，下文特举实施例，作详细说明。本发明的方法如无特殊说明，均为本领域常规方法。
实施例1
以泡沫镍（20mm×40mm×1.6mm）为衬底进行水热合成。泡沫镍首先在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇分别超声15分钟，最后在60℃烘箱中干燥10h。为了合成具有氧化钼纳米颗粒镶嵌的层状Ni(OH)2 .0.75H2O 纳米片，以Ni(NO3)2·6H2O作为Ni源，以Na2MoO4·2H2O作为Mo源，分别将8.72g Ni(NO3)2·6H2O和3.63g Na2MoO4·2H2O溶于含有2.7g 尿素的去离子水（100mL）中，搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时。 最后样品取出在去离子水中超声3分钟，60℃干燥6 h待用。
实施例2
以泡沫镍（20mm×40mm×1.6mm）为衬底进行水热合成。泡沫镍首先在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇分别超声15分钟，最后在60℃烘箱中干燥10h。为了合成具有氧化钼纳米颗粒镶嵌的层状Ni(OH)2 .0.75H2O 纳米片，以Ni(NO3)2·6H2O作为Ni源，以Na2MoO4·2H2O作为Mo源，分别将8.72g Ni(NO3)2·6H2O和3.63g Na2MoO4·2H2O溶于含有12.01g 尿素的去离子水（100mL）中，搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时。 最后样品取出在去离子水中超声3分钟，60℃干燥6 h待用。
实施例3
以泡沫镍（20mm×40mm×1.6mm）为衬底进行水热合成。泡沫镍首先在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇分别超声15分钟，最后在60℃烘箱中干燥10h。为了合成具有氧化钼纳米颗粒镶嵌的层状Ni(OH)2 .0.75H2O 纳米片，以Ni(NO3)2·6H2O作为Ni源，以Na2MoO4·2H2O作为Mo源，分别将8.72g Ni(NO3)2·6H2O和3.63g Na2MoO4·2H2O溶于含有21.62g 尿素的去离子水（100mL）中，搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时。 最后样品取出在去离子水中超声3分钟，60℃干燥6 h待用。
实施例4
以泡沫镍（20mm×40mm×1.6mm）为衬底进行水热合成。泡沫镍首先在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇分别超声15分钟，最后在60℃烘箱中干燥10h。为了合成具有氧化钼纳米颗粒镶嵌的层状Ni(OH)2 .0.75H2O 纳米片，以Ni(NO3)2·6H2O作为Ni源，以Na2MoO4·2H2O作为Mo源，分别将8.72g Ni(NO3)2·6H2O和3.63g Na2MoO4·2H2O溶于含有30.03g尿素的去离子水（100mL）中，搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时。 最后样品取出在去离子水中超声3分钟，60℃干燥6 h待用。
电化学特性测量：
为了构建非对称超级电容装置（ASC），分别使用实施例2的产物（2.2 mg cm-2）作为正极和活性炭（AC）作为负极。通过混合质量比为8:1:1的活性炭、乙炔黑和聚四氟乙烯（PTFE）制备负极材料，随后将其粘结在泡沫镍上，并在80℃下在空气中干燥10 h。最后ASC装置中正负极由纤维素基滤纸分离，并使用2 M KOH水溶液作为电解液。
使用电化学工作站（PGSTAT302N，AUTOLAB）在2 M KOH电解液中对样品进行电化学测量。通过循环伏安法（CV）、恒流充放电（GCD）和电化学阻抗谱（EIS）对合成样品的性能进行了评估。电极的比电容可根据方程（1）和（2）从GCD曲线计算得出：
其中CA（F cm−2） 是面积比电容，C（F g-1）是质量比电容，I（A）是放电电流，S（cm2）是电极的几何面积，m（g）是活性材料的质量，ΔV（V）是放电时间Δt（s）内的电位变化。
根据GCD曲线计算非对称超级电容装置（ASC）的能量密度（E，Wh kg-1）和功率密度（P，W kg-1），如下所示：
式中，C（F g-1）是根据放电曲线计算的特殊电容，ΔV（V）表示电位窗口，Δt（s）表示放电时间。
图1~图3为产物的形貌和微结构表征：
由图1中（a~d）观察可知随着反应液中尿素含量的增加（从实施例1尿素的含量为2.7g，到实施例4的30.03g），产物（纳米片）在泡沫镍上延2D方向扩展，其宽度尺寸为100 to400 nm，厚度为10 to 30 nm，纳米片互联的网状结构逐渐变大且呈现出层状薄片多孔的特征。这种独特的形貌结构将为离子运输提供更多的活性点位。
