CN106298263A - 一种铋/炭超级电容电池及其制备方法 - Google Patents
一种铋/炭超级电容电池及其制备方法 Download PDFInfo
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- CN106298263A CN106298263A CN201610967583.4A CN201610967583A CN106298263A CN 106298263 A CN106298263 A CN 106298263A CN 201610967583 A CN201610967583 A CN 201610967583A CN 106298263 A CN106298263 A CN 106298263A
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- Prior art keywords
- bismuth
- capacitance cell
- super capacitance
- pole
- solution
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- 239000000463 material Substances 0.000 claims abstract description 45
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- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 14
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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 claims description 2
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Abstract
本发明公开了一种铋/炭超级电容电池及其制备方法。本发明的超级电容电池以铋电极提供法拉第电容,炭电极提供双电层电容,碱溶液为电解质。所述的铋为0.005~5μm粒径的金属铋粉末、比表面积为5~500m2/g,其制备方法为:将适当摩尔比的助剂与一定浓度的铋离子配成混合溶液,然后向其滴加还原剂进行反应,制备出金属铋粉末材料。构造该电池时以铋电极为电容量限制电极,炭电极的电容量比铋电极电容量过剩0~30%。本发明超级电容电池的工作电压为0~1V,在电流密度为0.5A/g时的比电容为258mAh/g。该电池具有良好的电化学性能、环境友好,是一种具有广阔应用前景的新型化学电源。
Description
技术领域
本发明涉及一种铋/炭超级电容电池及其制备方法,属于电化学储能技术领域。
背景技术
随着社会的进步,人们对能源的需求飞速增长。目前最常见的储能器件包括电池和超级电容器两种,而在许多领域,这两者已不能很好地满足应用需求。为了同时获得较高的能量密度和功率密度,人们开始设计新型的超级电容电池,超级电容电池的一极是双电层电容电极,另一极是法拉第电容电极。超级电容电池综合了双电层电容器和电池的优点,它具有比传统电化学电容器更大的能量密度、比二次电池更高的功率密度,而且可快速充放电,使用寿命长,是一种高效实用的能量存储装置,具有广泛的应用前景。
电极活性材料是决定化学电源性能的关键因素,通常选用的电源活性材料是金属及金属氧化物、炭材料等。我国拥有十分丰富的铋资源,是世界上铋储量最大的国家,目前已探明的铋储量占世界总储量的70%以上。铋,83号元素,是一种具有共价键的典型的半金属元素,铋金属具有近似石墨的层状结构,熔点较低,仅有271℃,而沸点比熔点高1580℃,适宜用液相分散的方法制备纳米金属铋粉,且铋金属是一种绿色金属,因此铋已在医药、环保、化妆品、陶瓷、染料、润滑油、功能材料等领域显现出潜在的应用价值。
