CN108878173A - 一种石墨烯正极片异质结掺杂的制备方法 - Google Patents
一种石墨烯正极片异质结掺杂的制备方法 Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
本发明涉及一种石墨烯正极片异质结掺杂的制备方法。本发明属于化学电源技术领域。一种石墨烯正极片异质结掺杂的制备方法,采用等离子体增强化学气相沉积法掺杂异质结元素,工艺过程:1)将石墨烯材料、导电剂、粘结剂混合,溶解于有机溶剂中形成前驱体溶液,通过刮涂或擀膜方式制备石墨烯正极片;有机溶剂优选NMP或乙醇;2)将石墨烯正极片在真空100‑150℃条件下,保持12‑24h;3)将石墨烯正极片于PECVD设备抽真空至8*10‑4Pa;4)将硼烷或磷烷通入PECVD设备起辉,硼烷、磷烷气体分解,对石墨烯正极片进行掺杂。本发明石墨烯异质结的掺杂不再局限于化学方法,其使用范围明显拓宽,同时具有安全性高、易于制备和大规模生产等优点。
Description
技术领域
本发明属于化学电源技术领域,特别是涉及一种石墨烯正极片异质结掺杂的制备方法。
背景技术
由于能源危机和环境污染带来的问题日益严重,为了降低对燃油的消耗,研发电动汽车的工作变得日益紧迫。目前技术最成熟的电动汽车用动力电源(动力电池)是锂离子电池。但是锂离子电池的功率密度低,不能大电流充电,导致充电时间过长,在实际应用中带来诸多不便。此外,锂离子电池还存在着循环寿命短的问题,在实际应用中,由于电池组的频繁更换带来极高的使用成本,进一步限制了电动汽车的普及。
为了解决这些问题,人们不断尝试改进锂离子电池的电化学性能,甚至研发新型的电源,以取代锂离子电池。在新型电源的研发工作中,Nanotek仪器提出了一种被称为石墨烯表面锂离子交换电池的新型电池,也被称为石墨烯表面锂离子交换电池。该电池通过材料表面吸附锂离子和表面氧化还原反应进行储能,这种储能机理决定了其具有高功率密度的特性,可以进行快速的充放电,其充电时间可以少于1分钟。同时,由于电极结构在充放电过程中不发生改变,使得该新型电池具有极高的循环寿命。而报道中未做优化的石墨烯表面锂离子交换电池的能量密度也与锂离子电池基本相当,这些条件使得该新型电池具有极高的应用潜力,也很有可能在电动汽车领域得到广泛的应用。根据此新型电池,大家提出石墨烯基锂离子电容器作为一种新型的化学电容器,既有锂离子电池的高能量,又有电容器的高功率,在当前化学电源领域中,有非常广阔的应用前景。
石墨烯基锂离子电容器选取石墨烯材料作为基本材料,原因在于它具有特殊的结构以及优良的性质。石墨烯是由具有六边形结构的sp2杂化碳原子构成的二维单层材料,在石墨烯片层中存在着两种键:σ-σ键和π键。σ-σ键存在于石墨烯的二维平面上,由于其键能最强,故使其具有良好的刚性结构。π键则存在于石墨烯的二维平面外,是由垂直于平面的p电子轨道相互叠加形成的,这种离域大π键的存在有利于其电子导电性且为石墨烯片层之间提供较弱的作用力。新型储能电源因其高效、实用、“绿色”等特点而在储能装置中占有突出地位,而如此优良的碳材料-石墨烯也必将会在各种新型储能电源中发挥其作用。
目前,石墨烯基锂离子电容器中石墨烯正极片的放电比容量和库伦效率的提升受到限制,并且含氧官能团和活性位点在长循环过程中导致循环稳定性较差,容量保持率衰减较快,这些问题会大幅度降低石墨烯锂离子电容器的能量密度,因此,并不具备实际应用的潜力。
发明内容
本发明为解决公知技术中存在的技术问题而提供一种石墨烯正极片异质结掺杂的制备方法。
本发明的目的是提供一种石墨烯正极片异质结掺杂的制备方法。通过对石墨烯正极片进行异质结原子掺杂,如B、P、N等,可以对正极片表面进行修饰,增加其他官能团、活性位点或提高正极片的导电性,进而提高电池的放电比容量和循环稳定性。
