CN109087821A - 羟基氧化锰自支撑复合电极及其制备方法和应用 - Google Patents
羟基氧化锰自支撑复合电极及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PVIFNYFAXIMOKR-UHFFFAOYSA-M manganese(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Mn+3] PVIFNYFAXIMOKR-UHFFFAOYSA-M 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000006260 foam Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- -1 graphite alkene Chemical class 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229910003174 MnOOH Inorganic materials 0.000 abstract description 10
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- H01G11/84—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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/46—Metal oxides
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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
本发明公开了羟基氧化锰自支撑复合电极及其制备方法和应用。采用气相沉积和电沉积法制备得到NF/GF/MnOOH自支撑复合电极。该电极具有较高的容量、良好的倍率性能和较长的循环稳定性。
Description
技术领域
本发明涉及电池超级电容器电极制备技术,具体涉及羟基氧化锰自支撑复合电极及其制备方法和应用。
背景技术
在传统电极制作工艺中,一般是将活性物质、导电剂及粘结剂混合,制成浆料或薄膜,然后涂布或压制在集流体上,再在极片一端焊接上金属条作为极耳,从而制成电极。这种电极制作方法由于加入了粘结剂,往往导电性比较差;需要焊接极耳,增加了成本;整个过程步骤繁多,工艺复杂。自支撑结构的电极是一次成型制备方法,工艺简单,可以降低生产成本,并且不使用任何添加剂,可以提高电极的导电性,这对于电极电化学性能的提高也是非常重要的,因此,制备自支撑结构的电极对于超级电容器技术的研究具有重要意义。
发明内容
为了解决现有技术的不足,本发明提供了羟基氧化锰自支撑复合电极及其制备方法和应用。
本发明的技术方案是:羟基氧化锰自支撑复合电极的制备方法,将泡沫镍放置在坩埚中,再将坩埚放入高温管式炉中,将管式炉抽成真空,通入Ar和H2,将高温管式炉程序设置为以50℃min-1的速率升温至1000℃,恒温10min后通入CH4,之后接着恒温1h,然后关闭H2和CH4,自然冷却至室温后,关闭Ar,得到泡沫镍/泡沫石墨烯电极;配置0.1M硫酸钠和0.1M乙酸锰的混合(wt%=0.82:1)溶液为电解液,以制备的泡沫镍/泡沫石墨烯电极为工作电极,铂片为辅助电极,饱和甘汞电极为参比电极组成三电极体系,在电化学工作上选用循环伏安法,设定电压范围为0.5-1.2V,扫描速率为200mV/s,扫描时间为5min,得到泡沫镍/泡沫石墨烯/羟基氧化锰;将得到的电极依次水洗乙醇洗,放入真空干燥箱80℃烘24h,将烘干后的电极片放入马弗炉中,设置升温速度为10℃min-1至400度,保持6h后自然冷却至室温后取出即得。
本发明的进一步改进包括:
所述泡沫镍还包括预处理,具体包括将剪切好的泡沫镍放入烧杯中,加入丙酮,在超声波清洗机中超声10min。然后,放入真空干燥箱中80℃烘24h。
所述通入Ar、H2和CH4速率分别为200sccm、100sccm和100sccm。
本发明的另一目的在于提供了一种按照上述方法制得的羟基氧化锰自支撑复合电极。
本发明还提供了羟基氧化锰自支撑复合电极在制备超级电容器中的应用。