王彦敏等[山东交通学院学报4(2012)67-74.]以硝酸铋为原料,乙二醇为溶剂和还原剂,PVP为稳定剂,采用溶剂热法制备了单晶铋纳米带。赵彦保等[无机化学学报9(2003)997-1000.]以铋粒为起始原料,液体石蜡为溶剂,硬脂酸为修饰剂,采用分散法制备出硬脂酸修饰铋纳米微粒,并对其反应机理进行了研究。王轶等[延边大学学报:自然科学版3(2011)245-248.]以氯化铋为原料,水合肼为还原剂,油酸钠为表面活性剂,采用水相一步还原法制备出高纯度、粒径为20nm近似球形的超细金属铋纳米粒子,并探索了反应温度、还原剂浓度对铋纳米粒子的影响。唐春娟等[材料研究学报3(2011)273-277.]以五水硝酸铋为原料,水合肼为还原剂,CTAB为包覆剂,水和乙二胺为溶剂,详细研究了水和乙二胺的组分变化对产物的形貌和结构的影响,并进一步提出了乙二胺模板效应以及由乙二胺引起的从动力学向热力学转换控制晶体生长的生长机制。Dai等[Chemical Physics Letters591(2014)126–129.]通过改变表面活性剂的种类,制备出不同形貌的铋纳米粒子,其中采用P123为表面活性剂,能够制备出由六边形纳米棱柱组成的铋纳米花。Kim等[MaterialsChemistry and Physics 153(2015)316-322.]采用碱式碳酸铋为原料,在以四甘醇为溶剂、PVP为包覆剂的溶液中,通过两步煅烧法把直接碱式碳酸铋还原成球形铋纳米粒子。C JTang等[J Phys Chem C 113(2009)5422-5427.]分别以乙二醇和乙二胺为溶剂,通过溶剂热反应制备出铋纳米线和铋纳米花。Wang等[J Phys Chem B 110(2006)25702-25706.]通过改变PVP与铋原料的摩尔比,采用多元醇还原法,制备出不同形貌的单晶铋纳米粒子,并且在相同的合成条件下,通过引入痕量的Fe3+,能够把铋纳米立方体转换成铋纳米带。Wang等[J Phys Chem B 109(2005)7067-7072.]在室温下以DMF为溶剂,氯化铋为铋源,硼氢化钠为还原剂,PVP为封端剂,制备出铋纳米粒子;并探索了实验条件对铋纳米粒子的尺寸和单分散性的影响。Ma等[Colloids and Surfaces A:Physicochem Eng Aspects 395(2012)276-283.]以硝酸铋为铋源,酒石酸为络合剂,NaH2PO2·H2O为还原剂,通过调整酒石酸和氢氧化钠的量,采用液相表面修饰还原法制备出直径10-50nm的铋纳米粒及长度约为10μm宽度约为100nm的铋纳米带。Cheng等[Materials Letters 63(2009)2239-2242.]采用乙二醇为溶剂,利用多元醇热法,在198℃下回流2小时,制备出铋微球或纳米球,并进一步研究了其可能的生长机理。Zeng等[Advanced Materials 304(2016)1-8.]采用电化学沉积法制备出稳定的单晶态铋单质,并以铋为正极,NiCo2O4为负极,1mol/L KOH为电解液,制备出碱性二次电池,且经10000次循环后容量基本无衰减。Zuo等[Nanomaterials 4(2015)1756-1765]以Ti为基底,采用简单的水热法使铋单质均匀分散在Ti基质上,在1mol/L KOH电解质溶液中和0.5A/g电流密度下铋电极比电容量为170mAh/g。Timothy S.Arthur等[Electrochemistry Communications 16(2012)103-06.]采用电沉积法制备出单质Bi、Sb和Bi1-xSbx合金,并将其应用于Mg离子电池的正极材料。