本发明石墨烯正极片异质结掺杂的制备方法所采取的技术方案是:
一种石墨烯正极片异质结掺杂的制备方法,其特点是:石墨烯正极片异质结掺杂的制备方法,采用等离子体增强化学气相沉积法掺杂异质结元素,工艺过程:
1)将石墨烯材料、导电剂、粘结剂混合,溶解于有机溶剂中形成前驱体溶液,通过刮涂或擀膜方式制备石墨烯正极片;有机溶剂优选NMP或乙醇;
2)将石墨烯正极片在真空100-150℃条件下,保持12-24h;
3)将石墨烯正极片于PECVD设备抽真空至8*10-4Pa;
4)将硼烷或磷烷通入PECVD设备起辉,硼烷、磷烷气体分解,对石墨烯正极片进行掺杂。
本发明石墨烯正极片异质结掺杂的制备方法还可以采用如下技术方案:
所述的石墨烯正极片异质结掺杂的制备方法,其特点是:石墨烯材料为人工合成石墨或天然石墨制备的石墨烯,氧化石墨烯的一种或多种组合。
所述的石墨烯正极片异质结掺杂的制备方法,其特点是:导电剂为乙炔黑、SuperP、Super S、350G、碳纤维(VGCF)、碳纳米管(CNTs)、科琴黑(KetjenblackEC300J、KetjenblackEC600JD、Carbon ECP、Carbon ECP600JD)、石墨导电剂(KS-6、KS-15、SFG-15等)以及石墨烯中的一种或多种组合。
所述的石墨烯正极片异质结掺杂的制备方法,其特点是:粘结剂为水性或油性粘结剂,包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚氧化乙烯(PEO)、聚碳酸丙烯酯(PPC)、聚碳酸乙烯酯(PEC)、聚三亚甲基碳酸酯(PTMC)、聚乙烯醇(PVA)、羧甲基纤维素钠(CMC)、聚烯烃类(聚乙烯、聚丙烯及其共聚物)、改性SBR、氟化橡胶、聚氨酯中的一种或多种组合。
所述的石墨烯正极片异质结掺杂的制备方法,其特点是:溶解活性物质所用有机溶剂为四氢呋喃、碳酸丙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、乙腈、异丙醚、丙酮、丁酮、异丙醇、丁醇、己烷、环己烷、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、苯、甲苯、二甲基亚砜、四氯化碳、三氯化烯、吡咯、酒精中的一种或多种组合。
所述的石墨烯正极片异质结掺杂的制备方法,其特点是:异质结元素为B、P或N的一种或多种组合。
本发明石墨烯正极片异质结掺杂的制备方法,其石墨烯基锂离子电容器正极材料,为层状2D石墨烯材料或3D孔状石墨烯基材料。负极材料包括但不限于金属锂、锂合金LixM(M=In、B、Al、Ga、Sn、Si、Ge、Pb、As、Bi、Sb、Cu、Ag、Zn)、碳基材料(石墨、无定形碳、中间相炭微球、硬碳、软碳)、硅基材料(硅碳材料、纳米硅)、锡基材料以及钛酸锂(Li4Ti5O12)。
本发明具有的优点和积极效果是:
石墨烯正极片异质结掺杂的制备方法由于采用了本发明全新的技术方案,与现有技术相比,本发明石墨烯正极片异质结掺杂的制备方法不再局限于化学领域,其利用范围明显拓宽,同时具有易于制备和大规模生产的特点,是未来高能量高功率石墨烯基锂离子电容器的石墨烯正极片掺杂的优势候选。
附图说明
图1为本发明实施例1中所用的PECVD设备的结构示意图;
图2为本发明实施例1中石墨烯原料正极片的放电比容量和循环性能图;
图3为本发明实施例1中掺杂B元素后石墨烯正极片的放电比容量和循环性能图。
具体实施方式
为能进一步了解本发明的发明内容、特点及功效,兹例举以下实施例,并配合附图详细说明如下:
参阅附图1、图2和图3。
实施例1
一种石墨烯正极片异质结掺杂的制备方法,将石墨烯正极极片、锂离子电池电解液和负极组装制成锂离子电容器。包括以下工艺过程包括:
