CN103979615B - 硼掺杂α-Ni(OH)2及其制备方法、用途 - Google Patents

硼掺杂α-Ni(OH)2及其制备方法、用途 Download PDF

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CN103979615B
CN103979615B CN201410173459.1A CN201410173459A CN103979615B CN 103979615 B CN103979615 B CN 103979615B CN 201410173459 A CN201410173459 A CN 201410173459A CN 103979615 B CN103979615 B CN 103979615B
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CN103979615A (zh
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杨敬贺
李亚敏
杨朵
李旭影
陈威
吴玉峰
张文凯
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Henan University
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

本发明属于电化学、储能及无机材料技术领域，公开了一种硼掺杂α-Ni(OH)2及其制备方法、用途。硼掺杂α-Ni(OH)2是由纳米片相互交叠组装而成的花状多孔球。将镍源和P123混合并溶解在水中，分两次加入硼源，第一次加入后室温下搅拌至少2h，然后第二次加入，搅拌至少200min，过滤，干燥，得到硼掺杂的α-Ni(OH)2材料。本发明的优点是制备方法简单，制备的硼掺杂α-Ni(OH)2比表面高，可达400m2/g；在充放电电流为3A/g时，比电容高达~2296F/g，甚至经过2000次循环后，当电流密度为28.6A/g，比电容也没有明显的衰减，在电化学应用领域有较好的应用前景。

Description

硼掺杂α-Ni(OH)2及其制备方法、用途
技术领域
本发明属于电化学、储能及无机材料技术领域，涉及一种硼掺杂α-Ni(OH)2及其制备方法、用途。
背景技术
近年来，空气污染的日益严重以及人们对于新能源的迫切需求促进了可再生清洁能源的储存和转换的研究热情（X.Li,G.Zhang,X.Bai,X.Sun,X.Wang,E.Wang,H.Dai,HighlyconductinggraphenesheetsandLangmuir-Blodgettfilms,NatNanotechnol,3(2008)538-542.）。电化学超级电容器，一种比较有前景的汽车应用和便携设备的能源，因其较蓄电池具有较高的功率密度和较长的循环寿命而被认为是能源储存的候选者。根据电化学电容器储存电能的机理的不同，可以将它分为双电层电容器（EDLC）和赝电容器(Pesudocapaeitor)。双电层电容器的基本原理是利用电极和电解质之间形成的界面双电层来存储能量的一种新型电子元件，需要电极材料具有高的比表面，比如活性碳材料，而赝电容器在电极和电解质间总是存在法拉第氧化还原反应过程，如金属氢氧化物、导电聚合物等（J.H.Chang,M.Park,D.Ham,S.B.Ogale,R.S.Mane,S.H.Han,Liquid-phasesynthesizedmesoporouselectrochemicalsupercapacitorsofnickelhydroxide,ElectrochimActa,53(2008)5016-5021.）。赝电容器电子的储存是源于活性材料的氧化还原反应，因而可获得比双电层电容更高的电容量和能量密度。氢氧化镍因其具有明确的氧化还原反应、多种合成方法、成本低且在自然界中含量丰富等特点而被公认为是一种比较有前景的赝电容电极材料，因此通过合成高比表面的多孔性纳米结构的氢氧化镍来提高其比电容的方法意义重大。
发明内容
本发明所要解决的技术问题在于提供一种生产成本低、制备方法简单、比电容量大的硼掺杂α-Ni(OH)2及其制备方法、用途。
本发明的技术方案：
硼掺杂α-Ni(OH)2，其结构为：由纳米片相互交叠组装而成的花状多孔球。
进一步，纳米片的片长为50nm、片宽为50nm、片厚为5nm，花状多孔球的直径为300nm。
制备方法：将镍源和P123混合并溶解在水中，分两次加入硼源，第一次加入后室温下搅拌至少2h，然后第二次加入，搅拌至少200min，过滤，干燥，得到硼掺杂的α-Ni(OH)2材料。
所述镍源可以为硫酸镍、醋酸镍、氯化镍或硝酸镍；所述硼源可以为硼氢化钠、氧化硼或硼酸钠。
硼源优选以其水溶液形式加入。
硼掺杂α-Ni(OH)2的用途：用作电极材，更优选用作镍氢电池、镉镍电池或超级电容器的电极材料。
硼掺杂α-Ni(OH)2是基于表面活性剂自组装及与两种前驱体相互作用形成的。在反应过程中，随着体系PH值的增加，镍便会以硼掺杂的α相的Ni(OH)2析出，其中分两次加入硼源并且要长时间搅拌的目的是使硼氢化钠有足够的时间水解并游离出OH-，保持OH-具有一定的浓度和足够长的持续时间，以便更好地与镍接触反应。
本发明的优点是制备方法简单，制备的硼掺杂α-Ni(OH)2比表面高，可达400m2/g；在充放电电流为3A/g时，比电容高达~2296F/g，甚至经过2000次循环后，当电流密度为28.6A/g，比电容也没有明显的衰减，在电化学应用领域有较好的应用前景。
附图说明
图1为该材料的XRD图。
图2为该材料的XPS分析图。
图3为该材料的扫描电子显微镜（A，B）和透射电子显微镜（C，D）图。
图4A为该材料用于超级电容器电极材料依次在电流密度3A/g，6A/g，12A/g，24A/g和48A/g条件下，测得的恒流充放电曲线，其中Time(s)为充放电时间，Potentialvs.Ag/AgCl(V)为充放电的电压；图4B为由图4A所计算出的比电容，其中DischargeCurrent（A/g）放电比电流，SpecificCapacitance（F/g）为放电比电容；图4C为在电流密度28.6A/g条件下测定的充放电循环曲线，其中Time(s)为充放电时间，Potentialvs.Ag/AgCl(V)为充放电的电压；图4D为在电流密度28.6A/g条件下测定的充放电的循环稳定性图，其中CycleNumber为循环次数，CapacitanceRetention（%）为电容保持率。
具体实施方式
实施例1
称取8.6g六水合硝酸镍，加入到40ml蒸馏水中，搅拌分散15分钟，使镍盐充分溶解。称取4gP123（Aldrich，EO20PO70EO20，Ma=5800)，加入到400ml蒸馏水中，搅拌分散120分钟，使P123充分溶解。将硝酸镍溶液逐滴滴入P123溶液中，在40℃下搅拌2小时，然后自然降温，当温度下降至室温时，将20ml硼氢化钠溶液（含硼氢化钠1.5克）滴加到该混合溶液中，室温下搅拌2小时，然后再加入20ml硼氢化钠溶液（含硼氢化钠1.5克）到该混合溶液中，充分搅拌200分钟以后，生成浅绿色沉淀物，产物经蒸馏水、无水乙醇各洗涤3次，在真空干燥箱中80℃干燥24小时，即得到花状多孔球形的硼掺杂α-Ni(OH)2。
产物的XRD结果如图1所示，XPS分析图如图2所示，形貌观察如图3所示。图1和图2充分证明制备的产物确实为硼掺杂α-Ni(OH)2。由图3可知：该花状多孔球形的硼掺杂α-Ni(OH)2直径约为300nm，纳米片的长度约为50nm、宽度约为50nm、厚度约为5nm；其主要暴露晶面取向为（006）和（101）。
通过micro公司的ASAP2010分析仪，以氮气多图吸附的方法测量产物的BET比表面积，结果高达400m2/g。
图4A为该材料用于超级电容器电极材料依次在电流密度3A/g，6A/g，12A/g，24A/g和48A/g条件下，测得的恒流充放电曲线，其中Time(s)为充放电时间，Potentialvs.Ag/AgCl(V)为充放电的电压；图4B为由图4A所计算出的比电容，其中DischargeCurrent（A/g）放电比电流，SpecificCapacitance（F/g）为放电比电容；图4C为充放电循环，其中Time(s)为充放电时间，Potentialvs.Ag/AgCl(V)为充放电的电压；图4D为充放电的循环稳定性，其中CycleNumber为循环次数，CapacitanceRetention（%）为电容保持率。由图4B可知：在充放电电流为3A/g时，比电容高达~2296F/g；由图4D可知：当电流密度为28.6A/g，甚至经过2000次循环后，比电容也没有明显的衰减。

