CN111170374A - 一种泡沫镍担载硫化物/磷化物复合亚微米管电容材料及其制备方法 - Google Patents
一种泡沫镍担载硫化物/磷化物复合亚微米管电容材料及其制备方法 Download PDFInfo
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 7
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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Abstract
本发明提出了一种制备方法,在保持硫化物片状阵列结构的基础上,引入高导电性的磷化物,获得了泡沫镍担载硫化物/磷化物复合亚微米管电容材料;在水浴加热的条件下,通过机械搅拌制得Fe‑Co前驱体,然后对其依次进行磷化、硫化反应制得最终产物;该材料可直接应用于固态超级电容器的电极,兼具高比电容、高循环稳定性,在30mA/cm2的高电流密度下,经过10000次充放电循环后,电极的质量比电容仍有91.98%的保持率;本发明为高性能超级电容器电极提出了新方法,无需任何添加剂或模板,原材料便宜,环境友好,且易于控制。
Description
技术领域:
本发明涉及一种具有高比电容、高循环稳定性的超级电容器材料的制备方法,其特征为,在水浴加热的条件下,通过机械搅拌制得Fe-Co前驱体,然后对其依次进行磷化、硫化反应。该制备方法具有原料便宜,制备方法简单,对环境友好,易于控制的优点。
背景技术:
随着社会的发展,能源需求不断增加,再加上石油等能源的不可再生性,能源紧缺已经成为全球性问题。对环境友好型、清洁能源的探索,是目前研究的热点。超级电容器有着高功率密度、高循环稳定性及使用寿命长、安全等优点,是一种新型储能器件,而电极材料的选择、设计和制备是高性能超级电容器研发的重点。
超级电容器电极材料主要有:碳材料、金属化合物和导电聚合物。其中金属化合物的研究已经有了长足的发展,过渡金属氧化物已被广泛研究用于赝电容超级电容器,但其弱导电性导致了器件能量密度低和循环稳定性差,因此,探索兼具高导电性和高稳定性的赝电容电极材料是当前该领域一直追求的目标。
国际上大量研究报道,通过硫代替金属氧化物中的氧,可得到更柔性、稳定的结构;硫元素有着低于氧元素的电负性,并且阴离子交换使得材料带隙变窄,有助于性能地提升。过渡金属磷化物有着金属般的导电性,并且磷元素有着更多地价态,保证了储能过程中有着更多种的氧化还原反应。因此,如何综合利用磷化物和硫化物的优势,成为了我们研究的重点。另一方面,管状纳米结构因具有内外表面,可提供高活性比表面积,更有利于电荷的储存;且管状阵列形成的多孔结构缩短了离子的扩散距离,有利于电解液离子及电荷的转移。
本发明提出,在保持硫化物片状阵列结构的基础上,引入高导电性的磷化物,提出了一种制备方法,获得了兼具高比电容、高循环稳定性的硫化物/磷化物复合亚微米管电容材料。
发明内容:
本发明的目的:提出了一种新型硫化物/磷化物复合亚微米管电容材料及其制备方法。设计并制备了由纳米片交织构建的亚微米管,兼具高比表面积和高力学稳定性的优点,同时将高导电性的金属磷化物引入,从而保证了较高的电化学储能性能;在30mA/cm2的高电流密度下,经历10000次充放电循环后,该电极的质量比电容值仍有91.98%的保持率。
本发明的技术方案是:本发明在水浴加热的条件下,通过机械搅拌的方法,制得Fe-Co前驱体,然后对其进行磷化和硫化反应,从而获得具有高比电容、高循环稳定性的硫化物/磷化物复合亚微米管电容材料。将三价铁盐、二价钴盐溶于去离子水中,配成混合溶液和泡沫镍一起放入三颈瓶中,在35~45℃恒温水浴、40~50r/min机械搅拌下,滴加草酸溶液,之后再搅拌1~4h,得到泡沫镍担载Fe-Co前驱体;然后,将前驱体和次磷酸盐分别置于两个瓷舟中,在氮气保护下进行磷化;将得到的中间产物放入配置好的硫化钠溶液中,在100~120℃水热反应釜中硫化反应6~9h,待反应釜冷却,取出样品,用去离子水反复洗涤后在40~60℃空气中烘干,得到最终产物。