表 1. 不同合成条件下产物中O, Ni and Mo的原子比
图2中a为产物（实施例2）低倍TEM照片。该纳米片具有超薄、光滑的特性。高倍HRTEM像(图2中b)显示许多黑色圆形颗状物嵌入在2D纳米片，这些圆形颗粒直径约为3-5nm。纳米颗粒晶格条纹为0.195nm和0.210nm的晶面间距分别对应于NiMoO4的(4 0 -3)和(3 1 -3)面（图2中c）。而颗粒物外面的白色区域的晶格条纹间距为0.268nm和0.197nm分别对应含水氢氧化镍（Ni(OH)2·0.75H2O）的(1 0 1)和(0 1 8)面。图2中d为样品的选区电子衍射（SAED）照片。由图可知除Ni(OH)2·0.75H2O外，SAED图谱证实了NiMoO4纳米颗粒的存在。
图3中a为样品（实施例2）的X射线衍射图。从XRD图谱中可以发现， 除44.5°、51.8°、76.4° 峰位(PDF#04-0850)来自泡沫镍外，产物主要由含水氢氧化镍（Ni(OH)2·0.75H2O, PDF#38-0715）以及NiMoO4构成（NiMoO4，PDF#45-0142）。图3中b为样品（实施例2）的表面特性。Ni 2p光谱(图3中c) 被卷积为Ni 2p3/2和Ni 2p1/2两个态。结合能为854.01eV和871.55 eV的峰对应于Ni2+，结合能为856.02 eV和873.72 eV的峰对应于Ni3+。在Mo 3dXPS光谱中（图3中d），位于230.83和233.94 eV的两个峰分别对应于Mo 3d5/2和Mo 3d3/2。
图4~图9为产物的电化学特性：
图4和图5分别是尿素含量2.7g（实施例1）、12.01g（实施例2）、21.62g（实施例3）和30.03g（实施例4）产物的CV和GCD曲线。观察可知实施例2所合成样品的CV曲线面积大于其他样品，在电流密度为4 mA cm-2下他们的放电时间分别为351.3s、550.3s、488.5s和438.4s，对应的面电容分别为2.81、4.4、3.91和3.51 F cm-2。图6为不同的放电电流密度条件下产物（实施例2）的电容特性。由图可知，产物在电流密度为4 mA cm-2(1.8A g-1)下电容为4.4 cm-2 （2000 F g-1）, 8 mA cm-2 (3.6 A g-1) 下电容为3.56 F cm-2 (1618 F g-1) ，12 mA cm-2 (5.4 A g-1) 下电容为3.12 F cm-2 (1417 F g-1)。
图7为产物（实施例2）和活性炭的CV曲线。产物和活性炭分别在扫速10 mV s-1下电势窗口为-0.2~0.8 V 和-1~0 V下测试。图8 为ASC在0~1.6V电位窗口内0.4~2 A g-1电流密度下记录的GCD曲线。经计算可知在电流密度为0.4、0.8、1.2、1.6和2.0 A g-1时，ASC的比电容分别为199、118、105、98和94 F g-1。 此外，由公式（3）和（4）计算知：ASC在功率密度为318.84 W kg-1时，能量密度值达70.76 Wh kg-1。循环试验显示，ASC器件具有良好的稳定性（图9），在100mV S-1的扫描速率下5000次循环后，容量保持率高达82.2%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (4)
1.一种镶嵌有钼酸镍纳米颗粒的自支撑低晶相氢氧化镍纳米片电极的制备方法，其特征在于，包括以下步骤：
（1）以泡沫镍为衬底，将泡沫镍在2M HCl中超声清洗10min，去除表面氧化层，接着分别在去离子水和无水乙醇中分别超声15分钟，最后在60℃烘箱中干燥10h；
（2）以Ni(NO3)2·6H2O作为Ni源，以Na2MoO4·2H2O作为Mo源，分别将Ni(NO3)2·6H2O和Na2MoO4·2H2O溶于含有尿素的去离子水中，搅拌40分钟后，接着将泡沫镍和前驱体溶液转移到特氟隆内衬的不锈钢高压釜中，110℃水热反应10小时，最后样品取出在去离子水中超声3分钟，60℃干燥6 h。
2.根据权利要求1所述的制备方法，其特征在于，100 ml前驱体溶液中Ni(NO3)2·6H2O的含量为4.36-8.72g，Na2MoO4·2H2O的含量为3.63-7.26g，尿素的含量为2.7-30.03g。
3.如权利要求1或2所述的制备方法制得的自支撑低晶相Ni(OH)2·0.75H2O@NiMoO4纳米片电极。
4.如权利要求3所述的自支撑低晶相Ni(OH)2·0.75H2O@ NiMoO4纳米片电极在作为电极材料中的应用。
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