Claims (5)

1.硼掺杂α-Ni(OH)2，其特征在于其结构为：由纳米片相互交叠组装而成的花状多孔球；按下法制备获得：将镍源和P123混合并溶解在水中，分两次加入硼源，第一次加入后室温下搅拌至少2h，然后第二次加入，搅拌至少200min，过滤，干燥，得到硼掺杂的α-Ni(OH)2材料。
2.如权利要求1所述的硼掺杂α-Ni(OH)2，其特征在于：纳米片的片长为50nm、片宽为50nm、片厚为5nm，花状多孔球的直径为300nm。
3.如权利要求1或2所述的硼掺杂α-Ni(OH)2的制备方法，其特征在于：将镍源和P123混合并溶解在水中，分两次加入硼源，第一次加入后室温下搅拌至少2h，然后第二次加入，搅拌至少200min，过滤，干燥，得到硼掺杂的α-Ni(OH)2材料。
4.如权利要求3所述的硼掺杂α-Ni(OH)2的制备方法，其特征在于：所述镍源为硫酸镍、醋酸镍、氯化镍或硝酸镍；所述硼源为硼氢化钠。
5.如权利要求4所述的硼掺杂α-Ni(OH)2的制备方法，其特征在于：硼源以其水溶液形式加入。
CN201410173459.1A 2014-04-28 2014-04-28 硼掺杂α-Ni(OH)2及其制备方法、用途 Expired - Fee Related CN103979615B (zh)

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