上述方案中,制备Fe-Co前驱体过程所使用混合溶液中,三价铁盐Fe(NO3)3的浓度为8~12mM,二价钴盐Co(NO3)2的浓度为8~12mM,泡沫镍基底的尺寸为3cm×1cm。
上述方案中,制备Fe-Co前驱体过程中,草酸溶液浓度为8~12mM,体积为40~50mL,采用滴加的方式加入,滴加时间为8~10min。
上述方案中,制备中间产物磷化过程中所使用的次磷酸盐用量为0.03~0.06g,反应温度为280~320℃,升温速率为2~4℃/min,反应时间为2~4h。
上述方案中,硫化反应采用硫化钠溶液的浓度为9~14mM,反应条件为100~120℃,反应时间为6~9h。
本发明在最优化条件下制得的这种独特新型电极材料,它是泡沫镍担载硫化物/磷化物复合亚微米管电容材料,其特征在于,单根管的外径为1μm,管壁厚度为320nm,由硫化物片状阵列构成的多孔表层结构,磷化物位于纳米片的顶端;纳米片的厚度约为15nm。
所制得的泡沫镍担载硫化物/磷化物复合亚微米管材料,可直接应用于固态超级电容器的电极,无需粘结剂,其兼备高比电容、高循环稳定性的特点;与其它方法相比,本发明提出的制备方法无需任何添加剂或模板,原材料便宜,环境友好,且易于控制。
有益效果:
(1)本发明提出了在保持硫化物片状阵列结构的基础上,引入高导电性的磷化物,获得了兼具高比电容、高循环稳定性的硫化物/磷化物复合亚微米管电容材料。
(2)本发明提出一种制备新方法本:水浴加热的条件下,通过机械搅拌的方法,制得Fe-Co前驱体,然后对其进行磷化和硫化反应。
(3)与其他方法相比,该制备方法具有以下优点:
①制备过程简单,操作方便,重复性高;
②环境友好,整个制备过程不对环境造成污染;
③成本较低,具有良好的工业化应用前景。
附图说明:
图1为实施例1制备产物的(a)SEM图和(b)TEM图。
图2为实施例1制备产物的XRD图谱。
图3为实施例1制备产物的XPS图谱。
图4为实施例1制备产物的(a)循环伏安曲线;(b)恒电流充放电曲线;(c)不同电流密度下的质量比电容值;(d)重复充放电循环后的比电容保持率。
具体实施方式:
本发明中制备泡沫镍担载硫化物/磷化物复合亚微米管电容材料,具体实施方式如下:
实施例1
泡沫镍担载硫化物/磷化物复合亚微米管电容材料:将包含三价铁盐Fe(NO3)3和11mM的二价钴盐Co(NO3)2的混合溶液(两种浓度均为11mM)和长方形泡沫镍(3cm×1cm)一起放入三颈瓶中,在35℃恒温水浴、45r/min速度持续机械搅拌情况下,滴加11mM的草酸溶液,之后再搅拌3h,得到泡沫镍担载Fe-Co的前驱体。然后,将前驱体和0.05g次磷酸钠分别置于两个瓷舟中,在氮气保护下进行磷化;将得到的中间产物放入配置好的11mM硫化钠溶液中,在100℃水热反应釜中硫化反应6h,待反应釜冷却,取出样品,用去离子水反复洗涤后在50℃空气中烘干,得到最终产物。
图1a是实施例1制备产物的SEM图。可以看到,亚微米管均匀的分布在泡沫镍的骨架上,并且各个管之间相互独立。放大的SEM图像显示,单根管的外径为1μm,表面由相互连接的纳米片构成,片与片之间形成了多孔形貌,纳米片的厚度约为15nm。图1b为制备产物的TEM图,证明单根管内部为中空结构,管壁厚度为320nm。
图2是实施例1制备产物的XRD图谱,衍射峰分别对应于FeCo2S4和Fe2P,CoP,证实了最终产物为硫化物/磷化物复合材料。
图3是实施例1制备产物的产物XPS谱图。Fe 2p的高分辨XPS图谱(图3a)表明,两个主峰的位置分别位于709.6eV和723.5eV处,由此得知Fe元素的价态为二价Fe;Co 2p的高分辨XPS图谱(图3b)表明,两个主峰的位置分别位于779.2eV和794.9eV处,由此得知Co元素的价态为二价Co和三价Co;对于P元素的XPS测试结果(图3c),峰位主要出现在128.9,131.8和133.9eV三个位置。128.9和131.8eV处的峰分别对应于P 2p3/2和P 2p1/2,这证明样品中存在金属-磷化学键;而S 2p3/2和S 2p1/2的峰值主要位于157.8和160.8eV处(图3d),这表明S元素以S2-状态存在。