1)将石墨烯材料、导电剂、粘结剂按比例混合,溶解于NMP或乙醇等有机溶剂中形成前驱体溶液,通过刮涂或擀膜方式制备石墨烯正极片;
2)将石墨烯正极片放置于真空烘箱中100-150℃,保持12-24h;
3)将石墨烯正极片放置于PECVD设备中的架子拖上,抽真空至8×10-4Pa;
4)将硼烷、磷烷、氨气或者与氢气的混合气体通入设备中,设定功率起辉,硼烷、磷烷、氨气或与氢气的混合气等气体分解,对石墨烯正极片进行异质结掺杂。
具体操作过程:
将0.4g石墨烯原料与0.04g导电剂(SP)混合,加入2ml酒精,常温下搅拌2小时使其混合均匀,再加入1ml PTFE粘结剂,搅拌2小时至分散均匀形成类似于面团似的胶体;通过擀膜的方法擀出厚度约100-200um的石墨烯正极片;将正极切割成5cm×5cm的正方形,真空100℃下干燥12小时;将正方形正极片放置于PECVD设备的衬底架上,调节衬底间距为15cm,设定功率为100W,通入5sccm硼烷,起辉辉光溅射5min制备出B掺杂的石墨烯正极片;在氩气手套箱中配制锂离子电解液,加入10ml碳酸乙烯酯(EC)和碳酸二甲酯(DMC)溶剂,配置1mol/L的LiPF6溶液,常温下搅拌12小时使其混合均匀;在氩气气氛手套箱中将金属锂裁剪成Φ20的圆片。将通过上述过程制备的异质结掺杂石墨烯正极片、锂离子电解液、负极组装锂离子电容器,测试电池循环性能,电压范围为1.5V-4.2V,电流密度为100mA/g,测试温度为25℃。
本实施例以石墨烯材料作为主体制备的柔性石墨烯正极片,通过对石墨烯正极片进行异质结掺杂,获得库伦效率较高和放电比容量较稳定的锂离子电容器;具有易于制备和大规模生产等积极效果。
Claims (6)
1.一种石墨烯正极片异质结掺杂的制备方法,其特征是:石墨烯正极片异质结掺杂的制备方法,采用等离子体增强化学气相沉积法掺杂异质结元素,工艺过程:
1)将石墨烯材料、导电剂、粘结剂混合,溶解于有机溶剂中形成前驱体溶液,通过刮涂或擀膜方式制备石墨烯正极片;有机溶剂优选NMP或乙醇;
2)将石墨烯正极片在真空100-150℃条件下,保持12-24h;
3)将石墨烯正极片于PECVD设备抽真空至8*10-4Pa;
4)将硼烷或磷烷通入PECVD设备起辉,硼烷、磷烷气体分解,对石墨烯正极片进行掺杂。
2.根据权利要求1所述的石墨烯正极片异质结掺杂的制备方法,其特征是:石墨烯材料为人工合成石墨或天然石墨制备的石墨烯,氧化石墨烯的一种或多种组合。
3.根据权利要求1所述的石墨烯正极片异质结掺杂的制备方法,其特征是:导电剂为乙炔黑、Super P、Super S、350G、碳纤维、碳纳米管、科琴黑、石墨导电剂以及石墨烯中的一种或多种组合。
4.根据权利要求1所述的石墨烯正极片异质结掺杂的制备方法,其特征是:粘结剂为水性或油性粘结剂,为聚偏氟乙烯、聚四氟乙烯、聚氧化乙烯、聚碳酸丙烯酯、聚碳酸乙烯酯、聚三亚甲基碳酸酯、聚乙烯醇、羧甲基纤维素钠、聚乙烯、聚丙烯及其共聚物、改性SBR、氟化橡胶、聚氨酯中的一种或多种组合。
5.根据权利要求1、2或3所述的石墨烯正极片异质结掺杂的制备方法,其特征是:溶解活性物质所用有机溶剂为四氢呋喃、碳酸丙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、乙腈、异丙醚、丙酮、丁酮、异丙醇、丁醇、己烷、环己烷、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、苯、甲苯、二甲基亚砜、四氯化碳、三氯化烯、吡咯、酒精中的一种或多种组合。
6.根据权利要求1、2或3所述的石墨烯正极片异质结掺杂的制备方法,其特征是:异质结元素为B或P中的一种或两种组合。
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