本发明采用气相沉积和电沉积法制备得到NF/GF/MnOOH自支撑复合电极。本发明首次制备得到这种三相复合结构的自支撑电极,并研究了它在超级电容器性能。该电极具有较高的容量、良好的倍率性能和较长的循环稳定性。
附图说明
图1为实施例1制备的NF/GF/MnOOH自支撑复合电极的XRD图;
图2为实施1例制备的NF/GF/MnOOH自支撑复合电极的SEM图;
图3为实施1例制备的NF/GF/MnOOH自支撑复合电极的在各个电流密度下的充放电曲线图;
图4为实施1例制备的NF/GF/MnOOH自支撑复合电极的循环性能图。
具体实施方式
下面结合附图对本发明做详细说明。
实施例1
(1)将泡沫镍(NF)剪成的形状(1×1×1.5cm),放入烧杯中,加入丙酮,在超声波清洗机中超声10min。然后,放入真空干燥箱中80℃烘24h;
(2)将(1)中的NF放置在坩埚中,再将坩埚放入高温管式炉中,将管式炉抽成真空,通入Ar(200sccm)和H2(100sccm),将高温管式炉程序设置为以50℃m的速率升温至1000℃,恒温10min后通入CH4(100sccm),之后接着恒温1h,到达时间后,关闭H2和CH4,自然冷却至室温后,关闭Ar,得到泡沫镍/泡沫石墨烯(NF/GF电极)
(3)配置0.1M硫酸钠和0.1M乙酸锰的混合溶液为电解液,以上述制备的电极为工作电极,铂片为辅助电极,饱和甘汞电极为参比电极组成三电极体系,在电化学工作上选用循环伏安法,设定电压范围为0.5-1.2V,扫描速率为200mV/s,扫描时间为5min,得到泡沫镍/泡沫石墨烯/羟基氧化锰(NF/GF/MnOOH电极)
(4)将得到的电极水洗乙醇洗,放入真空干燥箱80℃烘24h。
(5)将(4)步骤所得的电极片放入马弗炉中,设置升温速度为10℃min-1,温400度,保持6h。自然冷却至室温后取出,得到如图1所示的自支撑复合电极。
(6)配置5M氢氧化钾溶液作为电解液,直接以上述得到的电极为工作电极,铂片电极为辅助电极,饱和甘汞电极为参比电极,组成三电极体系,浸泡24h后进行电化学性能的测试。测试的电压范围为0-0.35V,测试温度为室温。
检测结果:如图1所示为该复合电极的X射线衍射图。从图1可以看出该样品为NF、GF和MnOOH的复合物。图2为该复合电极的扫描电镜图,可以看出NF/GF/MnOOH复合材料是蜂窝状的微观结构。图3为上述电极在各个电流密度下的充放电曲线,从图上可以看出,当电流密度为0.5、1、2和5Ag-1时,该复合电极的比容量可以达到934、874、828、771Fg-1。图4为上述电极在2Ag-1充放电时的循环性能图,5000次循环后,容量保持率为85%。这说明本实施例所制备的NF/GF/MnOOH自支撑复合电极在超级电容器领域具有较好的应用潜力。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.羟基氧化锰自支撑复合电极的制备方法,其特征在于,将泡沫镍放置在坩埚中,再将坩埚放入高温管式炉中,将管式炉抽成真空,通入Ar和H2,将高温管式炉程序设置为以50℃min-1的速率升温至1000℃,恒温10min后通入CH4,之后接着恒温1h,然后关闭H2和CH4,自然冷却至室温后,关闭Ar,得到泡沫镍/泡沫石墨烯电极;配置0.1M硫酸钠和0.1M乙酸锰的混合溶液(wt%=0.82:1)为电解液,以制备的泡沫镍/泡沫石墨烯电极为工作电极,铂片为辅助电极,饱和甘汞电极为参比电极组成三电极体系,在电化学工作上选用循环伏安法,设定电压范围为0.5-1.2V,扫描速率为200mV/s,扫描时间为5min,得到泡沫镍/泡沫石墨烯/羟基氧化锰;将得到的电极依次水洗乙醇洗,放入真空干燥箱80℃烘24h,将烘干后的电极片放入马弗炉中,设置升温速度为10℃min-1至400度,保持6h后自然冷却至室温后取出即得。
2.根据权利要求1所述的方法,其特征在于,所述泡沫镍还包括预处理,具体包括将剪切好的泡沫镍放入烧杯中,加入丙酮,在超声波清洗机中超声10min。然后,放入真空干燥箱中80℃烘24h。
3.根据权利要求1所述的方法,其特征在于,所述通入Ar、H2和CH4速率分别为200sccm、100sccm和100sccm。
4.羟基氧化锰自支撑复合电极,其特征在于,按照权利要求1-3任一项所述方法制得。
5.羟基氧化锰自支撑复合电极作为超级电容器电极的应用。
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