发明专利[申请公开号CN101569934A]公开了“一种金属铋纳米粒的制备方法”,通过混合可溶性铋盐水溶液和修饰剂有机溶液,加入还原剂,搅拌加热回流,制备出粒径分布比较均一的金属铋纳米粒。发明专利[申请公开号CN102212880A]公开了“一种Bi单质纳米结构材料及其制备方法与应用”,将表面活性剂、水合肼和铋盐溶于水制备成悬浊液;将所述悬浊液在80~120℃条件下反应18~30小时,制备出由片状六方晶相Bi单质为结构单元组成的具有花朵状形貌的纳米颗粒,并将其制备成铋修饰电极,应用于水溶液中的重金属离子检测。发明专利[申请公开号CN102717095A]公开了“一种单分散铋纳米颗粒的制备方法”,本发明采用乙酸铋作为铋源,油胺或油酸作为包裹剂和表面活性稳定剂,在有机相体系中合成铋纳米颗粒,所制得的铋纳米颗粒具有较高的产率,很好的稳定性。发明专利[申请公开号CN102989507A]公开了“一种铋基光催化剂的制备及性能检测方法”,该发明首先将Bi(NO3)3·5H2O溶于醋酸,以乙二醇为反应介质,搅拌混匀,再加入一定体积的二甲基甲酰胺后,将得到的溶液经加热回流并搅拌即得到产物Bi-DMF花球。将制备的Bi-DMF花球在可见光条件下进行光催化性能测试,在2h内罗丹明由紫色褪为无色,降解完全。表明此球形铋基催化剂在可见光范围内,具有良好的光催化性能。发明专利[申请公开号CN105312086A]公开了“一种石榴状碳包覆铋纳米复合材料和其制备方法”,该发明在密闭容器中,将水溶性糖类、硝酸铋和聚乙烯吡咯烷酮溶于水,再加入有机酸,在160~260℃反应,经洗涤、干燥得到石榴状碳包覆铋纳米复合材料。并且该材料对黑索金的热分解有明显的催化作用,可将其应用于推进剂燃烧催化。发明专利[申请公开号CN104475133A]公开了“一种Bi/BiOCl光催化剂的制备方法”,本发明采用一步燃烧法,以硝酸铋、氯化铵和柠檬酸为原料,通过硝酸盐和柠檬酸间的氧化还原反应,制备出Bi/BiOCl复合光催化剂。
目前已有不少关于金属铋作为光催化剂和润滑剂等应用方面的报道,但关于铋在超级电容电池方面的研究与应用还未见相关报道。
发明内容
本发明的目的在于提供一种新型的铋/炭超级电容电池及其制备方法。本发明采用铋电极提供法拉第电容量,采用炭电极提供双电层电容量,组装成超级电容电池,提供较高比电容量的化学电源。
本发明的技术方案为:
一种铋/炭超级电容电池,其特征在于,包括铋电极和炭电极,铋电极提供法拉第电容,炭电极提供双电层电容,碱溶液作为电解液,构造该超级电容电池时,采用铋电极为电容量限制电极,炭电极的电容量比铋电极的电容量过剩0~30%。
所述的炭电极,采用的炭材料为活性炭、石墨化碳、或者石墨烯材料,其按元素组成的质量百分比计为:碳元素60~95%、氧元素0.01~25%、氢元素0.05~5%、氮元素0~15%;炭材料的粒径为0.05~3μm、比表面积为500~3000m2/g。
铋电极材料由粒径为0.005~5μm的金属铋粉末材料构成,其比表面积为5~500m2/g。
铋电极材料的制备方法包括如下步骤:
(1)将可溶性的铋原料溶于溶剂中,将其配制成铋离子浓度为0.01~5mol/L的溶液;或者将不溶性的铋原料溶于酸中,配制成铋离子浓度为0.01~5mol/L的溶液;
(2)将还原剂溶解于溶剂中配制成浓度为0.1~16mol/L还原剂溶液;
(3)按助剂(封端剂)与铋离子(0~10):1的摩尔比,将助剂加入到铋离子溶液中,充分混合;
(4)在温度为0~100℃和搅拌条件下,按还原剂与铋离子的摩尔比为(1~100):1将还原剂溶液滴加到含助剂的铋离子溶液中,滴加完成后继续搅拌反应1~360min后,将产物分别用水和乙醇洗涤,并进行固液分离,将固体物在30~100℃的真空干燥箱中烘干6~36h至恒重制备出铋粉末,即铋电极材料。
进一步地,所述的溶剂为水、甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙三醇、聚乙二醇、三乙醇胺、四甘醇、DMF中的一种或两种以上。
进一步地,所述的铋原料,包括金属铋、氧化铋、氢氧化铋、碳酸铋、碱式碳酸铋、硫酸氧铋、硝酸氧铋、硫酸铋、硝酸铋、卤化铋、乙酸铋、柠檬酸铋中的一种或两种以上。
进一步地,所述的酸溶液为盐酸、硫酸、醋酸或硝酸,其浓度为0.1~5mol/L。
进一步地,所述的还原剂为硼氢化钠、硼氢化钾、次亚磷酸钠、烷基胺硼烷、水合肼、脂肪醛、芳香醛中的一种或两种以上。
进一步地,所述的助剂为聚乙二醇、乙二醇、丙三醇、三乙醇胺、柠檬酸、抗坏血酸、酒石酸、油酸钠、CTAB、PVP中的一种或两种以上。