图4是实施例1制备产物电化学性能测试图。图4a为样品在不同扫描速率下的循环伏安CV曲线(5到40mV/s),可以观察到明显的氧化峰和还原峰,这表明硫化物/磷化物复合材料具有赝电容特性。图4b是硫化物/磷化物复合材料在不同电流密度下的恒流充放电曲线,放电阶段中存在着明显的放电平台,这与循环伏安曲线的氧化还原峰相对应,表明该材料具有良好的可逆性。图4c为不同电流密度下的比电容值,电极在电流密度为5mA/cm2时达到了3692F/g的面电容值;在电流密度升高至20mA/cm2时,电容保持率达到70%。图4d为硫化物/磷化物复合材料在30mA/cm2的扫描电流速率下,充放电10000圈的循环性能。经过10000次充放电过程后,电极材料的电容保持率高达91.98%,在最后2000圈中,电容值仅下降了0.61%,库伦效率也始终保持在90%左右,这证明了其优越的循环稳定性。
实施例2
在制备泡沫镍担载Fe-Co的前驱体过程中,将混合溶液中三价铁盐、二价钴盐、草酸溶液的浓度都改变为8mM,其他条件和实施例1相同。
实施例3
在制备泡沫镍担载Fe-Co的前驱体过程中,将混合溶液中三价铁盐、二价钴盐、草酸溶液的浓度都改变为9mM,其他条件和实施例1相同。
实施例4
在制备泡沫镍担载Fe-Co的前驱体过程中,将混合溶液中三价铁盐、二价钴盐、草酸溶液的浓度都改变为12mM,其他条件和实施例1相同。
实施例5
制备中间产物磷化过程中,将次磷酸盐用量改为0.02g,其他条件和实施例1相同。
实施例6
制备中间产物磷化过程中,将次磷酸盐用量改为0.06g,其他条件和实施例1相同。
实施例7
硫化反应过程中,将硫化钠溶液的浓度改为9mM,其他条件和实施例1相同。
实施例8
硫化反应过程中,将硫化钠溶液的浓度改为13mM,其他条件和实施例1相同。
所述实施例为本发明的优选的实施方式,但本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (7)
1.一种泡沫镍担载硫化物/磷化物复合亚微米管电容材料及其制备方法,其特征在于,将三价铁盐、二价钴盐溶于去离子水中,配成混合溶液和泡沫镍一起放入三颈瓶中,在35~45℃恒温水浴、40~50r/min机械搅拌下,滴加草酸溶液,之后再搅拌1~4h,得到泡沫镍担载Fe-Co前驱体;然后,将前驱体和次磷酸盐分别置于两个瓷舟中,在氮气保护下进行磷化;将得到的中间产物放入配置好的硫化钠溶液中,在100~120℃水热反应釜中硫化反应6~9h,待反应釜冷却,取出样品,用去离子水反复洗涤后在40~60℃空气中烘干,得到最终产物。
2.如权利要求书1所述的制备方法,其特征在于,制备Fe-Co前驱体过程所使用混合溶液中,三价铁盐Fe(NO3)3的浓度为8~12mM,二价钴盐Co(NO3)2的浓度为8~12mM,泡沫镍基底的尺寸为3cm×1cm。
3.如权利要求书1所述的制备方法,其特征在于,制备Fe-Co前驱体过程中,草酸溶液浓度为8~12mM,体积为40~50mL,采用滴加的方式加入,滴加时间为8~10min。
4.如权利要求书1所述的制备方法,其特征在于,.是通过先磷化再硫化的步骤制得;制备中间产物磷化过程中所使用的次磷酸盐用量为0.03~0.06g,反应温度为280~320℃,升温速率为2~4℃/min,反应时间为2~4h。
5.如权利要求书1所述的制备方法,其特征在于,硫化反应采用硫化钠溶液的浓度为9~14mM,反应条件为100~120℃,反应时间为6~9h。
6.如权利要求书1所述的泡沫镍担载硫化物/磷化物复合亚微米管电容材料,其特征在于,单根管的外径为1μm,管壁厚度约为320nm,由硫化物片状阵列构成的多孔表层结构,磷化物位于纳米片的顶端;纳米片的厚度约为15nm。
7.如权利要求书1所述的制备方法,所制得的泡沫镍担载硫化物/磷化物复合亚微米管材料,可直接应用于固态超级电容器的电极。
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