上述的铋/炭超级电容电池的制备方法,包括如下步骤:
(1)铋电极和炭电极的制备
将粘结剂溶于N-甲基吡咯烷酮中,配成0.02~1g/ml的溶液,再将铋或炭材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在集流体上,再将其在80~150℃的干燥箱中干燥5~36h,经辊压后裁成电极片,即得到铋电极或炭电极,所述铋或炭材料、导电剂及粘结剂满足如下质量百分比:铋或炭材料70~95%、导电剂3~15%、粘结剂2~15%;
(2)铋/炭超级电容电池的组装
将步骤(1)中得到的电极片按铋电极片、隔膜、炭电极片依次放入超级电容电池模具中构造成二电极的三明治结构,滴加电解液后将超级电容电池模具紧固密封,即构造成该超级电容电池。
进一步地,所述的导电剂为导电炭黑、乙炔黑、石墨、石墨烯中的一种或两种以上。
进一步地,所述的粘结剂为聚四氟乙烯、聚偏氟乙烯、羧甲基纤维素钠或丁苯橡胶中的一种或两种以上。
进一步地,所述的集流体为多孔网状、箔状或织物状的高电子导电率材料,涉及到泡沫镍、镍箔或镍网、铜网或铜箔、不锈钢网、不锈钢冲孔钢带或不锈钢箔、钛箔或钛网、铅箔或铅布、石墨化碳布或石墨烯布材料中的一种或两种以上;
进一步地,构造该超级电容电池时,采用铋电极为电容量限制电极,炭电极的电容量比铋电极的电容量过剩0~30%。
进一步地,所述的电解液为一种或两种以上碱金属氢氧化物的水溶液,其浓度为1~8mol/L。
进一步地,所述的隔膜为接枝聚丙烯无纺布、接枝PP微孔膜、玻璃纤维纸、尼龙无纺布、聚乙烯醇膜、石棉纸中的一种或两种以上。
所制备材料的结构与电化学性能测试
采用JEOLJEM-3010型扫描电子显微镜对所制备材料进行微观形貌及大小的测试;采用D/MAX-3C型粉末X-射线衍射仪对所制备的材料进行晶相结构的测试。
采用上海辰华公司生产的CHI660A电化学工作站、深圳市新威尔电子有限公司生产的BTS-3000电池测试仪对所构造的超级电容电池进行循环伏安、恒流充放电、循环寿命、倍率性能测试。
本发明的有益效果在于:
本发明以铋电极提供法拉第电容,炭电极提供双电层电容,构造出新型的超级电容电池,使其具有超级电容器和二次电池的优点,本发明所得的超级电容电池的工作电压窗口为0~1V,0.5A/g时的比电容为258mAh/g,5A/g时的比电容为213mAh/g。具有库仑效率高、循环寿命长、电容量大、对环境友好等优点,是一种具有广阔应用前景的新型化学电源。
附图说明
图1为实施例1所制备的铋粉末材料的扫描电子显微镜图。
图2为实施例2所制备的铋粉末材料的扫描电子显微镜图。
图3为实施例1所制备的铋粉末材料的X射线衍射图。
图4为实施例1中铋/炭超级电容电池在不同电流密度下的恒电流充放电测试图。
图5为实施例3中铋/炭超级电容电池在不同扫描速率下的循环伏安测试图。
图6为实施例4所制备的铋/炭超级电容电池在20mV/s扫描速率下不同周期的循环伏安图。
图7为实施例5中铋/炭超级电容电池在0.5A/g电流密度下的恒电流充放电测试图。
图8为实施例5中铋/炭超级电容电池的电流倍率性能图。
图9为实施例5中铋/炭超级电容电池的循环寿命图。
具体实施方式
下面以具体实施例进一步说明本发明,但本发明并不局限于此。
实施例1
(1)称取一定质量Bi(NO3)3·5H2O,溶解于10ml浓硝酸溶液中,加水稀释后,配制成0.5mol/L的Bi(NO3)3溶液,备用。
(2)将2.22gPVP、20mL 0.5mol/L的Bi(NO3)3溶液依次加入100mL圆底烧瓶中,混合均匀后,在室温下搅拌30min。
(3)按硼氢化钠和铋离子摩尔比为3:1,称取一定质量的硼氢化钠溶于20ml去离子水中配成硼氢化钠溶液,在室温下,一边搅拌一边将硼氢化钠溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌5min,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中90℃下干燥12h,制得铋材料。
(4)采用JEOLJEM-3010型扫描电子显微镜对实施例1所制备的铋粉末材料进行测试,如图1所示,该材料由粒径约为20-50nm的纳米粒组成花椰菜形貌。
(5)采用XRD-6000型X-射线衍射仪对实施例1所制备的铋粉末材料进行测试,如图3所示,样品在2θ=22°,24°,27°,38°,40°,45°,46°,49°,56°和59°等位置均有较明显的特征峰,和标准卡片(JCPDS No.44-1246)一致,其所对应的晶面分别为003、101、012、104、110、015、113、202、024和107。
(6)铋电极及炭电极的制备:按照铋或者炭材料80%、粘结剂PVDF12%及导电剂乙炔黑8%的质量百分比,首先将粘结剂溶于N-甲基吡咯烷酮中,配成0.02g/ml的溶液,再将铋或者炭材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在泡沫镍集流体上,再将其在100℃的真空干燥箱中烘干12h,经辊压后裁成电极片,即得到铋材料电极片或者炭材料电极片。
(7)将已制备的铋电极片/隔膜/炭电极片依次放入特制的电池模具中构造成二电极的三明治结构,再滴加6mol/LKOH电解液后将电池模具紧固密封,即组装成所述的铋/炭超级电容电池。
(8)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/炭超级电容电池在室温下进行恒流充放电测试,电压窗口为0~1V。由图4可知,该电容电池在0.5A/g的电流密度下比电容达到258mAh/g,在电流密度为1、2和5A/g时的比电容分别为254、242和213mAh/g。
实施例2
(1)称取1.99g柠檬酸铋溶解于20ml乙二醇溶液中。
(2)将0.5g酒石酸、2.0g氢氧化钠依次加入加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按NaH2PO2和铋离子摩尔比为80:1,称取一定质量的NaH2PO2溶于40ml去离子水中配成NaH2PO2溶液,在90℃下,一边搅拌一边将NaH2PO2液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌300min,直至溶液由澄清变为黑色,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中80℃下干燥18h,制得铋材料。
(4)采用JEOLJEM-3010型扫描电子显微镜对实施例2所制备的铋粉末材料进行测试,如图2所示,该材料由粒径约为0.5-5μm的颗粒组成
实施例3
(1)称取一定质量Bi2(SO4)3,溶解于10mL浓硫酸溶液中,配制成0.5mol/L的Bi2(SO4)3溶液,备用。
(2)将0.05g油酸钠加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按水合肼和铋离子摩尔比为80:1,量取80wt%的水合肼稀释成一定浓度的溶液,在90℃下,一边搅拌一边将水合肼溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌120min,直至溶液由澄清变为黑色,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中70℃下干燥24h,制得铋材料。
(4)铋电极及炭电极的制备:按照铋或者炭材料80%、粘结剂PVDF10%及导电剂乙炔黑10%的质量百分比,首先将粘结剂溶于N-甲基吡咯烷酮中,配成0.02g/ml的溶液,再将铋或者炭材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在泡沫镍集流体上,再将其在100℃的干燥箱中干燥12h,经辊压后裁成电极片,即得到铋材料电极片或者炭材料电极片。
(5)将已制备的炭电极片/隔膜/铋电极片依次放入特制的电池模具中构造成二电极的三明治结构,再滴加5mol/L KOH和1mol/L LiOH的混合电解液后将电池模具紧固密封,即组装成所述的铋/炭超级电容电池。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/炭超级电容电池在室温下进行循环伏安测试,电压窗口为0~1V。如图5所示,所制备铋电极在不同扫描速率下(5、10、20、50mV/s)的循环伏安曲线,表现出明显的法拉第反应特征,即使在较高的扫速下,氧化还原可逆性良好。
实施例4
(1)称取一定质量Bi(CH3COO)3,溶解于20ml乙酸溶液中,加水稀释后,配制成0.5mol/L的Bi(CH3COO)3溶液,备用。
(2)将0.01g柠檬酸和0.025g CTAB加入到步骤(1)溶液中,混合均匀后,在室温下搅拌30min。
(3)按水合肼和铋离子摩尔比为100:1,量取80wt%的水合肼稀释成一定浓度的溶液,在90℃下,一边搅拌一边将水合肼溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌90min,直至溶液由澄清变为黑色,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中100℃下干燥10h,制得铋材料。
步骤(4)、(5)分别同实施例1中的步骤(6)、(7)。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/炭超级电容电池在室温下进行循环伏安测试,电压窗口为0~1V。如图6所示,在20mV/s扫描速率下不同循环周期(第1次和第20次循环)的循环伏安曲线,氧化峰与还原峰分别为0.78V和0.47V,它们基本重合,说明此电极稳定可逆性良好。
实施例5
(1)称取一定质量BiCl3,溶解于10ml浓盐酸溶液中,加水稀释后,配制成0.5mol/L的BiCl3溶液,备用。
(2)将2.22gPVP、20mL 0.5mol/L的BiCl3溶液依次加入100mL圆底烧瓶中,混合均匀后,在室温下搅拌30min。
(3)按硼氢化钾和铋离子摩尔比为4:1,称取一定质量的硼氢化钾溶于20ml去离子水中配成硼氢化钾溶液,在室温下,一边搅拌一边将硼氢化钾溶液逐滴加入到步骤(2)溶液中,滴加完成后,继续搅拌5min,将所得物分别用蒸馏水和乙醇洗涤与抽滤多次至pH值为中性,放入真空干燥箱中60℃下干燥30h,制得铋材料。
步骤(4)、(5)分别同实施例1中的步骤(6)、(7)。
(6)采用上海辰华公司生产的CHI660A电化学工作站,对所构造的铋/炭超级电容电池在室温下进行恒流充放电测试,电压窗口为0~1V。由图7可知,在0.5A/g的电流密度下比电容达到215mAh/g。
(7)采用深圳市新威尔电子有限公司生产的BTS-3000电池测试仪,对所构造的铋/炭超级电容电池在室温下进行倍率性能和循环寿命测试,电压窗口为0~1V。由图8可见,在电流密度为0.5A/g时的比电容达到215mAh/g,当电流密度为5A/g时的比电容达到196mAh/g,容量保持率达91.2%,说明具有优越的电流倍率性能。对其进行循环寿命测试,由图9可见,在5A/g的电流密度下,经过1000次充放电循环之后以后还能保持初始比电容的73.8%,这说明其具有良好的循环稳定性能。
Claims (10)
1.一种铋/炭超级电容电池,其特征在于,铋电极提供法拉第电容,炭电极提供双电层电容,碱溶液作为电解液,构造该超级电容电池时,采用铋电极为电容量限制电极,炭电极的电容量比铋电极的电容量过剩0~30%。
2.根据权利要求1所述的铋/炭超级电容电池,其特征在于:所述的炭电极,所采用的炭材料为活性炭、石墨化碳、或者石墨烯材料,其元素组成按质量百分比计为:碳元素60~95%、氧元素0.01~25%、氢元素0.05~5%、氮元素0~15%;炭材料的粒径为0.05~3μm、比表面积为500~3000m2/g。
3.根据权利要求1所述的铋/炭超级电容电池,其特征在于,铋电极材料由粒径为0.005~5μm的金属铋粉末材料构成,其比表面积为5~500m2/g。
4.根据权利要求1、2或3所述的铋/炭超级电容电池,其特征在于,铋电极材料的制备方法包括如下步骤:
(1)将可溶性的铋原料溶于溶剂中,将其配制成铋离子浓度为0.01~5mol/L的溶液;或者将不溶性的铋原料溶于酸中,配制成铋离子浓度为0.01~5mol/L的溶液;
(2)将还原剂溶解于溶剂中配制成浓度为0.1~16mol/L还原剂溶液;
(3)按助剂与铋离子(0~10):1的摩尔比,将助剂加入到铋离子溶液中,充分混合;
(4)在温度为0~100℃和搅拌条件下,按还原剂与铋离子的摩尔比为(1~100):1将还原剂溶液滴加到含助剂的铋离子溶液中,滴加完成后继续搅拌反应1~360min后,将产物分别用水和乙醇洗涤,并进行固液分离,将固体物在30~100℃的真空干燥箱中烘干6~36h至恒重制备出铋粉末,即铋电极材料。
5.根据权利要求4所述的铋/炭超级电容电池,其特征在于,所述的溶剂为水、甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙三醇、聚乙二醇、三乙醇胺、四甘醇、二甲基甲酰胺中一种或两种以上;所述的酸溶液为盐酸、硫酸、醋酸或硝酸,其浓度为0.1~5mol/L。
6.根据权利要求4所述的铋/炭超级电容电池,其特征在于,所述的铋原料,包括金属铋、氧化铋、氢氧化铋、碳酸铋、碱式碳酸铋、硫酸氧铋、硝酸氧铋、硫酸铋、硝酸铋、卤化铋、乙酸铋、柠檬酸铋中的一种或两种以上。
7.根据权利要求4所述的铋/炭超级电容电池,其特征在于,所述的还原剂为硼氢化钠、硼氢化钾、次亚磷酸钠、烷基胺硼烷、水合肼、脂肪醛、芳香醛中的一种或两种以上。
8.根据权利要求4所述的铋/炭超级电容电池,其特征在于,所述的助剂为聚乙二醇、乙二醇、丙三醇、三乙醇胺、柠檬酸、抗坏血酸、酒石酸、油酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮中的一种或两种以上。
9.权利要求1至8任一项所述的铋/炭超级电容电池的制备方法,其特征在于,包括如下步骤:
(1)铋电极和炭电极的制备
将粘结剂溶于N-甲基吡咯烷酮中,配成0.02~1g/ml的溶液,再将铋或炭材料、导电剂加入到粘结剂溶液中,搅拌均匀至膏状,涂覆在集流体上,再将其在80~150℃的干燥箱中烘干5~36h,经辊压后裁成电极片,即得到铋电极或炭电极,所述铋或炭材料、导电剂及粘结剂满足如下质量百分比:铋或炭材料70~95%、导电剂3~15%、粘结剂2~15%;
(2)铋/炭超级电容电池的组装
将步骤(1)中得到的电极片按铋电极片、隔膜、炭电极片依次放入超级电容电池模具中构造成二电极的三明治结构,滴加电解液后将超级电容电池模具紧固密封,即组装成超级电容电池;构造该超级电容电池时,炭电极的电容量比铋电极的电容量过剩0~30%。
10.根据权利要求9所述的铋/炭超级电容电池的制备方法,其特征在于,所述的导电剂为导电炭黑、乙炔黑、石墨、石墨烯中的一种或两种以上;所述的粘结剂为聚四氟乙烯、聚偏氟乙烯、羧甲基纤维素钠或丁苯橡胶中的一种或两种以上;所述的集流体为多孔网状、箔状或织物状的高电子导电率材料,涉及到泡沫镍、镍箔或镍网、铜网或铜箔、不锈钢网、不锈钢冲孔钢带或不锈钢箔、钛箔或钛网、铅箔或铅布、石墨化碳布或石墨烯布材料中的一种或两种以上;所述的电解液为一种或两种以上碱金属氢氧化物的水溶液,其浓度为1~8mol/L;所述的隔膜为接枝聚丙烯无纺布、接枝PP微孔膜、玻璃纤维纸、尼龙无纺布、聚乙烯醇膜、石棉纸中的一种或两种以上。
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CN114744223A (zh) * | 2022-05-06 | 2022-07-12 | 湖北理工学院 | 一种铁铬氧化还原液流电池电极材料及其制备方法 |
CN114744223B (zh) * | 2022-05-06 | 2024-01-26 | 湖北理工学院 | 一种铁铬氧化还原液流电池电极材料及其制备方法 |
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